Thermoplastic resin material as well as preparation method and application thereof

Abstract

The invention discloses a thermoplastic resin material as well as a preparation method and application thereof. The thermoplastic resin material is prepared from the following raw materials in parts by weight: 100 parts of fatty acid terminated polyamide, 5 to 35 parts of thermoplastic master batch and 0.01 to 1 part of antioxidant, wherein the thermoplastic master batch is prepared from the following raw materials in percentage by weight: 20 to 68.5 percent of fatty acid terminated polyamide, 26 to 57 percent of polyolefin elastomer, 5 to 19 percent of fatty acid amide and 0.5 to 4 percent of isocyanate. The thermoplastic resin material provided by the invention has excellent impact resistance and demolding property, and is especially suitable for serving as a shuttlecock skirt material.

Description

Technical Field

[0001] The present invention relates to a thermoplastic material, and particularly to a thermoplastic resin material, a preparation method thereof and an application thereof. Background Art

[0002] With the development of badminton sports, the demand for badminton has increased significantly. The supply of animal feathers used to produce traditional badminton is severely insufficient, and the price has risen sharply. In addition, traditional badminton has insufficient durability, is easily damaged, and has a short effective service life. Plastic badminton generally refers to a badminton product composed of a plastic injection-molded skirt and a ball head. Compared with traditional badminton, it is less likely to be damaged, has a longer effective service life, and has an advantage in production cost, and has been widely used.

[0003] However, the skirt of plastic badminton is generally a mesh structure, which has the characteristics of complex structure, and has requirements for thin walls during injection molding, which increases the requirements for material fluidity and demoulding performance. At the same time, excellent durability needs to be maintained, which has become a difficult problem urgently to be solved in the industry.

[0004] Patent CN115093699A discloses a plastic badminton sphere composite material with high durability. By adding a nylon elastomer containing specific proportions of hard segments and soft segments to polyamide and using an amino acid crosslinking agent, the hard segments of the elastomer are crosslinked to improve the tear strength of the material. However, the raw material cost is relatively high, and this solution does not solve the problem of thin-wall injection molding, and it is even more impossible to ensure the durability of thin-wall injection molded products. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention provides a thermoplastic resin material, a preparation method thereof and an application thereof.

[0006] A thermoplastic resin material comprises the following raw materials in parts by weight:

[0007] 100 parts of fatty acid-terminated polyamide,

[0008] 5 - 35 parts of thermoplastic masterbatch, preferably 12 - 25 parts,

[0009] 0.01 - 1 part of antioxidant, preferably 0.05 - 0.5 part;

[0010] Wherein, the thermoplastic masterbatch comprises the following raw materials in weight percentages:

[0011] 20 - 68.5% of polyamide,

[0012] 26 - 57% of polyolefin elastomer,

[0013] 5 - 19% of fatty acid amide,

[0014] 0.5 - 4% of isocyanate.

[0015] As a preferred embodiment of the present invention, the fatty acid-capped polyamide is a polyamide capped with a long-chain fatty acid, and the long-chain fatty acid is selected from fatty acids having C 12 -C 24 , and preferably one or more of tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, and eicosanoic acid.

[0016] Furthermore, the preparation methods of the capped polyamide are well documented in the known art. For example, the methods disclosed in patents CN110818892A, CN116199877A, and CN116925342A can be referred to. In the present invention, the fatty acid-capped polyamide can be prepared by referring to the known methods. The fatty acid is added as a capping agent / molecular weight regulator before / during the polymerization reaction. As for the specific reaction conditions, those skilled in the art can make routine adjustments based on the disclosed content of the known art, and no limitations are made here. As a feasible example provided by the present invention, the following method can be referred to for preparing this raw material:

[0017] Dissolve the polyamide monomer and fatty acid in an organic solvent and heat the reaction under an inert atmosphere; preferably, the reaction temperature is 200-280°C, the reaction pressure is 0.5-1.5 MPa(G), and the reaction time is 0.5-4 h.

[0018] Among them, the polyamide monomer is a mixture of an organic diacid and an organic diamine in an equimolar ratio, or a lactam having a C6-C 12 ring;

[0019] The organic diacid is selected from one or more of adipic acid, sebacic acid, and dodecanedioic acid;

[0020] The organic diamine is selected from one or more of ethylenediamine, decanediamine, and dodecanediamine;

[0021] The lactam is selected from one or more of caprolactam and laurolactam.

