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CN116925343A - High temperature resistant long carbon chain semi-aromatic polyamide resin, preparation method thereof, composition and molded product - Google Patents

High temperature resistant long carbon chain semi-aromatic polyamide resin, preparation method thereof, composition and molded product Download PDF

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Publication number
CN116925343A
CN116925343A CN202210332272.6A CN202210332272A CN116925343A CN 116925343 A CN116925343 A CN 116925343A CN 202210332272 A CN202210332272 A CN 202210332272A CN 116925343 A CN116925343 A CN 116925343A
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China
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polyamide resin
resistant long
temperature
aromatic polyamide
carbon
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Inventor
冯梧桐
赵元博
刘修才
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Cathay R&D Center Co Ltd
CIBT America Inc
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Cathay R&D Center Co Ltd
CIBT America Inc
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Priority to CN202210332272.6A priority Critical patent/CN116925343A/en
Publication of CN116925343A publication Critical patent/CN116925343A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/044—Carbon nanohorns or nanobells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Polyamides (AREA)

Abstract

The invention discloses a high-temperature-resistant long carbon chain semi-aromatic polyamide resin, a preparation method, a composition and a molded product thereof, wherein polymerization monomers of the polyamide resin comprise diamine monomers and diacid monomers, the diamine monomers are selected from any one or two of 1, 11-undecanediamine and 1, 5-pentanediamine, the diacid monomers are selected from any one or more combination of terephthalic acid and derivatives thereof, and the mole fraction of the 1, 5-pentanediamine in the diamine monomers is 0-86%. The polyamide resin has a relative viscosity of 2.2-2.6, a melting point of over 287 ℃, and excellent color stability and melt flowability.

Description

High temperature resistant long carbon chain semi-aromatic polyamide resin, preparation method thereof, composition and molded product
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin, a preparation method, a composition and a molded product thereof.
Background
The high temperature resistant long carbon chain semi-aromatic polyamide is a polyamide with a melting point above 270 ℃, and a molecular main chain of the polyamide contains an aromatic ring structure and diamine or diacid monomer units with carbon number more than or equal to 10, and the polyamide has excellent heat resistance and excellent mechanical properties, so that the polyamide is widely applied to the fields of electronic devices, automobile engine peripheral parts, aerospace and the like. Among them, poly (paraphthaloyl undecanediamine) (abbreviated as PA 11T) is a long carbon chain semi-aromatic polyamide with excellent properties, and exhibits excellent mechanical strength, lower water absorption and excellent melt processability due to its both rigid benzene ring structure and flexible long carbon chain structure. Patent CN104817693B discloses PA11T and a preparation method, wherein the preparation method is carried out in a rotary drum type reaction kettle by using a one-pot method, the whole reaction temperature is lower than the melting point of PA11T, the whole reaction time is controlled within 15h, and the product is in a powder state. The method is suitable for laboratory small-sized experiment preparation, the problems of difficult powder discharge and storage exist in the enlarged production, and the relative viscosity of the PA11T prepared by the method is low (1.61-1.70), so that the problem of mechanical property deviation is caused.
The method of melting discharge and strand granulation is generally adopted in the industrial production of polyamide, which necessarily requires that the system temperature is above the melting point of the product, the melting point is usually 15-25 ℃ higher than the melting point for good melt fluidity, and the melting discharge time is usually 20-40 min in mass production, the high temperature maintenance can lead the color of the product to be worse and worse along with the extension of the discharge time, the degree of yellowing of the color can reflect the degradation degree of the polymer, and further the quality of the product is affected.
Carbon dots, namely carbon quantum dots (Carbon Quantum Dots, CQD) are novel nano materials with fluorescent properties, and the particle size is generally 1-10 nm, and the excellent performance of the carbon dots is considered as novel nano carbon materials with great development potential in the century. The common preparation materials of the carbon dots comprise citric acid, graphite, humic acid, ascorbic acid and the like, and can also be prepared from biomass raw materials such as leaves, fish scales, turtle shells and the like. The preparation method is, for example, a plasma method, a microwave radiation method, a hydrothermal reaction, electrochemical oxidation, a high-temperature carbonization method, an ultrasonic method, etc. The preparation raw materials are green and environment-friendly, and the process is simple and efficient.
