Nylon nucleating agent and modified nylon resin containing same

Abstract

The invention provides a nylon nucleating agent. The nylon nucleating agent comprises 50-65 parts by weight of polycarbonate and 35-50 parts by weight of fulvic acid modified peanut shell powder, the polycarbonate is prepared from the following raw materials: bisphenol A, 4-fluoro-3-hydroxy benzyl alcohol and 2-hydroxy-4-fluorobenzyl alcohol, and the molar ratio of the bisphenol A to the 4-fluoro-3-hydroxy benzyl alcohol to the 2-hydroxy-4-fluorobenzyl alcohol is (0.8 to 1.2) to (0.15 to 0.35) to (0.15 to 0.35). The invention also provides modified nylon resin containing the nylon nucleating agent. The modified nylon resin has the advantages of high flexural modulus, favorable aging resistance and low reduction rate of flexural modulus after aging.

Description

Technical Field

[0001] This invention patent relates to the technical field of nylon, in particular to a nylon nucleating agent and a modified nylon resin containing the nylon nucleating agent. Background Art

[0002] Nylon 6 (PA-6), also known as polyamide 6, is an early industrialized nylon material. It is well-known for its molecular chains usually being in a random coil shape and easily forming a folded chain sheet crystal structure during crystallization, and has excellent mechanical properties, and is often widely used as a general-purpose plastic. Nylon 6 is also widely used as fiber products due to its low strength, relatively softness, low melting point, good wear resistance, self-lubrication and solvent resistance, such as in the manufacture of clothing, fabrics, suitcases, tire cord fabrics, conveyor belts, transport belts, fishing nets, carpets, etc.; at the same time, it is also used as engineering plastic products for electronic devices, automobiles, railways, etc. or film products for food and drug packaging. Nylon 6 plays an important role in many fields due to its properties such as strength, wear resistance, chemical resistance, lightness, flexibility and thermal stability, and its application scope is still expanding with the development of technology.

[0003] Nucleating agents are commonly used modifiers in the injection molding process of nylon 6, which can improve the mechanical properties of nylon products and are a simple, easy and effective modification method to achieve high performance of nylon resins. However, there is still room for improvement in the performance improvement of nucleating agents for nylon resins in the prior art.

[0004] In view of this, it is necessary to provide an excellent nylon nucleating agent. Summary of the Invention

[0005] The present invention aims to solve at least one of the technical problems existing in the prior art to a certain extent. Thus, in the first aspect of the present invention, the present invention provides a nylon nucleating agent, comprising 50-65 parts by weight of polycarbonate and 35-50 parts by weight of fulvic acid-modified peanut shell powder; the raw materials for preparing the polycarbonate include bisphenol A, 4-fluoro-3-hydroxybenzyl alcohol and 2-hydroxy-4-fluorobenzyl alcohol, and the molar ratio of bisphenol A, 4-fluoro-3-hydroxybenzyl alcohol and 2-hydroxy-4-fluorobenzyl alcohol is (0.8-1.2):(0.15-0.35):(0.15-0.35); preferably, the molar ratio is 1:0.25:0.25.

[0006] Through the above technical solution, the polycarbonate prepared from bisphenol A, 4-fluoro-3-hydroxybenzyl alcohol, and 2-hydroxy-4-fluorobenzyl alcohol as monomers in a certain proportion can improve the crystalline morphology of nylon 6, increase the crystallinity of nylon, make the spherulite particles of nylon finer, contribute to improving the uniformity of the material, reducing stress concentration, and thus enhancing the flexural modulus and anti-aging ability of nylon. The fluorine atoms in 4-fluoro-3-hydroxybenzyl alcohol and 2-hydroxy-4-fluorobenzyl alcohol have relatively high electronegativity, which can enhance the interfacial bonding force of the composite material, thereby improving the overall mechanical properties of the composite material. The position of the fluorine element will affect the crystallization rate of the polymer. The combined use of 4-fluoro-3-hydroxybenzyl alcohol and 2-hydroxy-4-fluorobenzyl alcohol makes the polarity of the polycarbonate closer to that of nylon, and thus the compatibility is better. Moreover, the distribution of fluorine atoms makes the polarity distribution of the entire chain more uniform. This nucleating agent is more likely to be evenly dispersed in the polar nylon matrix, promoting heterogeneous nucleation, and thus improving the nucleation efficiency. The inventors found that when the molar ratio of bisphenol A, 4-fluoro-3-hydroxybenzyl alcohol, and 2-hydroxy-4-fluorobenzyl alcohol is (0.8 - 1.2):(0.15 - 0.35):(0.15 - 0.35), the flexural modulus and anti-aging performance of nylon are the best. As an inorganic nucleating agent, the fulvic acid-modified peanut shell powder has a higher specific surface area and more and more suitable indentations and microporous structures for crystallization after being modified by fulvic acid, which can provide more nucleation sites to promote crystallization. The polycarbonate prepared in this application further improves the compatibility of the fulvic acid-modified peanut shell powder in the matrix. The combined use of the two unexpectedly greatly enhances the nucleation effect of nylon.

