CN110066393B - Long-carbon-chain polyamide resin and preparation method thereof - Google Patents
Long-carbon-chain polyamide resin and preparation method thereof Download PDFInfo
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- CN110066393B CN110066393B CN201810065578.3A CN201810065578A CN110066393B CN 110066393 B CN110066393 B CN 110066393B CN 201810065578 A CN201810065578 A CN 201810065578A CN 110066393 B CN110066393 B CN 110066393B
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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
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic 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
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- C08G69/28—Preparatory processes
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Abstract
The invention provides long carbon chain polyamide resin and a preparation method thereof, the long carbon chain polyamide resin comprises 1, 5-pentanediamine and long carbon chain dibasic acid as raw materials, and the preparation process comprises the following steps: preparing polyamide salt aqueous solution under the protection of nitrogen or inert gas, adjusting the pH value to 6.60-7.49 by using a small amount of pentamethylene diamine or long carbon chain dibasic acid, adding one or more additives according to requirements to prepare the polyamide salt aqueous solution, and performing high-temperature polycondensation. The long carbon chain polyamide resin is obtained by regulating and controlling the pH value of the polyamide salt aqueous solution, and has the characteristics of small viscosity number fluctuation, easy processing, excellent performance and the like.
Description
Technical Field
The invention belongs to the technical field of polyamide materials, and particularly relates to long-carbon-chain polyamide resin and a preparation method thereof.
Background
In general, polyamides having a carbon chain length between 2 amide groups in the polyamide molecule of 10 or more are referred to as long carbon chain polyamides. Many properties of polyamides depend strongly on the concentration of amide groups in the polyamide, and the length of the carbon chain in the polyamide molecule directly determines the concentration of amide groups, the longer the carbon chain, the lower the concentration of amide groups. The polyamide properties change with increasing carbon chain length. The application of long carbon chain polyamide is related to various fields of automobiles, electronic appliances, machinery, military equipment and the like. Research and development on long carbon chain polyamides has long been an important and popular topic in the development of new polyamide products.
The long carbon chain polyamide has the following unique properties besides most of the universality of common polyamide, such as good mechanical property, wear resistance, lubricity, solvent resistance, easy molding processability and the like: (1) the water absorption is low. The water absorption of polyamides is mainly due to the strong affinity of polar amide groups in the polyamide molecules with water. The amide group concentration in the long carbon chain nylon molecule is smaller than that of ordinary polyamide, and therefore, the water absorption is low, for example, the water absorption of polyamide 12 is only 0.25%, and the water absorption of polyamide 6 is 1.8%. (2) The dimensional stability is good. Because the long carbon chain polyamide has low water absorption, the high toughness and hardness can be kept in a humid environment, and the mechanical property of the long carbon chain polyamide cannot be changed too much. The parts made of long carbon chain polyamide have good dimensional stability and high precision, and can be used in occasions with high precision requirement and humid environment. (3) The toughness and the flexibility are good. The long carbon chain polyamide molecule has a methine long chain which can be freely stretched and rotated, so that the toughness and flexibility are good, the rebound rate is high, the impact toughness and flexibility are high even at a low temperature, and a soft product and a cold-resistant part can be manufactured. (4) The wear resistance is excellent. The long carbon chain polyamide has a small abrasion coefficient and a low abrasion amount, for example, the abrasion amounts of polyamide 11, polyamide 12, polyamide 6 and polyamide 66 were 9.9mg, 8.2mg, 35.0mg and 27.0mg respectively under the same conditions (Wandong, application of nylon 11 and nylon 12 [ J ]. aging and application of synthetic materials, 1996(3): 17). The long carbon chain polyamide is particularly suitable for manufacturing wear-resistant parts because the long carbon chain polyamide does not generate serious abrasion and generate obvious abrasive dust when being rubbed with a smooth metal surface. (5) The electrical properties are excellent. The long carbon chain structure of long carbon chain polyamides imparts excellent electrical properties thereto. Since long carbon chain polyamides have low water absorption, they have excellent dielectric properties even in a humid environment, which is a characteristic that short carbon chain polyamides such as polyamide 6 and polyamide 66 do not have.
