Low water absorption high heat distortion temperature copolymer nylon resin

Abstract

The application is a kind of low water absorption and high heat distortion temperature copolymer nylon resin, which comprises the following components in weight percentage: 98% to 99.8% of nylon salt; 0.1% to 1% of end-capping agent; and 0.1% to 1% of hindered phenol monomer. The nylon salt comprises 60% to 80% of nylon 66 salt and 20% to 40% of nylon 6T salt. The end-capping agent is glycidyl ether containing silane and / or siloxane structure. The hindered phenol monomer comprises one or more of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), and tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane. The product of the application can meet the production requirements of differentiated copolymer nylon and has universal applicability. Without adding filling materials such as fiber, kaolin, talc, etc., the water absorption can be significantly reduced, the melting point and heat distortion temperature can be increased, and the inherent properties of nylon 66 resin are not affected.

Description

Technical Field

[0001] This invention relates to a copolymer nylon resin, specifically a copolymer nylon resin with low water absorption and high heat distortion temperature. Background Technology

[0002] Nylon 66 (PA66) resin, due to its strong crystallinity, possesses excellent strength, oil resistance, and abrasion resistance. However, it also suffers from drawbacks such as high water absorption, poor dimensional stability, low deformation temperature, and poor modulus. With the continuous expansion of nylon 66 resin applications in fields including engineering plastics and fibers, especially in the automotive sector, the demand for heat-resistant, deformation-resistant, and water-absorbent nylon resins is increasing, and the performance of conventional nylon 66 is insufficient to meet these requirements. Therefore, the art involves adding fillers such as fibers, kaolin, and talc to nylon 66 to reduce its water absorption and improve its strength. However, this reduces the toughness of the nylon material and increases its brittleness, necessitating the addition of toughening agents to improve toughness. During injection molding, these fillers easily penetrate the product surface, making it rough. The resin's fluidity decreases during injection molding, requiring increased injection pressure and speed. Furthermore, a higher proportion of filler increases the wear on the screw. If aromatic nylon resins are used to improve their heat resistance through blending or copolymerization, the secondary heating during the blending process can easily lead to oxidative yellowing of the nylon chips, further affecting their performance. While copolymerization modification can increase the melting point and heat distortion temperature of the product to some extent, its ability to reduce water absorption is limited and cannot meet the current market requirements for low-water-absorption nylon 66 products. The aforementioned conventional nylon 66 resins or modified nylon resins have defects such as low heat distortion temperature, high water content, and insufficient modulus. Especially in the automotive or electronics fields, where nylon materials are required to have low water absorption, high heat resistance, and high strength, there is an urgent need to develop a nylon resin with low water absorption and high heat distortion temperature. Summary of the Invention

[0003] Technical Problem: To overcome the above-mentioned technical defects, the purpose of this invention is to disclose a low water absorption and high heat distortion temperature copolymer nylon resin. The product of this invention can meet the production requirements of differentiated copolymer nylons, has universal applicability, and can significantly reduce water absorption, increase melting point and heat distortion temperature without adding fillers such as fibers, kaolin, or talc, without affecting the inherent properties of nylon 66 resin.

[0004] Technical solution: The present invention provides a low water absorption and high heat distortion temperature copolymer nylon resin, which is obtained by reacting the following components in parts by weight:

[0005] Nylon salt 98%–99.8%;

[0006] End-capping agent 0.1%–1%;

[0007] Hindered phenol monomers: 0.1%–1%;

[0008] Among them, nylon salts include 60% to 80% by weight of nylon 66 salt and 20% to 40% by weight of nylon 6T salt;

[0009] The capping agent is a glycidyl ether containing a silane and / or siloxane structure;

[0010] The functionality of the glycidyl ether containing silane and / or siloxane structures that has reactive groups on nylon salts is less than 2, preferably not more than 1.

[0011] Furthermore, the glycidyl ether containing silane and / or siloxane structures is obtained by reacting aminosilane and / or aminosiloxane with glycidyl ether;

[0012] The aminosilanes mentioned include one or more of 3-aminopropyltrimethylsilane;

[0013] The aminosiloxanes include one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethyloxysilane, 3-aminopropylmethyldiethoxysilane, 3-anilinepropyltrimethoxysilane, di(3-trimethoxysilylpropyl)amine, and 3-aminopropylmethyldimethoxysilane.