Disclosure of Invention
In order to solve the defects of the prior art and products, the invention provides a high-temperature-resistant long carbon chain semi-aromatic polyamide resin, a preparation method, a composition and a molded product thereof.
The first aspect of the invention provides a high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin (polyamide resin for short). The polymerization monomer of the polyamide resin comprises diamine monomer and diacid monomer, wherein the diamine monomer is selected from any one or two of 1, 11-undecanediamine and 1, 5-pentanediamine, the diacid monomer is selected from any one or more than two of terephthalic acid and derivatives thereof, and the mole fraction of the 1, 5-pentanediamine in the diamine monomer is 0-86%.
As a preferred embodiment of the present invention, the ratio of the amounts of the diamine monomer and the diacid monomer is (1.005-1.05): 1, and more preferably (1.005-1.03): 1.
As a preferred embodiment of the present invention, 1, 5-pentanediamine (abbreviated as pentanediamine) accounts for 0 to 20% or 55 to 86% of the mole fraction of the diamine monomer, more preferably 0 to 8% or 60 to 86% of the mole fraction, and still more preferably 5 to 8% or 60 to 86% of the mole fraction. For example 15%, 25%, 40%, 60%, 80% or 86%.
As a preferred embodiment of the present invention, the derivatives of terephthalic acid include, but are not limited to, any one or a combination of two or more of terephthaloyl chloride, dimethyl terephthalate and diethyl terephthalate.
As one embodiment of the invention, the high temperature resistant long carbon chain semi-aromatic polyamide resin comprises a diamine structural unit and a diacid structural unit which are formed by the polymerization reaction of the diamine monomer and the diacid monomer, wherein the sum of the diamine structural unit and the diacid structural unit accounts for more than 97wt percent of the polyamide resin, and more than 99wt percent.
As a preferred embodiment of the present invention, the high temperature resistant long carbon chain semi-aromatic polyamide resin further contains carbon dots, and the content of the carbon dots is 50 to 1200ppm, further 200 to 1200ppm, further 600 to 1200ppm.
As a preferred embodiment of the present invention, the particle diameter of the carbon dots is 1 to 10nm, and further 5 to 10nm.
As a preferred embodiment of the present invention, the functional groups on the surface of the carbon dots are hydroxyl groups and carboxyl groups.
The source of carbon dots or the production process is not particularly limited in the present invention. For example, it can be obtained commercially, or by reference to YINGRAN H, ling D Z, tai-Shung C.Na + functionalized carbon quantum dot incorporated thin-film nanocomposite membranes for selenium and arsenic removal[J]Journal of Membrane Science,2018,564:483-491 gives carbon dots whose surface functional groups are hydroxyl and carboxyl groups.
As an embodiment of the present invention, the carbon dots may be further modified, for example, doped with metal ions (e.g., sodium ions).
As an embodiment of the present invention, the surface of the carbon dot may further contain a small amount of other functional groups in addition to the hydroxyl group and the carboxyl group. As an embodiment of the present invention, the polyamide resin contains additives including, but not limited to, any one or a combination of two or more of a capping agent, a catalyst, a flame retardant, an antioxidant, an ultraviolet absorber, an infrared absorber, a crystallization nucleating agent, a fluorescent whitening agent, and an antistatic agent.
As an embodiment of the present invention, the content of the additive in the polyamide resin is 0.01% to 3%.
In a preferred embodiment of the present invention, the melting point of the polyamide resin is 270℃or higher, and more preferably 285℃or higher.
In a preferred embodiment of the present invention, the polyamide resin has a relative viscosity of 2.2 to 2.6, and more preferably 2.3 to 2.4.
In a preferred embodiment of the present invention, the YI value of the polyamide resin is M when the polyamide resin is kept at a temperature 30℃higher than the melting point for 40 minutes, the YI value of the polyamide resin is N when the polyamide resin is kept at a temperature 0 minutes, and the M/N is 1 to 1.2, and further 1 to 1.06.