The current polyamide products are basically prepared by taking petroleum derivatives as raw materials, and generally have complex synthesis process and certain pollution. For a long time, it has been expected that a cyclic society will be built by using a renewable plant resource grown by absorbing carbon dioxide from the air as a starting material to produce a bio-based polyamide having properties equivalent to those of the conventional polyamide variety, thereby eliminating the dependence on non-renewable energy. Under such a background, Kessel organisms first obtained 1, 5-pentanediamine by decarboxylation of lysine and achieved mass production (see patent CN102851307B), and synthesized a series of bio-based polyamides, polyamide 5X (PA5X) (see patent CN 103145979B). Among them, PA510 has many unique properties as a polyamide having the shortest carbon chain among long-carbon-chain polyamides. However, in the polymerization process, when the traditional polymerization process is used for polymerization, the viscosity number difference of the slices obtained before and after the pelletizing process is very large, and the viscosity number difference seriously influences the application of the slices in the fields of injection molding, spinning and film drawing.
Disclosure of Invention
In order to solve the problems that the viscosity number fluctuation of the bio-based long carbon chain polyamide resin produced by the traditional polymerization process is too large and the post-processing and the performance are influenced, the invention optimizes the polymerization process, particularly regulates and controls the pH value of the polyamide salt water solution to obtain the long carbon chain bio-based polyamide with the viscosity number fluctuation of less than 15 mL/g.
The invention provides a long carbon chain polyamide resin, which comprises the following structural formula:
-NH-(CH 2 ) 5 -NH-CO-R-CO-
wherein R is an alkylene group having 8 to 10 carbon atoms. Preferably, R is a C8 alkylene group or a C10 alkylene group.
The long carbon chain polyamide resin of the present invention has a viscosity number fluctuation of less than 15mL/g, preferably a viscosity number fluctuation of less than 10mL/g, more preferably a viscosity number fluctuation of less than 6 mL/g.
The viscosity number of the long carbon chain polyamide resin is 120-300mL/g, preferably 125-220 mL/g.
The content of the terminal amino group in the long-carbon-chain polyamide resin of the present invention is 11 to 39mol/ton, preferably 15 to 35mol/ton, and more preferably 17 to 33 mol/ton.
The raw materials for producing the long-carbon-chain polyamide resin comprise 1, 5-pentanediamine (namely pentanediamine or cadaverine or pentamethylene diamine) and long-carbon-chain dibasic acid, and can also comprise additives, wherein the mass of the additives accounts for less than 40% of the total mass of the raw materials for producing the long-carbon-chain polyamide resin, and preferably, the mass of the additives accounts for less than 20% of the total mass of the raw materials for producing the long-carbon-chain polyamide resin.
The long carbon chain dibasic acid is aliphatic long carbon chain dibasic acid, and the 1, 5-pentanediamine and/or the aliphatic long carbon chain dibasic acid is prepared by a biological method. Biological production as used herein includes production of products (e.g., pentanediamines, long chain diacids, etc.) from bio-based feedstocks via bioconversion processes (e.g., fermentation, enzymatic conversion); or producing products (such as long chain dibasic acids) from petroleum-based raw materials by a biotransformation process; or chemically producing products (e.g., sebacic acid, etc.) using bio-based feedstocks. Alternatively, the 1, 5-pentanediamine and/or the aliphatic long carbon chain diacid contains a renewable source of organic carbon that meets ASTM D6866 standard.
The aliphatic long carbon chain dibasic acid is preferably any one or more of sebacic acid, undecanedioic acid and dodecanedioic acid, and more preferably sebacic acid or dodecanedioic acid.
The invention also provides a method for preparing the long-carbon-chain polyamide resin, which comprises the following steps:
1) under the protection of nitrogen or inert gas, adding reaction raw materials into a reaction container, preparing a polyamide salt aqueous solution, and adjusting the pH value by using pentanediamine or long carbon chain dibasic acid;
2) transferring the polyamide salt aqueous solution obtained in the step 1) to a polymerization kettle for polycondensation reaction.
The pH of the aqueous solution of the polyamide salt in step 1) is adjusted to a value of 6.60 to 7.49, preferably 6.80 to 7.42.
