Ethylene glycol-resistant nylon material and preparation method thereof

Abstract

The invention discloses an ethylene glycol-resistant nylon material and a preparation method thereof. The ethylene glycol-resistant nylon material comprises the following raw materials in parts by mass: 100 parts of nylon 66; 30 to 35 parts of glass fiber; 0.8 to 1.4 parts of a silane coupling agent; 6.7 to 9.2 parts of modified graphene oxide; the modified graphene oxide is obtained by modification after transesterification of hydroxyl groups on the surface of graphene oxide and phosphite triester, the phosphite triester modified graphene oxide can enhance the strength of polyamide, on the other hand, the electron cloud effect of the graphene oxide is enhanced through the introduced phosphite ester, and by means of the electron mobility of the phosphite ester, the polyamide can be effectively dispersed in the graphene oxide. The electropositivity of carbonyl carbon in polyamide is weakened, the possibility that carbonyl in polyamide reacts with hydroxyl in ethylene glycol is reduced, and the ethylene glycol resistance of the nylon material is improved; the phosphite ester can also preferentially replace carbonyl carbon in polyamide to react with hydroxyl in ethylene glycol, so that alcoholysis of polyamide is delayed, and the nylon material has excellent strength and ethylene glycol resistance.

Description

Technical Field

[0001] The present application relates to an automobile water tank, and in particular to an ethylene glycol-resistant nylon material and a preparation method thereof. Background Art

[0002] Nylon, also known as polyamide, is a widely used engineering plastic. It has excellent physical and mechanical properties and is widely used in the manufacture of parts for machinery, automobiles, chemicals and electrical devices.

[0003] Nylon components in different working environments have different performance requirements for nylon materials. For example, in order to prevent the water in the nylon car water tank from freezing and solidifying after the car is turned off in winter, ethylene glycol is often added to the water in the car water tank as antifreeze to protect the car's cooling system from freezing damage. However, due to the swelling and alcoholysis of ethylene glycol on polyamide, cracking and dissolution defects are prone to occur after long-term use.

[0004] Therefore, in order to extend the service life of nylon components in an ethylene glycol contact environment, it is necessary to develop and obtain a nylon material that is resistant to ethylene glycol. Summary of the invention

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

[0006] The above first invention objective of the present invention is achieved through the following technical solutions: A glycol-resistant nylon material comprising the following raw materials in parts by weight: Nylon 66 100 parts 30-35 parts of glass fiber; Silane coupling agent 0.8-1.4 parts; 6.7-9.2 parts of modified graphene oxide; The modified graphene oxide is obtained by modifying the surface hydroxyl groups of the graphene oxide through an ester exchange reaction with triester phosphite.

[0007] By adopting the above technical solution, nylon is modified with glass fiber to improve the strength of nylon material and basic ethylene glycol resistance; Graphene oxide can enhance the strength of polyamide on the one hand, and on the other hand, it has electron mobility, which is beneficial to the electron cloud effect to weaken the positive charge of carbonyl carbon in polyamide, thereby reducing the possibility of carbonyl in polyamide reacting with hydroxyl in ethylene glycol, and improving the ethylene glycol resistance of nylon materials; After graphene oxide is modified by phosphite triester transesterification reaction, phosphite triester reacts with hydroxyl groups on graphene oxide, so that phosphite is connected to the surface of graphene oxide, enhancing the electron cloud effect of graphene oxide. At the same time, phosphite can preferentially replace carbonyl carbon in polyamide and react with hydroxyl groups in ethylene glycol, thereby delaying the alcoholysis of polyamide. Therefore, the nylon material of the present application has excellent strength and ethylene glycol resistance.

[0008] Optionally: the triester phosphite is triphenyl phosphite.

[0009] By adopting the above technical scheme, the carbonyl group in triphenyl phosphite reacts with the hydroxyl group of ethylene glycol more preferentially than the carbonyl group in polyamide, and the reaction product can improve the alcoholysis and hydrolysis resistance of the nylon material, thereby further improving the ethylene glycol resistance of the nylon material.

