A high-toughness PSU plastic and preparation method thereof

Abstract

The invention relates to the technical field of PSU plastic machines, and in particular to a high-toughness PSU plastic and a preparation method thereof. The high-toughness PSU plastic is composed of the following raw materials: 60-80 parts of PSU resin, 5-20 parts of toughening agent, 0.3-1 part of lubricant, 0.1-0.5 part of antioxidant, 0.1-0.5 part of light stabilizer, and 5-12 parts of compatibilizer. In the invention, the mechanical properties of the PSU plastic can be effectively improved by the fibrous toughening agent, the toughness of the PSU plastic can be improved, and the application occasions of the PSU plastic can be expanded. In the invention, uniformly distributed micropores exist on the titanium dioxide film outside the cellulose, so that when the toughening agent is mixed with the PSU resin, the cellulose can still contact with the organic component, the compatibility of the toughening agent and the PSU resin is improved, the toughening agents are not easy to agglomerate, and the modification effect is good.

Description

Technical Field

[0001] The invention relates to the technical field of PSU plastic machines, and in particular to a high-toughness PSU plastic and a preparation method thereof. Background Art

[0002] Polysulfone resin (PSU) is a white granular solid, a thermoplastic special engineering plastic with excellent comprehensive performance. It is mainly used to produce polyester cotton, non-woven fabrics, etc., and is used as heat-resistant, corrosion-resistant, high-strength parts and insulation parts, industrial films, etc. in electrical appliances, electronics, instruments, meters and aerospace departments. However, PSU plastic has poor melt fluidity, is difficult to process and shape, and has poor impact toughness and is not wear-resistant, which limits its further application.

[0003] Studies have shown that adding an appropriate amount of inorganic nanoparticles such as zinc oxide and titanium oxide to plastic resins can effectively improve the mechanical properties of plastics, such as improving the toughness of plastics. However, inorganic nanoparticles are not compatible with plastic resins and are prone to agglomeration during the injection molding process, so the performance improvement of the resin is not ideal.

[0004] Therefore, we proposed a high-toughness PSU plastic and a preparation method thereof to solve the above problems. Summary of the invention

[0005] The purpose of the present invention is to solve the shortcomings of the prior art and to propose a high-toughness PSU plastic and a preparation method thereof.

[0006] A high-toughness PSU plastic is composed of the following raw materials: 60-80 parts of PSU resin, 5-20 parts of toughening agent, 0.3-1 part of lubricant, 0.1-0.5 part of antioxidant, 0.1-0.5 part of light stabilizer and 5-12 parts of compatibilizer.

[0007] Preferably, the preparation method of the toughening agent comprises the following steps:

[0008] Step 1, weigh chitosan and cellulose, the mass ratio of chitosan to cellulose is 1:10-20, prepare an acetic acid solution with a mass percentage concentration of 1%-5%, add chitosan to the acetic acid solution with a mass percentage concentration of 1%-5%, the mass ratio of chitosan to the acetic acid solution is 1:100-400, dissolve chitosan in the acetic acid solution to form a chitosan acetic acid solution; weigh anhydrous copper sulfate, the mass ratio of anhydrous copper sulfate to cellulose is 1:40-60, soak cellulose in the chitosan acetic acid solution for 2-4 hours, then add anhydrous copper sulfate, continue soaking for 1-2 hours, after completion, filter, and dry to obtain modified cellulose;

[0009] Step 2, weighing tetrabutyl titanate and acetylacetone, the mass ratio of tetrabutyl titanate to cellulose is 1:10-20, the mass ratio of acetylacetone to cellulose is 1:40-60, adding tetrabutyl titanate and acetylacetone to a mixed solution of ethanol and water, the mass ratio of ethanol to water in the mixed solution is 45-50:1, stirring for 10-15 minutes, then adding modified cellulose, continuing to stir for 1-2 hours, aging, separating solids, and heat treating the solids obtained after separation at a temperature of 280-350° C. for 30-60 minutes under a nitrogen atmosphere to obtain modified cellulose coated with titanium dioxide on the surface;

[0010] Step 3, weighing a silane coupling agent, wherein the mass ratio of the silane coupling agent to cellulose is 1:8-15, and fully mixing the silane coupling agent with the modified cellulose coated with titanium dioxide on the surface to obtain a toughening agent.

[0011] Preferably, in step 1, after filtration, vacuum freeze-drying is performed to obtain modified cellulose.

[0012] Preferably, in step 2, during the stirring process, the temperature is controlled at 15-35° C., and after aging, the solid is separated by a centrifuge.