The mass concentration of the polyamide salt aqueous solution in the step 1) is 30-80%, and the preferred mass concentration is 40-70%.
The preparation of the polyamide salt aqueous solution in step 1) further comprises the addition of additives.
Preferably, the additive in step 1) is an antioxidant.
The polymerization process listed in the step 2) is a conventional polycondensation process, and the reaction conditions are as follows: heating until the pressure in the reaction vessel rises to 1.3-3.0 Mpa, exhausting and maintaining the pressure, reducing the pressure in the reaction vessel to 0-0.1 Mpa (gauge pressure) when the temperature of the system rises to 230-320 ℃, and maintaining the vacuum degree for 5-120 min.
By adopting the scheme, the invention has the beneficial effects that:
the invention adopts raw materials of 1, 5-pentanediamine, aliphatic long carbon chain dibasic acid and various additives to obtain the bio-based long carbon chain polyamide resin with viscosity fluctuation less than 15mL/g through an optimized polymerization process. Overcomes the defect of large viscosity number fluctuation of the long carbon chain bio-based polyamide prepared by the traditional polymerization process. Too large viscosity fluctuation can cause a plurality of problems in the processing process, such as unsmooth feeding, broken filaments in spinning, poor mechanical property of products, no film formation and the like.
In addition, one or more of the raw materials used in the invention are derived from renewable plants, belong to environment-friendly materials on the whole, relieve the dependence on non-renewable energy sources, and are beneficial to building a circulating society.
Detailed Description
The long carbon chain polyamide resin of the present invention comprises the following structural formula:
-NH-(CH 2 ) 5 -NH-CO-R-CO-
wherein R is an alkylene group having 8 to 10 carbon atoms. Preferably, R is a C8 alkylene group or a C10 alkylene group.
The long carbon chain polyamide resin of the present invention has a viscosity number fluctuation of less than 15mL/g, preferably a viscosity number fluctuation of less than 10mL/g, and more preferably a viscosity number fluctuation of less than 6 mL/g.
The viscosity number fluctuation refers to that the viscosity numbers of any plurality of samples in the same batch of polymerization or packaging bags are sliced, and the maximum difference value of the viscosity numbers of the samples and the viscosity numbers of the samples is detected respectively. The viscosity number fluctuation of the long carbon chain polyamide resin obtained by polymerizing pentamethylene diamine and long carbon chain dibasic acid by using the traditional polymerization process is more than 20mL/g, and the viscosity number fluctuation range can seriously influence the use of the long carbon chain polyamide resin in downstream processing, for example, the feeding is not smooth on a screw, molten drops are generated in the spinning process, the long carbon chain polyamide resin cannot be processed into a film, and the product performance can be seriously influenced. The viscosity number fluctuation of the bio-based long carbon chain nylon obtained by the method can be controlled below 15mL/g, even below 6mL/g, and the requirements of downstream customers on processability and mechanical properties are completely met.
The viscosity number of the long carbon chain polyamide resin is 120-300mL/g, preferably 125-220 mL/g.
The viscosity number is an indicator of the molecular weight, and a higher viscosity number indicates a higher molecular weight of the polymer, and a higher molecular weight indicates a higher strength of the polyamide. This is because if the molecular weight is higher, the smaller the amount of molecular chain terminals present per unit, the fewer defects that may be fibers. Meanwhile, because the molecular chains are longer, each molecular chain interacts with more molecular chains (such as physical entanglement, hydrogen bonds, van der waals forces and the like) to uniformly transfer various stresses, and therefore, the molecular chains are uniformly oriented in the processing process. On the other hand, the viscosity number in sulfuric acid is preferably kept in a suitable range, and since an excessively high viscosity number may result in a decrease in the fluidity of the solution, affecting the appearance and processing efficiency of the sample, the viscosity number is more preferably 125-220 mL/g.
The long carbon chain polyamide resin of the present invention may have an amino group-terminated content of 11 to 39mol/ton, preferably 15 to 35mol/ton, and more preferably 17 to 33 mol/ton. The reason is as follows: we find that when the content of the terminal amino group is high, the viscosity number fluctuation range of the product is small, and the viscosity number of the obtained polyamide is improved due to the fact that the content of the terminal amino group is too low, so that the long carbon chain polyamide resin with applicable value cannot be obtained.