[0014] The aminofunctionality of the aminosilane and / or aminosiloxane does not exceed 2;

[0015] The glycidyl ethers mentioned include one or more of glycerol triglycidyl ether, di(2-epoxypropyl) ether, butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, and glycerol propoxy triglycidyl ether;

[0016] The hindered phenolic monomers include one or more combinations of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, 4,4'-butylenebis(6-tert-butyl-3-methylphenol), and tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane;

[0017] Another object of the present invention is to provide a method for preparing a copolymer nylon resin with low water absorption and high heat distortion temperature:

[0018] Nylon 66 salt solution and Nylon 6T salt solution are mixed and stirred evenly to obtain a mixed salt solution; the above mixed salt solution is evaporated and concentrated to remove the solvent, and an end-capping agent is added during the evaporation and concentration process to continue the reaction to obtain a polymer; hindered phenol monomers are added to the above polymer to obtain a low water absorption and high heat distortion temperature copolymer nylon resin.

[0019] The solvent includes one or a combination of two of water and ethanol;

[0020] The mass content of the mixed salt solution is 30-60%;

[0021] The evaporation and concentration reaction temperature is 120–150℃, and the pressure is 0.25–0.35 MPa.

[0022] Beneficial effects: By introducing a certain amount of PA6T into the copolymerization of nylon 66 and adding specific end-capping agents and hindered phenolic monomers to the copolymerized nylon resin, the melting point of the copolymerized nylon resin is effectively controlled at 270±5℃, the heat distortion temperature is 70~80℃, and the water absorption rate is below 0.6%. The product of this invention can meet the production requirements of differentiated copolymerized nylons and has universal applicability. Without adding fillers such as fibers, kaolin, and talc, it can still significantly reduce the water absorption rate, increase the melting point and heat distortion temperature, and does not affect the properties of the nylon 66 resin itself. Detailed Implementation

[0023] The aforementioned low water absorption and high heat distortion temperature copolymer nylon resin is obtained by reacting the following components in parts by weight:

[0024] Nylon salt 98%–99.8%;

[0025] End-capping agent 0.1%–1%;

[0026] Hindered phenol monomers: 0.1%–1%;

[0027] Among them, the nylon salts include 60% to 80% by weight of nylon 66 salt and 20% to 40% by weight of nylon 6T salt;

[0028] As an example, the nylon 66 salt and nylon 6T salt can be obtained directly from the market, or they can be obtained by neutralization reaction of adipic acid and hexamethylenediamine, and nylon 6T salt can be obtained by neutralization reaction of terephthalic acid and hexamethylenediamine.

[0029] The capping agent is a glycidyl ether containing a silane and / or siloxane structure;

[0030] The functionality of the glycidyl ether containing silane and / or siloxane structures that has reactive groups on nylon salts is less than 2, preferably not more than 1.

[0031] In some embodiments of the present invention, the reactive groups include epoxy groups;

[0032] Furthermore, the glycidyl ether containing silane and / or siloxane structures is obtained by reacting aminosilane and / or aminosiloxane with glycidyl ether;

[0033] The aminosilanes mentioned include one or more of 3-aminopropyltrimethylsilane;

[0034] The aminosiloxanes include one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethyloxysilane, 3-aminopropylmethyldiethoxysilane, 3-anilinepropyltrimethoxysilane, di(3-trimethoxysilylpropyl)amine, and 3-aminopropylmethyldimethoxysilane.

[0035] The aminofunctionality of the aminosilane and / or aminosiloxane does not exceed 2;

[0036] The glycidyl ethers mentioned include one or more of glycerol triglycidyl ether, di(2-epoxypropyl) ether, butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, and glycerol propoxy triglycidyl ether;

[0037] In some embodiments of the present invention, the preparation method of the glycidyl ether containing silane and / or siloxane structures is as follows:

[0038] The glycidyl ether is prepared by reacting aminosilane and / or aminosiloxane with glycidyl ether at 100-110°C for 1-3 hours. The epoxy group of the prepared glycidyl ether containing silane and / or siloxane structure has a functionality of less than 2, preferably not more than 1.

[0039] In this invention, glycidyl ether containing silane and / or siloxane structures is used as a capping agent. This capping agent participates in the capping reaction while introducing hydrophobic groups into the polyamide molecular chain, thereby improving the effect of reducing the water absorption properties of copolynylon.

[0040] The hindered phenolic monomers include one or more combinations of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, 4,4'-butylenebis(6-tert-butyl-3-methylphenol), and tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane;

[0041] In this invention, the hindered phenolic monomer used can exist in the amorphous region of the copolynylon resin, thereby further reducing the water absorption rate of the resin.

