CN113185689A - Low-water-absorption copolymerized nylon resin and preparation method thereof - Google Patents
Low-water-absorption copolymerized nylon resin and preparation method thereof Download PDFInfo
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- CN113185689A CN113185689A CN202110589612.9A CN202110589612A CN113185689A CN 113185689 A CN113185689 A CN 113185689A CN 202110589612 A CN202110589612 A CN 202110589612A CN 113185689 A CN113185689 A CN 113185689A
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Abstract
The invention provides a low water absorption copolymerized nylon resin and a preparation method thereof, belonging to the technical field of high polymer materials. The preparation raw materials of the low water absorption copolymerized nylon resin provided by the invention comprise: alicyclic diamine, long carbon chain dibasic acid, amino-terminated organosilicon and catalyst. The diamine with an alicyclic structure, the dibasic acid with a long carbon chain structure and the amino-terminated organic silicon containing a hydrophobic group in the raw materials for preparing the low water absorption copolymerized nylon resin can obviously reduce the content of amide groups on a main chain of a nylon molecule and reduce the water absorption after the low water absorption copolymerized nylon resin is prepared, so that the copolymerized nylon resin with low water absorption rate and better heat resistance is obtained. The results of the examples show that the low water absorption copolymerized nylon resin provided by the invention has the water absorption rate as low as 0.03%, the initial decomposition temperature as high as 387.4 ℃, and the bending strength as high as 98 MPa.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a low-water-absorption copolymerized nylon resin and a preparation method thereof.
Background
Nylon (PA) is a translucent or opaque, opalescent semicrystalline resin, has high rigidity and toughness over a wide temperature range, has good abrasion resistance, creep resistance and oil resistance, and has wide applications in many fields. However, PA has a strong water absorption due to the presence of a high density hydrophilic amide group (-NHCO-). Under the conditions of 23 ℃ and 50% of relative humidity, the equilibrium water absorption rate is about 2.5%; when the relative humidity is 100%, the equilibrium water absorption rate is as high as 5%. After the PA absorbs water, the mechanical property, the electrical property and the like of the PA are obviously reduced, and the use safety and the service life of the product are seriously influenced. On the other hand, the size of PA before and after water absorption is greatly changed, some products need to be subjected to moisture absorption treatment, the cost is increased, and the application of the PA in the field needing high size stability is limited.
At present, effective methods for reducing the water absorption of PA mainly comprise two main types, one is blending with inorganic filler or other resins, and the other is reducing the content of amide groups on the main chain of nylon molecules by molecular design. Chinese patent 201911211679.8 discloses a low water absorption nylon masterbatch and a preparation method thereof, wherein nylon, nylon 6 powder, polycondensate of fatty alcohol and epoxy ethylene and antioxidant are used as raw materials to prepare the low water absorption nylon masterbatch. However, the low water absorption nylon reported by the method still has the problem of high water absorption. Further, PA has a thermal decomposition temperature of about 250 ℃ and is inferior in heat resistance. Accordingly, it is highly desirable to provide a low water absorption copolymerized nylon resin having excellent mechanical properties and heat resistance and a method for preparing the same.
Disclosure of Invention
The invention aims to provide a low-water-absorption copolymerized nylon resin and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a low water absorption copolymerized nylon resin, which is prepared from the following raw materials: long carbon chain dibasic acid, alicyclic diamine, amino-terminated organosilicon and catalyst;
the ratio of the amount of the alicyclic diamine to the amount of the amino terminated silicone is (10-19) to 1;
the ratio of the amount of the alicyclic diamine and the amino-terminated organosilicon to the amount of the long carbon chain dibasic acid is (0.97-1): 1;
the mass ratio of the long carbon chain dibasic acid, the alicyclic diamine and the amino-terminated organic silicon to the catalyst is 100 (0.1-0.5).
Preferably, the cycloaliphatic diamine comprises
Preferably, the long carbon chain dibasic acid comprises one or more of sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid and octadecanedioic acid.