[0010] Optionally: the modification method of the modified graphene oxide is as follows: Under a nitrogen atmosphere, phosphite triester is dissolved in an appropriate amount of an organic solvent, a catalyst is added, and the mixture is stirred evenly to obtain material A; graphene oxide is added to the decomposition liquid, and the mixture is dispersed by ultrasonic vibration to obtain material B; Heat material A to 152-156°C, add material B, and stir to react; After the reaction is completed, the reactants are separated by centrifugation to obtain a precipitate, and the precipitate is washed and dried to obtain modified graphene oxide.

[0011] By adopting the above technical solution, graphene oxide can fully contact and react with triester phosphite, thereby improving the modification effect and enhancing the ethylene glycol resistance of nylon materials.

[0012] Optionally, the usage ratio of the triester phosphite to graphene oxide is 0.04 to 0.06 mol / g.

[0013] By adopting the above technical solution, the obtained modified graphene oxide has better effect and the nylon material has better ethylene glycol resistance.

[0014] Optional: also includes 8 to 9.6 parts of polysulfone resin.

[0015] By adopting the above technical solution, the polysulfone resin contains aromatic groups, which can improve the ethylene glycol resistance of the nylon material.

[0016] Optionally: the polysulfone resin is a polyarylsulfone resin.

[0017] By adopting the above technical solution, the nylon material has better ethylene glycol resistance and strength properties.

[0018] Optional: Also include 1.3 to 1.7 parts of DOPO.

[0019] By adopting the above technical solution, the alcoholysis of polyamide polymerization chain can be inhibited and the stability of nylon material can be improved.

[0020] The above second invention objective of the present invention is achieved through the following technical solutions: The method for preparing ethylene glycol-resistant nylon material comprises the following steps: The raw materials are weighed according to their mass fractions, mixed evenly to obtain a mixed raw material, and then sent to a screw extruder for melt extrusion to obtain an ethylene glycol-resistant nylon material.

[0021] By adopting the above technical solution, the obtained nylon material has good strength and good ethylene glycol resistance.

[0022] In summary, this application has at least the following beneficial effects: Graphene oxide modified by triester phosphite is added to the raw materials to enhance the strength of polyamide. On the other hand, the electron cloud effect of graphene oxide is enhanced by the added phosphite, and its electron mobility is utilized to weaken the positive charge of carbonyl carbon in polyamide, thereby reducing the possibility of reaction between carbonyl group in polyamide and hydroxyl group in ethylene glycol, thereby improving the ethylene glycol resistance of nylon material; at the same time, phosphite can preferentially replace carbonyl carbon in polyamide, react with hydroxyl group in ethylene glycol, and then delay the alcoholysis of polyamide, thereby making the nylon material of the present application have excellent strength and ethylene glycol resistance. DETAILED DESCRIPTION

[0023] raw material Graphene oxide is a commercially available product with a thickness of 1 nm, 1-2 layers, an average diameter of 30 μm, and a specific surface area of ​​200 m 2 / g, purity>95wt%.

[0024] Triphenyl phosphate and tributyl phosphate are commercially available industrial grade products.

[0025] DOPO is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which is a commercially available product.

[0026] Nylon 66 is POM American DuPont 100AL NC010 product.

[0027] The glass fiber is an alkali-free glass fiber with a length of 3 mm and a diameter of 5 μm.

[0028] The polyarylsulfone resin is a product of Solvay LTG-3000 from the United States.

[0029] The polyethersulfone resin is PES E1010 product of BASF, Germany.

[0030] The silane coupling agent is 3-aminopropylmethyldiethoxysilane.

[0031] Preparation Example 1 A modified graphene oxide is obtained by modifying graphene oxide with triester phosphite.

[0032] The specific preparation method is as follows: Under nitrogen atmosphere, add 155 g of triester phosphite to 400 g of liquid A and stir to dissolve, then add 1.1 g of p-toluenesulfonic acid and stir evenly to obtain material A; 10 g of graphene oxide was added to 80 g of liquid A, and dispersed by ultrasonic vibration to obtain material B; Heat material A to 154±2℃, add material B, and stir to react for 10h; After the reaction is completed, the reactants are separated by centrifugation to obtain a precipitate, which is washed with liquid A and dried to obtain modified graphene oxide.

[0033] The phosphite triester is triphenyl phosphite, and the liquid A is toluene.