[0013] Preferably, the compatibilizer is at least one of maleic anhydride, acrylic acid and polypropylene grafted maleic anhydride.

[0014] Preferably, the antioxidant is at least one of monophenol, bisphenol, triphenol, polyphenol, hydroquinone, thiobisphenol, naphthylamine, diphenylamine and p-phenylenediamine.

[0015] Preferably, the lubricant is at least one of silicone oil, white mineral oil, fatty acid amide, barium stearate, magnesium stearate, zinc stearate, pentaerythritol stearate, polyethylene wax, and paraffin.

[0016] Preferably, the light stabilizer is at least one of alkylated monophenol, alkylated bisphenol, diphenyl phosphite, triphenyl phosphite, hydroxybenzotriazole, and hindered amine.

[0017] Preferably, a method for preparing a high-toughness PSU plastic comprises the following steps: mixing the raw materials except the toughening agent in parts by weight and adding them from the main feeding port of a twin-screw extruder, adding the toughening agent from the side feeding port of the twin-screw extruder, melt blending, and obtaining the high-toughness PSU plastic after extrusion.

[0018] Preferably, the temperature range of each zone of the extruder is 270-350° C., and the main engine speed is 210-560 r / min.

[0019] The beneficial effects of the present invention are:

[0020] 1. In the present invention, the fibrous toughening agent can effectively improve the mechanical properties of PSU plastics, improve the toughness of PSU plastics, and expand the application occasions of PSU plastics.

[0021] 2. In the present invention, when preparing the toughening agent, cellulose is first modified by chitosan to improve the adsorption capacity of cellulose for copper sulfate. The copper sulfate on the cellulose has a certain antibacterial effect. Then, tetrabutyl titanate is coated on the surface of cellulose to form a thin film on the cellulose. After subsequent heat treatment, a titanium dioxide film is generated on the surface of the cellulose. During the heat treatment, copper sulfate pentahydrate will first lose water to generate anhydrous copper sulfate. When the water evaporates, pores will be formed on the tetrabutyl titanate film. In the toughening agent finally formed, uniformly distributed micropores will exist on the titanium dioxide film on the outside of the cellulose, so that when the toughening agent is mixed with the PSU resin, the cellulose can still contact with the organic component, thereby improving the compatibility of the toughening agent with the PSU resin, and the toughening agents are not easy to agglomerate, and the modification effect is good. DETAILED DESCRIPTION

[0022] The present invention will be further explained below in conjunction with specific embodiments.

[0023] In the following embodiments, the experimental methods or test methods, unless otherwise specified, are conventional methods; reagents and materials, unless otherwise specified, are obtained from conventional commercial channels or prepared by conventional methods, wherein: PSU resin was purchased from Dongguan Shengfengyuan Plastic Material Co., Ltd., cellulose is hydroxypropyl methylcellulose purchased from Jinan Runhui Chemical Co., Ltd., chitosan and tetrabutyl titanate were purchased from Jiangsu Caiwei Biotechnology Co., Ltd., and silane coupling agent is KH560 purchased from Jiangsu Jiujia Biotechnology Co., Ltd.

[0024] In Example 1, a high-toughness PSU plastic is composed of the following raw materials: 60 parts of PSU resin, 5 parts of toughening agent, 0.3 parts of lubricant, 0.1 parts of antioxidant, 0.1 parts of light stabilizer, and 5 parts of compatibilizer.

[0025] The preparation method of the toughening agent comprises the following steps:

[0026] Step 1, weigh chitosan and cellulose, the mass ratio of chitosan to cellulose is 1:10, prepare an acetic acid solution with a mass percentage concentration of 1%, add chitosan to the acetic acid solution with a mass percentage concentration of 1% to 5%, the mass ratio of chitosan to the acetic acid solution is 1:100, dissolve chitosan in the acetic acid solution to form a chitosan acetic acid solution; weigh anhydrous copper sulfate, the mass ratio of anhydrous copper sulfate to cellulose is 1:40, immerse cellulose in the chitosan acetic acid solution for 2h, then add anhydrous copper sulfate, continue immersing for 1h, after completion, filter, and dry to obtain modified cellulose;

[0027] Step 2, weighing tetrabutyl titanate and acetylacetone, the mass ratio of tetrabutyl titanate to cellulose is 1:10, and the mass ratio of acetylacetone to cellulose is 1:40, adding tetrabutyl titanate and acetylacetone to a mixed solution of ethanol and water, the mass ratio of ethanol to water in the mixed solution is 45:1, stirring for 10 minutes, then adding modified cellulose, continuing to stir for 1 hour, aging, separating the solid, and heat treating the solid obtained after separation at 280° C. for 30 minutes under a nitrogen atmosphere to obtain modified cellulose coated with titanium dioxide on the surface;

[0028] Step 3, weighing a silane coupling agent, wherein the mass ratio of the silane coupling agent to cellulose is 1:8, and fully mixing the silane coupling agent with the modified cellulose coated with titanium dioxide on the surface to obtain a toughening agent.