Preferably, the amino-terminated organosilicon comprises one or more of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane, shin-over PAM-E, shin-over KF-8008, shin-over KF-8010, shin-over KF-8012, shin-over X-22-161A, shin-over X-22-161B, shin-over X-22-9409 and shin-over X-22-1660B-3.
Preferably, the catalyst comprises one or more of phosphoric acid, phosphorous acid and sodium hypophosphite.
The invention also provides a preparation method of the low water absorption copolymerized nylon resin, which comprises the following steps: mixing alicyclic diamine, long carbon chain dibasic acid, amino-terminated organic silicon and a catalyst, and carrying out melt polycondensation reaction to obtain the low-water-absorption copolymerized nylon resin.
Preferably, the melt polycondensation reaction includes a pre-reaction and a polycondensation reaction which are sequentially performed.
Preferably, the temperature of the pre-reaction is 200-220 ℃, and the pressure of the pre-reaction is 1.5-2.5 MPa.
Preferably, the temperature of the polycondensation reaction is 240-250 ℃, the pressure of the polycondensation reaction is 1.5-2.0 MPa, and the time of the polycondensation reaction is 1-2 h.
Preferably, the melt polycondensation reaction is carried out under the protection of high-purity nitrogen.
The invention provides a low water absorption copolymerized nylon resin, which is prepared from the following raw materials: long carbon chain dibasic acid, alicyclic diamine, amino-terminated organosilicon and catalyst; the ratio of the amount of the alicyclic diamine to the amount of the amino terminated silicone is (10-19) to 1; the ratio of the amount of the alicyclic diamine and the amino-terminated organosilicon to the amount of the long carbon chain dibasic acid is (0.97-1): 1; the mass ratio of the long carbon chain dibasic acid, the alicyclic diamine and the amino-terminated organic silicon to the catalyst is 100 (0.1-0.5). The diamine with an alicyclic structure in the raw materials for preparing the low-water-absorption copolymerized nylon resin improves the rigidity of a copolymerized nylon molecular chain to a certain extent, so that the heat resistance of the copolymerized nylon resin is improved; the amino-terminated organic silicon containing hydrophobic groups can improve the hydrophobicity of the copolymerized nylon resin and reduce the water absorption. The diamine with an alicyclic structure, the dibasic acid with a long carbon chain structure and the amino-terminated organic silicon containing a hydrophobic group in the raw materials for preparing the low water absorption copolymerized nylon resin can obviously reduce the content of amide groups on a main chain of a nylon molecule and reduce the water absorption after the low water absorption copolymerized nylon resin is prepared, so that the copolymerized nylon resin with low water absorption rate and better heat resistance is obtained. The results of the examples show that the low water absorption copolymerized nylon resin provided by the invention has the characteristics of low water absorption rate of 0.03%, initial decomposition temperature of 387.4 ℃ and bending strength of 98MPa, low water absorption, high heat resistance and excellent mechanical properties.
Detailed Description
The invention provides a low water absorption copolymerized nylon resin, which is prepared from the following raw materials: long carbon chain dibasic acid, alicyclic diamine, amino-terminated organosilicon and catalyst;
the ratio of the amount of the alicyclic diamine to the amount of the amino terminated silicone is (10-19) to 1;
the ratio of the amount of the alicyclic diamine and the amino-terminated organosilicon to the amount of the long carbon chain dibasic acid is (0.97-1): 1;
the mass ratio of the long carbon chain dibasic acid, the alicyclic diamine and the amino-terminated organic silicon to the catalyst is 100 (0.1-0.5).
In the present invention, the raw materials for preparing the copolymerized nylon resin having low water absorption are those commercially available in the conventional art, unless otherwise specified.
In the present invention, the raw material for preparing the low water absorbent copolymerized nylon resin includes a long carbon chain dibasic acid. In the invention, the long carbon chain dibasic acid can be condensed with alicyclic diamine to obtain a polyamide polymer containing amido bonds, and the mechanical property of the copolymerized nylon resin can be improved. In the present invention, when the long carbon chain dibasic acid is used in the above range, the low water absorption copolymerized nylon resin can have excellent mechanical properties.