[0034] The ratio of triester phosphite in material A to graphene oxide in material B is 0.05 mol triester phosphite / 1 g graphene oxide.

[0035] Preparation Example 2 A modified graphene oxide, which differs from Preparation Example 1 as follows: Liquid A is DMF, and the phosphate triester is tributyl phosphate; Material A is a mixture of 133 g of tributyl phosphate, 400 g of DMF, and 1.1 g of p-toluenesulfonic acid, and the ratio of triester phosphite in material A to graphene oxide in material B is 0.05 mol triester phosphite / 1 g of graphene oxide.

[0036] Preparation Example 3 A modified graphene oxide, which differs from Preparation Example 1 in that material A is a mixture of 93 g tributyl phosphate, 400 g DMF, and 1.1 g p-toluenesulfonic acid, and the ratio of triester phosphite in material A to graphene oxide in material B is 0.03 mol triester phosphite / 1 g graphene oxide.

[0037] Preparation Example 4 A modified graphene oxide, which differs from Preparation Example 1 in that material A is a mixture of 124 g tributyl phosphate, 400 g DMF, and 1.1 g p-toluenesulfonic acid, and the ratio of triester phosphite in material A to graphene oxide in material B is 0.04 mol triester phosphite / 1 g graphene oxide.

[0038] Preparation Example 5 A modified graphene oxide, which differs from Preparation Example 1 in that material A is a mixture of 186 g tributyl phosphate, 400 g DMF, and 1.1 g p-toluenesulfonic acid, and the ratio of triester phosphite in material A to graphene oxide in material B is 0.06 mol triester phosphite / 1 g graphene oxide.

[0039] Preparation Example 6 A modified graphene oxide, which differs from Preparation Example 1 in that material A is a mixture of 217 g tributyl phosphate, 400 g DMF, and 1.1 g p-toluenesulfonic acid, and the ratio of triester phosphite in material A to graphene oxide in material B is 0.07 mol triester phosphite / 1 g graphene oxide.

[0040] Example 1 Disclosed is ethylene glycol-resistant nylon, whose raw materials are nylon 66, glass fiber, silane coupling agent, modified graphene oxide, polysulfone resin and DOPO.

[0041] The modified graphene oxide was prepared in Preparation Example 1.

[0042] The polysulfone resin is a polyarylsulfone resin.

[0043] The preparation method of ethylene glycol resistant nylon is as follows: 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; The mixed raw materials are fed into a screw extruder for melt extrusion to obtain ethylene glycol-resistant nylon material.

[0044] Example 2 A glycol-resistant nylon, which is different from Example 1 in that the modified graphene oxide is prepared according to Preparation Example 2.

[0045] Example 3 A glycol-resistant nylon, which is different from Example 1 in that the modified graphene oxide is prepared according to Preparation Example 3.

[0046] Example 4 A glycol-resistant nylon, which is different from Example 1 in that the modified graphene oxide is prepared according to Preparation Example 4.

[0047] Example 5 A glycol-resistant nylon, which is different from Example 1 in that the modified graphene oxide is prepared according to Preparation Example 5.

[0048] Example 6 A glycol-resistant nylon, which is different from Example 1 in that the modified graphene oxide is prepared according to Preparation Example 6.

[0049] Example 7 A glycol-resistant nylon, which is different from Example 1 in that the amount of polysulfone resin used is 0, that is, no polysulfone resin is added to the raw materials.

[0050] Example 8 A glycol-resistant nylon, which is different from Example 1 in that the polysulfone resin is a polyethersulfone resin.

[0051] Example 9 A glycol-resistant nylon, which is different from Example 1 in that the amount of DOPO used is 0, that is, no DOPO is added.

[0052] Example 10 A glycol-resistant nylon, which differs from Example 1 in that the amount of raw materials used is different. Embodiment 11 A glycol-resistant nylon, which differs from Example 1 in that the amount of raw materials used is different. Comparative Example 1 A nylon, whose raw materials are nylon 66, glass fiber, silane coupling agent, polysulfone resin and DOPO.

[0053] The modified graphene oxide was prepared in Preparation Example 1.

[0054] The polysulfone resin is a polyarylsulfone resin.