[0007] The fulvic acid-modified peanut shell powder has indentations and microporous structures different from other inorganic nucleating agents. The modification of fulvic acid can enhance the mechanical strength of the peanut shell powder and at the same time change the indentation structure on its surface, so that the indentations on its surface can just accommodate nylon and make it arranged neatly, promoting nucleation. In addition, the fulvic acid-modified peanut shell powder has good dispersibility in the system, which can enhance the interfacial bonding force of the composite material, thereby improving the flexural modulus and aging performance of nylon.

[0008] Preferably, in the raw materials for preparing the polycarbonate, the molar ratio of the sum of the molar amounts of 4-fluoro-3-hydroxybenzyl alcohol and 2-hydroxy-4-fluorobenzyl alcohol to the molar amount of bisphenol A is 0.3 - 0.7:0.8 - 1.2.

[0009] Preferably, in the raw materials for preparing the polycarbonate, the molar ratio of 4-fluoro-3-hydroxybenzyl alcohol to 2-hydroxy-4-fluorobenzyl alcohol is 0.66 - 1.5:1.

[0010] Preferably, the method for preparing the fulvic acid-modified peanut shell powder includes: adding fulvic acid and peanut shell powder into an organic solvent, mixing evenly, adding p-toluenesulfonic acid, heating for reaction, cooling, filtering, washing the filter residue, and drying to obtain the fulvic acid-modified peanut shell powder.

[0011] Preferably, the mass ratio of the fulvic acid to the peanut shell powder is 0.375 - 0.6:1.

[0012] Through the above technical solution, the mass ratio of fulvic acid to peanut shell powder needs to be controlled within a certain ratio. When the mass ratio of fulvic acid to peanut shell powder is too high, the indentation of the peanut shell powder by fulvic acid will have a destructive effect, affecting nylon nucleation. When the mass ratio of fulvic acid to peanut shell powder is too low, the dispersibility of the fulvic acid-modified peanut shell powder in the system becomes poor, and the interfacial bonding force of the composite material becomes weak. Through the experimental research of the inventor, when the mass ratio of fulvic acid to peanut shell powder is 0.375 - 0.6:1, the performance of the modified nylon resin is optimal.

[0013] Preferably, the peanut shell powder is modified peanut shell powder, and the method for preparing the modified peanut shell powder includes: adding peanut shell powder into an alkali solution for soaking, filtering, washing the filter residue, and drying to obtain the modified peanut shell powder.

[0014] Preferably, the method for preparing the polycarbonate includes: using bisphenol A, 4-fluoro-3-hydroxybenzyl alcohol, and 2-hydroxy-4-fluorobenzyl alcohol as copolymerization monomers, and preparing the polycarbonate by the phosgene method.

[0015] In the second aspect of the present invention, the present invention provides a modified nylon resin, which includes 97 - 99 parts by weight of nylon resin and 1 - 3 parts by weight of the above nylon nucleating agent.

[0016] Preferably, the nylon resin is at least one of PA6, PA66, PA11, PA12, PA46, PA610, PA612, and PAl010.

