A glycol-resistant nylon material and its preparation method

Abstract

The present application discloses a glycol-resistant nylon material and a preparation method thereof, comprising the following raw materials in parts by mass: 100 parts of nylon 66; 30 - 35 parts of glass fiber; 0.8 - 1.4 parts of silane coupling agent; 6.7 - 9.2 parts of modified graphene oxide. The modified graphene oxide is obtained by the transesterification reaction of the hydroxyl groups on the surface of graphene oxide with phosphite. The phosphite-modified graphene oxide can enhance the strength of polyamide. On the other hand, by introducing phosphite, the electron cloud effect of graphene oxide is enhanced, and by using its electron mobility, the positive charge of the carbonyl carbon in polyamide is weakened, reducing the possibility of the reaction between the carbonyl group in polyamide and the hydroxyl group in glycol, and improving the glycol resistance of the nylon material. The phosphite can also preferentially replace the carbonyl carbon in polyamide and react with the hydroxyl group in glycol, thereby delaying the alcoholysis of polyamide. Therefore, the nylon material of the present application has excellent strength and glycol resistance.

Description

Technical Field

[0001] This application relates to an automobile water tank, and more particularly to a nylon material resistant to ethylene glycol and a preparation method thereof. Background Art

[0002] Nylon, also known as polyamide, is a widely used engineering plastic with excellent physical and mechanical properties and is widely used in manufacturing parts of machinery, automobiles, chemical and electrical devices.

[0003] Nylon components in different working environments have different performance requirements for nylon materials. For example, in a nylon automobile water tank, to prevent the water in the water tank from freezing and solidifying after the automobile engine shuts off in winter, ethylene glycol is often added to the water in the automobile water tank as an antifreeze to protect the cooling system of the automobile from freezing damage. However, due to the swelling and alcoholysis effects of ethylene glycol on polyamide, defects such as cracking and dissolution holes are likely to occur under long-term use.

[0004] Therefore, in order to extend the service life of nylon components in an environment where they are in contact with ethylene glycol, it is necessary to develop a corresponding nylon material resistant to ethylene glycol. Summary of the Invention

[0005] To extend the service life of nylon components in an environment where they are in contact with ethylene glycol, a nylon material resistant to ethylene glycol and a preparation method thereof are provided.

[0006] The above first object of the present invention is achieved by the following technical solutions:

[0007] A nylon material resistant to ethylene glycol, comprising the following raw materials in parts by mass:

[0008] 100 parts of nylon 66

[0009] 30 - 35 parts of glass fiber;

[0010] 0.8 - 1.4 parts of silane coupling agent;

[0011] 6.7 - 9.2 parts of modified graphene oxide;

[0012] The modified graphene oxide is obtained by the transesterification reaction of the hydroxyl groups on the surface of graphene oxide with trialkyl phosphite.

[0013] By adopting the above technical solutions, the nylon is modified with glass fiber to improve the strength of the nylon material and the basic ethylene glycol resistance performance;

[0014] Graphene oxide, on the one hand, can enhance the strength of polyamide, and on the other hand, it has electron mobility, which is conducive to the electron cloud effect and can weaken the positive charge of the carbonyl carbon in polyamide, thereby reducing the possibility of the reaction between the carbonyl group in polyamide and the hydroxyl group in ethylene glycol and improving the ethylene glycol resistance performance of the nylon material;

[0015] After the graphene oxide is modified by the transesterification reaction of trialkyl phosphite, the trialkyl phosphite reacts with the hydroxyl groups on the graphene oxide, enabling the phosphite to be attached to the surface of the graphene oxide, enhancing the electron cloud interaction of the graphene oxide. Meanwhile, the phosphite can preferentially replace the carbonyl carbon in the polyamide and react with the hydroxyl groups in ethylene glycol, thereby delaying the alcoholysis of the polyamide.

[0016] As a result, the nylon material of the present application has excellent strength and ethylene glycol resistance.

[0017] Optionally: The trialkyl phosphite is triphenyl phosphite.

[0018] By adopting the above technical solution, the carbonyl group in triphenyl phosphite reacts more preferentially with the hydroxyl group of ethylene glycol than the carbonyl group in the polyamide, and the reaction product can improve the alcoholysis and hydrolysis resistance of the nylon material, thereby further enhancing the ethylene glycol resistance of the nylon material.

