CN113667115A - Semi-aromatic high-temperature-resistant PA6T/11 material and preparation method thereof - Google Patents
Semi-aromatic high-temperature-resistant PA6T/11 material and preparation method thereof Download PDFInfo
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- CN113667115A CN113667115A CN202111031197.1A CN202111031197A CN113667115A CN 113667115 A CN113667115 A CN 113667115A CN 202111031197 A CN202111031197 A CN 202111031197A CN 113667115 A CN113667115 A CN 113667115A
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- 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
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G69/04—Preparatory processes
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Abstract
The invention belongs to the field of polymer synthesis, and relates to a semi-aromatic high-temperature-resistant PA6T/11 material and a preparation method thereof, wherein the raw materials for producing the semi-aromatic high-temperature-resistant PA6T/11 material comprise the following components in parts by weight: 60-75 parts of PA6T salt, 25-40 parts of 11-aminoundecanoic acid, 0.05-0.1 part of nucleating agent, 0.03-0.05 part of catalyst and 80-120 parts of solvent. The invention also discloses a preparation method of the material. The raw materials of the invention are more environment-friendly, which is beneficial to green sustainable development, and the prepared composite material has good toughness and reduced melting point. The invention has the advantages of few process steps, short polymerization period, high production efficiency, low production cost and the like, and the synthesized resin has low water absorption and stable performance and creates conditions for continuous industrial production in the future.
Description
Technical Field
The invention belongs to the field of polymer synthesis, and particularly relates to a semi-aromatic high-temperature-resistant PA6T/11 material and a preparation method thereof.
Background
With the rapid development of scientific technology, the semi-aromatic nylon becomes a high-performance engineering plastic which is concerned by the outstanding high-temperature resistance, and more industrialized products emerge endlessly, wherein the most representative products are: PA46 from DSM (Dismann), PA6T from Dupont (DuPont), Amoco (Amoxico), EMS, Solvay, Mitsui, Japan, and PA9T from Kuraray, Japan. PA6T attracts attention due to low hygroscopicity, dimensional stability, high strength and excellent chemical resistance, and meanwhile, PA6T is low in cost, is a high-temperature-resistant PA material with the highest market share at present, and is widely applied to the industries of automobiles, electric appliances and electronics.
The PA6T which is commercialized at present is actually a copolymerization modified variety thereof, and due to the introduction of a comonomer, the melting temperature of the PA6T can be reduced to be lower than 300 ℃ so as to facilitate processing, and simultaneously, the crystallinity and the crystallization capacity of the PA6T are reduced, so that the size stability and the chemical resistance of the PA6T are deteriorated. Nowadays, new PA6T varieties with improved performance are continuously provided by various companies to adapt to the continuously expanded high-temperature-resistant nylon market. The monomer raw materials used in the PA6T copolymerization products which are industrialized at present, such as PA6T/66, PA6T/6 and the like, are mostly derived from petroleum, do not meet the requirements of realizing industrialized production by renewable resources, and have the idea of energy conservation and sustainable development.
In addition, the PA6T copolymer products on the market are mostly prepared by solid-phase polymerization, when the polyamide is solidified in a melt phase, most of the reactive end groups and water can be excluded from the crystalline phase, any further reaction taking place in the amorphous phase, while still part of the reactive end groups are trapped in the crystalline phase and cannot participate in the reaction, this results in part of the starting material remaining unchanged during the polymerization, leading to a broadening of the relative molecular mass distribution as the reaction proceeds, while temperature inhomogeneities, diffusion effects and non-equilibrium reaction conditions also broaden it, when the polyamide formed by solid-phase polymerization is melt-processed by injection molding or extrusion, the system is rebalanced to adjust the end groups in the amorphous phase and the end groups trapped in the crystalline phase, the relative molecular mass distribution is rapidly restored to normal in a short time, so that the viscosity and the apparent relative molecular mass are rapidly decreased, thereby affecting the stability of the properties of the polymer product.
Moreover, the polymerization method has the disadvantages of multiple process steps, long polymerization period, high production cost and high water absorption of the synthetic resin, and limits the wide application of the synthetic resin in large-scale industrial production.