[0017] The beneficial effects of the present invention are as follows:

[0018] 1. The present invention provides a nylon nucleating agent, which includes 50 - 65 parts by weight of polycarbonate and 35 - 50 parts by weight of fulvic acid-modified peanut shell powder. The raw materials for preparing the polycarbonate include bisphenol A, 4-fluoro-3-hydroxybenzyl alcohol, and 2-hydroxy-4-fluorobenzyl alcohol, and the molar ratio of bisphenol A, 4-fluoro-3-hydroxybenzyl alcohol, and 2-hydroxy-4-fluorobenzyl alcohol is (0.8 - 1.2):(0.15 - 0.35):

[0019] (0.15 - 0.35). The polycarbonate prepared from bisphenol A, 4-fluoro-3-hydroxybenzyl alcohol, and 2-hydroxy-4-fluorobenzyl alcohol as monomers in a certain proportion can improve the crystalline morphology of nylon 6, increase the crystallinity of nylon, make the spherulite particles of nylon finer, help improve the uniformity of the material, reduce stress concentration, and thus improve the flexural modulus and anti-aging ability of nylon. The fluorine atoms in 4-fluoro-3-hydroxybenzyl alcohol and 2-hydroxy-4-fluorobenzyl alcohol have high electronegativity, which can enhance the interfacial bonding force of the composite material, thereby improving the overall mechanical properties of the composite material. The position of the fluorine element will affect the crystallization rate of the polymer. The combined use of 4-fluoro-3-hydroxybenzyl alcohol and 2-hydroxy-4-fluorobenzyl alcohol makes the polarity of the polycarbonate closer to that of nylon, and thus has better compatibility. Moreover, the distribution of fluorine atoms makes the polarity distribution of the whole chain more uniform. This nucleating agent is more likely to be uniformly dispersed in the polar nylon matrix, thereby improving the nucleation efficiency. As an inorganic nucleating agent, the fulvic acid-modified peanut shell powder has a higher specific surface area and more and more suitable indentations and microporous structures for crystallization after being modified by fulvic acid. The indentations on the surface can just accommodate nylon and make it arranged neatly, promoting nucleation. In addition, the fulvic acid-modified peanut shell powder has good dispersibility in the system, which can enhance the interfacial bonding force of the composite material, thereby improving the flexural modulus of nylon.

[0020] 2. The present invention provides a modified nylon resin, which includes 97 - 99 parts by weight of nylon resin and 1 - 3 parts by weight of the above-mentioned nylon nucleating agent. This modified nylon resin has a high flexural modulus, good anti-aging performance, and a low flexural modulus decline rate after aging. Specific Embodiments

[0021] The following further illustrates the present invention with specific examples, but the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. For the following examples, those without specific conditions are carried out according to conventional conditions or the conditions recommended by the manufacturer. The methods used, unless otherwise specified, are all conventional methods well-known in the art. The consumables and reagents used, unless otherwise specified, are all commercially available. Unless otherwise stated, the professional and scientific terms used herein have the same meaning as those familiar to skilled personnel in the art. In addition, any method or material similar or equivalent to the recorded content can also be applied to the present invention. The peanut shell powder is obtained by drying peanut shells and refining the particle size to 10 - 30 μm. The walnut shell powder is obtained by drying walnut shells and refining the particle size to 10 - 30 μm. The fulvic acid is purchased from Zhengzhou Aikemu Chemical Co., Ltd., CAS: 479-66-3. The humic acid is purchased from Hubei Nuona Technology Co., Ltd., CAS: 1415-93-6. 4-Fluoro-3-hydroxybenzyl alcohol: CAS number: 934241-78-8. 2-Hydroxy-4-fluorobenzyl alcohol: CAS number: 773873-09-9.

[0022] Preparation Example 1

[0023] Method for preparing polycarbonate, comprising the following steps:

[0024] Add 228.2 g (1.0 mol) of bisphenol A, 35.5 g (0.25 mol) of 4-fluoro-3-hydroxybenzyl alcohol, 35.5 g (0.25 mol) of 2-hydroxy-4-fluorobenzyl alcohol, 124 g (3.1 mol) of sodium hydroxide, 780 g of water, and 1500 g of dichloromethane into a reaction vessel with nitrogen protection. Introduce 1.75 mol of phosgene for interfacial polycondensation reaction. The reaction temperature is 28 °C, and the reaction time is 30 min to obtain a prepolymer. Add 4.5 g of p-tert-butylphenol as a capping agent to the prepolymer. After complete dissolution, add 60 g of a 1% triethylamine dichloromethane solution. The dropping time is 60 min. Dropwise add an aqueous NaOH solution with a mass concentration of 32%. The total molar amount of the dropped NaOH is 480% of the total molar amount of the excess phosgene to obtain a polymerization solution. Separate, purify, and remove the organic solvent to obtain polycarbonate.