The raw materials for producing the long carbon chain polyamide resin comprise 1, 5-pentanediamine and long carbon chain dibasic acid.
Pentanediamine (i.e., 1, 5-pentanediamine or cadaverine, pentamethylenediamine) may be prepared biologically or chemically and may contain a renewable source of organic carbon in accordance with ASTM D6866. As is known to those skilled in the art, the removal of carboxyl groups at both ends of lysine or lysine salt by lysine decarboxylase (EC 4.1.1.18) produces pentanediamine. For example, L-lysine decarboxylase property and application research (Jiangli, Nanjing university, Master thesis) discloses a specific biological method for preparing pentanediamine. For example, the research on the transformation of L-lysine into cadaverine by microorganisms (ZhuJing, Tianjin science and technology university, Master's paper, 2009.3) also discloses a specific biological method for preparing pentanediamine.
The long carbon chain dibasic acid is aliphatic long carbon chain dibasic acid. The aliphatic long carbon chain dibasic acid may also be prepared biologically or chemically, and may also contain a renewable source of organic carbon that meets ASTM D6866 standard. Provided that at least one of the pentanediamine and the aliphatic long carbon chain dibasic acid is a bio-based product.
The aliphatic long carbon chain dibasic acid can be any one or combination of sebacic acid, undecanedioic acid and dodecanedioic acid, and is preferably sebacic acid or dodecanedioic acid.
The raw material for producing a long-carbon-chain polyamide resin of the present invention may further include an additive, and the mass of the additive accounts for 40% or less of the total mass of the raw material for producing a long-carbon-chain polyamide resin, and preferably accounts for 20% or less of the total mass of the raw material for producing a long-carbon-chain polyamide resin.
The additive can be any one or the combination of several of an antioxidant, a heat-resistant stabilizer, a weather-resistant agent, a pigment, a gloss enhancer, a dye, a crystal nucleating agent, a delustering agent, a plasticizer, an antistatic agent and a flame retardant.
Among them, the heat stabilizer includes, but is not limited to, hindered phenol-based compounds, hydroquinone-based compounds, thiazole-based compounds, phosphorus-based compounds (e.g., phenylphosphonic acid), imidazole-based compounds (e.g., 2-mercaptobenzimidazole) and substitution products thereof, copper halide and iodine compounds, and the like.
Weathering agents include, but are not limited to, resorcinol, salicylates, benzotriazoles, benzophenones, hindered amines, and the like.
Pigments include, but are not limited to, cadmium sulfide, phthalocyanines, carbon black, and the like.
Gloss enhancers include, but are not limited to, titanium oxide and calcium carbonate, among others.
Dyes include, but are not limited to nigrosine and nigrosine, and the like.
Crystal nucleating agents include, but are not limited to talc, silica, kaolin, clay, and the like.
Plasticizers include, but are not limited to, octyl paraben, N-butylbenzenesulfonamide, and the like.
Antistatic agents include, but are not limited to, alkyl sulfate type anionic antioxidants, quaternary ammonium type cationic antistatic agents, non-ionic antistatic agents (such as polyoxyethylene sorbitan monostearate), and betaine-based amphoteric antistatic agents, and the like.
Flame retardants include, but are not limited to, melamine cyanurate, hydroxides (such as magnesium hydroxide or aluminum hydroxide), ammonium polyphosphate, brominated polystyrene, brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resins, combinations of any bromine-based flame retardant with antimony trioxide, and the like.
Preferably, the additive is an antioxidant.
The invention also provides a method for preparing the long-carbon-chain polyamide resin, which comprises the following steps:
1) under the protection of nitrogen or inert gas, adding reaction raw materials into a reaction container, preparing a polyamide salt aqueous solution, and adjusting the pH value by using a small amount of pentamethylene diamine or long carbon chain dibasic acid;
2) transferring the polyamide salt aqueous solution obtained in the step 1) to a polymerization kettle for polycondensation reaction.
The mass concentration of the polyamide salt aqueous solution in step 1) is 30-80%, preferably 40-70%, because on the one hand the concentration is limited by the upper limit of solubility, and an excessively low concentration leads to a high energy consumption.
