Long-carbon-chain transparent polyamide copolymer material containing aromatic rings and aliphatic rings and preparation method of long-carbon-chain transparent polyamide copolymer material

Abstract

The invention relates to a long carbon chain transparent polyamide copolymer material containing aromatic rings and aliphatic rings, which comprises the following raw materials: binary acid, diamine, a catalyst, a nucleating agent and deionized water, the binary acid comprises 10-90 mol% of aromatic binary acid and 10-90 mol% of long carbon chain binary acid, the binary acid comprises 10-82% by mole of alicyclic diamine and 18-90% by mole of long carbon chain diamine, the molar ratio of the binary acid to the diamine is 1: (1-1.02), the mass of the catalyst is 0.3-0.5% of the total mass of the binary acid and the diamine, the mass of the nucleating agent is 0.3-0.5% of the total mass of the binary acid and the diamine, and the mass of the deionized water is 50-200% of the total mass of the binary acid and the diamine. According to the present invention, the monomer having the cyclic structure is introduced to the main chain, such that the regularity of the nylon molecular chain is destroyed, the hydrogen bond and the crystallinity are reduced, the amorphous amorphous nylon is obtained, the crystallinity is reduced or fine crystals are formed, and the light transmittance, i.e. The light transmittance, is increased so as to improve the transparency of the obtained transparent polyamide material;

Description

Technical Field

[0001] This invention belongs to the field of polymers, and particularly relates to a transparent polyamide copolymer containing aromatic and aliphatic rings with long carbon chains and its preparation method. Background Technology

[0002] Polyamide, also known as nylon, is a thermoplastic polymer whose main chain contains repeating amide (-CO-NH-) structural units. Polyamides possess many excellent properties, such as high crystallinity, high surface hardness, wear resistance, low coefficient of friction, self-lubrication, shock absorption, and sound damping. In recent years, with the rapid development of industries such as electronics, new energy vehicles, and LEDs, the market demand for polyamide materials in high-performance products has increased significantly, especially for high-performance polyamide materials. However, different polyamide polymers have varying properties, with distinct advantages and disadvantages. Therefore, in order to obtain polyamide materials with superior performance, industrial processes often involve physical or chemical modification to achieve better application results. Copolymerization of polyamides is a commonly used chemical modification method. Through molecular structure design, suitable comonomers are selected based on the chemical structure of the target polymer to obtain materials with the desired properties. For polyamides, the density of amide bonds and the length of alkyl chains in the molecule have a crucial impact on their properties. Generally speaking, appropriately reducing the density of amide bonds weakens intermolecular hydrogen bonding interactions and molecular polarity, resulting in transparency in the material. In addition, longer alkyl chains improve the flexibility of molecular chains, enhance the ductility and plasticity of materials, and compared to shorter alkyl chains, longer alkyl chains have a smaller proportion of end groups and a lower density of amide bonds. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and provide a transparent polyamide copolymer material containing aromatic rings and aliphatic rings with long carbon chains.

[0004] The present invention also provides a method for preparing a transparent polyamide copolymer containing aromatic rings and aliphatic rings with long carbon chains.

[0005] This invention introduces a cyclic monomer into the main chain, which disrupts the regularity of the nylon molecular chain, reduces hydrogen bonding and crystallinity, and yields amorphous nylon. The reduced crystallinity or the formation of fine crystals increases light transmittance, thereby improving the transparency of the resulting naphthalene-containing transparent polyamide material.

[0006] A transparent polyamide copolymer containing aromatic and alicyclic long-chain carbon chains is characterized by comprising the following raw materials: a diacid, a diamine, a catalyst, a nucleating agent, and deionized water. The diacid comprises 10-90% molar fraction of an aromatic diacid and 10-90% molar fraction of a long-chain diacid; the diamine comprises 10-82% molar fraction of an alicyclic diamine and 18-90% molar fraction of a long-chain diamine; the molar ratio of the diacid to the diamine is 1:1-1.02; the catalyst mass is 0.3-0.5% of the total mass of the diacid and diamine; the nucleating agent mass is 0.3-0.5% of the total mass of the diacid and diamine; and the deionized water mass is 50-200% of the total mass of the diacid and diamine.

[0007] Further, the aromatic dicarboxylic acid is one of 1,3-phthalic acid and 2,6-naphthalenedicarboxylic acid; the long-chain dicarboxylic acid is one of dodecanoic acid, sebacic acid, and tetradecanoic acid; the alicyclic diamine is one of 1,3-cyclohexanediamine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, and 1,3-di(aminomethyl)cyclohexane; and the long-chain diamine is one of decanediamine, dodecanediamine, and tetradecanediamine.