[0042] Another object of the present invention is to provide a method for preparing a copolymer nylon resin with low water absorption and high heat distortion temperature:

[0043] Nylon 66 salt solution and Nylon 6T salt solution are mixed and stirred evenly to obtain a mixed salt solution; the above mixed salt solution is evaporated and concentrated to remove the solvent, and an end-capping agent is added during the evaporation and concentration process to continue the reaction to obtain a polymer; hindered phenol monomers are added to the above polymer to obtain a low water absorption and high heat distortion temperature copolymer nylon resin.

[0044] The solvent includes one or a combination of two of water and ethanol;

[0045] The mass content of the mixed salt solution is 30-60%;

[0046] The evaporation and concentration reaction temperature is 120–150℃, and the pressure is 0.25–0.35 MPa.

[0047] As an example, the preparation method of low water absorption and high heat distortion temperature copolymer nylon resin specifically includes:

[0048] Step (1): At 70-75℃, mix and stir the nylon 6T salt solution and the nylon 66 salt solution to obtain a mixed salt solution, wherein the mass concentration of the nylon 6T salt solution is 25-30% and the mass concentration of the nylon 66 salt solution is 50-60%.

[0049] Step (2): The mixed salt solution is heated to 120-150°C and pressurized to 0.25-0.35 MPa under a protective gas atmosphere, and evaporated and concentrated to a solution with a mass concentration of 70-80%. At this stage, the capping agent is added and the reaction is continued for 0.5-1 h.

[0050] Step (3): Increase the temperature and pressure to 210-230℃ and 1.85-2.0MPa respectively, and maintain these temperatures and pressures for 40-90 minutes. During this stage, add the hindered phenol monomer. Gradually reduce the pressure to 0-0.01MPa, and control the entire depressurization time to 40-80 minutes. During this period, gradually increase the temperature of the mixture to 280-295℃. Maintain the temperature at 280-295℃ and stir the mixture at 0-0.01MPa pressure for 30-60 minutes. Finally, extrude the molten polymer and granulate it underwater to obtain copolynylon.

[0051] Preferably, a catalyst may be added in steps (1) and / or (2) to accelerate the reaction rate, wherein the catalyst is phosphoric acid, phosphorous acid, hypophosphorous acid, hypophosphorous acid or their salt compounds.

[0052] The principles and features of this invention are described below with reference to specific examples. These examples are provided to facilitate a better understanding of the invention by those skilled in the art. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0053] Example 1

[0054] The aforementioned low water absorption and high heat distortion temperature copolymer nylon resin is obtained by reacting the following components in parts by weight:

[0055] Nylon salt 99.45%;

[0056] End-capping agent 1 0.25%;

[0057] Hindered phenol monomer 0.3%;

[0058] The nylon salts include 75 parts by weight of nylon 66 salt and 25 parts by weight of nylon 6T salt.

[0059] End-capping agent 1 is obtained by reacting 3-aminopropyltrimethylsilane with glycerol triglycidyl ether, and the average functionality of the epoxy group is 1.

[0060] The hindered phenol monomer is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine.

[0061] Example 2

[0062] The aforementioned low water absorption and high heat distortion temperature copolymer nylon resin is obtained by reacting the following components in parts by weight:

[0063] Nylon salt 99.45%;

[0064] End-capping agent 2 0.2%;

[0065] Hindered phenol monomer 0.35%;

[0066] The nylon salts include 80 parts by weight of nylon 66 salt and 20 parts by weight of nylon 6T salt.

[0067] End-capping agent 2 is obtained by reacting 3-aminopropyltrimethylsilane with trimethylolpropane triglycidyl ether, and the average functionality of the epoxy group is 1.

[0068] The hindered phenolic monomers are N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine and 4,4'-butylenebis(6-tert-butyl-3-methylphenol) in a mass ratio of 4:1.

[0069] Example 3

[0070] The aforementioned low water absorption and high heat distortion temperature copolymer nylon resin is obtained by reacting the following components in parts by weight:

[0071] 99% Nylon Salt;

[0072] End-capping agent 1 0.5%;

[0073] 0.5% hindered phenol monomer;

[0074] The nylon salts include 60 parts by weight of nylon 66 salt and 40 parts by weight of nylon 6T salt.

[0075] End-capping agent 1 is obtained by reacting 3-aminopropyltrimethylsilane with glycerol triglycidyl ether, and the average functionality of the epoxy group is 1.

[0076] The hindered phenol monomer is 4,4'-butylidenebis(6-tert-butyl-3-methylphenol).

[0077] Example 4

[0078] The aforementioned low water absorption and high heat distortion temperature copolymer nylon resin is obtained by reacting the following components in parts by weight:

[0079] Nylon salt 99.8%;

[0080] End-capping agent 3 0.1%;

[0081] Hindered phenol monomer 0.1%;

[0082] The nylon salts include 75 parts by weight of nylon 66 salt and 25 parts by weight of nylon 6T salt.

