Highly transparent polyamide resin and method for producing the same

Abstract

The application discloses a kind of high transparent polyamide resin and its preparation method, high transparent polyamide resin includes the following weight parts component reaction obtained: polyamide 610 salt 100 parts;Steric hindered polyamide salt 0.5~3 parts;Or: polyamide 610 salt 100 parts;Semi-aromatic polyamide salt 3~17 parts;Steric hindered polyamide salt 0.5~3 parts;The application is by introducing specific steric hindered polyamide in polyamide 610, effectively improve the transparency of polyamide 610, more importantly, the introduction of steric hindered polyamide does not cause the degradation of the mechanical properties of polyamide 610.In addition, by the compounding of steric hindered polyamide and semi-aromatic polyamide, the transparency and mechanical properties of polyamide 610 can be further improved.

Description

Technical Field

[0001] This invention relates to a highly transparent polyamide and its preparation, specifically to a highly transparent copolyamide resin and its preparation method, and articles made from this transparent polyamide resin. Background Technology

[0002] Polyamide 610, as a type of crystalline polyamide material, possesses excellent mechanical properties, good heat resistance, good solvent resistance, and low water absorption. However, due to its crystallinity, it easily forms spheres with diameters significantly larger than the wavelength of visible light during the crystallization process, making it difficult for visible light to pass through the material and thus exhibiting opacity. With the expansion of polyamide 610's application areas, especially in fields such as precision optical instruments, protective covers, and instrument panels where both transparency and mechanical properties are highly demanding, conventional opaque polyamide 610 is insufficient to meet the requirements of these specialized markets.

[0003] Therefore, research on transparent polyamide 610 has attracted increasing attention. Currently, the preparation of transparent polyamide 610 is mainly achieved by inhibiting the crystallization of polyamide. This is done by altering or suppressing the crystallization process of polyamide through various methods, reducing the crystallinity of the material to form amorphous or semi-morphous polymers, or reducing the size of the crystal spheres to below the visible light wavelength range. However, transparent polyamide 610 prepared using these methods often suffers from reduced mechanical strength, heat resistance, and solvent resistance due to the decreased crystallinity and smaller crystal sphere size. Therefore, achieving a polyamide 610 that combines high transparency with good mechanical strength is a pressing technical challenge that needs to be addressed. Summary of the Invention

[0004] Technical problem: In order to overcome the above technical defects, the purpose of this invention is to disclose a high-transparency polyamide resin and its preparation method. By compounding sterically hindered polyamide and semi-aromatic polyamide, the transparency and mechanical properties of polyamide 610 can be further improved.

[0005] Technical solution: The present invention provides a high-transparency polyamide resin comprising the following components in parts by weight, obtained by reaction:

[0006] 100 parts of polyamide 610 salt;

[0007] 0.5 to 3 parts of sterically hindered polyamide salt;

[0008] Furthermore, the transparent polyamide is obtained by reacting the following components in parts by weight:

[0009] 100 parts of polyamide 610 salt;

[0010] 3-17 parts of semi-aromatic polyamide salt;

[0011] 0.5 to 3 parts of sterically hindered polyamide salt;

[0012] The sterically hindered polyamide salt is a sterically hindered polyamide salt with a functionality greater than or equal to 3 and less than 4, generated by the neutralization reaction of a sterically hindered monobasic acid and a tetraamine.

[0013] The semi-aromatic polyamide salt is a semi-aromatic polyamide salt generated by the neutralization reaction of an aromatic dicarboxylic acid and a C2-C12 aliphatic diamine;

[0014] The ratio of the total molar amount of carboxyl groups in the aromatic dicarboxylic acid to the total molar amount of amino groups in the C2-C12 aliphatic diamine is 1:1 to 1.05.

[0015] The sterically hindered monocarboxylic acid contains a benzene ring or heterocycle and its derivative structure, and the number of carbon atoms is 4 to 30. The benzene ring and its derivative structure includes one or more of benzene, naphthalene, and fluorene. The heterocycle and its derivative structure includes one or more of pyridine, pyrimidine, furan, and pyran.