The second aspect of the invention provides a method for preparing a high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin, which is characterized by comprising the following steps:
1) Under the atmosphere of inert gas or nitrogen, carrying out drainage concentration on the polyamide salt solution at 120-140 ℃, then heating to 235-260 ℃, and reacting for 0.5-3 h under the pressure of 2.3-3.3 MPa;
2) The pressure in the reaction system is reduced to 0-0.1 MPa by draining and reducing, the temperature of the reaction system after the pressure reduction is over 285-353 ℃, and then the reaction system is vacuumized until the vacuum degree is below-0.02 MPa, and the pressure is kept for 0-300 s, so as to obtain the polyamide melt.
The polyamide salt is obtained by reacting diamine monomer and diacid monomer to form salt.
In one embodiment, the method comprises step a) prior to step 1): adding diamine monomer and diacid monomer into water, heating to 120-155 deg.c, optionally maintaining at 120-155 deg.c for 0.5-3 hr to form polyamide salt solution.
In one embodiment, the drainage of step 1) is concentrated to a concentration of polyamide salts of 40 to 80wt%, further 55 to 65wt%.
In one embodiment, the reaction time of step 1) is 0.5 to 2 hours.
In one embodiment, the draining and depressurizing step 2) reduces the pressure in the reaction system to 0-0.05 MPa, and further 0-0.02 MPa.
In one embodiment, the vacuum is applied in step 2) to a vacuum level of-0.05 MPa to-0.1 MPa.
In one embodiment, the time for maintaining the vacuum in step 2) is 0 to 90 seconds, and more preferably 5 to 90 seconds.
In one embodiment, the solution of the polyamide salt of step 1) contains additives and carbon dots.
In one embodiment, the additive is added at any stage of step a) and/or step 1).
Preferably, the raw materials of step a) further comprise additives. The additives are added during the preparation of the polyamide salt solution.
In one embodiment, carbon dots are added at any stage of step a) and/or step 1). Preferably, the feedstock of step a) further comprises carbon dots. Carbon dots are added during the preparation of the polyamide salt solution.
In one embodiment, the feedstock of step a) further comprises carbon dots and additives. Carbon dots and additives are added during the preparation of the polyamide salt solution.
The carbon dots and additives have the same definition as described above.
In one embodiment, the method comprises step 3): and (3) carrying out water-cooling bracing and granulating on the polyamide melt to obtain the polyamide resin.
The third aspect of the invention provides a composition, the components of which comprise the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin or the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin prepared by the preparation method of the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin.
The fourth aspect of the invention provides a molded article prepared from the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin as a raw material.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
1. the high-temperature-resistant long carbon chain semi-aromatic polyamide resin can be polymerized by adopting a one-step condensation polymerization process, and the method is simple and easy to operate and has good industrialized prospect.
2. The long carbon chain polyamide is easy to cause deviation of shorter carbon chain polyamide with melt fluidity due to large entanglement of long chains, and the poor fluidity can cause the deviation of melting and discharging time, thereby causing the problem of poor polymer color. The carbon dots are of a sphere structure, the surface of the carbon dots contains abundant hydroxyl and carboxyl, the carbon dots are introduced into the long carbon chain polyamide, the carbon dots can serve as end capping agents, exposed end amino groups are reduced, and further weak links of high-temperature degradation are reduced, the sphere structure of the carbon dots can play a role in self lubrication, further the melt fluidity of the long carbon chain polymer is improved, and the color stability of the long carbon chain polyamide in the melt discharge process can be improved due to the synergistic effect caused by the introduction of the carbon dots.
3. The carbon dots are considered to form extremely strong hydrogen bonding, and the introduction of ppm-level carbon dots can play a role in physical and chemical micro-crosslinking, so that the mechanical strength of the material can be improved, and the heat resistance of the material can be improved.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
1) The melting point test method comprises the following steps:
with reference to standard ISO 11357-3, the rate of temperature increase: 20 ℃/min.
2) Relative viscosity eta r Is characterized by comprising the following steps:
concentrated sulfuric acid process with Ubbelohde viscometer: accurately weighing 0.5+ -0.0002 g of dried polyamide resin sample, adding 50mL of concentrated sulfuric acid (96%) to dissolve to obtain polyamide solution, measuring in a constant temperature water bath at 25+ -0.02deg.C, and respectively recording the flowing time t of concentrated sulfuric acid 0 And polyamide solution flow-through time t.