Disclosure of Invention
In order to solve the problems, the invention discloses a semi-aromatic high-temperature-resistant PA6T/11 material and a preparation method thereof, wherein a high-temperature melt polymerization method is adopted to prepare the semi-aromatic high-temperature-resistant PA6T/11 material, and the semi-aromatic high-temperature-resistant PA6T/11 material has the advantages of few polymerization process steps, short polymerization period and low production cost; in addition, the reaction monomer 11-aminoundecanoic acid of PA6T/11 copolyamide comes from castor, and China is one of the main castor production areas in the world, has sufficient raw material sources, and meets the requirements of environmental protection and sustainable development.
In order to achieve the purpose, the invention adopts the following technical scheme:
a semi-aromatic high temperature resistant PA6T/11 material, prepared from components comprising:
60-75 parts of PA6T salt;
25-40 parts of 11-aminoundecanoic acid;
0.05-0.1 part of nucleating agent;
0.03-0.05 part of catalyst;
80-120 parts of a solvent;
the PA6T salt is prepared by the following method: weighing equimolar amounts of terephthalic acid and hexamethylenediamine, dissolving hexamethylenediamine in a reaction kettle filled with distilled water, heating to 50 ℃ under a stirring state, adding the terephthalic acid into the reaction kettle, continuously reacting for 1.5 hours under the stirring state to obtain a clear aqueous solution, adjusting the pH value of the solution to 7.2 by using the terephthalic acid and the hexamethylenediamine, cooling and crystallizing the obtained clear water, performing suction filtration by using a Buchner funnel, and drying in an oven to obtain white needle crystals, namely PA6T salt. The preparation process is as follows:
the purity of the 11-aminoundecanoic acid is more than 99.9%, no purification treatment is needed, the 11-aminoundecanoic acid is derived from castor oil, the content of green and environment-friendly raw materials is higher, and the environment-friendly value is higher;
the nucleating agent is selected from at least one of barium sulfate, titanium dioxide, silicon dioxide and calcium carbonate, and barium sulfate is preferred;
the catalyst is selected from one or more of sodium hypophosphite, potassium hypophosphite, sodium phosphite, magnesium hypophosphite, calcium hypophosphite or zinc hypophosphite, and preferably the sodium hypophosphite;
the solvent is selected from safe and environment-friendly deionized water.
A preparation method of a semi-aromatic high-temperature-resistant PA6T/11 material comprises the following steps:
(1) mixing PA6T salt: 60-75 parts of 11-aminoundecanoic acid: 25-40 parts of a nucleating agent: 0.05-0.1 part of catalyst: 0.03-0.05 part of the mixture is ground in a mortar to be fully and uniformly mixed, then the mixture is added into a high-pressure polymerization reaction kettle provided with a high-efficiency stirring device, 80-120 parts of solvent deionized water is weighed into the reaction kettle, the high-pressure polymerization reaction kettle is sealed, stirring is started, the stirring speed is 100-150r/min, high-purity inert gas is used for replacing air in the kettle for 3-5 times, and finally, 0.1-0.3MPa of inert gas is reserved as protective gas;
(2) heating the reaction kettle to raise the temperature at the rate of 2-4 ℃/min, raising the pressure in the kettle, releasing the water in the system to keep the reaction kettle in a constant pressure state when the pressure is 2.5-3.5MPa, reacting at the constant temperature and the constant pressure for 1.5-3.5h when the temperature is 275-290 ℃, and slowly releasing the pressure of the reaction kettle for 1-1.5h until the pressure is normal when the temperature in the reaction kettle is raised to 315 ℃;
(3) after the pressure in the kettle is released to the normal pressure, controlling the temperature in the kettle to be 310-.
In the step (1), the inert gas is nitrogen, carbon dioxide, argon or helium, preferably nitrogen.
The invention has the beneficial effects that:
(1) the monomer 11-aminoundecanoic acid in PA6T/11 provides a flexible chain segment for main chain molecules of PA6T/11, so that the flexibility of the main chain molecules is increased, the toughness is improved, and the melting point is reduced, so that PA6T becomes a material which is relatively easy to mold and process;
(2) the 11-aminoundecanoic acid in PA6T/11 is derived from castor oil, has sufficient raw materials, has higher environmental protection value and is beneficial to green sustainable development;
(3) the PA6T/11 is prepared by adopting a melt polycondensation method, the method has the advantages of few process steps, short polymerization period, high production efficiency, low production cost and the like, and the synthesized resin has low water absorption and stable performance and creates conditions for continuous industrial production in the future;
(4) the polymerization solvent adopts deionized water, and is economical, practical, green and environment-friendly.