[0008] Furthermore, the catalyst is one or more of sodium hypophosphite, sodium phosphite, potassium hypophosphite, and magnesium hypophosphite combined with stannous chloride, wherein the mass of stannous chloride is 0.1 to 0.2% of the total mass of the dicarboxylic acid and the diamine.

[0009] Furthermore, the nucleating agent is one of calcium carbonate, barium sulfate, silicon dioxide, titanium dioxide, and talc.

[0010] A method for preparing a transparent polyamide copolymer containing aromatic rings and aliphatic rings with long carbon chains includes the following steps:

[0011] (1) Take the materials according to the formula into a high temperature and high pressure reactor, stir evenly and maintain a pressure of 0.1~0.5 MPa under an inert atmosphere, then heat to 70~90 ℃ while stirring and react for 2~3 h to form polyamide salt. The stirring speed is 150~250 r / min.

[0012] (2) Continue heating and stirring until the pressure reaches 1.5~2.0 MPa. Then, release the solvent system to keep the high-temperature and high-pressure reactor under constant pressure. After the temperature in the high-temperature and high-pressure reactor continues to rise to 250~280 ℃, maintain it for 2~3 h. Then, depressurize to normal pressure within 1.5~2 h, reduce the stirring speed to 10~50 r / min, and maintain it at 250~280 ℃ for 1~2 h. Then, keep the temperature constant, evacuate to -0.1 MPa and maintain it for 1 h before discharging to obtain the finished product.

[0013] Furthermore, the inert gas in the inert atmosphere is one of nitrogen, argon, or helium.

[0014] The beneficial effects of this invention are:

[0015] 1. This invention introduces a cyclic monomer into the main chain, which disrupts the regularity of the nylon molecular chain, reduces hydrogen bonds and crystallinity, and obtains amorphous amorphous nylon. The reduced crystallinity or the formation of fine crystals increases the light transmittance, thereby improving the transparency of the obtained naphthalene-containing transparent polyamide material.

[0016] 2. In this invention, aromatic monomers (1,3-phthalic acid, 2,6-naphthalenedicarboxylic acid) and other monomers with rigid planar structures are introduced and embedded into the polyamide molecular backbone. On the one hand, this increases the rigidity of the molecular chain, inhibits the thermal motion of chain segments, and raises the glass transition temperature (Tg) of the molecular chain. g On the other hand, the conjugation effect and strong polarity of aromatic rings enhance the π-π stacking and hydrogen bond interactions between molecular chains, making the molecular chains more compact and forming a stable supramolecular structure, thereby improving the heat distortion temperature and long-term heat resistance of the material. Detailed Implementation

[0017] The present invention will be further described below with reference to embodiments. The following description of the embodiments is only for the purpose of helping to understand the present invention.

[0018] Example 1: A transparent polyamide copolymer containing aromatic and aliphatic ring long-chain components, comprising the following raw materials: diacid, diamine, catalyst, nucleating agent, and deionized water. The diacid comprises 10% molar fraction of aromatic diacid and 90% molar fraction of long-chain diacid. The diamine comprises 10% molar fraction of alicyclic diamine and 90% molar fraction of long-chain diamine. The molar ratio of diacid to diamine is 1:1. The aromatic diacid is 1,3-phenylenediic acid; the long-chain diacid is dodecanoic acid; the alicyclic diamine is 1,3-cyclohexanediamine; and the long-chain diamine is decanediamine. The catalyst mass is 0.3% of the total mass of the diacid and diamine. The catalyst is a combination of sodium hypophosphite and stannous chloride, and the stannous chloride mass is 0.1% of the total mass of the diacid and diamine. The nucleating agent accounts for 0.3% of the total mass of the diacid and diamine, and is one of the calcium carbonate components. The deionized water accounts for 50% of the total mass of the diacid and diamine.

[0019] Example 2: A transparent polyamide copolymer containing aromatic and aliphatic ring long-chain components, comprising the following raw materials: diacid, diamine, catalyst, nucleating agent, and deionized water. The diacid comprises 50% molar fraction of an aromatic diacid and 50% molar fraction of a long-chain diacid. The diamine comprises 50% molar fraction of an alicyclic diamine and 50% molar fraction of a long-chain diamine. The molar ratio of the diacid to the diamine is 1:1.01. The aromatic diacid is 2,6-naphthalenedicarboxylic acid; the long-chain diacid is sebacic acid; the alicyclic diamine is 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane; and the long-chain diamine is dodecanediamine. The catalyst mass is 0.4% of the total mass of the diacid and diamine. The catalyst is a combination of sodium phosphite and stannous chloride, and the stannous chloride mass is 0.15% of the total mass of the diacid and diamine. The nucleating agent is 0.4% of the total mass of the diacid and diamine, and the nucleating agent is barium sulfate. The deionized water is 100% of the total mass of the diacid and diamine.