[0025] Preparation Example 2

[0026] The difference between Preparation Example 2 and Preparation Example 1 lies in that the molar amounts of the monomers bisphenol A, 4-fluoro-3-hydroxybenzyl alcohol, and 2-hydroxy-4-fluorobenzyl alcohol are different. Specifically, bisphenol A is 1.0 mol, 4-fluoro-3-hydroxybenzyl alcohol is 0.2 mol, and 2-hydroxy-4-fluorobenzyl alcohol is 0.3 mol.

[0027] Preparation Example 3

[0028] The difference between Preparation Example 3 and Preparation Example 1 lies in that the molar amounts of the monomers bisphenol A, 4-fluoro-3-hydroxybenzyl alcohol, and 2-hydroxy-4-fluorobenzyl alcohol are different. Specifically, bisphenol A is 1.0 mol, 4-fluoro-3-hydroxybenzyl alcohol is 0.3 mol, and 2-hydroxy-4-fluorobenzyl alcohol is 0.2 mol.

[0029] Preparation Example 4

[0030] The difference between Preparation Example 4 and Preparation Example 1 lies in that the molar amounts of the monomers bisphenol A, 4-fluoro-3-hydroxybenzyl alcohol, and 2-hydroxy-4-fluorobenzyl alcohol are different. Specifically, bisphenol A is 0.8 mol, 4-fluoro-3-hydroxybenzyl alcohol is 0.35 mol, and 2-hydroxy-4-fluorobenzyl alcohol is 0.35 mol.

[0031] Preparation Example 5

[0032] The difference between Preparation Example 5 and Preparation Example 1 lies in that the molar amounts of the monomers bisphenol A, 4-fluoro-3-hydroxybenzyl alcohol, and 2-hydroxy-4-fluorobenzyl alcohol are different. Specifically, bisphenol A is 1.2 mol, 4-fluoro-3-hydroxybenzyl alcohol is 0.15 mol, and 2-hydroxy-4-fluorobenzyl alcohol is 0.15 mol.

[0033] Preparation Example 6

[0034] The difference between Preparation Example 6 and Preparation Example 1 is that monomer 2-hydroxy-4-fluorobenzyl alcohol is not added, and the molar amounts of monomers bisphenol A and 4-fluoro-3-hydroxybenzyl alcohol are specifically: 1.0 mol of bisphenol A and 0.5 mol of 4-fluoro-3-hydroxybenzyl alcohol.

[0035] Preparation Example 7

[0036] The difference between Preparation Example 7 and Preparation Example 1 is that monomer 4-fluoro-3-hydroxybenzyl alcohol is not added, and the molar amounts of monomers bisphenol A and 2-hydroxy-4-fluorobenzyl alcohol are: 1.0 mol of bisphenol A and 0.5 mol of 2-hydroxy-4-fluorobenzyl alcohol.

[0037] Preparation Example 8

[0038] A method for preparing fulvic acid-modified peanut shell powder includes the following steps:

[0039] Step a: Soak 50 g of peanut shell powder in 400 g of a 15% sodium hydroxide solution for 30 min, filter, wash the filter residue with deionized water until neutral, and dry to obtain modified peanut shell powder;

[0040] Step b: Add 20 g of fulvic acid and 40 g of modified peanut shell powder to 100 mL of cyclohexane, mix evenly, add 4 g of p-toluenesulfonic acid, then reflux at 120 °C for 1 h, cool to room temperature, filter, wash the filter residue with deionized water until neutral, and dry to obtain fulvic acid-modified peanut shell powder.

