Polyolefin composition as well as preparation method and application thereof

Abstract

The invention discloses a polyolefin composition as well as a preparation method and application thereof, and belongs to the field of high polymer materials. According to the application, a specific amount of polysulfone resin is added into the polyolefin resin, so that the skid resistance and the dimensional stability of the polyolefin resin are improved; according to the present invention, the specific amount of the surfactant type antistatic agent is added so as to improve the antistatic property and the skid resistance, and the surfactant type antistatic agent and the polysulfone resin can synergistically improve the skid resistance, such that the obtained polyolefin composition has characteristics of high surface friction coefficient, good antistatic property and good dimensional stability, the material is suitable for products such as non-slip mats, wood-plastic floors, loose tubes and the like.

Description

Technical Field

[0001] The present application relates to the field of polymer materials, and specifically relates to a polyolefin composition, a preparation method thereof, and an application thereof. Background Art

[0002] Due to its good chemical stability, corrosion resistance, electrical insulation, and processing performance, polyolefin materials have been widely used in many fields. For example, in the home or industrial fields, polyolefins are used to manufacture anti-slip mats, etc.; in the building materials field, they are used to manufacture wood-plastic floors, etc.; in the communication industry, they are used to manufacture loose tubes for optical fiber protection.

[0003] However, traditional polyolefin materials usually have a low surface friction coefficient, and in some application scenarios that require a high friction coefficient, such as anti-slip mats, wood-plastic floors, and loose tubes for optical fibers, their performance cannot meet the requirements. At the same time, polyolefin materials are prone to generating static electricity during use, which may lead to safety hazards such as fires and explosions, and will also affect the service performance and lifespan of the products. Therefore, developing a polyolefin material with a high surface friction coefficient and antistatic properties has important technical value and market potential. Summary of the Invention

[0004] Based on the defects existing in the prior art, the purpose of the present application is to provide a polyolefin composition, a preparation method thereof, and an application thereof, and the obtained polyolefin composition has both a high surface friction coefficient and good antistatic properties and dimensional stability.

[0005] To achieve the above purpose, in the first aspect, the present application provides a polyolefin composition, which comprises the following components in parts by weight:

[0006]

[0007] The inventors have found through research that adding polysulfone resin to polyolefin resin can change its surface morphology. Polysulfone resin has high strength and hardness and is distributed as rigid particles in the polyolefin matrix resin, forming an uneven shape at the contact surface with the polyolefin matrix resin, which helps to improve the surface friction coefficient of the material. At the same time, polysulfone resin has an amorphous structure and has high dimensional stability, which can reduce the linear thermal expansion coefficient of the polyolefin composition and improve its dimensional stability; adding a surfactant-type antistatic agent can not only reduce the surface resistance of the material and avoid the accumulation of charges due to long-term friction, but also the surfactant-type antistatic agent contains a polar end, which can generate a large adhesion force when the material contacts objects such as sliders, improving the surface friction coefficient of the material. In addition, the surfactant-type antistatic agent will make the polysulfone resin be discretely distributed on the material surface, which is beneficial to the formation of the surface uneven shape, so that the surface friction coefficient of the material is higher and the anti-slip property is better.

[0008] Under the combined action of the above-mentioned components in specific dosages, the polyolefin composition has both a high surface friction coefficient, good antistatic property and dimensional stability, and is suitable as a material for products such as anti-slip mats, wood-plastic floors, and loose tubes.

[0009] The polyolefin resin is 69 to 82 parts by weight, such as 69 parts by weight, 70 parts by weight, 72 parts by weight, 74 parts by weight, 76 parts by weight, 78 parts by weight, 80 parts by weight, 82 parts by weight or an interval range formed by any two of the above values.

[0010] The polysulfone resin is 10 to 30 parts by weight, such as 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight or an interval range formed by any two of the above values.

[0011] The surfactant-type antistatic agent is 5 to 15 parts by weight, such as 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight or an interval range formed by any two of the above values.

[0012] The compatibilizer is 1 to 10 parts by weight, such as 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight or an interval range formed by any two of the above values.

[0013] Preferably, the polysulfone resin includes at least one of bisphenol A polysulfone (PSU), polyphenylene sulfone (PPSU), and polyethersulfone (PESU).

[0014] Preferably, the melt flow rate of the polysulfone resin at a temperature of 380 °C and a load of 2.16 kg is 1 to 30 g / 10 min. For example, the melt flow rate of the polysulfone resin at a temperature of 380 °C and a load of 2.16 kg is 1 g / 10 min, 3 g / 10 min, 5 g / 10 min, 10 g / 10 min, 15 g / 10 min, 20 g / 10 min, 25 g / 10 min, 30 g / 10 min or an interval range formed by any two of the above values.

[0015] The melt flow rate of the polysulfone resin at a temperature of 380 °C and a load of 2.16 kg is measured according to ASTM-D1238-2010.