[0083] End-capping agent 3 is obtained by reacting 3-aminopropyltriethyloxysilane with glycerol triglycidyl ether, and the average functionality of the epoxy group is 1.

[0084] The hindered phenol monomer is tris(2-methyl-4-hydroxy-5-tert-butylbenzene)butane.

[0085] Example 5

[0086] The aforementioned low water absorption and high heat distortion temperature copolymer nylon resin is obtained by reacting the following components in parts by weight:

[0087] Nylon salt 99.45%;

[0088] End-capping agent 1 0.25%;

[0089] Hindered phenol monomer 0.3%;

[0090] The nylon salts include 100% by weight of nylon 66 salt;

[0091] End-capping agent 1 is obtained by reacting 3-aminopropyltrimethylsilane with glycerol triglycidyl ether, and the average functionality of the epoxy group is 1.

[0092] The hindered phenol monomer is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine.

[0093] Example 6

[0094] The aforementioned low water absorption and high heat distortion temperature copolymer nylon resin is obtained by reacting the following components in parts by weight:

[0095] Nylon salt 99.45%;

[0096] End-capping agent 1 0.25%;

[0097] Hindered phenol monomer 0.3%;

[0098] Among them, the nylon salt includes 50 parts by weight of nylon 66 salt and 50 parts by weight of nylon 6T salt;

[0099] End-capping agent 1 is obtained by reacting 3-aminopropyltrimethylsilane with glycerol triglycidyl ether, and the average functionality of the epoxy group is 1.

[0100] The hindered phenol monomer is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine.

[0101] Example 7

[0102] The aforementioned low water absorption and high heat distortion temperature copolymer nylon resin is obtained by reacting the following components in parts by weight:

[0103] Nylon salt 99.45%;

[0104] End-capping agent 1 0.25%;

[0105] Hindered phenol monomer 0.3%;

[0106] Among them, the nylon salt includes 35 parts by weight of nylon 66 salt and 65 parts by weight of nylon 6T salt;

[0107] End-capping agent 1 is obtained by reacting 3-aminopropyltrimethylsilane with glycerol triglycidyl ether, and the average functionality of the epoxy group is 1.

[0108] The hindered phenol monomer is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine.

[0109] Example 8

[0110] The aforementioned low water absorption and high heat distortion temperature copolymer nylon resin is obtained by reacting the following components in parts by weight:

[0111] Nylon salt 99.45%;

[0112] End-capping agent 1 0.25%;

[0113] Hindered phenol monomer 0.3%;

[0114] The nylon salts include 85 parts by weight of nylon 66 salt and 15 parts by weight of nylon 6T salt;

[0115] End-capping agent 1 is obtained by reacting 3-aminopropyltrimethylsilane with glycerol triglycidyl ether, and the average functionality of the epoxy group is 1.

[0116] The hindered phenol monomer is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine.

[0117] Example 9

[0118] The aforementioned low water absorption and high heat distortion temperature copolymer nylon resin is obtained by reacting the following components in parts by weight:

[0119] Nylon salt 99.45%;

[0120] End-capping agent 1 0.25%;

[0121] Hindered phenol monomer 0.3%;

[0122] The nylon salts include 75 parts by weight of nylon 66 salt and 25 parts by weight of nylon 9T salt;

[0123] End-capping agent 1 is obtained by reacting 3-aminopropyltrimethylsilane with glycerol triglycidyl ether, and the average functionality of the epoxy group is 1.

[0124] The hindered phenol monomer is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine.

[0125] Example 10

[0126] The aforementioned low water absorption and high heat distortion temperature copolymer nylon resin is obtained by reacting the following components in parts by weight:

[0127] Nylon salt 99.45%;

[0128] End-capping agent 4 0.2%;

[0129] Hindered phenol monomer 0.35%;

[0130] The nylon salts include 80 parts by weight of nylon 66 salt and 20 parts by weight of nylon 6T salt.

[0131] Capping agent 4 is glycerol triglycidyl ether;

[0132] The hindered phenolic monomers are N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine and 4,4'-butylenebis(6-tert-butyl-3-methylphenol) in a mass ratio of 4:1.

[0133] Example 11

[0134] The aforementioned low water absorption and high heat distortion temperature copolymer nylon resin is obtained by reacting the following components in parts by weight:

[0135] Nylon salt 99.45%;

[0136] End-capping agent 5 0.2%;

[0137] Hindered phenol monomer 0.35%;

[0138] The nylon salts include 80 parts by weight of nylon 66 salt and 20 parts by weight of nylon 6T salt.