In the present invention, the long carbon chain dibasic acid preferably includes one or more of sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid and octadecanedioic acid, and more preferably one or more of sebacic acid, undecanedioic acid, dodecanedioic acid and octadecanedioic acid. In the invention, the long carbon chain dibasic acid is more favorable for further improving the mechanical property of the copolymerized nylon resin. In the invention, when the long carbon chain dibasic acid is composed of the above components, the dosage of the different long carbon chain dibasic acids is not particularly limited, and can be adjusted according to actual needs.
In the present invention, the raw material for preparing the low water absorbent copolymerized nylon resin includes alicyclic diamine. In the present invention, the alicyclic diamine can increase the crosslinking density of the copolymerized nylon resin, and thus the copolymerized nylon resin has excellent heat resistance. In the present invention, when the amount of the alicyclic diamine is in the above range, the low water absorbent copolymerized nylon resin can have excellent heat resistance.
In the present invention, the alicyclic diamine preferably includes
In the present invention, the raw material for preparing the low water absorption copolymerized nylon resin includes amino terminated silicone. In the invention, the amino-terminated organic silicon contains hydrophobic groups, so that the hydrophobicity of the copolymerized nylon resin can be improved, and the water absorption is reduced. In the present invention, when the amino-terminated silicone is used in the above range, the copolymerized nylon resin having low water absorption can have excellent low water absorption.
In the invention, the amino-terminated organosilicon preferably comprises one or more of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane, shin-over PAM-E, shin-over KF-8008, shin-over KF-8010, shin-over KF-8012, shin-over X-22-161A, shin-over X-22-161B, shin-over X-22-9409 and shin-over X-22-1660B-3, and more preferably one or more of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane, shin-over KF-8008, shin-over KF-8010 and shin-over X-22-161A. In the invention, the Xinyue PAM-E, the Xinyue KF-8008, the Xinyue KF-8010, the Xinyue KF-8012, the Xinyue X-22-161A, the Xinyue X-22-161B, the Xinyue X-22-9409 and the Xinyue X-22-1660B-3 are all types of amino-terminated organosilicon, the source of the amino-terminated organosilicon is not particularly limited, and commercially available products known by technicians in the field can be adopted. In the present invention, the source of the amino-terminated silicone is preferably shin-Etsu chemical industries, Inc. In the present invention, when the amino-terminated silicone is of the above-mentioned kind, the hydrophobicity of the copolymerized nylon resin can be further improved, and the water absorption can be reduced. In the invention, when the amino-terminated organosilicon consists of the above components, the dosage of the different amino-terminated organosilicon is not specially limited, and can be adjusted according to actual needs.
In the present invention, the ratio of the amounts of the alicyclic diamine and the amino terminated silicone is (10-19): 1, preferably (10-15): 1. In the present invention, when the ratio of the amounts of the alicyclic diamine and the amino terminated silicone is in the above range, the low water absorbent copolymerized nylon resin can have excellent heat resistance and mechanical properties.
In the present invention, the ratio of the amount of the alicyclic diamine and the amino terminated silicone to the amount of the long carbon chain dibasic acid is (0.97 to 1):1, preferably (0.98 to 1): 1. In the present invention, when the ratio of the amount of the alicyclic diamine and the amino terminated silicone to the amount of the long carbon chain dibasic acid is in the above range, the low water absorbent copolymerized nylon resin can have excellent heat resistance and mechanical properties.
In the present invention, the raw material for preparing the low water absorbent copolymerized nylon resin includes a catalyst. The catalyst of the present invention is not particularly limited in kind, and it may be a catalyst known to those skilled in the art that can catalyze the polycondensation reaction. In the present invention, the catalyst preferably includes one or more of phosphoric acid, phosphorous acid and sodium hypophosphite, and more preferably phosphoric acid or phosphorous acid. In the present invention, the catalyst is capable of catalyzing the progress of the melt polycondensation reaction.