[0029] In step 1, after filtering, vacuum freeze drying is performed to obtain modified cellulose.

[0030] In step 2, during the stirring process, the temperature is controlled at 15° C., and after aging, the solid is separated by a centrifuge.

[0031] The compatibilizer is maleic anhydride.

[0032] The antioxidant is hydroquinone.

[0033] The lubricant is silicone oil.

[0034] The light stabilizer is alkylated monophenol.

[0035] A method for preparing a high-toughness PSU plastic comprises the following steps: raw materials except a toughening agent are mixed by weight and added from a main feed port of a twin-screw extruder, the toughening agent is added from a side feed port of the twin-screw extruder, melt-blended, and extruded to obtain a high-toughness PSU plastic.

[0036] The temperature range of each zone of the extruder is 270~340℃, and the main engine speed is 210r / min.

[0037] In Example 2, a high-toughness PSU plastic is composed of the following raw materials: 80 parts of PSU resin, 20 parts of toughening agent, 1 part of lubricant, 0.5 parts of antioxidant, 0.5 parts of light stabilizer, and 12 parts of compatibilizer.

[0038] The preparation method of the toughening agent comprises the following steps:

[0039] Step 1, weigh chitosan and cellulose, the mass ratio of chitosan to cellulose is 1:20, prepare an acetic acid solution with a mass percentage concentration of 5%, add chitosan to the acetic acid solution with a mass percentage concentration of 5%, the mass ratio of chitosan to the acetic acid solution is 1:400, dissolve chitosan in the acetic acid solution to form a chitosan acetic acid solution; weigh anhydrous copper sulfate, the mass ratio of anhydrous copper sulfate to cellulose is 1:60, immerse cellulose in the chitosan acetic acid solution for 4 hours, then add anhydrous copper sulfate, continue immersing for 2 hours, after completion, filter, and dry to obtain modified cellulose;

[0040] Step 2, weighing tetrabutyl titanate and acetylacetone, the mass ratio of tetrabutyl titanate to cellulose is 1:20, the mass ratio of acetylacetone to cellulose is 1:60, adding tetrabutyl titanate and acetylacetone to a mixed solution of ethanol and water, the mass ratio of ethanol to water in the mixed solution is 450:1, stirring for 15 minutes, then adding modified cellulose, continuing to stir for 2 hours, aging, separating the solid, and heat-treating the solid obtained after separation at 350° C. for 60 minutes under a nitrogen atmosphere to obtain modified cellulose coated with titanium dioxide on the surface;

[0041] Step 3, weighing a silane coupling agent, wherein the mass ratio of the silane coupling agent to cellulose is 1:15, and fully mixing the silane coupling agent with the modified cellulose coated with titanium dioxide on the surface to obtain a toughening agent.

[0042] In step 1, after filtering, vacuum freeze drying is performed to obtain modified cellulose.

[0043] In step 2, during the stirring process, the temperature is controlled at 35° C., and after aging, the solid is separated by a centrifuge.

[0044] The compatibilizer is acrylic acid.

[0045] The antioxidant is a mixture of diphenylamine and p-phenylenediamine in a mass ratio of 1:1.

[0046] The lubricant is a mixture of silicone oil and white mineral oil in a mass ratio of 2:1.

[0047] The light stabilizer is alkylated bisphenol.

[0048] A method for preparing a high-toughness PSU plastic comprises the following steps: raw materials except a toughening agent are mixed by weight and added from a main feed port of a twin-screw extruder, the toughening agent is added from a side feed port of the twin-screw extruder, melt-blended, and extruded to obtain a high-toughness PSU plastic.

[0049] The temperature range of each zone of the extruder is 280~350℃, and the main engine speed is 560r / min.

[0050] In Example 3, a high-toughness PSU plastic is composed of the following raw materials: 70 parts of PSU resin, 12 parts of toughening agent, 0.6 parts of lubricant, 0.4 parts of antioxidant, 0.3 parts of light stabilizer, and 8 parts of compatibilizer.