The relative viscosity number calculation formula:
relative viscosity eta r ＝t/t 0 。
3) Yellow index (YI value): see HG/T3862-2006.
4) Discharge speed: in seconds per 100g of polyamide melt flowing out of the bottom valve of the reactor.
The antioxidant used in the examples and comparative examples is antioxidant H10, the catalyst is sodium hypophosphite, and the capping agent is benzoic acid or acetic acid. Carbon dots, carboxyl and hydroxyl as functional groups on the surface, and the particle size is 5-10 nm.
In the examples and comparative examples "%" represent mass percent and the amounts of antioxidant, catalyst, capping agent, carbon sites are based on the sum of the masses of all diamine and diacid monomers. The unit ppm represents mass percent, 100 ppm=0.01%.
The pressures described in the examples and comparative examples are both gauge pressures.
Example 1
Uniformly mixing 1.01mol of 1, 11-undecanediamine, 1.00mol of terephthalic acid, 0.03 percent of catalyst, 0.3 percent of antioxidant, 0.24 percent of benzoic acid, 50ppm of carbon point and water, setting the stirring speed to 80rpm, heating to 120 ℃ in nitrogen atmosphere, and keeping the temperature for 1h to prepare 50 weight percent nylon salt solution; heating to raise the temperature of the reaction system to 130 ℃, and keeping the temperature to be 65% by concentration; raising the temperature to 240 ℃ again, and keeping the pressure to 2.5MPa for reaction for 1h; the pressure in the reaction system is reduced to 0MPa by draining and reducing, and the temperature of the reaction system is 304 ℃ after the pressure reduction is finished; vacuumizing to make the vacuum degree be-0.07 MPa, and keeping for 20s to obtain a polyamide melt; and (3) carrying out water-cooling bracing and granulating on the polyamide melt to obtain the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin.
Example 2
Uniformly mixing 0.90mol of 1, 11-undecanediamine, 0.13mol of 1, 5-pentanediamine, 1.00mol of terephthalic acid, 0.03 percent of catalyst, 0.3 percent of antioxidant, 0.22 percent of benzoic acid and 100ppm of carbon point with water, setting the stirring speed to 80rpm, heating to 135 ℃ in nitrogen atmosphere and maintaining the temperature for 1h to prepare 50 weight percent nylon salt solution; stopping heating to cool the reaction system to 125 ℃, and keeping the temperature to drain water and concentrate to 65%; raising the temperature to 245 ℃ again, and keeping the pressure to 2.6MPa for reaction for 1h; the pressure in the reaction system is reduced to 0MPa by draining and reducing, and the temperature of the reaction system is 293 ℃ after the pressure reduction is finished; vacuumizing to make the vacuum degree be-0.08 MPa, and keeping for 10s to obtain a polyamide melt; and (3) carrying out water-cooling bracing and granulating on the polyamide melt to obtain the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin.
Example 3
Uniformly mixing 0.81mol of 1, 11-undecanediamine, 0.21mol of 1, 5-pentanediamine, 1.00mol of terephthalic acid, 0.03 percent of catalyst, 0.3 percent of antioxidant, 0.20 percent of benzoic acid, 200ppm of carbon point and water, setting the stirring speed to 80rpm, heating to 140 ℃ in nitrogen atmosphere and maintaining the temperature for 1h to prepare 50 weight percent nylon salt solution; stopping heating to cool the reaction system to 130 ℃, and keeping the temperature to drain water and concentrate to 70%; raising the temperature to 250 ℃ again, and keeping the pressure of 2.8MPa for reaction for 0.6h; the pressure in the reaction system is reduced to 0MPa by draining and reducing, and the temperature of the reaction system is 288 ℃ after the pressure reduction is finished; vacuumizing to make the vacuum degree be-0.08 MPa, and keeping for 15s to obtain a polyamide melt; and (3) carrying out water-cooling bracing and granulating on the polyamide melt to obtain the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin.