[0041] Preparation Example 9

[0042] The difference between Preparation Example 9 and Preparation Example 8 is that in step b, the amount of fulvic acid used is different. In Preparation Example 9, the amount of fulvic acid used is 15 g.

[0043] Preparation Example 10

[0044] The difference between Preparation Example 10 and Preparation Example 8 is that in step b, the amount of fulvic acid used is different. In Preparation Example 10, the amount of fulvic acid used is 24 g.

[0045] Preparation Example 11

[0046] The difference between Preparation Example 11 and Preparation Example 8 is that the preparation method of the fulvic acid-modified peanut shell powder does not include step a. The peanut shell powder is directly subjected to fulvic acid modification treatment, that is, 20 g of fulvic acid and 40 g of peanut shell powder are added to 100 mL of cyclohexane, mixed evenly, 4 g of p-toluenesulfonic acid is added, and then refluxed at 120 °C for 1 h. After the reaction is completed, it is cooled to room temperature, filtered, and the filter residue is washed with deionized water until neutral and dried to obtain the fulvic acid-modified peanut shell powder.

[0047] Preparation Example 12

[0048] The difference between Preparation Example 12 and Preparation Example 8 is that the fulvic acid is replaced with an equal mass of humic acid to obtain the humic acid-modified peanut shell powder.

[0049] Preparation Example 13

[0050] The difference between Preparation Example 13 and Preparation Example 8 is that the peanut shell powder is replaced with an equal mass of walnut shell powder to obtain the fulvic acid-modified walnut shell powder.

[0051] Example 1

[0052] The nylon nucleating agent is obtained by mixing 60 parts by weight of polycarbonate prepared by the preparation method of Preparation Example 1 and 40 parts by weight of fulvic acid-modified peanut shell powder prepared by the preparation method of Preparation Example 8.

[0053] Example 2

[0054] The difference between Example 2 and Example 1 is that the polycarbonate is prepared by the preparation method of Preparation Example 2.

[0055] Example 3

[0056] The difference between Example 3 and Example 1 is that the polycarbonate is prepared by the preparation method of Preparation Example 3.

[0057] Example 4

[0058] The difference between Example 4 and Example 1 is that the polycarbonate is prepared by the preparation method of Preparation Example 4.

[0059] Example 5

[0060] The difference between Example 5 and Example 1 is that the polycarbonate is prepared by the preparation method of Preparation Example 5.

[0061] Example 6

[0062] The difference between Example 6 and Example 1 is that the fulvic acid-modified peanut shell powder is prepared by the preparation method of Preparation Example 9.

[0063] Example 7

[0064] Example 7 is different from Example 1 in that the fulvic acid-modified peanut shell powder is prepared by the preparation method of Preparation Example 10.

[0065] Example 8

[0066] Example 8 is different from Example 1 in that the fulvic acid-modified peanut shell powder is prepared by the preparation method of Preparation Example 11.

[0067] Example 9

[0068] The nylon nucleating agent is obtained by mixing 50 parts by weight of polycarbonate prepared by the preparation method of Preparation Example 1 and 50 parts by weight of fulvic acid-modified peanut shell powder prepared by the preparation method of Preparation Example 8.

[0069] Example 10

[0070] The nylon nucleating agent is obtained by mixing 65 parts by weight of polycarbonate prepared by the preparation method of Preparation Example 1 and 35 parts by weight of fulvic acid-modified peanut shell powder prepared by the preparation method of Preparation Example 8.

[0071] Comparative Example 1

[0072] Comparative Example 1 is different from Example 1 in that the polycarbonate in the nylon nucleating agent is replaced with an equal mass of fulvic acid-modified peanut shell powder prepared by the preparation method of Preparation Example 8.

[0073] Comparative Example 2

[0074] Comparative Example 2 is different from Example 1 in that the fulvic acid-modified peanut shell powder in the nylon nucleating agent is replaced with an equal mass of polycarbonate prepared by the preparation method of Preparation Example 1.

[0075] Comparative Example 3

[0076] Comparative Example 3 is different from Example 1 in that the unmodified peanut shell powder is used to replace the fulvic acid-modified peanut shell powder.