[0016] There is no special restriction on the selection of the surfactant type antistatic agent, and the surfactant type antistatic agent commonly used in polyolefin resin can be selected. The surfactant type antistatic agent includes at least one of a cationic antistatic agent, an anionic antistatic agent, a zwitterionic antistatic agent, and a nonionic antistatic agent. Exemplarily, the cationic antistatic agent includes at least one of a quaternary ammonium salt, a quaternary thio salt, and an alkyl amino acid salt; the anionic antistatic agent includes at least one of an alkyl sulfonate, a sulfate, a phosphate, a carboxylate, and a higher fatty acid salt (the number of carbon atoms is more than 10, such as 10, 12, 14, 16, 18 or 20, etc.); the zwitterionic antistatic agent includes at least one of a quaternary ammonium carboxylic acid inner salt and an imidazoline metal salt; the nonionic antistatic agent includes at least one of polyethylene glycol esters, polyethylene glycol ethers, polyol fatty acid esters (the polyols here refer to alcohols containing two or more hydroxyl groups, such as 2, 3 or 4 hydroxyl groups, etc.), fatty acid alkanolamides, and fatty amine ethoxy ethers.

[0017] Preferably, the compatibilizer is a polymer grafted polar monomer. The use of polymer grafted polar monomer can well improve the compatibility of polysulfone resin and polyolefin resin.

[0018] Preferably, the polymer in the polymer-grafted polar monomer includes at least one of polyethylene, polypropylene, ethylene-octene copolymer (POE), ethylene-vinyl acetate copolymer (EVA), and ethylene-ethyl acrylate copolymer (EEA). More preferably, the polymer in the polymer-grafted polar monomer includes at least one of ethylene-octene copolymer, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer. More preferably, the polymer in the polymer-grafted polar monomer includes ethylene-octene copolymer.

[0019] When the polymer in the polymer-grafted polar monomer includes at least one of ethylene-octene copolymer, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer, especially when it includes ethylene-octene copolymer, it contains an elastic end with good elasticity, so that when the material is subjected to external force, the point of application can produce corresponding deformation, wrap the slider to prevent movement, improve the surface friction coefficient of the material, and also make the material have better dimensional stability.

[0020] Preferably, the polar monomer in the polymer-grafted polar monomer includes at least one of maleic anhydride and maleic anhydride derivatives.

[0021] Preferably, the polymer-grafted polar monomer includes at least one of polyethylene-grafted maleic anhydride (PE-g-MAH), polypropylene-grafted maleic anhydride (PP-g-MAH), ethylene-octene copolymer-grafted maleic anhydride (POE-g-MAH), ethylene-vinyl acetate copolymer-grafted maleic anhydride (EVA-g-MAH), and ethylene-ethyl acrylate copolymer-grafted maleic anhydride (EEA-g-MAH).

[0022] Preferably, the grafting rate of maleic anhydride in the PE-g-MAH is 0.5 wt.% to 2.0 wt.%, for example, 0.5 wt.%, 0.8 wt.%, 1.0 wt.%, 1.2 wt.%, 1.4 wt.%, 1.6 wt.%, 1.8 wt.%, 2 wt.% or the range formed by any two of the above values.

[0023] Preferably, the grafting rate of maleic anhydride in the PP-g-MAH is 0.5 wt.% to 2.0 wt.%, for example, 0.5 wt.%, 0.8 wt.%, 1.0 wt.%, 1.2 wt.%, 1.4 wt.%, 1.6 wt.%, 1.8 wt.%, 2 wt.% or the range formed by any two of the above values.

[0024] Preferably, the grafting rate of maleic anhydride in the POE-g-MAH is 0.5 wt.% to 2.0 wt.%, for example, 0.5 wt.%, 0.8 wt.%, 1.0 wt.%, 1.2 wt.%, 1.4 wt.%, 1.6 wt.%, 1.8 wt.%, 2 wt.% or the range formed by any two of the above values.

[0025] Preferably, the grafting rate of maleic anhydride in the EVA-g-MAH is 0.5 wt.% to 2.0 wt.%, for example, 0.5 wt.%, 0.8 wt.%, 1.0 wt.%, 1.2 wt.%, 1.4 wt.%, 1.6 wt.%, 1.8 wt.%, 2 wt.% or the range formed by any two of the above values.

[0026] Preferably, the grafting rate of maleic anhydride in the EEA-g-MAH is 0.5 wt.% to 2.0 wt.%, for example, 0.5 wt.%, 0.8 wt.%, 1.0 wt.%, 1.2 wt.%, 1.4 wt.%, 1.6 wt.%, 1.8 wt.%, 2 wt.% or the range formed by any two of the above values.

[0027] The grafting rate of maleic anhydride in the PE-g-MAH, PP-g-MAH, POE-g-MAH, EVA-g-MAH and EEA-g-MAH is measured by the back titration method. Weigh 0.5 g of the grafted compatibilizer and place it in a 250 mL distillation flask. Add 80 mL of xylene and heat under reflux for 30 min until the grafted product dissolves. After cooling, add an excessive amount of 0.05 mol / L KOH-ethanol standard solution (10 mL), then heat to 80 °C and react for 2 h, and cool to below the boiling point of ethanol. Using phenolphthalein as an indicator, titrate the excessive KOH-ethanol standard solution with HCl-isopropanol standard solution while it is hot, record the amount of alkali consumed in excess V1 and the amount of acid neutralized V2, and then calculate the grafting rate of maleic anhydride through the corresponding calculation.