In the present invention, the ratio of the mass of the long carbon chain dibasic acid, the alicyclic diamine and the amino terminated silicone to the mass of the catalyst is 100 (0.1-0.5), preferably 100 (0.4-0.5). In the present invention, when the ratio of the mass of the long carbon chain dibasic acid, the alicyclic diamine, and the amino terminated silicone to the mass of the catalyst is in the above range, the melt polycondensation reaction can be sufficiently performed.
According to the preparation method of the low water absorption copolymerized nylon resin, diamine with an alicyclic structure, dibasic acid with a long carbon chain structure and amino-terminated organic silicon containing a hydrophobic group in the raw materials are used, and the content of amide groups on a main chain of nylon molecules can be obviously reduced and the water absorption can be reduced by controlling the using amount of each component after the low water absorption copolymerized nylon resin is prepared, so that the copolymerized nylon resin with low water absorption rate and better heat resistance can be obtained.
The invention also provides a preparation method of the low water absorption copolymerized nylon resin, which comprises the following steps: mixing alicyclic diamine, long carbon chain dibasic acid, amino-terminated organic silicon and a catalyst, and carrying out melt polycondensation reaction to obtain the low-water-absorption copolymerized nylon resin.
The operation mode of mixing the alicyclic diamine, the long carbon chain dibasic acid, the amino-terminated organic silicon and the catalyst is not particularly limited, and the components can be uniformly mixed by adopting a mixing mode well known by the technical personnel in the field.
The apparatus for the melt polycondensation reaction is not particularly limited in the present invention, and a reaction vessel known to those skilled in the art may be used.
In the present invention, the melt polycondensation reaction preferably includes a pre-reaction and a polycondensation reaction which are carried out in this order.
In the invention, the pre-reaction temperature is preferably 200-220 ℃, and more preferably 210-220 ℃. The temperature rise rate of the temperature rise from the room temperature to the pre-reaction temperature is not particularly limited, and the temperature rise rate can be adjusted according to experimental needs, so that the temperature of the reaction system can be raised to the pre-reaction temperature. In the present invention, when the temperature of the pre-reaction is within the above range, the components can be sufficiently melted, and a partial pre-polymerization reaction can occur, which is advantageous for the sufficient progress of the subsequent polycondensation reaction.
In the present invention, the pre-reaction pressure is preferably 1.5 to 2.5MPa, and more preferably 2.0 to 2.5 MPa. In the present invention, the pre-reaction is advantageously carried out at a pressure within the above range.
In the invention, the pre-reaction time is preferably 1.0-2.0 h, and more preferably 1.0-1.5 h. In the present invention, when the pre-reaction time is within the above range, the components can be fully melted, and partial pre-polymerization reaction can occur, which is beneficial to fully performing the subsequent polycondensation reaction.
In the invention, the temperature of the polycondensation reaction is preferably 240-250 ℃, and more preferably 245-250 ℃; the time of the polycondensation reaction is preferably 1-2 h, and more preferably 1.5-2 h; the pressure of the polycondensation reaction is preferably 1.5 to 2.0MPa, and more preferably 1.5 to 1.8 MPa. In the present invention, when the temperature, time and pressure of the polycondensation reaction are within the above ranges, the polycondensation reaction can be sufficiently completed, and the overall performance of the low water absorption copolymerized nylon resin can be improved.
The temperature rise rate of the pre-reaction temperature to the polycondensation reaction temperature is not particularly limited, and the temperature rise rate can be adjusted according to experimental needs, so that the temperature of the reaction system can be raised to the polycondensation reaction temperature. In the present invention, when the temperature of the polycondensation reaction is in the above range, the polymerization reaction of each component can be sufficiently performed.