Example 4
Uniformly mixing 0.41mol of 1, 11-undecanediamine, 0.60mol of 1, 5-pentanediamine, 1.00mol of terephthalic acid, 0.03 percent of catalyst, 0.3 percent of antioxidant, 0.12 percent of benzoic acid and 600ppm of carbon point with water, setting the stirring speed to 80rpm, heating to 145 ℃ in nitrogen atmosphere and maintaining the temperature for 1h to prepare 50 weight percent nylon salt solution; stopping heating to cool the reaction system to 125 ℃, and keeping the temperature to drain water and concentrate to 75%; raising the temperature to 245 ℃ again, and keeping the pressure of 2.6MPa for reaction for 1.5h; the pressure in the reaction system is reduced to 0MPa by draining and reducing, and the temperature of the reaction system is 302 ℃ after the pressure reduction is finished; vacuumizing to make the vacuum degree be-0.08 MPa, and keeping for 12s to obtain a polyamide melt; and (3) carrying out water-cooling bracing and granulating on the polyamide melt to obtain the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin.
Example 5
Uniformly mixing 0.32mol of 1, 11-undecanediamine, 0.70mol of 1, 5-pentanediamine, 1.00mol of terephthalic acid, 0.03 percent of catalyst, 0.3 percent of antioxidant, 0.10 percent of benzoic acid and 700ppm of carbon point with water, setting the stirring speed to 80rpm, heating to 150 ℃ in nitrogen atmosphere and maintaining the temperature for 1h to prepare 50 weight percent nylon salt solution; stopping heating to cool the reaction system to 120 ℃, and keeping the temperature, draining water and concentrating to 60%; raising the temperature to 255 ℃ again, and keeping the pressure of 2.7MPa for reaction for 1.2 hours; the pressure in the reaction system is reduced to 0MPa by draining and reducing, and the temperature of the reaction system is 331 ℃ after the pressure reduction is finished; vacuumizing to make the vacuum degree be-0.08 MPa, and keeping for 10s to obtain a polyamide melt; and (3) carrying out water-cooling bracing and granulating on the polyamide melt to obtain the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin.
Example 6
Uniformly mixing 0.20mol of 1, 11-undecanediamine, 0.81mol of 1, 5-pentanediamine, 1.00mol of terephthalic acid, 0.03 percent of catalyst, 0.3 percent of antioxidant, 0.08 percent of benzoic acid and 800ppm of carbon point with water, setting the stirring speed to 80rpm, heating to 145 ℃ in nitrogen atmosphere and maintaining the temperature for 1h to prepare 50 weight percent nylon salt solution; stopping heating to cool the reaction system to 125 ℃, and keeping the temperature to drain water and concentrate to 65%; raising the temperature to 260 ℃ again, and keeping the pressure to 2.6MPa for reaction for 1.5h; the pressure in the reaction system is reduced to 0MPa by draining and reducing, and the temperature of the reaction system is 343 ℃ after the pressure reduction is finished; vacuumizing to make the vacuum degree be-0.08 MPa, and keeping for 8s to obtain a polyamide melt; and (3) carrying out water-cooling bracing and granulating on the polyamide melt to obtain the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin.
Example 7
Uniformly mixing 0.15mol of 1, 11-undecanediamine, 0.86mol of 1, 5-pentanediamine, 1.00mol of terephthalic acid, 0.03 percent of catalyst, 0.3 percent of antioxidant, 0.06 percent of benzoic acid and 900ppm of carbon point with water, setting the stirring speed to 80rpm, heating to 143 ℃ in nitrogen atmosphere and maintaining the temperature for 1h to prepare 50 weight percent nylon salt solution; stopping heating to cool the reaction system to 125 ℃, and keeping the temperature, draining water and concentrating to 60%; raising the temperature to 250 ℃ again, and keeping the pressure to 2.5MPa for reaction for 1.2 hours; the pressure in the reaction system is reduced to 0MPa by draining and reducing, and the temperature of the reaction system is 348 ℃ after the pressure reduction is finished; vacuumizing to make the vacuum degree be-0.08 MPa, and keeping for 10s to obtain a polyamide melt; and (3) carrying out water-cooling bracing and granulating on the polyamide melt to obtain the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin.