[0019] Optionally: The modification method of the modified graphene oxide is as follows:

[0020] Under a nitrogen atmosphere, the trialkyl phosphite is dissolved in an appropriate amount of organic solvent, and then a catalyst is added and stirred evenly to obtain Material A; the graphene oxide is added to the decomposition solution and dispersed by ultrasonic oscillation to obtain Material B;

[0021] Material A is heated to 152 - 156 °C, and Material B is added and stirred for reaction;

[0022] After the reaction is completed, the reactants are centrifuged to obtain a precipitate. After washing and drying the precipitate, the modified graphene oxide is obtained.

[0023] By adopting the above technical solution, the graphene oxide can fully contact and react with the trialkyl phosphite, improving the modification effect and enhancing the ethylene glycol resistance of the nylon material.

[0024] Optionally: The dosage ratio of the trialkyl phosphite to the graphene oxide is 0.04 - 0.06 mol / g.

[0025] By adopting the above technical solution, the obtained modified graphene oxide has a good effect, and the nylon material has better ethylene glycol resistance.

[0026] Optionally: It further includes 8 - 9.6 parts of polysulfone resin.

[0027] By adopting the above technical solution, the polysulfone resin contains aromatic groups, which can improve the ethylene glycol resistance of the nylon material.

[0028] Optionally: The polysulfone resin is polyarylsulfone resin.

[0029] By adopting the above technical solution, the nylon material has excellent ethylene glycol resistance and strength performance.

[0030] Optionally: It also includes 1.3 - 1.7 parts of DOPO.

[0031] By adopting the above technical solution, the alcoholysis of the polyamide polymerization chain can be inhibited, and the stability of the nylon material can be improved.

[0032] The above second object of the present invention is achieved by the following technical solutions:

[0033] A method for preparing an ethylene glycol-resistant nylon material, comprising the following steps:

[0034] Weigh the raw materials by mass parts, mix the raw materials evenly to obtain a mixed raw material, and then send it into a screw extruder for melt extrusion to obtain an ethylene glycol-resistant nylon material.

[0035] By adopting the above technical solution, the obtained nylon material has good strength and good ethylene glycol resistance.

[0036] In summary, the present application has at least the following beneficial effects:

[0037] Adding graphene oxide modified with phosphite triester to the raw materials can enhance the strength of polyamide. On the other hand, the electron cloud effect of graphene oxide is enhanced by the introduced phosphite ester, and by using its electron mobility, the positive charge of the carbonyl carbon in polyamide is weakened, thereby reducing the possibility of the reaction between the carbonyl in polyamide and the hydroxyl group in ethylene glycol, and improving the ethylene glycol resistance of the nylon material; at the same time, the phosphite ester can preferentially replace the carbonyl carbon in polyamide and react with the hydroxyl group in ethylene glycol, thereby delaying the alcoholysis of polyamide. As a result, the nylon material of the present application has excellent strength and ethylene glycol resistance. Detailed implementation mode

[0038] Raw materials

[0039] The graphene oxide is a commercially available product with a thickness of 1 nm, 1 - 2 layers, an average sheet diameter of 30 μm, a specific surface area of 200 m 2 / g, and a purity > 95 wt%.

[0040] Triphenyl phosphite and tributyl phosphite are commercially available industrial-grade products.

[0041] DOPO is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which is a commercially available product.

[0042] Nylon 66 is the POM product 100AL NC010 of DuPont, USA.

[0043] The glass fiber is an alkali-free glass fiber with a length of 3 mm and a diameter of 5 μm.

[0044] The polyarylsulfone resin is the product LTG-3000 of Solvay in the United States.

[0045] The polyethersulfone resin is the product PES E1010 of BASF in Germany.

[0046] The silane coupling agent is 3-aminopropylmethyldiethoxysilane.

[0047] Preparation Example 1

[0048] A modified graphene oxide is obtained by modifying graphene oxide with phosphite.