[0020] Example 3: A transparent polyamide copolymer containing aromatic and aliphatic ring long-chain components, comprising the following raw materials: diacid, diamine, catalyst, nucleating agent, and deionized water. The diacid comprises 90% molar fraction of aromatic diacid and 10% molar fraction of long-chain diacid. The diamine comprises 82% molar fraction of alicyclic diamine and 18% molar fraction of long-chain diamine. The molar ratio of diacid to diamine is 1:1.02. The aromatic diacid is 1,3-phenylenediic acid; the long-chain diacid is tetradecanoic acid; the alicyclic diamine is 1,3-di(aminomethyl)cyclohexane; and the long-chain diamine is tetradecanediamine. The catalyst mass is 0.5% of the total mass of the diacid and diamine. The catalyst is a combination of potassium hypophosphite and stannous chloride, and the stannous chloride mass is 0.2% of the total mass of the diacid and diamine. The nucleating agent is 0.5% of the total mass of the diacid and diamine, and the nucleating agent is silicon dioxide. The deionized water is 200% of the total mass of the diacid and diamine.

[0021] Example 4: Referring to Example 1, the aromatic dicarboxylic acid is one of 1,3-phthalic acid and 2,6-naphthalenedicarboxylic acid; the long-chain dicarboxylic acid is one of dodecanoic acid, sebacic acid, and tetradecanoic acid; the alicyclic diamine is one of 1,3-cyclohexanediamine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, and 1,3-di(aminomethyl)cyclohexane; the long-chain diamine is one of decanediamine, dodecanediamine, and tetradecanediamine; the catalyst is one or a combination of sodium hypophosphite, sodium phosphite, potassium hypophosphite, and magnesium hypophosphite with stannous chloride; and the nucleating agent is one of calcium carbonate, barium sulfate, silicon dioxide, titanium dioxide, and talc.

[0022] Example 5: A method for preparing a transparent polyamide copolymer containing aromatic and aliphatic ring long carbon chains, comprising the following steps:

[0023] (1) Take the materials according to the formulation of Example 1 into a high temperature and high pressure reactor, stir evenly and under an inert atmosphere, the inert gas under the inert atmosphere is nitrogen, maintain a pressure of 0.1 MPa, and then stir and heat to 70 ℃ for 2 h to form polyamide salt. The stirring speed is 150 r / min.

[0024] (2) Continue heating and stirring until the pressure reaches 1.5 MPa. Then, release the solvent system to keep the high-temperature and high-pressure reactor under constant pressure. After the temperature in the high-temperature and high-pressure reactor continues to rise to 250 ℃, maintain it for 2 h. Then, depressurize to normal pressure within 1.5 h, reduce the stirring speed to 10 r / min, and maintain it at 250 ℃ for 1 h. Then, keep the temperature constant, evacuate to -0.1 MPa and maintain it for 1 h before discharging to obtain the finished product.

[0025] Example 6: A method for preparing a transparent polyamide copolymer containing aromatic and aliphatic ring long carbon chains, comprising the following steps:

[0026] (1) Take the materials according to the formula of Example 2 into a high temperature and high pressure reactor, stir evenly and under an inert atmosphere, the inert gas under the inert atmosphere is argon, maintain a pressure of 0.2 MPa, and then stir and heat to 80 ℃ for 2.5 h to form polyamide salt. The stirring speed is 200 r / min.

[0027] (2) Continue heating and stirring until the pressure reaches 1.7 MPa. Then, release the solvent system to keep the high-temperature and high-pressure reactor under constant pressure. After the temperature in the high-temperature and high-pressure reactor continues to rise to 260 ℃, maintain it for 2.5 h. Then, depressurize to normal pressure within 1.8 h, reduce the stirring speed to 30 r / min, and maintain it at 260 ℃ for 1.5 h. Then, keep the temperature constant, evacuate to -0.1 MPa and maintain it for 1 h before discharging to obtain the finished product.

[0028] Example 7: A method for preparing a transparent polyamide copolymer containing aromatic and aliphatic ring long carbon chains, comprising the following steps:

[0029] (1) Take the materials according to the formula of Example 3 into a high temperature and high pressure reactor, stir evenly and under an inert atmosphere, the inert gas under the inert atmosphere is helium, maintain a pressure of 0.5 MPa, and then stir and heat to 90°C for 3 h to form polyamide salt. The stirring speed is 250 r / min.

[0030] (2) Continue heating and stirring until the pressure reaches 2.0 MPa. Then, release the solvent system to keep the high-temperature and high-pressure reactor under constant pressure. After the temperature in the high-temperature and high-pressure reactor continues to rise to 280 ℃, maintain it for 3 h. Then, depressurize to normal pressure within 2 h, reduce the stirring speed to 50 r / min, and maintain it at 280 ℃ for 2 h. Then, keep the temperature constant, evacuate to -0.1 MPa and maintain it for 1 h before discharging to obtain the finished product.