Detailed Description
The present invention will be further illustrated below with reference to specific embodiments, which are to be understood as merely illustrative and not limitative of the scope of the present invention.
In the following examples, the following detection methods were employed:
the melting point test is obtained by testing and analyzing a differential scanning calorimeter (DSC thermal analyzer).
Tensile properties were measured according to ASTM D638-10, tensile rate 5 mm/min.
The notched impact strength of the simply supported beam was measured according to ASTM D6110-10.
Flexural strength was measured according to ASTM D790-10, with a pressing speed of 1.25 mm/min.
Water absorption test:
placing the sample in a dryer at room temperature, placing a beaker containing saturated saline solution at the bottom of the dryer, maintaining the relative humidity of the dryer at 75%, taking out the sample every 24 h, weighing, and recording as Gi(i =1, 2, 3, 4 …), the weighed sample was still placed back in the desiccator. After 20 days, the sample was placed in an oven to dry (70 ℃, 24 h), and then placed in a desiccatorThe sample is weighed as G after cooling to room temperature0. The water content (W) in the sample was calculated according to the following formulai) % wherein the water absorption in the present invention is consistently calculated as water absorption after 10 days (240 h):
Wi=(Gi-G0)／Gi ×100％
example 1
Taking a component PA6T salt: 60 parts, 11-aminoundecanoic acid: 40 parts of nucleating agent barium sulfate: 0.1 part of sodium hypophosphite serving as a catalyst: 0.03 part of the mixture is ground in a mortar to be fully and uniformly mixed, then the mixture is added into a high-pressure polymerization reaction kettle provided with a high-efficiency stirring device, 80 parts of solvent deionized water is weighed into the reaction kettle, the high-pressure polymerization reaction kettle is sealed, stirring is started, the stirring speed is 100r/min, the air in the kettle is replaced for 3 times by using a high-purity nitrogen displacement body, and finally 0.1MPa of nitrogen is reserved as protective gas;
heating the reaction kettle to raise the temperature, wherein the temperature raising rate is 2 ℃/min, the pressure in the reaction kettle rises, when the pressure is 2.5MPa, the reaction kettle is in a constant pressure state by releasing the moisture of the system, when the temperature is raised to 275 ℃, the reaction kettle is subjected to constant temperature and constant pressure reaction for 1.5h, and then when the temperature in the reaction kettle is raised to 290 ℃, the reaction kettle is subjected to slow pressure release treatment for 1h until the pressure is normal;
after the pressure in the kettle is released to normal pressure, the temperature in the kettle is controlled to be 310 ℃ for constant temperature reaction for 10min, then the vacuum pumping reaction is carried out for 0.5h, the vacuum degree is-0.09 MPa, finally nitrogen is filled into the kettle, the pressure is increased to 0.5MPa, and the semi-aromatic high temperature resistant PA6T/11 material is obtained.
Example 2
Taking a component PA6T salt: 75 parts of 11-aminoundecanoic acid: 25 parts of nucleating agent titanium dioxide: 0.05 part of catalyst potassium hypophosphite: 0.05 part of the mixture is ground in a mortar to be fully and uniformly mixed, then the mixture is added into a high-pressure polymerization reaction kettle provided with a high-efficiency stirring device, 120 parts of solvent deionized water is weighed into the reaction kettle, the high-pressure polymerization reaction kettle is sealed, stirring is started, the stirring speed is 150r/min, high-purity carbon dioxide gas is used for replacing the air in the kettle for 5 times, and finally, 0.3MPa of carbon dioxide gas is reserved as protective gas;
(2) heating the reaction kettle to raise the temperature, wherein the temperature raising rate is 4 ℃/min, the pressure in the reaction kettle rises, when the pressure is 3.5MPa, the reaction kettle is in a constant pressure state by releasing the moisture of the system, when the temperature is raised to 290 ℃, the reaction kettle is subjected to constant temperature and constant pressure reaction for 3.5h, and then when the temperature in the reaction kettle is raised to 315 ℃, the reaction kettle is subjected to slow pressure release treatment for 1.5h until the pressure is normal;
(3) and (3) after the pressure in the kettle is released to normal pressure, controlling the temperature in the kettle to be 335 ℃ for constant-temperature reaction for 30min, then vacuumizing for reaction for 1h, wherein the vacuum degree is-0.05 MPa, finally filling inert gas into the kettle, pressurizing to 1.2MPa, and discharging to obtain the semi-aromatic high-temperature-resistant PA6T/11 material.