[0016] Furthermore, the sterically hindered monocarboxylic acid includes one or more of benzoic acid, phenylacetic acid, phenylbenzoic acid, phenylphenylacetic acid, naphtholic acid, naphthaleneacetic acid, fluorenic acid, 4-(1,2,2-triphenylvinyl)benzoic acid, pyridinecarboxylic acid, pyrimidinecarboxylic acid, and furanylcarboxylic acid;

[0017] The tetraamine mentioned is pentaerythritol tetraamine;

[0018] The aromatic dicarboxylic acid is one or more of phthalic acid, biphenyl dicarboxylic acid, naphthalenedicarboxylic acid, stilbene dicarboxylic acid, and fluorenone dicarboxylic acid;

[0019] The C2-C12 aliphatic diamines include one or more of ethylenediamine, propylenediamine, butyldiamine, pentanediamine, hexanediamine, heptamethamine, octanediamine, decanediamine, and dodecyldiamine.

[0020] The method for preparing the high-transparency polyamide resin of the present invention includes:

[0021] A mixed salt solution is obtained by mixing and stirring polyamide 610 salt solution, sterically hindered polyamide salt solution and / or semi-aromatic polyamide salt solution until homogeneous.

[0022] The above mixed salt solution was evaporated and concentrated to remove the solvent, and then reacted fully to obtain a highly crystalline polyamide polymer.

[0023] The solvents are water and ethanol;

[0024] The mass content of the mixed salt solution is 50-60%;

[0025] The reaction temperature is 150–280℃ and the pressure is 0.25–2.0 MPa.

[0026] Beneficial effects: This invention effectively improves the transparency of polyamide 610 by introducing a specific sterically hindered polyamide. More importantly, the introduction of the sterically hindered polyamide does not cause a deterioration in the mechanical properties of polyamide 610. Furthermore, the transparency and mechanical properties of polyamide 610 can be further improved by compounding the sterically hindered polyamide with a semi-aromatic polyamide. Detailed Implementation

[0027] The high-transparency polyamide is obtained by reacting the following components in parts by weight:

[0028] 100 parts of polyamide 610 salt;

[0029] 0.5 to 3 parts of sterically hindered polyamide salt;

[0030] Furthermore, the transparent polyamide is obtained by reacting the following components in parts by weight:

[0031] 100 parts of polyamide 610 salt;

[0032] 3-17 parts of semi-aromatic polyamide salt;

[0033] 0.5 to 3 parts of sterically hindered polyamide salt;

[0034] More preferably,

[0035] Furthermore, the transparent polyamide is obtained by reacting the following components in parts by weight:

[0036] 100 parts of polyamide 610 salt;

[0037] 3-5 parts of semi-aromatic polyamide salt;

[0038] 0.5 to 2 parts of sterically hindered polyamide salt;

[0039] The sterically hindered polyamide salt is a sterically hindered polyamide salt with a functionality greater than or equal to 3 and less than 4, generated by the neutralization reaction of a sterically hindered monobasic acid and a tetraamine.

[0040] In this invention, the molar ratio of the sterically hindered monocarboxylic acid to the tetraamine is 1:1 to 1.2.

[0041] The semi-aromatic polyamide salt is a semi-aromatic polyamide salt generated by the neutralization reaction of an aromatic dicarboxylic acid and a C2-C12 aliphatic diamine;

[0042] The ratio of the total molar amount of carboxyl groups in the aromatic dicarboxylic acid to the total molar amount of amino groups in the C2-C12 aliphatic diamine is 1:1 to 1.05.

[0043] The sterically hindered monocarboxylic acid contains a benzene ring or heterocycle and its derivative structure, and the number of carbon atoms is 4 to 30. The benzene ring and its derivative structure includes one or more of benzene, naphthalene, and fluorene. The heterocycle and its derivative structure includes one or more of pyridine, pyrimidine, furan, and pyran.

[0044] Furthermore, the sterically hindered monocarboxylic acid includes one or more of benzoic acid, phenylacetic acid, phenylbenzoic acid, phenylphenylacetic acid, naphtholic acid, naphthaleneacetic acid, fluorenic acid, 4-(1,2,2-triphenylvinyl)benzoic acid, pyridinecarboxylic acid, pyrimidinecarboxylic acid, and furanylcarboxylic acid;

[0045] As an example, the sterically hindered monocarboxylic acids include benzoic acid, phenylacetic acid, 4-phenylbenzoic acid, 2-phenylphenylacetic acid, 1-naphthoic acid, 2-naphthoic acid, fluorene-1-carboxylic acid, 1-(4-carboxyphenyl)-1,2,2-triphenylene, 2-pyridinecarboxylic acid, and 4-pyrimidinecarboxylic acid.