In the present invention, the melt polycondensation reaction is preferably carried out under the protection of high-purity nitrogen gas. In the present invention, the high-purity nitrogen gas can prevent the occurrence of side reactions. The method of introducing high-purity nitrogen gas during the melt polycondensation reaction is not particularly limited in the present invention, and a method of introducing nitrogen gas well known to those skilled in the art may be employed. In the invention, the method for introducing high-purity nitrogen during the melt polycondensation reaction is preferably that alicyclic diamine, long-carbon-chain dibasic acid, amino-terminated organic silicon and a catalyst are mixed and then placed in a reaction kettle, and then the air in the reaction kettle is replaced by high-purity nitrogen for 3-4 times.
In the present invention, the method of treatment after the melt polycondensation is not particularly limited, and a method of treatment after the melt polycondensation known to those skilled in the art may be used. In the invention, the post-treatment method of the melt polycondensation preferably comprises the steps of discharging gas from a reaction kettle after the melt polycondensation to normal pressure, discharging water in a system, gradually vacuumizing to reduce the pressure of the system to-0.03 to-0.07 MPa, and discharging to obtain the low water absorption copolymerized nylon resin.
The preparation method of the low water absorption copolymerized nylon resin provided by the invention can promote the full progress of the melt polycondensation reaction by controlling the temperature, time and pressure of the reaction, so that the low water absorption copolymerized nylon resin with excellent comprehensive performance can be obtained, and the low water absorption copolymerized nylon resin has excellent heat resistance and mechanical property.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 1, 4-cyclohexanediamine (3.43kg, 30mol), 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (0.75kg, 3mol) and sebacic acid (6.67kg, 33mol) into a reaction kettle, adding 50g of sodium hypophosphite and 500g of deionized water, replacing air in the reaction kettle for 3-4 times by high-purity nitrogen, heating to 210 ℃, keeping the pressure in the kettle at 1.8MPa, reacting for 1h at the temperature and the pressure, heating to 250 ℃, keeping the pressure in the kettle at 2.0MPa, maintaining the pressure for 1.5h, discharging the water in the system to the normal pressure, gradually vacuumizing to reduce the pressure of the system to-0.03-0.07 MPa, and discharging to obtain the low-water-absorption copolymerized nylon resin. In this example, the ratio of the amount of cycloaliphatic diamine to amino terminated silicone is 10: 1; the ratio of the amount of the substance of the alicyclic diamine and the amino-terminated organosilicon to the amount of the substance of the long carbon chain dibasic acid is 1: 1; the mass ratio of the dibasic acid, diamine and amino terminated organosilicon to the mass of the catalyst is 100: 0.49.
Example 2
3,3 '-dimethyl-4, 4' -diaminodicyclohexyl alkyl methane (7.15kg, 30mol), 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyl disiloxane (0.75kg, 3mol) and sebacic acid (6.67kg, 33mol) are put into a reaction kettle, 60g of sodium hypophosphite and 700g of deionized water are added, air in the reaction kettle is replaced by high-purity nitrogen for 3-4 times, the temperature is raised to 210 ℃, the pressure in the kettle is maintained at 1.9MPa, after reaction (1.5) h at the temperature and the pressure, the temperature is raised to 250 ℃, the pressure in the kettle is maintained at 2.0MPa, the pressure is maintained for 2h, the gas is released to normal pressure, water in the system is discharged, then the vacuum is gradually pumped, the pressure of the system is reduced to-0.05 MPa, and the low water absorption copolymerized nylon resin is obtained by discharging. In this example, the ratio of the amount of cycloaliphatic diamine to amino terminated silicone is 10: 1; the ratio of the amount of the substance of the alicyclic diamine and the amino-terminated organosilicon to the amount of the substance of the long carbon chain dibasic acid is 1: 1; the mass ratio of the dibasic acid, diamine and amino terminated organosilicon to the mass of the catalyst is 100: 0.43.