[0077] Comparative Example 4

[0078] Comparative Example 4 is different from Example 1 in that the polycarbonate is prepared by the preparation method of Preparation Example 6.

[0079] Comparative Example 5

[0080] Comparative Example 5 is different from Example 1 in that the polycarbonate is prepared by the preparation method of Preparation Example 7.

[0081] Comparative Example 6

[0082] Comparative Example 6 is different from Example 1 in that the fulvic acid-modified peanut shell powder is replaced with humic acid-modified peanut shell powder prepared by the preparation method of Preparation Example 12.

[0083] Comparative Example 7

[0084] The difference between Comparative Example 7 and Example 1 is that the fulvic acid-modified walnut shell powder prepared by the preparation method of Preparation Example 13 is used to replace the fulvic acid-modified peanut shell powder.

[0085] Application Examples 1-10 and Comparative Application Examples 1-7

[0086] The nylon resin (PA6, Baling Petrochemical) was dried in a vacuum oven at 80 °C for 24 hours, and then mixed with the nylon nucleating agents prepared in the above Examples 1-10 and Comparative Examples 1-7 at a weight ratio of 98:2 in a high-speed stirrer for 1 minute, and then melt-blended and pelletized using a twin-screw extruder (length-diameter ratio 30:1, diameter 25 mm). The temperatures of each section of the extruder were 230 °C, 235 °C, 235 °C, 235 °C, 230 °C, and 220 °C. After cooling, injection molding was carried out using an injection molding machine to produce standard test specimens.

[0087] Test 1:

[0088] The standard test specimens obtained from the application examples and comparative application examples were subjected to a flexural property test according to the ISO178 test standard, and the results are shown in Table 1 below:

[0089] Table 1

[0090]

[0091]

[0092] Combining the comparison of Comparative Application Examples 1, 2 and Application Example 1 with Table 1, it can be seen that when the nylon nucleating agent uses only fulvic acid-modified peanut shell powder or polycarbonate alone, the flexural modulus of the obtained modified nylon resin is significantly reduced.

[0093] Combining the comparison of Comparative Application Example 3 and Application Example 1 with Table 1, it can be seen that when the peanut shell powder is not modified, the flexural modulus of the obtained modified nylon resin is significantly reduced.

[0094] Combining the comparison of Comparative Application Examples 4, 5 and Application Example 1 with Table 1, it can be seen that when preparing polycarbonate, when only bisphenol A and monomer 4-fluoro-3-hydroxybenzyl alcohol or bisphenol A and monomer 2-hydroxy-4-fluorobenzyl alcohol are used as monomer raw materials, the flexural modulus of the obtained modified nylon resin is significantly reduced.

[0095] Combining the comparison of Comparative Application Example 6 and Application Example 1 with Table 1, it can be seen that when preparing fulvic acid-modified peanut shell powder, when humic acid is used to replace fulvic acid in equal mass, the flexural modulus of the obtained modified nylon resin is significantly reduced.

[0096] Comparing Application Example 7 with Application Example 1 and combining with Table 1, it can be seen that when preparing fulvic acid-modified peanut shell powder, when walnut shell powder is used to replace peanut shell powder with the same mass, the flexural modulus of the obtained modified nylon resin is significantly reduced.

[0097] Test 2:

[0098] The aging test is carried out according to the standard of GB / T16422.2-1999. Conditions: 1. Light cycle: irradiance 0.51W / (m 2 .nm)(340nm); black standard temperature 65°C; chamber temperature 38°C; relative humidity 50%; time 102min; 2. Light + spray cycle: irradiance 0.51W / (m 2 .nm)(340nm); black standard temperature 65°C; chamber temperature 38°C; relative humidity 50%; time 18min. The total aging time is 1000 hours. Measure the flexural modulus after aging of some application examples and comparative application examples, and calculate the flexural modulus decline rate. The flexural modulus decline rate = (flexural modulus before aging - flexural modulus after aging) / flexural modulus before aging. The results are shown in Table 2 below.

[0099] Table 2

[0100]

[0101] Comparing Comparative Application Examples 1 and 2 with Application Example 1 and combining with Table 2, it can be seen that when the nylon nucleating agent uses fulvic acid-modified peanut shell powder or polycarbonate alone, the flexural modulus decline rate of the obtained modified nylon resin becomes larger.