[0049] The specific preparation method is as follows:

[0050] Under a nitrogen atmosphere, 155 g of phosphite is added to 400 g of liquid A and stirred until dissolved, then 1.1 g of p-toluenesulfonic acid is added and stirred evenly to obtain material A;

[0051] 10 g of graphene oxide is added to 80 g of liquid A and dispersed by ultrasonic oscillation to obtain material B;

[0052] Material A is heated to 154 ± 2 °C, and material B is added, followed by stirring and reacting for 10 h;

[0053] After the reaction ends, the reaction product is centrifuged to obtain a precipitate. After washing and drying the precipitate with liquid A, the modified graphene oxide is obtained.

[0054] The phosphite is triphenyl phosphite, and the liquid A is toluene.

[0055] The ratio of phosphite in material A to graphene oxide in material B is 0.05 mol of phosphite / 1 g of graphene oxide.

[0056] Preparation Example 2

[0057] A modified graphene oxide, the difference from Preparation Example 1 is as follows:

[0058] The liquid A is DMF, and the phosphite is tributyl phosphite;

[0059] Material A is a mixture of 133 g of tributyl phosphite, 400 g of DMF, and 1.1 g of p-toluenesulfonic acid. The ratio of phosphite in material A to graphene oxide in material B is 0.05 mol of phosphite / 1 g of graphene oxide.

[0060] Preparation Example 3

[0061] A modified graphene oxide, which is different from Preparation Example 1 in that Material A is a mixture of 93 g of tributyl phosphite, 400 g of DMF, and 1.1 g of p-toluenesulfonic acid, and the ratio of phosphite in Material A to graphene oxide in Material B is 0.03 mol of phosphite / 1 g of graphene oxide.

[0062] Preparation Example 4

[0063] A modified graphene oxide, which is different from Preparation Example 1 in that Material A is a mixture of 124 g of tributyl phosphite, 400 g of DMF, and 1.1 g of p-toluenesulfonic acid, and the ratio of phosphite in Material A to graphene oxide in Material B is 0.04 mol of phosphite / 1 g of graphene oxide.

[0064] Preparation Example 5

[0065] A modified graphene oxide, which is different from Preparation Example 1 in that Material A is a mixture of 186 g of tributyl phosphite, 400 g of DMF, and 1.1 g of p-toluenesulfonic acid, and the ratio of phosphite in Material A to graphene oxide in Material B is 0.06 mol of phosphite / 1 g of graphene oxide.

[0066] Preparation Example 6

[0067] A modified graphene oxide, which is different from Preparation Example 1 in that Material A is a mixture of 217 g of tributyl phosphite, 400 g of DMF, and 1.1 g of p-toluenesulfonic acid, and the ratio of phosphite in Material A to graphene oxide in Material B is 0.07 mol of phosphite / 1 g of graphene oxide.

[0068] Example 1

[0069] A glycol-resistant nylon, the raw materials of which are nylon 66, glass fiber, silane coupling agent, modified graphene oxide, polysulfone resin, and DOPO.

[0070] The modified graphene oxide is prepared by Preparation Example 1.

[0071] The polysulfone resin is a polyarylsulfone resin.

[0072] The preparation method of the glycol-resistant nylon is as follows:

[0073] Weigh 100 kg of nylon 66, 33.6 kg of glass fiber, 1.2 kg of silane coupling agent, 8.8 kg of modified graphene oxide, and 9.2 kg of polysulfone resin, mix them evenly to obtain a mixed raw material;

[0074] Feed the mixed raw material into a screw extruder for melt extrusion to obtain a glycol-resistant nylon material.

[0075] Example 2

[0076] A glycol-resistant nylon, which is different from Example 1 in that the modified graphene oxide is prepared by Preparation Example 2.

[0077] Example 3

[0078] A glycol-resistant nylon, which is different from Example 1 in that the modified graphene oxide is prepared by Preparation Example 3.

[0079] Example 4

[0080] A glycol-resistant nylon, which is different from Example 1 in that the modified graphene oxide is prepared by Preparation Example 4.

[0081] Example 5

[0082] A glycol-resistant nylon, which is different from Example 1 in that the modified graphene oxide is prepared by Preparation Example 5.

[0083] Example 6

[0084] A glycol-resistant nylon, which is different from Example 1 in that the modified graphene oxide is prepared by Preparation Example 6.