Example 3
3,3 '-dimethyl-4, 4' -diaminodicyclohexyl alkyl methane (7.15kg, 30mol), 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyl disiloxane (0.75kg, 3mol) and undecanedioic acid (7.14kg, 33mol) are put into a reaction kettle, 60g of sodium hypophosphite and 700g of deionized water are added, air in the reaction kettle is replaced by high-purity nitrogen for 3-4 times, the temperature is raised to 210 ℃, the pressure in the kettle is maintained at 2.0MPa, the reaction is carried out for 1.5h at the temperature and under the pressure, the temperature is raised to 250 ℃, the pressure in the kettle is maintained at 2.0MPa, the pressure is maintained for 2h, the gas is released to normal pressure, the water in the system is discharged, then the vacuum is gradually pumped, the pressure of the system is reduced to-0.05 MPa, and the low water absorption copolymerized nylon resin is obtained by discharging. In this example, the ratio of the amount of cycloaliphatic diamine to amino terminated silicone is 10: 1; the ratio of the amount of the substance of the alicyclic diamine and the amino-terminated organosilicon to the amount of the substance of the long carbon chain dibasic acid is 1: 1; the mass ratio of the dibasic acid, diamine and amino terminated organosilicon to the catalyst is 100: 0.4.
Example 4
3,3 '-dimethyl-4, 4' -diaminodicyclohexyl alkyl methane (7.15kg, 30mol), 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyl disiloxane (0.75kg, 3mol) and dodecanedioic acid (7.60kg, 33mol) are put into a reaction kettle, 60g of sodium hypophosphite and 700g of deionized water are added, air in the reaction kettle is replaced by high-purity nitrogen for 3-4 times, the temperature is raised to 210 ℃, the pressure in the kettle is maintained at 2.2MPa, after reaction is carried out for 1h at the temperature and the pressure, the temperature is raised to 250 ℃, the pressure in the kettle is maintained at 1.9MPa, the pressure is maintained for 1.5h, the gas is released to the normal pressure, the water in the system is discharged, then the vacuum is gradually pumped, the pressure of the system is reduced to-0.05 MPa, and the low water absorption copolymerized nylon resin is obtained by discharging. In this example, the ratio of the amount of cycloaliphatic diamine to amino terminated silicone is 10: 1; the ratio of the amount of the substance of the alicyclic diamine and the amino-terminated organosilicon to the amount of the substance of the long carbon chain dibasic acid is 1: 1; the mass ratio of the dibasic acid, diamine and amino terminated organosilicon to the mass of the catalyst is 100: 0.39.
Example 5
3,3 '-dimethyl-4, 4' -diaminodicyclohexyl alkyl methane (7.15kg, 30mol), 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyl disiloxane (0.75kg, 3mol) and octadecanedioic acid 10.38kg, 33mol) are put into a reaction kettle, 70g of sodium hypophosphite and 1000g of deionized water are added, air in the reaction kettle is replaced by high-purity nitrogen for 3-4 times, the temperature is raised to 210 ℃, the pressure in the kettle is maintained at 1.8MPa, the temperature is raised to 250 ℃ after 1.5h of reaction under the temperature and the pressure, the pressure in the kettle is maintained at 1.9MPa, the pressure is maintained for 1h, the air is released to the normal pressure, water in the system is discharged, then the vacuum is gradually pumped, the pressure of the system is reduced to-0.05 MPa, and the low water absorption copolymerized nylon resin is obtained by discharging. In this example, the ratio of the amount of cycloaliphatic diamine to amino terminated silicone is 10: 1; the ratio of the amount of the substance of the alicyclic diamine and the amino-terminated organosilicon to the amount of the substance of the long carbon chain dibasic acid is 1: 1; the mass ratio of the dibasic acid, diamine and amino terminated organosilicon to the mass of the catalyst is 100: 0.38.