Example 8
Uniformly mixing 0.15mol of 1, 11-undecanediamine, 0.86mol of 1, 5-pentanediamine, 1.00mol of terephthalic acid, 0.03 percent of catalyst, 0.3 percent of antioxidant, 0.06 percent of benzoic acid and 50ppm of carbon point with water, setting the stirring speed to 80rpm, heating to 143 ℃ in nitrogen atmosphere and maintaining the temperature for 1h to prepare 50 weight percent nylon salt solution; stopping heating to cool the reaction system to 125 ℃, and keeping the temperature, draining water and concentrating to 60%; raising the temperature to 250 ℃ again, and keeping the pressure to 2.5MPa for reaction for 1.2 hours; the pressure in the reaction system is reduced to 0MPa by draining and reducing, and the temperature of the reaction system is 348 ℃ after the pressure reduction is finished; vacuumizing to make the vacuum degree be-0.08 MPa, and keeping for 10s to obtain a polyamide melt; and (3) carrying out water-cooling bracing and granulating on the polyamide melt to obtain the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin.
Example 9
Uniformly mixing 1.01mol of 1, 11-undecanediamine, 1.00mol of terephthalic acid, 0.03 percent of catalyst, 0.3 percent of antioxidant, 0.24 percent of acetic acid, 50ppm of carbon point and water, setting the stirring speed to be 80rpm, heating to 130 ℃ in nitrogen atmosphere and keeping the temperature for 1h to prepare 50wt percent of nylon salt solution, and keeping the temperature drainage concentrated to 65 percent; raising the temperature to 240 ℃ again, and keeping the pressure to 2.5MPa for reaction for 1h; the pressure in the reaction system is reduced to 0MPa by draining and reducing, and the temperature of the reaction system is 304 ℃ after the pressure reduction is finished; vacuumizing to make the vacuum degree be-0.07 MPa, and keeping for 20s to obtain a polyamide melt; and (3) bracing and granulating the polyamide melt to obtain the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin.
Comparative example 1
Uniformly mixing 1.01mol of 1, 11-undecanediamine, 1.00mol of terephthalic acid, 0.03 percent of catalyst, 0.3 percent of antioxidant, 0.24 percent of benzoic acid and water, setting the stirring speed to 80rpm, heating to 130 ℃ in nitrogen atmosphere and keeping the temperature for 1h to prepare 50wt percent of nylon salt solution, and keeping the temperature to drain water and concentrate to 65 percent; raising the temperature to 240 ℃ again, and keeping the pressure to 2.5MPa for reaction for 1h; the pressure in the reaction system is reduced to 0MPa by draining and reducing, and the temperature of the reaction system is 304 ℃ after the pressure reduction is finished; vacuumizing to make the vacuum degree be-0.07 MPa, and keeping for 20s to obtain a polyamide melt; and (3) bracing and granulating the polyamide melt to obtain the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin.
Comparative example 2
Uniformly mixing 1.01mol of 1, 11-undecanediamine, 1.00mol of terephthalic acid, 0.03 percent of catalyst, 0.3 percent of antioxidant and 0.24 percent of acetic acid with water, setting the stirring speed to be 80rpm, heating to 130 ℃ in nitrogen atmosphere and keeping the temperature for 1h to prepare 50wt percent of nylon salt solution, and keeping the temperature drainage concentrated to 65 percent; raising the temperature to 240 ℃ again, and keeping the pressure to 2.5MPa for reaction for 1h; the pressure in the reaction system is reduced to 0MPa by draining and reducing, and the temperature of the reaction system is 304 ℃ after the pressure reduction is finished; vacuumizing to make the vacuum degree be-0.07 MPa, and keeping for 20s to obtain a polyamide melt; and (3) bracing and granulating the polyamide melt to obtain the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin.
TABLE 1
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (10)

1. The high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin is characterized in that the polymerization monomers of the polyamide resin comprise diamine monomers and diacid monomers, wherein the diamine monomers are selected from any one or two of 1, 11-undecanediamine and 1, 5-pentanediamine, the diacid monomers are selected from any one or more than two of terephthalic acid and derivatives thereof, and the mole fraction of the 1, 5-pentanediamine in the diamine monomers is 0-86%.