[0022] As a preferred embodiment of the present invention, the polyamide is selected from polyamides having a molecular weight of 5000-50000, preferably 10000-25000, and preferably one or more of polyamide 6, polyamide 66, polyamide 612, polyamide 1010, polyamide 1012, polyamide 11, and polyamide 12.

[0023] As a preferred embodiment of the present invention, the polyolefin elastomer is an ethylene-α-olefin copolymer and / or a functionalized ethylene-α-olefin copolymer;

[0024] Preferably, the functionalized ethylene-α-olefin copolymer is a maleic anhydride or glycidyl methacrylate grafted ethylene-α-olefin copolymer; the preparation method of the functionalized ethylene-α-olefin copolymer is well known in the industry and will not be elaborated here.

[0025] Preferably, the polyolefin elastomer has a melt index of 5 - 30 g / 10 min at 235 °C and 5 kg.

[0026] As a preferred embodiment of the present invention, the fatty acid amide is one or more of methylene distearamide, N,N'-1,2-ethylenebis(dodecanamide), ethylene bisstearamide, N,N-dihydroxyethyl decanamide, and ethylene bisoleamide.

[0027] As a preferred embodiment of the present invention, the isocyanate is one or more of 2,4-toluene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, and isophorone diisocyanate.

[0028] As a preferred embodiment of the present invention, the antioxidant is a phosphite ester, preferably one or more of tris(2,4-di-tert-butylphenyl) phosphite, tris(4-octylphenyl) phosphite, and tris[(4-octylethyl)phenyl] phosphite.

[0029] A preparation method of a thermoplastic resin material as described above, comprising:

[0030] 1) Mix fatty acid-terminated polyamide, polyolefin elastomer, fatty acid amide, and isocyanate by weight percentage and melt-extrude at 150 - 250 °C to obtain a thermoplastic masterbatch;

[0031] 2) Mix fatty acid-terminated polyamide, thermoplastic masterbatch, and antioxidant by mass parts and melt-extrude at 200 - 280 °C, cool, and pelletize to obtain a thermoplastic resin material.

[0032] An application of a thermoplastic resin material as described above or a thermoplastic resin material prepared by the method described above as a badminton skirt material.

[0033] The present invention first improves the system compatibility and overall dispersibility through a thermoplastic masterbatch with a specific composition, and has the advantage of strong impact resistance, which is beneficial to improving the impact resistance of injection-molded products; in addition, the introduction of long-chain fatty acid-terminated polyamide significantly improves the fluidity and demoulding property of the product while enhancing the toughness of the product, which is more conducive to preparing thin-walled products with complex mold structures, and thus is suitable for preparing badminton skirt materials. Detailed Embodiments

[0034] The present invention will be further described below through specific embodiments. The embodiments of the present invention are only for the description of the present invention and do not limit the scope of the present invention.

[0035] The information of the main raw materials in the present invention is as follows:

[0036] Polyolefin elastomer MH5020C: maleic anhydride grafted polyolefin, melt index 5.2 g / 10 min, Mitsui;

[0037] Polyolefin elastomer XLT8677: melt index 12.0 g / 10 min, Dow;

[0038] Polyolefin elastomer SOG-03: maleic anhydride grafted polyolefin, melt index 26.7 g / 10 min, Kayeong Polymer;

[0039] Ethylene bisoleamide: Hubei Xinghengye Technology Co., Ltd.;

[0040] N,N'-1,2-ethylenedidodecanamide: Shanghai Kaywei Chemical Technology Co., Ltd.;

[0041] Ethylene bisstearamide: Kao Corporation;

[0042] 2,4-Toluene diisocyanate (TDI): Wanhua Chemical

[0043] Hexamethylene diisocyanate (HDI): Wanhua Chemical

[0044] Isophorone diisocyanate (IPDI): Wanhua Chemical

[0045] Other raw materials and reagents can be obtained through commercial channels without special instructions.

[0046] The main performance test methods involved in the following embodiments of the present invention are as follows:

[0047] (1) Notched Izod impact strength: Tested according to the standard ISO 179-1:2023;

[0048] (2) Tensile strength: Tested according to the ISO 527-2:2012 standard;

[0049] (3) Melt index: Tested according to the ISO 1133-1:2022 standard, test conditions 235 °C, 5 kg;

[0050] (4) Injection molding cycle: The pellets of the thermoplastic resin material are injection molded (50 mm * 50 mm * 1 mm) according to the following method, and the cooling time for the sample to be completely demolded is tested:

[0051] Inject the thermoplastic resin material particles at 200 - 260 °C, control the cooling time to ensure the integrity of the sample and automatic demolding, and count the cooling duration as an index for judging the injection cycle of the sample.