[0051] The preparation method of the toughening agent comprises the following steps:

[0052] Step 1, weigh chitosan and cellulose, the mass ratio of chitosan to cellulose is 1:14, prepare an acetic acid solution with a mass percentage concentration of 3%, add chitosan to the acetic acid solution with a mass percentage concentration of 3%, the mass ratio of chitosan to the acetic acid solution is 1:300, dissolve chitosan in the acetic acid solution to form a chitosan acetic acid solution; weigh anhydrous copper sulfate, the mass ratio of anhydrous copper sulfate to cellulose is 1:50, immerse cellulose in the chitosan acetic acid solution for 3 hours, then add anhydrous copper sulfate, continue immersing for 1.5 hours, and after completion, filter and dry to obtain modified cellulose;

[0053] Step 2, weighing tetrabutyl titanate and acetylacetone, the mass ratio of tetrabutyl titanate to cellulose is 1:15, the mass ratio of acetylacetone to cellulose is 1:50, adding tetrabutyl titanate and acetylacetone to a mixed solution of ethanol and water, the mass ratio of ethanol to water in the mixed solution is 48:1, stirring for 12 minutes, then adding modified cellulose, continuing to stir for 1.5 hours, aging, separating the solid, and heat-treating the solid obtained after separation at 320° C. for 40 minutes under a nitrogen atmosphere to obtain modified cellulose coated with titanium dioxide on the surface;

[0054] Step 3, weighing a silane coupling agent, wherein the mass ratio of the silane coupling agent to cellulose is 1:10, and fully mixing the silane coupling agent with the modified cellulose coated with titanium dioxide on the surface to obtain a toughening agent.

[0055] In step 1, after filtering, vacuum freeze drying is performed to obtain modified cellulose.

[0056] In step 2, during the stirring process, the temperature is controlled at 25° C., and after aging, the solid is separated by a centrifuge.

[0057] The compatibilizer is polypropylene grafted with maleic anhydride.

[0058] The antioxidant is thiobisphenol.

[0059] The lubricant is pentaerythritol stearate.

[0060] The light stabilizer is hydroxybenzotriazole.

[0061] A method for preparing a high-toughness PSU plastic comprises the following steps: raw materials except a toughening agent are mixed by weight and added from a main feed port of a twin-screw extruder, the toughening agent is added from a side feed port of the twin-screw extruder, melt-blended, and extruded to obtain a high-toughness PSU plastic.

[0062] The temperature range of each zone of the extruder is 280~340℃, and the main engine speed is 280r / min.

[0063] In Examples 1-3,

[0064] The compatibilizer is at least one of maleic anhydride, acrylic acid and polypropylene grafted maleic anhydride.

[0065] The antioxidant is at least one of monophenol, bisphenol, triphenol, polyphenol, hydroquinone, thiobisphenol, naphthylamine, diphenylamine and p-phenylenediamine.

[0066] The lubricant is at least one of silicone oil, white mineral oil, fatty acid amide, barium stearate, magnesium stearate, zinc stearate, pentaerythritol stearate, polyethylene wax and paraffin.

[0067] The light stabilizer is at least one of alkylated monophenol, alkylated bisphenol, diphenyl phosphite, triphenyl phosphite, hydroxybenzotriazole and hindered amine.

[0068] In Comparative Example 1, compared with Example 3, no toughening agent was added, and the rest was the same as Example 3.

[0069] In Comparative Example 2, compared with Example 3, an equal mass of nano-titanium dioxide is used to replace the toughening agent, the particle size of the nano-titanium dioxide is 10-40 nm, and the rest is the same as Example 3.

[0070] In Comparative Example 3, compared with Comparative Example 2, the surface of nano-titanium dioxide is modified by a silane coupling agent, the mass ratio of the silane coupling agent to the nano-titanium dioxide is 1:8, the particle size of the nano-titanium dioxide is 10-40 nm, and the rest is the same as Comparative Example 2.

[0071] In Comparative Example 4, compared with Example 3, copper sulfate was not added during the preparation of the toughening agent, and the rest was the same as Example 3.

[0072] In Comparative Example 5, compared with Example 3, tetrabutyl titanate was not added during the preparation of the toughening agent, and the rest was the same as Example 3.

[0073] The modified PSU plastics of Examples 1-5 and Comparative Examples 1-4 were tested for performance, including tensile strength test and impact performance test.

[0074] Tensile strength: Tested in accordance with GB / T1040.1-2018K "Determination of tensile properties of plastics Part 1: General principles".

[0075] Impact performance: Tested in accordance with GB / T1843-2008 "Determination of cantilever beam impact strength of plastics".

[0076] The test results are shown in Table 1.