[0046] The tetraamine mentioned is pentaerythritol tetraamine;

[0047] The aromatic dicarboxylic acid is one or more of phthalic acid, biphenyl dicarboxylic acid, naphthalenedicarboxylic acid, stilbene dicarboxylic acid, and fluorenone dicarboxylic acid;

[0048] As an example, the aromatic dicarboxylic acid is one or more of terephthalic acid, isophthalic acid, 4,4'-biphenyl dicarboxylic acid, 4,4-stilbene dicarboxylic acid, 9-fluorenone-2,7-dicarboxylic acid, and 1,4-naphthalenedicarboxylic acid.

[0049] The C2-C12 aliphatic diamines include one or more of ethylenediamine, propylenediamine, butyldiamine, pentanediamine, hexanediamine, heptamethamine, octanediamine, decanediamine, and dodecyldiamine;

[0050] As an example, the C2-C12 aliphatic diamine is one or more of hexamethylenediamine, pentanediamine, and butanediamine;

[0051] The preparation method of the high-transparency polyamide resin of the present invention:

[0052] A mixed salt solution is obtained by mixing and stirring polyamide 610 salt solution, sterically hindered polyamide salt solution and / or semi-aromatic polyamide salt solution until homogeneous.

[0053] The above mixed salt solution was evaporated and concentrated to remove the solvent, and then reacted fully to obtain a highly crystalline polyamide polymer.

[0054] The solvents are water and ethanol;

[0055] The mass content of the mixed salt solution is 50-60%;

[0056] The reaction temperature is 150–280℃ and the pressure is 0.25–2.0 MPa.

[0057] In a specific embodiment of the present invention, the preparation method of the high-transparency polyamide resin includes the following:

[0058] Step 1: Mix and stir the polyamide 610 salt solution, sterically hindered polyamide salt solution and / or semi-aromatic polyamide salt solution until homogeneous to obtain a mixed salt solution. Mix and stir the solution at 50-80℃ until homogeneous to obtain a mixed salt solution.

[0059] Step 2: Under a protective gas atmosphere, heat the mixed salt solution to 150–180°C and pressurize it to 0.25–0.35 MPa, evaporating and concentrating it to a mass concentration of 70–80%. Increase the temperature and pressure to 210–260°C and 1.75–1.85 MPa, respectively, and maintain these temperatures and pressures for 40–80 minutes. Gradually decrease the pressure to 0–0.01 MPa, controlling the entire depressurization time to 40–80 minutes, while gradually increasing the temperature of the mixture to 270–290°C. Maintain the temperature at 270–290°C and stir the mixture under a pressure of 0–0.01 MPa for 30–60 minutes. Finally, extrude the molten polymer and granulate it underwater to obtain a transparent copolyamide.

[0060] Preferably, a catalyst may be added in step 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;

[0061] Additives known in the art may be added in step 1 and / or 2, including antioxidants, photothermal stabilizers, end-group modifiers, flame retardants, and high-temperature resistant additives;

[0062] The antioxidants mentioned are selected from hindered phenols, thioesters, phosphites, and aromatic amines.

[0063] The photothermal stabilizer is selected from hindered amines, benzotriazoles, or benzophenones.

[0064] The end-group regulator is selected from one or more of n-butylamine, n-pentylamine, n-hexylamine, benzylamine, phenethylamine, acetic acid, propionic acid, butyric acid, benzoic acid, and phenylacetic acid;

[0065] The heat-resistant agent is selected from organic copper, inorganic copper salts, and aromatic amine high-temperature resistant additives;

[0066] The flame retardant is selected from organophosphorus, organoaluminum, and melamine flame retardants.

[0067] 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.