[0055] The preparation method of ethylene glycol resistant nylon is as follows: 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, and mix them evenly to obtain a mixed raw material; The mixed raw materials are fed into a screw extruder for melt extrusion to obtain ethylene glycol-resistant nylon material.

[0056] Comparative Example 2 Disclosed is ethylene glycol-resistant nylon, whose raw materials are nylon 66, glass fiber, silane coupling agent, graphene oxide, polysulfone resin and DOPO.

[0057] The polysulfone resin is a polyarylsulfone resin.

[0058] The preparation method of ethylene glycol resistant nylon is as follows: 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, and obtain a mixed raw material; The mixed raw materials are fed into a screw extruder for melt extrusion to obtain ethylene glycol-resistant nylon material.

[0059] The tensile strength, bending strength and ethylene glycol resistance of the nylon materials obtained in Examples 1 to 11 and Comparative Examples 1 to 2 were tested.

[0060] Tensile strength test: The test is carried out according to ASTM / D638, and the test results are expressed in tensile strength.

[0061] Bending strength test: The test is carried out according to ASTM / D790, and the test results are expressed in bending strength.

[0062] Ethylene glycol resistance test: prepare a mixed solution of ethylene glycol and water in a mass ratio of 1:1, prepare specimens according to ASTM / D638 and ASTM / D790, and soak the specimens in the mixed solution at 135°C for 120 hours. After soaking, test the tensile strength according to ASTM / D638, and test the flexural strength according to ASTM / D790. Calculate the tensile strength retention rate and flexural strength retention rate based on the tensile strength test results and the flexural strength test results. The results are expressed as the tensile strength retention rate and the flexural strength retention rate. The higher the tensile strength retention rate and the flexural strength retention rate, the better the ethylene glycol resistance.

[0063] The test results are shown in Table 1 below.

[0064] Table 1. Test results of Examples 1 to 11 and Comparative Examples 1 to 2 Tensile strength / MPa Bending strength / MPa Tensile strength retention rate / % Bending strength retention rate / % 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 Example 9 193.41 262.83 76.85 70.30 Example 10 192.13 266.92 77.57 72.02 Embodiment 11 192.20 265.79 76.71 71.17 Comparative Example 1 176.32 242.61 27.46 22.89 Comparative Example 2 180.79 247.90 43.80 39.53 Combined with Table 1, by comparing Example 1 with Comparative Examples 1 to 12, it can be seen that the tensile strength and flexural strength of Example 1 are greater than those of Comparative Examples 1 to 2, and the tensile strength retention rate and flexural strength retention rate of Example 1 are significantly greater than those of Comparative Examples 1 to 2. Therefore, the strength of the nylon material of Example 1 is better than that of Comparative Examples 1 to 2, and the ethylene glycol resistance of the nylon material of Example 1 is significantly better than that of Comparative Examples 1 to 2. The reason is that the graphene oxide modified by triester phosphite can enhance the strength of polyamide on the one hand, and enhance the electron cloud effect of graphene oxide by the inserted phosphite on the other hand, and utilize its electron mobility to weaken the positive charge of carbonyl carbon in polyamide, thereby reducing the possibility of carbonyl in polyamide reacting with hydroxyl in ethylene glycol, and improving the ethylene glycol resistance of nylon material; at the same time, phosphite can preferentially replace carbonyl carbon in polyamide, react with hydroxyl in ethylene glycol, and then delay the alcoholysis of polyamide, thereby making the nylon material of the present application have excellent strength and ethylene glycol resistance.

[0065] By comparing Example 1 and 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 tensile strength retention rate and flexural strength retention rate of Example 1 are greater than those of Example 2. The reason is that the modified graphene oxide in Example 1 uses triphenyl phosphite, and its carbonyl group has a higher priority in reacting with the hydroxyl group of ethylene glycol than the carbonyl group in polyamide, and the reaction product can improve the alcoholysis and hydrolysis resistance of the nylon material, thereby further improving the ethylene glycol resistance of the nylon material.