[0052]

Preparation Example 1

[0053] Disperse 10 KG of caprolactam and 0.4 KG of lauric acid in ethanol, gradually heat up to 280 °C under nitrogen protection, the system pressure reaches 1.5 MPa(G), keep the pressure for 1 h, slowly release the gas to atmospheric pressure, cool down to 240 °C, react for 2 h, keep the temperature and evacuate for 1.5 h. After the reaction ends, release the vacuum with nitrogen and pressurize to 0.5 MPa(G) to obtain end-capped polyamide A with a number-average molecular weight of 9700.

[0054]

Preparation Example 2

[0055] Disperse 10 KG of laurolactam and 0.6 KG of stearic acid in ethanol, gradually heat up to 260 °C under nitrogen protection, the system pressure reaches 1.5 MPa(G), keep the pressure for 1 h, slowly release the gas to atmospheric pressure, cool down to 200 °C, react for 2 h, keep the temperature and evacuate for 1.5 h. After the reaction ends, release the vacuum with nitrogen and pressurize to 0.5 MPa(G) to obtain end-capped polyamide B with a number-average molecular weight of 19100.

[0056]

Preparation Example 3

[0057] Dissolve 5 KG of hexamethylenediamine, 5 KG of adipic acid, and 0.2 KG of myristic acid in water, gradually heat up to 90 °C under nitrogen protection, the system pressure is 0.1 MPa(G), keep the pressure for 2 h, continue to heat up to 240 °C, react for 3 h, keep the temperature and evacuate for 1.5 h. After the reaction ends, release the vacuum with nitrogen and pressurize to 0.5 MPa(G) to obtain end-capped polyamide C with a number-average molecular weight of 28800.

[0058]

Example 1

[0059] Prepare the thermoplastic resin material according to the following method:

[0060] (1) Add 28.5% of polyolefin elastomer XLT8677, 66% of end-capped polyamide A, 5% of ethylene bisoleamide, and 0.5% of TDI by mass percentage, mix and then add them into a continuous mixer. Set the mixing temperature of the continuous mixer at 220 °C, and the extrusion temperatures of each section at 220 °C, 240 °C, and 240 °C. After mixing, melting extrusion, cooling, and pelletizing, obtain the thermoplastic masterbatch;

[0061] (2) By weight, 100 parts of end-capped polyamide A, 15 parts of thermoplastic masterbatch, and 0.2 part of antioxidant 168 are premixed in a low-speed mixer, and then added into a twin-screw extruder. The materials are melt-extruded at zone temperatures of 100°C, 200°C, 220°C, 240°C, 240°C, 240°C, 230°C, and 230°C respectively, cooled, and pelletized to obtain a thermoplastic resin material.

[0062]

Example 2 - 6

[0063] A thermoplastic resin material is prepared by referring to the method substantially the same as that in Example 1, with the only difference being the difference in the raw materials and their amounts shown in Table 1.

[0064] Table 1. Different raw materials and their amounts in Examples 1 - 6

[0065]

[0066]

[0067]

Comparative Example 1

[0068] A thermoplastic resin material is prepared by referring to the method substantially the same as that in Example 1, with the only difference being that TDI is not added during the preparation of the thermoplastic masterbatch in step (1).

[0069]

Comparative Example 2

[0070] A thermoplastic resin material is prepared by referring to the method substantially the same as that in Example 1, with the only difference being that end-capped polyamide A is replaced by end-capped polyamide D during the preparation of the thermoplastic material in step (2);

[0071] The preparation method of end-capped polyamide D is as follows:

[0072] 10 KG of caprolactam and 0.4 KG of benzoic acid are dispersed in ethanol. Under nitrogen protection, the temperature is gradually raised to 280°C, the system pressure reaches 1.5 MPa(G), the pressure is maintained for 1 h, the gas is slowly released to atmospheric pressure, the temperature is lowered to 240°C, the reaction is carried out for 2 h, and vacuum is drawn at a constant temperature for 1.5 h. After the reaction ends, the vacuum is released with nitrogen, and the pressure is increased to 0.5 MPa(G) to obtain end-capped polyamide D with a number-average molecular weight of 9100.