[0068] Example 1

[0069] 100 parts of polyamide 610 salt;

[0070] 0.9 parts of sterically hindered polyamide salt;

[0071] Among them, the sterically hindered polyamide salt is a sterically hindered polyamide salt with a functionality of 3.2 generated by the neutralization reaction of 2-naphthoic acid and pentaerythritol.

[0072] Example 2

[0073] 100 parts of polyamide 610 salt;

[0074] 0.5 parts of sterically hindered polyamide salt;

[0075] Among them, the sterically hindered polyamide salt is a sterically hindered polyamide salt with a functionality of 3.4 generated by the neutralization reaction of 4-phenylbenzoic acid and pentaerythritol.

[0076] Example 3

[0077] 100 parts of polyamide 610 salt;

[0078] Three parts of sterically hindered polyamide salt;

[0079] Among them, the sterically hindered polyamide salt is a sterically hindered polyamide salt with a functionality of 3.8 generated by the neutralization reaction of 1-(4-carboxyphenyl)-1,2,2-tristyrene and pentaerythritol.

[0080] Example 4

[0081] 100 parts of polyamide 610 salt;

[0082] One part of sterically hindered polyamide salt;

[0083] 5 parts of semi-aromatic polyamide salt;

[0084] Among them, the sterically hindered polyamide salt is a sterically hindered polyamide salt with a functionality of 3 generated by the neutralization reaction of benzoic acid and pentaerythritol.

[0085] The semi-aromatic polyamide salt is a semi-aromatic polyamide salt generated by the neutralization reaction of terephthalic acid and hexamethylenediamine, with a total molar ratio of carboxyl groups to total molar amino groups of 1:1.

[0086] Example 5

[0087] 100 parts of polyamide 610 salt;

[0088] 0.5 parts of sterically hindered polyamide salt;

[0089] 10 parts of semi-aromatic polyamide salt;

[0090] Among them, the sterically hindered polyamide salt is a sterically hindered polyamide salt with a functionality of 3.4 generated by the neutralization reaction of 4-phenylbenzoic acid and pentaerythritol.

[0091] The semi-aromatic polyamide salt is a semi-aromatic polyamide salt generated by the neutralization reaction of terephthalic acid and pentanediamine, with a total molar ratio of carboxyl groups to total molar amino groups of 1:1.

[0092] Example 6

[0093] 100 parts of polyamide 610 salt;

[0094] Two parts of sterically hindered polyamide salt;

[0095] 3 parts of semi-aromatic polyamide salt;

[0096] Among them, the sterically hindered polyamide salt is a sterically hindered polyamide salt with a functionality of 3.2 generated by the neutralization reaction of 2-naphthoic acid and pentaerythritol.

[0097] The semi-aromatic polyamide salt is a semi-aromatic polyamide salt generated by the neutralization reaction of 4,4'-biphenyldicarboxylic acid and hexamethylenediamine, and the ratio of the total molar amount of carboxyl groups to the total molar amount of amino groups is 1:1.01.

[0098] Example 7

[0099] 100 parts of polyamide 610 salt;

[0100] 1.9 parts of sterically hindered polyamide salt;

[0101] 17 parts of semi-aromatic polyamide salt;

[0102] Among them, the sterically hindered polyamide salt is a sterically hindered polyamide salt with a functionality of 3.8 generated by the neutralization reaction of 1-(4-carboxyphenyl)-1,2,2-tristyrene and pentaerythritol.

[0103] The semi-aromatic polyamide salt is a semi-aromatic polyamide salt generated by the neutralization reaction of isophthalic acid and hexamethylenediamine, and the ratio of the total molar amount of carboxyl groups to the total molar amount of amino groups is 1:1.01.

[0104] Example 8

[0105] 100 parts of polyamide 610 salt;

[0106] 0.9 parts of sterically hindered polyamide salt;

[0107] Among them, the sterically hindered polyamide salt is a sterically hindered polyamide salt with a functionality of 2.3 generated by the neutralization reaction of 2-naphthoic acid and pentaerythritol.

[0108] Example 9

[0109] 100 parts of polyamide 610 salt;

[0110] One part of sterically hindered polyamide salt;

[0111] 5 parts of semi-aromatic polyamide salt;

[0112] Among them, the sterically hindered polyamide salt is a sterically hindered polyamide salt with a functionality of 2 generated by the neutralization reaction of benzoic acid and pentaerythritol.