The pH value of the polyamide salt aqueous solution in the step 1) is adjusted to 6.60-7.49, preferably 6.80-7.42, the pH value of the initial polyamide salt aqueous solution has great influence on the viscosity number fluctuation of the long carbon chain polyamide resin, and the viscosity number is not easy to control in a small fluctuation range even if various process parameters are adjusted at a higher pH value, which is probably because the long carbon chain polyamide 5X has the polymerization capability of the super-conventional nylon, and if the pH value is not seriously lower, the polymerization process cannot be slowed down, so that the pH value of the long carbon chain polyamide with small viscosity number fluctuation is required to be lower than the pH value for preparing the conventional polyamide. However, the pH value is too low, and the mechanical properties of the obtained long carbon chain polyamide resin are affected, which may be caused by low polymerization degree, so that the pH value needs to be accurately controlled within a proper range.
One or more additives can be added in the step 1) according to the requirement.
The polymerization process listed in the step 2) is a conventional polycondensation process, and the reaction conditions are as follows: heating until the pressure in the reaction vessel rises to 1.3-3.0 Mpa, exhausting and maintaining the pressure, reducing the pressure in the reaction vessel to 0-0.1 Mpa (gauge pressure) when the temperature of the system rises to 230-320 ℃, and maintaining the vacuum degree for 5-120 min. The polymerization conditions may be specifically adjusted.
The present invention will be further described with reference to examples and comparative examples.
The long carbon chain polyamide resin was characterized by the following characterization method:
(1) viscosity number
Concentrated sulfuric acid method by Ubbelohde viscometer: a dried polyamide sample (e.g. PA66) is weighed accurately at 0.25. + -. 0.0002g, dissolved in 50mL of concentrated sulfuric acid (96%), measured in a thermostatted water bath at 25 ℃ and the time t of passage of the concentrated sulfuric acid is recorded 0 And the time t for the solution to flow through the polyamide sample (e.g., PA 66).
Viscosity number calculation formula: viscosity number VN ═ t/t 0 -1)/C；
t-solution flow time;
t 0 -the time of solvent flow;
c-concentration of polymer (g/mL).
(2) Content of terminal amino groups
1g of polyamide chips were dissolved at 30 ℃ in 50ml of a phenol/ethanol mixed solution (phenol/ethanol ═ 80/20) with shaking, and the solution was neutralized and titrated with 0.02mol/L hydrochloric acid. The amount of 0.02mol/L hydrochloric acid used was determined. The above phenol/ethanol mixed solvent was titrated with 0.02mol/L hydrochloric acid for a blank, and the amount of 0.02mol/L hydrochloric acid was determined. From the difference between the amounts, the content of terminal amino groups per 1 ton of polyamide sample was obtained.
(3) pH value
The aqueous polyamide salt solution was diluted to 10% wt and measured at 30 ℃ using a pH meter.
Example 1 Polyamide 510
1) A100 liter polymerization vessel (type K/SY 166-2007) was purged with nitrogen, 15kg of pure water was added to the reaction vessel, 11.75kg (115.2mol) of pentamethylenediamine (containing a renewable organic carbon meeting ASTM D6866 standard), after stirring, 23.25kg (115.2mol) of sebacic acid was added, and the pH was adjusted to 7.49 with a small amount of pentamethylenediamine or sebacic acid (30 ℃ C. salt solution was diluted to 10% test result) to prepare a polyamide salt aqueous solution.
2) And under the nitrogen environment, gradually increasing the oil bath temperature to 292 ℃, starting to exhaust when the pressure in the polymerization kettle is increased to 2.0Mpa, vacuumizing to-0.08 Mpa when the temperature in the kettle reaches 265 ℃, and keeping the vacuum degree for 35min to obtain the polyamide 510.
Example 2 Polyamide 510
1) A100 liter polymerization vessel (type K/SY 166-2007) was purged with nitrogen, 15kg of pure water was added to the reaction vessel, 11.75kg (115.2mol) of pentamethylenediamine (containing a renewable organic carbon meeting ASTM D6866 standard) was then added, and after stirring, 23.25kg (115.2mol) of sebacic acid was added, and the pH was adjusted to 7.40 with a small amount of pentamethylenediamine or sebacic acid (30 ℃ C. saline solution was diluted to 10% test result), to prepare a polyamide aqueous solution.