[0031] Comparative Example 1: Referring to Example 1, the aromatic dicarboxylic acid was replaced with adipic acid.

[0032] Comparative Example 2: Referring to Example 2, the alicyclic diamine was replaced with hexamethylenediamine.

[0033] Comparative Example 3: Referring to Example 3, the alicyclic diamine was replaced with hexamethylenediamine.

[0034] Comparative Example 4: Referring to Example 5, the ingredients were prepared according to the formula of Comparative Example 1.

[0035] Comparative Example 5: Referring to Example 6, the ingredients were prepared according to the formula of Comparative Example 2.

[0036] Comparative Example 6: Referring to Example 7, the ingredients were prepared according to the formula of Comparative Example 3.

[0037] Performance Examples Glass transition temperature (°C) Decomposition temperature (°C) relative viscosity Density (g / ml) Tensile strength (MPa) Elongation at break (%) Example 5 110.90 436.20 1.96 1.14 59.05 222.20 Example 6 110.30 448.40 2.02 1.07 58.31 231.25 Example 7 122.40 450.80 2.03 1.08 59.51 223.33 Comparative Example 4 79.20 430.30 1.98 1.15 43.30 180.00 Comparative Example 5 100.10 422.30 2.01 1.14 42.21 186.11 Comparative Example 6 100.60 428.00 1.98 1.13 41.92 180.72

[0038] It should be noted that those skilled in the art can make various modifications to this invention without departing from its principles, and these modifications and improvements also fall within the scope of protection of the claims of this invention.

Claims

1. A transparent polyamide copolymer containing aromatic and aliphatic ring long carbon chains, characterized in that, The raw materials include the following components: diacid, diamine, catalyst, nucleating agent, and deionized water. The diacid comprises 10-90% molar fraction of aromatic diacid and 10-90% molar fraction of long-chain diacid. The diamine comprises 10-82% molar fraction of alicyclic diamine and 18-90% molar fraction of long-chain diamine. The molar ratio of the diacid to the diamine is 1:1 to 1.

02. The mass of the catalyst is 0.3-0.5% of the total mass of the diacid and diamine. The mass of the nucleating agent is 0.3-0.5% of the total mass of the diacid and diamine. The mass of the deionized water is 50-200% of the total mass of the diacid and diamine.

2. The transparent polyamide copolymer containing aromatic and aliphatic ring long carbon chains according to claim 1, characterized in that, The aromatic dicarboxylic acid is one of 1,3-phthalic acid and 2,6-naphthalenedicarboxylic acid; the long-chain dicarboxylic acid is one of dodecanoic acid, sebacic acid, and tetradecanoic acid; the alicyclic diamine is one of 1,3-cyclohexanediamine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, and 1,3-di(aminomethyl)cyclohexane; the long-chain diamine is one of decanediamine, dodecanediamine, and tetradecanediamine.

3. The transparent polyamide copolymer containing aromatic and aliphatic ring long carbon chains according to claim 1, characterized in that, The catalyst is one or more of sodium hypophosphite, sodium phosphite, potassium hypophosphite, and magnesium hypophosphite combined with stannous chloride, wherein the mass of stannous chloride is 0.1 to 0.2% of the total mass of the dicarboxylic acid and the diamine.

4. The transparent polyamide copolymer containing aromatic and aliphatic ring long carbon chains according to claim 1, characterized in that, The nucleating agent is one of calcium carbonate, barium sulfate, silicon dioxide, titanium dioxide, and talc.

5. A method for preparing a transparent polyamide copolymer containing aromatic rings and aliphatic rings with long carbon chains as described in any one of claims 1 to 4, characterized in that, Includes the following steps: (1) Take the materials according to the formula into a high temperature and high pressure reactor, stir evenly and maintain a pressure of 0.1~0.5 MPa under an inert atmosphere, then heat to 70~90 ℃ while stirring and react for 2~3 h to form polyamide salt. The stirring speed is 150~250 r / min. (2) Continue heating and stirring until the pressure reaches 1.5~2.0 MPa. Then, release the solvent system to keep the high-temperature and high-pressure reactor under constant pressure. After the temperature in the high-temperature and high-pressure reactor continues to rise to 250~280 ℃, maintain it for 2~3 h. Then, depressurize to normal pressure within 1.5~2 h, reduce the stirring speed to 10~50 r / min, and maintain it at 250~280 ℃ for 1~2 h. Then, keep the temperature constant, evacuate to -0.1 MPa and maintain it for 1 h before discharging to obtain the finished product.

6. The method for preparing the transparent polyamide copolymer containing aromatic rings and aliphatic rings with long carbon chains according to claim 5, characterized in that, The inert gas in the inert atmosphere is one of nitrogen, argon, or helium.