Example 3
Taking a component PA6T salt: 67.5 parts, 11-aminoundecanoic acid: 32.5 parts of nucleating agent silicon dioxide: 0.04 part of catalyst calcium hypophosphite: 0.075 part, grinding in a mortar to fully and uniformly mix, then adding the mixture into a high-pressure polymerization reaction kettle provided with a high-efficiency stirring device, weighing 100 parts of solvent deionized water in the reaction kettle, sealing the high-pressure polymerization reaction kettle, starting stirring, wherein the stirring speed is 120r/min, replacing air in the kettle with high-purity carbon dioxide gas for 4 times, and finally reserving 0.2MPa of carbon dioxide gas as protective gas;
(2) heating the reaction kettle to raise the temperature, wherein the temperature raising rate is 3 ℃/min, the pressure in the reaction kettle rises, when the pressure is 3.0MPa, the reaction kettle is in a constant pressure state by releasing the moisture of the system, when the temperature is raised to 280 ℃, the reaction kettle is subjected to constant temperature and constant pressure reaction for 2.5h, and then when the temperature in the reaction kettle is raised to 310 ℃, the reaction kettle is subjected to slow pressure release treatment for 1.5h until the pressure is normal;
(3) and (3) after the pressure in the kettle is released to normal pressure, controlling the temperature in the kettle to be 320 ℃ for constant-temperature reaction for 20min, then vacuumizing for reaction for 0.75h, wherein the vacuum degree is-0.07 MPa, and finally filling inert gas into the kettle, pressurizing to 0.8MPa, and discharging to obtain the semi-aromatic high-temperature-resistant PA6T/11 material.
The semi-aromatic high-temperature resistant PA6T/11 material synthesized in each example is taken to be subjected to injection molding to obtain a standard test sample bar, relevant performance tests are carried out, meanwhile, materials such as PA6T/66 and PA6T/6 are also subjected to injection molding, and the measured performance is respectively taken as comparative example 1 and comparative example 2.
The results of the performance tests of examples 1-3 and comparative examples 1-2 are shown in Table 1.
TABLE 1
As can be seen from the performance test results of the examples, the melting point of the semi-aromatic high-temperature-resistant PA6T/11 material is reduced along with the increase of the content of the 11-aminoundecanoic acid, so that PA6T becomes a usable material, and the processing window is widened. This is because the increase of the content of 11-aminoundecanoic acid increases the proportion of the structural unit in the PA6T/11 repeating unit, and the molecular chain flexibility of the PA6T/11 copolyamide is increased, so that the melting temperature is reduced.
The comparison of the conventional mechanical properties shows that the tensile strength and the elongation at break of the semi-aromatic high-temperature resistant PA6T/11 material are improved relative to PA6T/66, PA6T/6 and the like, which shows that the overall rigidity is reduced, the toughness is improved, and the theoretical rule is met. The water absorption data shows that the water absorption of the PA6T/11 copolymer material does not change greatly with the increase of the content of the 11-aminoundecanoic acid, because the water absorption of the polyamide depends on the density of the amide groups in the molecular chain, the amide groups have hydrophilicity, and the higher the density of the amide groups, the higher the water absorption of the polyamide. After the polyamide absorbs water, the intermolecular force is weakened, the dimensional stability is lowered, and the like. But are all smaller than materials such as PA6T/66 and PA6T/6, and therefore the dimensional stability of the materials is ideal.