2) And under the nitrogen environment, gradually increasing the oil bath temperature to 285 ℃, starting to exhaust when the pressure in the polymerization kettle is increased to 1.7Mpa, vacuumizing to-0.06 Mpa when the temperature in the kettle reaches 262 ℃, and keeping the vacuum degree for 30min to obtain the polyamide 510.
Example 3 Polyamide 510
1) A100 liter polymerization vessel (type K/SY 166-2007) was purged with nitrogen, 15kg of pure water was added to the reaction vessel, 11.75kg (115.2mol) of pentamethylenediamine (containing a renewable organic carbon meeting ASTM D6866 standard) was then added, and after stirring, 23.25kg (115.2mol) of sebacic acid was added, and the pH was adjusted to 7.19 with a small amount of pentamethylenediamine or sebacic acid (30 ℃ saline solution was diluted to 10% of the test result), to prepare a polyamide aqueous solution.
2) Under the nitrogen environment, the oil bath temperature is gradually increased to 288 ℃, the air is exhausted when the pressure in the polymerization kettle is increased to 2.5Mpa, the vacuum degree is vacuumized to-0.07 Mpa when the temperature in the polymerization kettle reaches 260 ℃, and the vacuum degree is maintained for 28min, so that the polyamide 510 is prepared.
Example 4 Polyamide 510
1) A100-liter polymerization kettle (K/SY166-2007 type) is used for replacing air with nitrogen, 15kg of pure water is added into the reaction kettle, 11.75kg (115.2mol) of pentanediamine (containing organic carbon of renewable source meeting the ASTM D6866 standard) is added, after stirring, 23.25kg (115.2mol) of sebacic acid is added, the pH value is adjusted to 6.60 by a small amount of pentanediamine or sebacic acid (the salt solution at 30 ℃ is diluted to 10% of detection result), and 25g of antioxidant H10 is added to prepare the polyamide salt water solution.
2) And (3) gradually raising the oil bath temperature to 290 ℃ in a nitrogen environment, starting to exhaust when the pressure in the polymerization kettle rises to 1.0Mpa, vacuumizing to-0.08 Mpa when the temperature in the polymerization kettle reaches 270 ℃, and keeping the vacuum degree for 30min to obtain the polyamide 510.
Example 5 Polyamide 512
1) A100 liter polymerization vessel (type K/SY 166-2007) was purged with nitrogen, 15kg of pure water was added to the reaction vessel, 11.75kg (115.2mol) of pentamethylenediamine (containing a renewable organic carbon meeting ASTM D6866 standard), 26.47kg (115.2mol) of sebacic acid was added after stirring, and the pH was adjusted to 7.23 with a small amount of pentamethylenediamine or dodecanedioic acid (30 ℃ saline solution was diluted to 10% of the test result) to prepare a polyamide salt aqueous solution.
2) Under the nitrogen environment, the oil bath temperature is gradually increased to 288 ℃, the air is exhausted when the pressure in the polymerization kettle is increased to 1.5Mpa, the vacuum degree is vacuumized to-0.07 Mpa when the temperature in the polymerization kettle reaches 262 ℃, and the vacuum degree is maintained for 35min, thus obtaining the polyamide 512.
Comparative example 1 Polyamide 510
1) A100 liter polymerization vessel (type K/SY 166-2007) was purged with nitrogen, 15kg of pure water was added to the reaction vessel, 11.75kg (115.2mol) of pentamethylenediamine (containing a renewable organic carbon meeting ASTM D6866 standard), after stirring, 23.25kg (115.2mol) of sebacic acid was added, and the pH was adjusted to 7.70 with a small amount of pentamethylenediamine and sebacic acid (30 ℃ C. salt solution was diluted to 10% test result) to prepare a polyamide salt aqueous solution.
2) And (3) gradually raising the temperature of the oil bath to 285 ℃ in a nitrogen environment, starting to exhaust when the pressure in the polymerization kettle is raised to 1.7Mpa, vacuumizing to-0.06 Mpa when the temperature in the polymerization kettle reaches 262 ℃, and maintaining the vacuum degree for 30min to obtain the polyamide 510.