2. The high temperature resistant long carbon chain semi-aromatic polyamide resin according to claim 1, wherein the mole fraction of 1, 5-pentanediamine is 0-20% or 55% -86% of diamine monomer;
and/or the ratio of the amounts of the diamine monomer and the diacid monomer is (1.005-1.05): 1, further (1.005-1.03): 1;
and/or the polyamide resin contains carbon dots, wherein the content of the carbon dots is 50-1200 ppm, further 200-1200 ppm, further 600-1200 ppm;
and/or the polyamide resin contains carbon dots, the particle size of the carbon dots is 1-10 nm, and further 5-10 nm;
and/or the polyamide resin comprises diamine structural units and diacid structural units formed by polymerization reaction of diamine monomers and diacid monomers, wherein the sum of the diamine structural units and the diacid structural units accounts for more than 97wt% of the polyamide resin, and more than 99 wt%;
and/or the polyamide resin contains additives including, but not limited to, any one or a combination of two or more of a capping agent, a catalyst, a flame retardant, an antioxidant, an ultraviolet absorber, an infrared absorber, a crystallization nucleating agent, a fluorescent whitening agent and an antistatic agent;
and/or the content of the additive in the polyamide resin is 0.01-3%.
3. The high temperature resistant long carbon chain semi-aromatic polyamide resin according to claim 1, wherein the melting point of the polyamide resin is 270 ℃ or higher, and further 285 ℃ or higher.
4. The high temperature resistant long carbon chain semi-aromatic polyamide resin according to claim 1, wherein the polyamide resin has a relative viscosity of 2.2 to 2.6, and further 2.3 to 2.4.
5. The high temperature resistant long carbon chain semi-aromatic polyamide resin according to claim 1, wherein the polyamide resin has a YI value of M when kept at a temperature 30 ℃ higher than the melting point for 40min, a YI value of N when kept at 0min, and a M/N of 1 to 1.2, and further 1 to 1.06.
6. The preparation method of the high-temperature-resistant long-carbon-chain semi-aromatic polyamide resin is characterized by comprising the following steps of:
1) Under the atmosphere of inert gas or nitrogen, carrying out drainage concentration on the polyamide salt solution at 120-140 ℃, then heating to 235-260 ℃, and reacting for 0.5-3 h under the pressure of 2.3-3.3 MPa;
2) The pressure in the reaction system is reduced to 0-0.1 MPa by draining and reducing, the temperature of the reaction system after the pressure reduction is over 285-353 ℃, and then the reaction system is vacuumized until the vacuum degree is below-0.02 MPa, and the pressure is kept for 0-300 s, so as to obtain the polyamide melt.
7. The method of claim 6, wherein the step of providing the first layer comprises,
step 1) the drainage is concentrated to a concentration of polyamide salt of 40 to 80 weight percent, and further 55 to 65 weight percent;
and/or, the reaction time in the step 1) is 0.5-2 h;
and/or, step 2) the drainage is depressurized to reduce the pressure in the reaction system to 0-0.05 MPa, and further 0-0.02 MPa;
and/or, in the step 2), vacuumizing to the vacuum degree of-0.05 MPa to-0.1 MPa;
and/or, the time for maintaining the vacuum in the step 2) is 0 to 90 seconds, and further 5 to 90 seconds.
8. The method according to claim 6, wherein the polyamide salt is obtained by reacting a diamine monomer and a diacid monomer to form a salt;
and/or, the method comprises a step a) preceding step 1): adding diamine monomer and diacid monomer into water, heating to 120-155 deg.c, optionally maintaining at 120-155 deg.c for 0.5-3 hr to form polyamide salt solution.
9. The method according to claim 6 or 7 or 8, characterized in that the additive is added at any stage of step a) and/or step 1);
and/or adding carbon dots at any stage of step a) and/or step 1);
and/or, comprising step 3): and (3) carrying out water-cooling bracing and granulating on the polyamide melt to obtain the polyamide resin.
10. A composition comprising the high temperature resistant long carbon chain semi-aromatic polyamide resin according to any one of claims 1 to 5, or the high temperature resistant long carbon chain semi-aromatic polyamide resin produced by the production method of the high temperature resistant long carbon chain semi-aromatic polyamide resin according to any one of claims 6 to 9.
CN202210332272.6A 2022-03-30 2022-03-30 High temperature resistant long carbon chain semi-aromatic polyamide resin, preparation method thereof, composition and molded product Pending CN116925343A (en)

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