[0066] The usage ratio of triester phosphite to graphene oxide in the modification process of modified graphene oxide is different, and the characteristics of the modified products are different. Combined with Example 1 and Examples 3 to 6, the ethylene glycol resistance is from best to worst in the order of Example 1, Example 5, Example 4, Example 6, and Example 3, and the ethylene glycol resistance is from best to worst in the order of Example 1, Example 5, Example 4, Example 6, and Example 3. Therefore, the usage ratio of triester phosphite to graphene oxide in the modification process of modified graphene oxide in the present application is preferably 0.04 to 0.06 mol triester phosphite / g graphene oxide.

[0067] Comparing Example 1 with Examples 7 and 8, Example 1 further added polyarylsulfone resin to the raw materials compared with Example 7, and Example 8 further added polyethersulfone resin to the raw materials 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 ethylene glycol resistance of Example 1 is greater than that of Example 8, and the ethylene glycol resistance of Example 8 is greater than that of Example 7. Thus, the addition of polysulfone resin, which contains aromatic groups, can improve the ethylene glycol resistance of nylon materials. At the same time, when polyarylsulfone resin is used, the ethylene glycol resistance and nylon strength are both excellent.

[0068] By comparing Example 1 and Example 9, it can be seen that the tensile strength and bending strength of Example 1 are greater than those of Example 9, and the ethylene glycol resistance of Example 1 is greater than that of Example 9. Therefore, the addition of DOPO can inhibit the alcoholysis of the polyamide polymerization chain and improve the stability of the nylon material.

[0069] In combination with Example 1, Examples 10-11, and Comparative Examples 1-2, it can be seen that the tensile strength and flexural strength of Examples 10-11 are similar to those of Example 1, and the ethylene glycol resistance of Examples 10-11 is similar to that of Example 1. At the same time, the ethylene glycol resistance of Examples 10-11 is significantly better than that of Comparative Examples 1-2. Therefore, when the mass ratio of the raw materials of the nylon material of the present application is controlled to be nylon 66: glass fiber: silane coupling agent: modified graphene oxide is 100: (30-35): (0.8-1.4): (6.7-9.2), the obtained nylon material has both excellent strength and ethylene glycol resistance.

[0070] This specific embodiment is only an explanation of the present invention, and it is not a limitation of the present invention. After reading this specification, those skilled in the art can make non-creative modifications to this embodiment as needed, but as long as it is within the scope of protection required by the present invention, it will be protected by the patent law.

Claims

1. A glycol-resistant nylon material, characterized in that: Including the following raw materials by mass: Nylon 66 100 parts; 30~35 parts of glass fiber; Silane coupling agent 0.8~1.4 parts; 6.7-9.2 parts of modified graphene oxide; The modified graphene oxide is obtained by modifying the surface hydroxyl groups of the graphene oxide through an ester exchange reaction with triester phosphite.

2. The glycol-resistant nylon material according to claim 1, characterized in that: The phosphite triester is triphenyl phosphite.

3. The glycol-resistant nylon material according to claim 1, characterized in that: The modification method of the modified graphene oxide is as follows: Under nitrogen atmosphere, dissolve triester of phosphite in an appropriate amount of organic solvent, add catalyst, stir evenly, and obtain material A; Adding graphene oxide to the decomposition liquid and dispersing it by ultrasonic vibration to obtain material B; Heat material A to 152-156°C, add material B, and stir to react; After the reaction is completed, the reactants are separated by centrifugation to obtain a precipitate, and the precipitate is washed and dried to obtain modified graphene oxide.

4. The glycol-resistant nylon material according to claim 3, characterized in that: The usage ratio of the triester phosphite to graphene oxide is 0.04-0.06 mol / g.

5. The glycol-resistant nylon material according to claim 1, wherein: It also includes 8 to 9.6 parts of polysulfone resin.

6. The glycol-resistant nylon material according to claim 5, characterized in that: The polysulfone resin is a polyarylsulfone resin.

7. The glycol-resistant nylon material according to claim 1, characterized in that: Also includes 1.3~1.7 parts of DOPO.

8. The method for preparing the glycol-resistant nylon material according to any one of claims 1 to 7, characterized in that: The following steps are involved: The raw materials are weighed according to their mass fractions, mixed evenly to obtain a mixed raw material, and then sent to a screw extruder for melt extrusion to obtain an ethylene glycol-resistant nylon material.