Example 6
3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane (7.15kg, 30mol), Xinyue KF-8008 terminal amino group organosilicon (1.2kg, 3mol) and 7.60kg of dodecanedioic acid are put into a reaction kettle, 60g of sodium hypophosphite and 700g of deionized water are added, air in the reaction kettle is replaced by high-purity nitrogen for 3-4 times, the temperature is increased to 210 ℃, the pressure in the kettle is kept at 1.8MPa, the temperature is increased to 250 ℃ after reaction is carried out for 1 hour under the temperature and the pressure, the pressure in the kettle is kept at 2.0MPa, the pressure is maintained for 1.5 hours, the air is released to normal pressure, water in the system is discharged, then the vacuum is gradually pumped, the pressure of the system is reduced to-0.05 MPa, and the low water absorption copolymerized nylon resin is obtained after discharging. In this example, the ratio of the amount of cycloaliphatic diamine to amino terminated silicone is 10: 1; the ratio of the amount of the substance of the alicyclic diamine and the amino-terminated organosilicon to the amount of the substance of the long carbon chain dibasic acid is 1: 1; the mass ratio of the dibasic acid, diamine and amino terminated organosilicon to the mass of the catalyst is 100: 0.37.
Example 7
3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane (7.15kg, 30mol), Xinyue KF-8010 terminal amino organosilicon (1.35kg, 3mol) and dodecanedioic acid (7.60kg, 33mol) are put into a reaction kettle, 60g of sodium hypophosphite and 700g of deionized water are added, air in the reaction kettle is replaced by high-purity nitrogen for 3-4 times, the temperature is increased to 210 ℃, the pressure in the kettle is kept at 1.8MPa, the temperature is increased to 250 ℃, the pressure in the kettle is kept at 2.0MPa after 1h of reaction at the temperature and the pressure, the pressure is kept at 2.0MPa, the pressure is released to normal pressure, water in the system is discharged, then the vacuum is gradually pumped, the pressure of the system is reduced to-0.06 MPa, and the low water absorption copolymerized nylon resin is obtained after discharging. In this example, the ratio of the amount of cycloaliphatic diamine to amino terminated silicone is 10: 1; the ratio of the amount of the substance of the alicyclic diamine and the amino-terminated organosilicon to the amount of the substance of the long carbon chain dibasic acid is 1: 1; the mass ratio of the dibasic acid, diamine and amino terminated organosilicon to the mass of the catalyst is 100: 0.37.
Example 8
3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane (7.15kg, 30mol), Xinyue X-22-161A terminal amino organosilicon (1.5kg, 3mol) and dodecanedioic acid (7.60kg, 33mol) are put into a reaction kettle, 60g of sodium hypophosphite and 700g of deionized water are added, air in the reaction kettle is replaced by high-purity nitrogen for 3-4 times, the temperature is increased to 210 ℃, the pressure in the kettle is kept at 1.8MPa, the temperature is increased to 250 ℃, the pressure in the kettle is kept at 2.0MPa after 1h of reaction at the temperature and the pressure, the pressure is kept at normal pressure after 2h of reaction, water in the system is discharged, the vacuum is gradually pumped, the pressure of the system is reduced to-0.06 MPa, and the low-water-absorption copolymerized nylon resin is obtained after discharging. In this example, the ratio of the amount of cycloaliphatic diamine to amino terminated silicone is 10: 1; the ratio of the amount of the substance of the alicyclic diamine and the amino-terminated organosilicon to the amount of the substance of the long carbon chain dibasic acid is 1: 1; the mass ratio of the dibasic acid, diamine and amino terminated organosilicon to the mass of the catalyst is 100: 0.37.
Test example 1
Tensile specimens of the low water absorption copolymerized nylon resins prepared in examples 1 to 8 were respectively treated in a constant temperature and humidity chamber for 24 hours, and tested by using a testing machine with the test standard of GB/T1040.2-2006, to obtain the tensile strengths of the low water absorption copolymerized nylon resins prepared in examples 1 to 8 as shown in Table 1.
Bending sample bars of the low water absorption copolymerized nylon resins prepared in examples 1-8 are respectively placed in a constant temperature and humidity chamber for treatment for 24h, and are tested by using a testing machine, wherein the test standard is GB/T9341-.
Impact sample bars of the low water absorption copolymerized nylon resins prepared in examples 1 to 8 are respectively placed in a constant temperature and humidity chamber for treatment for 24 hours, and tested by using a testing machine, wherein the testing standard is GB/T1043.1-2008, and the impact strength of the low water absorption copolymerized nylon resins prepared in examples 1 to 8 is shown in Table 1.