[0077] Table 1

[0078]

[0079] It can be seen from Table 1 that the PSU plastic prepared by the present invention has good tensile strength and impact resistance and high toughness; in Comparative Example 1, no toughening agent is added, and its tensile strength and impact performance are significantly reduced; in Comparative Example 2, an equal mass of nano titanium dioxide is used instead of the toughening agent, and its tensile strength and impact performance are better than those of Comparative Example 1; in Comparative Example 3, compared with Comparative Example 2, the surface of nano titanium dioxide is modified by a silane coupling agent, and its tensile strength and impact performance are better than those of Comparative Example 2; in Comparative Example 4, copper sulfate is not added during the preparation of the toughening agent, and its tensile strength and impact performance are slightly inferior to those of Example 3; in Comparative Example 5, tetrabutyl titanate is not added during the preparation of the toughening agent, and its tensile strength and impact performance are significantly lower than those of Example 3, but higher than those of Comparative Example 3.

[0080] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A high-toughness PSU plastic, characterized in that: The invention is composed of the following raw materials: 60-80 parts of PSU resin, 5-20 parts of toughening agent, 0.3-1 parts of lubricant, 0.1-0.5 parts of antioxidant, 0.1-0.5 parts of light stabilizer and 5-12 parts of compatibilizer; The preparation method of the toughening agent comprises the following steps: Step 1, weigh chitosan and cellulose, the mass ratio of chitosan to cellulose is 1:10-20, prepare an acetic acid solution with a mass percentage concentration of 1%-5%, add chitosan to the acetic acid solution with a mass percentage concentration of 1%-5%, the mass ratio of chitosan to the acetic acid solution is 1:100-400, dissolve chitosan in the acetic acid solution to form a chitosan acetic acid solution; weigh anhydrous copper sulfate, the mass ratio of anhydrous copper sulfate to cellulose is 1:40-60, soak cellulose in the chitosan acetic acid solution for 2-4 hours, then add anhydrous copper sulfate, continue soaking for 1-2 hours, after completion, filter, and dry to obtain modified cellulose; Step 2, weighing tetrabutyl titanate and acetylacetone, the mass ratio of tetrabutyl titanate to cellulose is 1:10-20, the mass ratio of acetylacetone to cellulose is 1:40-60, adding tetrabutyl titanate and acetylacetone to a mixed solution of ethanol and water, the mass ratio of ethanol to water in the mixed solution is 45-50:1, stirring for 10-15 minutes, then adding modified cellulose, continuing to stir for 1-2 hours, aging, separating solids, and heat treating the solids obtained after separation at a temperature of 280-350° C. for 30-60 minutes under a nitrogen atmosphere to obtain modified cellulose coated with titanium dioxide on the surface; Step 3, weighing a silane coupling agent, wherein the mass ratio of the silane coupling agent to cellulose is 1:8-15, and fully mixing the silane coupling agent with the modified cellulose coated with titanium dioxide on the surface to obtain a toughening agent.

2. A high-toughness PSU plastic according to claim 1, characterized in that: In the step 1, after filtering, vacuum freeze drying is performed to obtain modified cellulose.

3. The high-toughness PSU plastic according to claim 1, characterized in that: In the step 2, the temperature is controlled at 15-35° C. during the stirring process, and after aging, the solid is separated by a centrifuge.

4. The high-toughness PSU plastic according to claim 1, characterized in that: The compatibilizer is at least one of maleic anhydride, acrylic acid and polypropylene grafted maleic anhydride.

5. The high-toughness PSU plastic according to claim 1, characterized in that: The antioxidant is at least one of monophenol, bisphenol, triphenol, polyphenol, hydroquinone, thiobisphenol, naphthylamine, diphenylamine and p-phenylenediamine.

6. The high-toughness PSU plastic according to claim 1, characterized in that: The lubricant is at least one of silicone oil, white mineral oil, fatty acid amide, barium stearate, magnesium stearate, zinc stearate, pentaerythritol stearate, polyethylene wax and paraffin.

7. The high-toughness PSU plastic according to claim 1, characterized in that: The light stabilizer is at least one of alkylated monophenol, alkylated bisphenol, diphenyl phosphite, triphenyl phosphite, hydroxybenzotriazole and hindered amine.

8. A method for preparing a high-toughness PSU plastic according to any one of claims 1 to 7, characterized in that: The following steps are involved: The raw materials except the toughening agent are mixed by weight and added from the main feeding port of the twin-screw extruder, and the toughening agent is added from the side feeding port of the twin-screw extruder, melt-blended, and high-toughness PSU plastic is obtained after extrusion.

9. The high-toughness PSU plastic according to claim 8, characterized in that: The temperature range of each zone of the extruder is 270-350° C., and the main engine speed is 210-560 r / min.

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