After the polyamide resin is prepared, nitrogen is filled into a polymerization kettle to reach the pressure of 0.4Mpa, melting and discharging are started, a granulator is used for granulation, samples are taken every 8kg in the granulation process, four samples are taken in total, and the viscosity number fluctuation is the maximum difference value between any two viscosity numbers in the four samples. Drying at 110 deg.C for 24 hr, and packaging. The slice detection results are shown in table 1.
TABLE 1 data for sample testing of each example
The data in table 1 show that the viscosity number fluctuation of the bio-based long carbon chain polyamide resin prepared by the invention is obviously smaller than that of the bio-based long carbon chain polyamide prepared by the traditional polymerization process, the viscosity number fluctuation can be controlled in a smaller range by adjusting the pH value of the polyamide salt aqueous solution in the polymerization process, and the bio-based polyamide resin is suitable for downstream processing, has excellent performance and has huge market prospect.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present 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 above embodiments, 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 (6)
1. A preparation method of long carbon chain polyamide resin is characterized by comprising the following steps:
1) under the protection of nitrogen or inert gas, adding reaction raw materials comprising 1, 5-pentanediamine and long carbon chain dibasic acid into a reaction container, preparing a polyamide salt aqueous solution, and adjusting the pH value by using the 1, 5-pentanediamine or the long carbon chain dibasic acid; wherein the long carbon chain dibasic acid comprises any one or more of sebacic acid, undecanedioic acid and dodecanedioic acid;
2) transferring the polyamide salt aqueous solution obtained in the step 1) to a polymerization kettle for polycondensation;
wherein the pH of the polyamide salt aqueous solution is adjusted to 7.4 or 7.49 in step 1); diluting the aqueous polyamide salt solution to 10% wt, the pH being measured at 30 ℃ using a pH meter;
the conditions of the polycondensation reaction in the step 2) are as follows: heating until the pressure in the reaction vessel rises to 1.3-3.0 Mpa, starting to exhaust and maintaining the pressure, reducing the pressure in the reaction vessel to 0-0.1 Mpa when the temperature of the system rises to 230-320 ℃, and maintaining the vacuum degree for 5-120 min;
the long carbon chain polyamide resin comprises the following structural formula:
wherein R is C8-C10 alkylene, and the fluctuation of the viscosity number of the long carbon chain polyamide resin is less than 6 mL/g.
2. The method for producing a long-carbon-chain polyamide resin according to claim 1, wherein the raw material for producing a long-carbon-chain polyamide resin further comprises an additive, and the mass of the additive accounts for 40% or less of the total mass of the raw material for producing a long-carbon-chain polyamide resin.
3. The method for producing a long carbon-chain polyamide resin according to claim 2, wherein the mass of the additive is 20% or less of the total mass of the raw materials for producing the long carbon-chain polyamide resin.
4. The method for producing a long carbon chain polyamide resin according to claim 2, wherein the additive comprises any one or more of an antioxidant, a heat stabilizer, a pigment, a gloss enhancer, a dye, a crystal nucleating agent, a delustering agent, a plasticizer, an antistatic agent, and a flame retardant.
5. The process for producing a long-carbon-chain polyamide resin according to claim 1, wherein the concentration of the aqueous solution of the polyamide salt in the step 1) is 30 to 80% by mass.
6. The process for producing a long-carbon-chain polyamide resin according to claim 1, wherein the concentration by mass of the aqueous solution of the polyamide salt in the step 1) is 40 to 70%.
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| CN114907688B (en) * | 2021-02-09 | 2024-04-05 | 上海凯赛生物技术股份有限公司 | Long carbon chain polyamide 5X film and preparation method thereof |
| CN114410107B (en) * | 2021-12-24 | 2024-02-20 | 上海普利特复合材料股份有限公司 | Multi-component copolymerized body flame-retardant long carbon chain polyamide composition and preparation method thereof |
| CN114805791B (en) * | 2022-05-25 | 2023-10-24 | 北京化工大学 | Preparation method of long carbon chain polyamide based on pentanediamine |
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