[0113] The semi-aromatic polyamide salt is a semi-aromatic polyamide salt generated by the neutralization reaction of terephthalic acid and hexamethylenediamine, with a total molar ratio of carboxyl groups to total molar amino groups of 1:1.

[0114] Example 10

[0115] 100 parts of polyamide 610 salt;

[0116] One part of sterically hindered polyamide salt;

[0117] 5 parts aliphatic polyamide salt;

[0118] Among them, the sterically hindered polyamide salt is a sterically hindered polyamide salt with a functionality of 3 generated by the neutralization reaction of benzoic acid and pentaerythritol.

[0119] The semi-aromatic polyamide salt is an aliphatic polyamide salt generated by the neutralization reaction of adipic acid and pentanediamine, with a total molar ratio of carboxyl groups to total molar amino groups of 1:1.

[0120] Comparative Example 1

[0121] 100 parts of polyamide 610 salt.

[0122] Comparative Example 2

[0123] 100 parts of polyamide 610 salt;

[0124] 0.9 parts of non-sterically hindered polyamide salt;

[0125] Among them, the non-sterile polyamide salt is a non-sterile polyamide salt with a functionality of 3.2 generated by the neutralization reaction of formic acid and pentaerythritol.

[0126] Polyamides were obtained by reacting the components according to the weight proportions of the examples and comparative examples, and the following performance tests were performed:

[0127]

[0128]

Claims

1. A transparent polyamide resin, characterized in that, The transparent polyamide resin is obtained by reacting the following components in parts by weight: 100 parts of polyamide 610 salt; 0.5 to 3 parts of sterically hindered polyamide salt; The sterically hindered polyamide salt is a sterically hindered polyamide salt with a functionality greater than or equal to 3 and less than 4, generated by the neutralization reaction of a sterically hindered monobasic acid and a tetraamine. The sterically hindered monocarboxylic acid includes one or more of benzoic acid, phenylacetic acid, phenylbenzoic acid, phenylphenylacetic acid, naphtholic acid, naphthaleneacetic acid, fluorenic acid, 4-(1,2,2-triphenylvinyl)benzoic acid, pyridinecarboxylic acid, pyrimidinecarboxylic acid, or furanoic acid; the tetraamine is pentaerythritol tetramine.

2. The transparent polyamide resin according to claim 1, characterized in that, The transparent polyamide resin further comprises the following components in parts by weight, obtained by reaction: 3 to 17 parts of semi-aromatic polyamide salt.

3. The transparent polyamide resin according to claim 2, characterized in that... The semi-aromatic polyamide salt is a semi-aromatic polyamide salt generated by the neutralization reaction of an aromatic dicarboxylic acid and a C2~C12 aliphatic diamine.

4. The transparent polyamide resin according to claim 3, characterized in that... The ratio of the total molar amount of carboxyl groups in the aromatic dicarboxylic acid to the total molar amount of amino groups in the C2-C12 aliphatic diamine is 1:1 to 1.

05.

5. The transparent polyamide resin according to claim 3, characterized in that, The aromatic dicarboxylic acid is one or more of phthalic acid, biphenyl dicarboxylic acid, naphthalenedicarboxylic acid, stilbene dicarboxylic acid, and fluorenone dicarboxylic acid.

6. The transparent polyamide resin according to claim 3, characterized in that, The C2-C12 aliphatic diamines include one or more of ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexanediamine, heptamethamine, octanediamine, decanediamine, or dodecyldiamine.

7. A method for preparing a transparent polyamide resin as described in claim 1 or 2, characterized in that, The preparation method of the transparent polyamide resin is as follows: a polyamide 610 salt solution, a sterically hindered polyamide salt solution, or a polyamide 610 salt solution, a sterically hindered polyamide salt solution, and a semi-aromatic polyamide salt solution are mixed, and water or ethanol is added as a solvent and stirred evenly. The reaction temperature is 150~280℃ and the pressure is 0.25~2.0MPa to obtain a mixed salt solution. The mass content of the mixed salt solution is 50~60%. The above mixed salt solution is evaporated and concentrated to remove the solvent and reacted fully to obtain a highly crystalline polyamide polymer.

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