5-8 mg of the low water absorption copolymerized nylon resin prepared in examples 1-8 were weighed, respectively, the sample was heated to 270 ℃ under the protection of nitrogen gas and melted for 3min, quenched with liquid nitrogen, then the quenched sample was heated to 350 ℃, cooled to room temperature, and then heated to 350 ℃, and the heating rates were all 10 ℃/min, and the melting points of the low water absorption copolymerized nylon resin prepared in examples 1-8 were shown in table 1.
5-8 mg of the low water absorption copolymerized nylon resin prepared in examples 1-8 were weighed, respectively, and the sample was heated to 700 ℃ under the protection of nitrogen, and the initial decomposition temperature of the low water absorption copolymerized nylon resin prepared in examples 1-8 was as shown in Table 1, with the weight loss of 5%.
Samples of the low water absorption copolymerized nylon resins prepared in examples 1 to 8 were respectively dried in an oven at 100 ℃, cooled along with the oven, and tested according to the ASTM D570-98 standard, and the water absorption rates of the low water absorption copolymerized nylon resins prepared in examples 1 to 8 were as shown in table 1.
TABLE 1 test results of low water absorption copolymerized nylon resin prepared in examples 1 to 8
As can be seen from the above table, the low water absorption copolymerized nylon resin provided by the invention has low water absorption rate and excellent mechanical properties and heat resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The low-water-absorption copolymerized nylon resin is prepared from the following raw materials: long carbon chain dibasic acid, alicyclic diamine, amino-terminated organosilicon and catalyst;
the ratio of the amount of the alicyclic diamine to the amount of the amino terminated silicone is (10-19) to 1;
the ratio of the amount of the alicyclic diamine and the amino-terminated organosilicon to the amount of the long carbon chain dibasic acid is (0.97-1): 1;
the mass ratio of the long carbon chain dibasic acid, the alicyclic diamine and the amino-terminated organic silicon to the catalyst is 100 (0.1-0.5).
2. The copolymerized nylon resin of claim 1, wherein the alicyclic diamine comprises at least one selected from the group consisting of
3. The copolymerized nylon resin of claim 1, wherein the long carbon chain dibasic acid comprises one or more of sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, and octadecanedioic acid.
4. The copolymerized nylon resin with low water absorption of claim 1, wherein the amino-terminated silicone comprises one or more of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane, Xinyue PAM-E, Xinyue KF-8008, Xinyue KF-8010, Xinyue KF-8012, Xinyue X-22-161A, Xinyue X-22-161B, Xinyue X-22-9409 and Xinyue X-22-1660B-3.
5. The copolymerized nylon resin with low water absorption according to claim 1, wherein the catalyst comprises one or more of phosphoric acid, phosphorous acid and sodium hypophosphite.
6. The method for preparing a low water absorption copolymerized nylon resin of any one of claims 1 to 5, comprising the steps of: mixing alicyclic diamine, long carbon chain dibasic acid, amino-terminated organic silicon and a catalyst, and carrying out melt polycondensation reaction to obtain the low-water-absorption copolymerized nylon resin.
7. The method for preparing a low water absorption copolymerized nylon resin according to claim 6, wherein the melt polycondensation reaction includes a pre-reaction and a polycondensation reaction, which are sequentially performed.
8. The method for preparing a low water absorption copolymerized nylon resin according to claim 7, wherein the pre-reaction temperature is 200 to 220 ℃ and the pre-reaction pressure is 1.5 to 2.5 MPa.
9. The method for preparing a low water absorption copolymerized nylon resin according to claim 7, wherein the temperature of the polycondensation reaction is 240 to 250 ℃, the pressure of the polycondensation reaction is 1.5 to 2.0MPa, and the time of the polycondensation reaction is 1 to 2 hours.
10. The method for preparing a low water absorption copolymerized nylon resin according to claim 6, wherein the melt polycondensation reaction is performed under the protection of high purity nitrogen gas.
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