[0139] End-capping agent 5 is obtained by reacting diethylamine with glycerol triglycidyl ether, and the average functionality of the epoxy groups is 1.

[0140] The hindered phenolic monomers are N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine and 4,4'-butylenebis(6-tert-butyl-3-methylphenol) in a mass ratio of 4:1.

[0141] Example 12

[0142] The aforementioned low water absorption and high heat distortion temperature copolymer nylon resin is obtained by reacting the following components in parts by weight:

[0143] Nylon salt 99.45%;

[0144] End-capping agent 6 0.2%;

[0145] Hindered phenol monomer 0.35%;

[0146] The nylon salts include 80 parts by weight of nylon 66 salt and 20 parts by weight of nylon 6T salt.

[0147] Capping agent 6 is acetic acid;

[0148] The hindered phenolic monomers are N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine and 4,4'-butylenebis(6-tert-butyl-3-methylphenol) in a mass ratio of 4:1.

[0149] Example 13

[0150] The aforementioned low water absorption and high heat distortion temperature copolymer nylon resin is obtained by reacting the following components in parts by weight:

[0151] Nylon salt 99.45%;

[0152] End-capping agent 2 0.2%;

[0153] Hindered amine monomer 0.35%;

[0154] The nylon salts include 80 parts by weight of nylon 66 salt and 20 parts by weight of nylon 6T salt.

[0155] End-capping agent 2 is obtained by reacting 3-aminopropyltrimethylsilane with trimethylolpropane triglycidyl ether, and the average functionality of the epoxy group is 1.

[0156] The hindered amine monomer is bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate.

[0157] Comparative Example 1

[0158] The difference from Example 1 is that no capping agent is added; otherwise, it is the same as Example 1.

[0159] Comparative Example 2

[0160] The difference from Example 1 is that no hindered phenol monomer is added; otherwise, it is the same as Example 1.

[0161] Nylon resins were prepared by fractional reaction according to the weight proportions of Examples 1-13 and Comparative Examples 1-2, and the following performance tests were performed:

[0162]

Claims

1. A low water absorption high heat distortion temperature copolymer nylon resin characterized by The copolymerization reaction comprises the following components by weight: Nylon salt 98%~99.8%; End-capping agent 0.1%~1%; Hindered phenol monomer 0.1%~1%; The nylon salt comprises 60%~80% by weight of nylon 66 salt and 20%~40% by weight of nylon 6T salt; The hindered phenol monomer comprises one or more of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), and tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane; The end-capping agent is a glycidyl ether containing a silane and / or siloxane structure; The glycidyl ether containing a silane and / or siloxane structure has a functionality of less than 2 with respect to the reactive groups of the nylon salt; The glycidyl ether containing a silane and / or siloxane structure is obtained by reacting an amine-based silane and / or amine-based siloxane with a glycidyl ether, wherein the glycidyl ether comprises one or more of glycerol triglycidyl ether, di(2-epoxypropyl) ether, butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, and glycerol propoxy triglycidyl ether.

2. The low water absorption, high heat distortion temperature copolyamide resin of claim 1, wherein, The amine-based silane comprises one or more of 3-aminopropyltrimethylsilane, and the amine-based siloxane comprises one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethyloxysilane, 3-aminopropylmethyldiethoxysilane, 3-anilinopropyltrimethoxysilane, bis(3-trimethoxysilylpropyl)amine, and 3-aminopropylmethyldimethoxysilane.

3. The low water absorption, high heat distortion temperature copolyamide resin of claim 2, wherein, The amine-based silane and / or amine-based siloxane have an amine group functionality of no more than 2.

4. A process for producing a low water absorption high heat distortion temperature copolyamide resin as claimed in claim 3, characterized by, The method for preparing the low-water-absorption high-heat-distortion-temperature copolymerized nylon resin comprises the following steps: Mixing a nylon 66 salt solution and a nylon 6T salt solution to obtain a mixed salt solution; evaporating and concentrating the mixed salt solution to remove the solvent, and adding an end-capping agent to continue the reaction to obtain a polymer; and adding a hindered phenol monomer to the polymer to obtain the low-water-absorption high-heat-distortion-temperature copolymerized nylon resin; The solvent comprises one or more of water and ethanol; The mass content of the mixed salt solution is 30%~60%; The evaporation and concentration reaction temperature is 120~150°C, and the pressure is 0.25~0.35 MPa.

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