[0102] Comparing Comparative Application Example 3 with Application Example 1 and combining with Table 2, it can be seen that when the peanut shell powder is not modified, the flexural modulus decline rate of the obtained modified nylon resin becomes larger.

[0103] Comparing Comparative Application Examples 4 and 5 with Application Example 1 and combining with Table 2, it can be seen that when preparing polycarbonate, when only bisphenol A and monomer 4-fluoro-3-hydroxybenzyl alcohol or bisphenol A and monomer 2-hydroxy-4-fluorobenzyl alcohol are used as monomer raw materials, the flexural modulus decline rate of the obtained modified nylon resin becomes larger.

[0104] Comparing Comparative Application Example 6 with Application Example 1 and combining with Table 2, it can be seen that when preparing fulvic acid-modified peanut shell powder, when humic acid is used to replace fulvic acid with the same mass, the flexural modulus decline rate of the obtained modified nylon resin becomes larger.

[0105] Comparing Comparative Application Example 7 with Application Example 1 and combining with Table 2, it can be seen that when preparing fulvic acid-modified peanut shell powder, when walnut shell powder is used to replace peanut shell powder with the same mass, the flexural modulus decline rate of the obtained modified nylon resin becomes larger.

[0106] Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those of ordinary skill in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present invention, and all such changes, modifications, substitutions, and variations should be included within the protection scope of the present invention.

Claims

1. A nylon nucleating agent, characterized in that: The invention comprises 50-65 parts by weight of polycarbonate and 35-50 parts by weight of fulvic acid modified peanut shell powder; raw materials for preparing the polycarbonate comprise bisphenol A, 4-fluoro-3-hydroxybenzyl alcohol and 2-hydroxy-4-fluorobenzyl alcohol, and the molar ratio of the bisphenol A, 4-fluoro-3-hydroxybenzyl alcohol and 2-hydroxy-4-fluorobenzyl alcohol is (0.8-1.2):(0.15-0.35):(0.15-0.35).

2. The nylon nucleating agent according to claim 1, characterized in that In the raw materials for preparing the polycarbonate, the ratio of the molar amount of the 4-fluoro-3-hydroxybenzyl alcohol and the 2-hydroxy-4-fluorobenzyl alcohol to the molar amount of bisphenol A is 0.3-0.7:0.8-1.

2.

3. The nylon nucleating agent according to claim 1, characterized in that In the raw materials for preparing the polycarbonate, the molar ratio of the 4-fluoro-3-hydroxybenzyl alcohol to the 2-hydroxy-4-fluorobenzyl alcohol is 0.66-1.5:

1.

4. The nylon nucleating agent according to claim 1, characterized in that The preparation method of the fulvic acid modified peanut shell powder comprises: adding fulvic acid and peanut shell powder into an organic solvent, mixing evenly, adding p-toluenesulfonic acid, heating for reaction, cooling, filtering, washing the filter residue, and drying to obtain the fulvic acid modified peanut shell powder.

5. The nylon nucleating agent according to claim 4, characterized in that The mass ratio of the fulvic acid to the peanut shell powder is 0.375-0.6:

1.

6. The nylon nucleating agent according to claim 4, characterized in that The peanut shell powder is a modified peanut shell powder. The preparation method of the modified peanut shell powder comprises: adding the peanut shell powder into an alkali solution for soaking, filtering, washing the filter residue, and drying to obtain the modified peanut shell powder.

7. The nylon nucleating agent according to claim 1, characterized in that The preparation method of the polycarbonate comprises: using bisphenol A, 4-fluoro-3-hydroxybenzyl alcohol and 2-hydroxy-4-fluorobenzyl alcohol as copolymer monomers, and preparing the polycarbonate through a phosgene method.

8. A modified nylon resin, characterized in that: The invention comprises 97-99 parts by weight of nylon resin and 1-3 parts by weight of the nylon nucleating agent according to any one of claims 1-7.

9. The modified nylon resin according to claim 8, characterized in that The nylon resin is at least one of PA6, PA66, PA11, PA12, PA46, PA610, PA612 and PA1010.

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