[0085] Example 7

[0086] A glycol-resistant nylon, which is different from Example 1 in that the amount of polysulfone resin is 0, that is, no polysulfone resin is added to the raw materials.

[0087] Example 8

[0088] A glycol-resistant nylon, which is different from Example 1 in that the polysulfone resin is a polyethersulfone resin.

[0089] Comparative Example 1

[0090] A nylon, the raw materials of which are nylon 66, glass fiber, silane coupling agent, polysulfone resin, and DOPO.

[0091] The modified graphene oxide is prepared by Preparation Example 1.

[0092] The polysulfone resin is a polyarylsulfone resin.

[0093] The preparation method of the glycol-resistant nylon is as follows:

[0094] Weigh 100 kg of nylon 66, 33.6 kg of glass fiber, 1.2 kg of silane coupling agent, and 9.2 kg of polysulfone resin, mix them evenly to obtain a mixed raw material;

[0095] Feed the mixed raw material into a screw extruder for melt extrusion to obtain a glycol-resistant nylon material.

[0096] Comparative Example 2

[0097] A glycol-resistant nylon, the raw materials of which are nylon 66, glass fiber, silane coupling agent, graphene oxide, polysulfone resin, and DOPO.

[0098] The polysulfone resin is polyarylsulfone resin.

[0099] The preparation method of the glycol-resistant nylon is as follows:

[0100] Weigh 100 kg of nylon 66, 33.6 kg of glass fiber, 1.2 kg of silane coupling agent, 8.8 kg of graphene oxide, and 9.2 kg of polysulfone resin, mix them evenly to obtain a mixed raw material;

[0101] Feed the mixed raw material into a screw extruder for melt extrusion to obtain the glycol-resistant nylon material.

[0102] Test the tensile strength, flexural strength, and glycol resistance performance of the nylon materials obtained in Examples 1 - 11 and Comparative Examples 1 - 2.

[0103] Tensile strength test: Conduct the test according to ASTM / D638, and the test results are expressed in terms of tensile strength.

[0104] Flexural strength test: Conduct the test according to ASTM / D790, and the test results are expressed in terms of flexural strength.

[0105] Glycol resistance performance test: Prepare a mixed solution of ethylene glycol and water with a mass ratio of 1:1. Prepare specimens according to ASTM / D638 and ASTM / D790, soak the specimens in the mixed solution at 135 °C for 120 h continuously. After the soaking is completed, conduct the tensile strength test according to ASTM / D638 and the flexural strength test according to ASTM / D790, and calculate the tensile strength retention rate and flexural strength retention rate in combination with the tensile strength test results and flexural strength test results. The results are expressed in terms of the tensile strength retention rate and flexural strength retention rate. The higher the tensile strength retention rate and flexural strength retention rate, the better the glycol resistance performance.

[0106] The test results are shown in Table 1 below.

[0107] Table 1. Test result table of Examples 1 - 8 and Comparative Examples 1 - 2

[0108] Tensile strength / MPa Flexural strength / MPa Retention rate of tensile strength / % Retention rate of flexural strength / % Example 1 194.52 271.19 79.35 73.77 Example 2 189.83 256.44 71.92 64.81 Example 3 190.42 263.04 72.02 63.61 Example 4 191.41 264.62 75.21 66.46 Example 5 190.56 263.08 75.53 67.13 Example 6 189.80 265.24 72.72 65.62 Example 7 184.95 254.77 74.02 68.12 Example 8 189.74 258.41 76.55 69.94 Comparative example 1 176.32 242.61 27.46 22.89 Comparative example 2 180.79 247.90 43.80 39.53

[0109] Combined with Table 1, by comparing Example 1 with Comparative Examples 1-2, it can be seen that the tensile strength and flexural strength of Example 1 are greater than those of Comparative Examples 1-2. At the same time, the retention rates of tensile strength and flexural strength of Example 1 are significantly greater than those of Comparative Examples 1-2. Therefore, the strength of the nylon material in Example 1 is superior to that of Comparative Examples 1-2, and the glycol resistance of the nylon material in Example 1 is significantly superior to that of Comparative Examples 1-2. The reason is that the graphene oxide modified by phosphite triester can, on the one hand, enhance the strength of polyamide, and on the other hand, enhance the electron cloud effect of graphene oxide through the incorporated phosphite ester. Utilizing its electron mobility, it weakens the positive charge of the carbonyl carbon in polyamide, thereby reducing the possibility of the reaction between the carbonyl in polyamide and the hydroxyl group in glycol, and improving the glycol resistance of the nylon material; at the same time, the phosphite ester can preferentially replace the carbonyl carbon in polyamide and react with the hydroxyl group in glycol, thereby delaying the alcoholysis of polyamide. As a result, the nylon material of the present application has excellent strength and glycol resistance.