The embodiments described above are presented to enable those skilled in the art to make and use the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. A semi-aromatic high-temperature-resistant PA6T/11 material is characterized in that: comprising the following components:
60-75 parts of PA6T salt;
25-40 parts of 11-aminoundecanoic acid;
0.05-0.1 part of nucleating agent;
0.03-0.05 part of catalyst;
80-120 parts of a solvent.
2. The semi-aromatic refractory PA6T/11 material of claim 1, wherein: the PA6T salt was prepared by the following method: weighing equimolar amounts of terephthalic acid and hexamethylenediamine, dissolving hexamethylenediamine in a reaction kettle filled with distilled water, heating to 50 ℃ under a stirring state, adding the terephthalic acid into the reaction kettle, continuously reacting for 1.5 hours under the stirring state to obtain a clear aqueous solution, adjusting the pH value of the solution to 7.2 by using the terephthalic acid and the hexamethylenediamine, cooling and crystallizing the obtained clear water, performing suction filtration by using a Buchner funnel, and drying in an oven to obtain white needle crystals, namely PA6T salt; the preparation process is as follows:
3. the semi-aromatic refractory PA6T/11 material of claim 1, wherein: the purity of the 11-aminoundecanoic acid is more than 99.9%.
4. The semi-aromatic refractory PA6T/11 material of claim 1 or 3, wherein: the 11-aminoundecanoic acid is derived from castor oil.
5. The semi-aromatic refractory PA6T/11 material of claim 1, wherein: the nucleating agent is at least one selected from barium sulfate, titanium dioxide, silicon dioxide and calcium carbonate.
6. The semi-aromatic refractory PA6T/11 material of claim 1, wherein: the catalyst is selected from one or more of sodium hypophosphite, potassium hypophosphite, sodium phosphite, magnesium hypophosphite, calcium hypophosphite or zinc hypophosphite.
7. The semi-aromatic refractory PA6T/11 material of claim 1, wherein: the solvent is selected from safe and environment-friendly deionized water.
8. A preparation method of a semi-aromatic high-temperature-resistant PA6T/11 material is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing PA6T salt: 60-75 parts of 11-aminoundecanoic acid: 25-40 parts of a nucleating agent: 0.05-0.1 part of catalyst: 0.03-0.05 part of the mixture is ground in a mortar to be fully and uniformly mixed, then the mixture is added into a high-pressure polymerization reaction kettle provided with a stirring device, 80-120 parts of solvent deionized water is weighed in the reaction kettle, the high-pressure polymerization reaction kettle is sealed, stirring is started, the stirring speed is 100-150r/min, high-purity inert gas is used for replacing air in the kettle for 3-5 times, and finally, 0.1-0.3MPa of inert gas is reserved as protective gas;
(2) heating the reaction kettle to raise the temperature at the rate of 2-4 ℃/min, raising the pressure in the kettle, releasing the water in the system to keep the reaction kettle in a constant pressure state when the pressure is 2.5-3.5MPa, reacting at the constant temperature and the constant pressure for 1.5-3.5h when the temperature is 275-290 ℃, and then carrying out pressure relief treatment on the reaction kettle for 1-1.5h until the pressure is normal when the temperature in the reaction kettle is raised to 315 ℃;
(3) after the pressure in the kettle is released to the normal pressure, controlling the temperature in the kettle to be 310-.
9. The preparation method of the semi-aromatic high temperature resistant PA6T/11 material as claimed in claim 8, wherein: in the step (1), the inert gas is at least one of nitrogen, carbon dioxide, argon or helium.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796257A (en) * | 2012-01-06 | 2012-11-28 | 东莞市信诺橡塑工业有限公司 | Long carbon-chain semi-aromatic polyamide and synthetic method of same |
| CN106916298A (en) * | 2015-12-25 | 2017-07-04 | 上海杰事杰新材料(集团)股份有限公司 | A kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796257A (en) * | 2012-01-06 | 2012-11-28 | 东莞市信诺橡塑工业有限公司 | Long carbon-chain semi-aromatic polyamide and synthetic method of same |
| CN106916298A (en) * | 2015-12-25 | 2017-07-04 | 上海杰事杰新材料(集团)股份有限公司 | A kind of environment friendly biological base semi-aromatic PA10T/11 copolymeric materials and preparation method thereof |
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Application publication date: 20211119 |