[0073]

Comparative Example 3

[0074] A thermoplastic resin material is prepared according to the following method:

[0075] By weight, 109.9 parts of blocked polyamide A, 4.275 parts of polyolefin elastomer XLT8677, 0.75 part of ethylene bisoleamide, 0.075 part of TDI, and 0.2 part of antioxidant 168 are premixed in a low-speed mixer and then added to a twin-screw extruder. The molten extrusion is carried out at zone temperatures of 100°C, 200°C, 220°C, 240°C, 240°C, 240°C, 230°C, and 230°C respectively, followed by cooling and pelletizing to obtain a thermoplastic resin material.

[0076] The thermoplastic resin materials prepared in each example and comparative example are injection-molded and their basic properties are tested. The results are shown in Table 2:

[0077] Table 2. Performance test results

[0078]

[0079] It can be seen from the test results in Table 2 that in Comparative Example 1, no TDI is added during the preparation of the thermoplastic masterbatch, which significantly affects the impact strength and injection molding cycle of the material; in Comparative Example 2, the polyamide capped with long-chain fatty acids is not contained, resulting in a decrease in fluidity and impact strength, and a significant prolongation of the injection molding cycle of the material; in Comparative Example 3, the components are directly mixed and extruded without preparing the masterbatch, not only reducing the fluidity but also significantly decreasing the impact strength, and prolonging the injection molding cycle of the material.

[0080] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the method of the present invention, several improvements and supplements can be made, and these improvements and supplements should also be regarded as the protection scope of the present invention.

Claims

1. A thermoplastic resin material, characterized in that, Comprising the following raw materials by weight parts: 100 parts of fatty acid-terminated polyamide, 5 - 35 parts of thermoplastic masterbatch, preferably 12 - 25 parts, 0.01 - 1 part of antioxidant, preferably 0.05 - 0.5 part; Wherein, the thermoplastic masterbatch comprises the following raw materials in weight percentages: Fatty acid-terminated polyamide, 20 - 68.5%, Polyolefin elastomer, 26 - 57%, Fatty acid amide, 5 - 19%, Isocyanate, 0.5 - 4%.

2. The thermoplastic resin material according to claim 1, characterized in that, The fatty acid-capped polyamide is a polyamide capped with a long-chain fatty acid, and the long-chain fatty acid is selected from fatty acids having C 12 -C 24 , and preferably one or more of tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, and eicosanoic acid.

3. The thermoplastic resin material according to claim 2, wherein The polyamide is selected from polyamides with a molecular weight of 5000 - 50000, preferably one or more of polyamide 6, polyamide 66, polyamide 612, polyamide 1010, polyamide 1012, polyamide 11, polyamide 12.

4. The thermoplastic resin material according to any one of claims 1 to 3, characterized in that, The polyolefin elastomer is an ethylene-α-olefin copolymer and / or a functionalized ethylene-α-olefin copolymer; Preferably, the functionalized ethylene-α-olefin copolymer is an ethylene-α-olefin copolymer grafted with maleic anhydride or glycidyl methacrylate; Preferably, the polyolefin elastomer has a melt index of 5 - 30 g / 10 min at 235°C and 5 kg.

5. The thermoplastic resin material according to any one of claims 1 to 4, characterized in that, The fatty acid amide is one or more of methylene bis-stearamide, N,N'-1,2-ethylenebis-dodecanamide, ethylene bis-stearate, N,N-dihydroxyethyl decanamide, ethylene bis-oleamide.

6. The thermoplastic resin material according to any one of claims 1-5, characterized in that, The isocyanate is one or more of 2,4-toluene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate.

7. The thermoplastic resin material according to any one of claims 1-6, characterized in that, The antioxidant is a phosphite, preferably one or more of tris(2,4-di-tert-butylphenyl) phosphite, tris(4-octylphenyl) phosphite, tris[(4-octylethyl)phenyl] phosphite.

8. A method for preparing a thermoplastic resin material according to any one of claims 1 to 7, characterized in that, Including: 1) Mix fatty acid-terminated polyamide, polyolefin elastomer, fatty acid amide, and isocyanate by weight percentage and melt-extrude at 150 - 250°C to obtain a thermoplastic masterbatch; 2) Mix fatty acid-terminated polyamide, thermoplastic masterbatch, and antioxidant by mass parts and melt-extrude at 200 - 280°C, then cool and pelletize to obtain a thermoplastic resin material.

9. Use of the thermoplastic resin material according to any one of claims 1 - 7 or the thermoplastic resin material prepared by the method of claim 8 as a badminton skirt material.

Images