[0110] By comparing Example 1 with Example 2, it can be seen that the tensile strength and flexural strength of Example 1 are greater than those of Example 2. At the same time, the retention rates of tensile strength and flexural strength of Example 1 are greater than those of Example 2. The reason is that the modified graphene oxide in Example 1 uses triphenyl phosphite as the phosphite triester. Its carbonyl is more reactive with the hydroxyl group of glycol than the carbonyl in polyamide, and the reaction product can improve the alcoholysis and hydrolysis resistance of the nylon material. Therefore, the glycol resistance of the nylon material is further improved.

[0111] In the modification process of modified graphene oxide, different dosage ratios of phosphite triester to graphene oxide result in different characteristics of the modified products. Combining Example 1 with Examples 3-6, the glycol resistance from excellent to poor is in the order of Example 1, Example 5, Example 4, Example 6, Example 3. Therefore, in the modification process of modified graphene oxide in the present application, the dosage ratio of phosphite triester to graphene oxide is preferably 0.04 - 0.06 mol of phosphite triester / g of graphene oxide.

[0112] By comparing Example 1 with Examples 7-8, in addition to the raw materials, Example 1 also added polyarylsulfone resin compared with Example 7, and Example 8 also added polyethersulfone resin compared with Example 7. The tensile strength and flexural strength of Example 1 are greater than those of Example 8, and the tensile strength and flexural strength of Example 8 are greater than those of Example 7; the glycol resistance of Example 1 is greater than that of Example 8, and the glycol resistance of Example 8 is greater than that of Example 7. Thus, adding polysulfone resin, the polysulfone resin contains aromatic groups, which can improve the glycol resistance of the nylon material. At the same time, when using polyarylsulfone resin, both the glycol resistance and the nylon strength are relatively excellent.

[0113] This specific embodiment is only an interpretation of the present invention and does not limit the present invention. After reading this specification, those skilled in the art may make modifications to this embodiment without creative contributions as needed, but as long as it is within the scope of protection required by the present invention, it is protected by the patent law.

Claims

1. A nylon material resistant to ethylene glycol, characterized in that, It includes raw materials in the following parts by mass: 100 parts of nylon 66; 30 - 35 parts of glass fiber; 0.8 - 1.4 parts of silane coupling agent; 6.7 - 9.2 parts of modified graphene oxide; The modified graphene oxide is obtained by the transesterification reaction between the hydroxyl groups on the surface of graphene oxide and phosphite; The modification method of the modified graphene oxide is as follows: Under a nitrogen atmosphere, dissolve phosphite in an appropriate amount of organic solvent, then add a catalyst and stir evenly to obtain material A; Add graphene oxide to toluene and disperse it by ultrasonic oscillation to obtain material B; Heat material A to 152 - 156 °C, add material B, and stir for reaction; After the reaction ends, centrifuge the reactants to obtain a precipitate. After washing and drying the precipitate, modified graphene oxide is obtained; The dosage ratio of phosphite to graphene oxide is 0.04 - 0.06 mol / g; The phosphite is tributyl phosphite or triphenyl phosphite.

2. The nylon material resistant to ethylene glycol according to claim 1, wherein, It also includes 9.2 parts of polysulfone resin.

3. The nylon material resistant to ethylene glycol according to claim 2, characterized in that, The polysulfone resin is polyarylsulfone resin.

4. The method for preparing the ethylene glycol-resistant nylon material according to any one of claims 1 to 3, characterized in that, It includes the following steps: Weigh the raw materials according to the parts by mass, mix the raw materials evenly to obtain a mixed raw material, and then send it into a screw extruder for melt extrusion to obtain the ethylene glycol - resistant nylon material.