[0028] Preferably, the polyolefin resin includes at least one of polyethylene and polypropylene, wherein the polyethylene includes at least one of high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, and the polypropylene includes at least one of random polypropylene, homopolypropylene, and copolymer polypropylene.

[0029] Preferably, the melt flow rate of the polyolefin resin at a temperature of 230 °C and a load of 2.16 kg is 1-70 g / min, such as 1 g / min, 5 g / min, 10 g / min, 15 g / min, 20 g / min, 25 g / min, 30 g / min, 35 g / min, 40 g / min, 45 g / min, 50 g / min, 55 g / min, 60 g / min, 65 g / min, 70 g / min or the range formed by any two of the above values.

[0030] The melt flow rate of the polyolefin resin at a temperature of 230 °C and a load of 2.16 kg is measured according to ASTM-D1238-2010.

[0031] Preferably, the weight percentage of the polyolefin resin in the polyolefin composition is greater than 55%, such as 56%, 60%, 65%, 70%, 75%, 80%, 83.7% or the range formed by any two of the above values.

[0032] Preferably, the polyolefin composition further comprises the following components in parts by weight: 0.5-2 parts of other additives, and the other additives include at least one of antioxidants, light stabilizers, lubricants, and colorants.

[0033] Exemplarily, the antioxidant includes at least one of phenolic antioxidants, phosphite antioxidants, divalent sulfur antioxidants, and hindered amine antioxidants.

[0034] Exemplarily, the light stabilizer includes at least one of o-hydroxybenzophenone, benzotriazole, salicylate, and hindered amines.

[0035] Exemplarily, the lubricant includes at least one of amide lubricants, metal soap lubricants, and low-molecular-weight ester lubricants.

[0036] Exemplarily, the colorant includes at least one of carbon black, titanium dioxide, zinc sulfide, and iron oxide red.

[0037] In a second aspect, the present application provides a method for preparing the polyolefin composition, comprising the following steps:

[0038] Mix and disperse all raw materials, melt extrude, and pelletize to obtain the polyolefin composition.

[0039] Preferably, the melt extrusion is carried out in a twin-screw extruder.

[0040] Preferably, the aspect ratio of the twin-screw extruder is (36-48):1, the screw rotation speed is 150-600 r / min, and the melt extrusion temperature is 120-260 °C.

[0041] In a third aspect, the present application further provides a manufactured article formed by using the polyolefin composition.

[0042] The manufactured article can be a manufactured article in household items, electronic components, household appliances, gardening equipment, medical technology equipment, motor vehicle parts, or vehicle body parts, especially a manufactured article with a high surface friction coefficient, good antistatic property, and dimensional stability. For example, flat pads (such as anti-slip pads), wood-plastic floors, loose tube sleeves, vehicle footrests, etc.

[0043] The forming method includes at least one of injection molding, extrusion molding, or compression molding.

[0044] In a fourth aspect, the present application further provides the application of the polyolefin composition in the preparation of household items, electronic components, household appliances, gardening equipment, medical technology equipment, motor vehicle parts, or vehicle body parts.

[0045] Specifically, the above polyolefin composite material is used in the preparation of a manufactured article with a high surface friction coefficient, good antistatic property, and dimensional stability; specifically, it can be used to prepare wood-plastic floors, loose tube sleeves, vehicle footrests, various flat pads (such as anti-slip pads), etc.

[0046] Compared with the prior art, the beneficial effects of the present application are as follows:

[0047] (1) In the present application, by adding a specific amount of polysulfone resin to the polyolefin resin, its anti-slip property and dimensional stability are improved; by adding a specific amount of surfactant-type antistatic agent, its antistatic property and anti-slip property are improved, and the surfactant-type antistatic agent and the polysulfone resin can synergistically improve its anti-slip property.

[0048] (2) Under the combined action of the components in the specific amounts of the polyolefin composition of the present application, it has both a high surface friction coefficient and good antistatic and dimensional stability, and is suitable as a material for products such as flat cushions, wood-plastic floors, loose tubes, vehicle footrests, etc. Detailed implementation manners

[0049] To better illustrate the purpose, technical solutions and advantages of the present application, the present application will be further described below in conjunction with specific examples and comparative examples. The purpose is to understand the content of the present application in detail, rather than a limitation to the present application. All other examples obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present application. The experimental reagents and instruments involved in the implementation of the present application are all common ordinary reagents and instruments unless otherwise specified. In the present application, among the technical features described in an open-ended manner, it includes a closed technical solution composed of the listed features, and also includes an open technical solution containing the listed features.

[0050] Each of the following examples and comparative examples provides a polyolefin composition. The formulations of these polyolefin compositions are shown in Tables 1 and 2. Their preparation methods include the following steps: Mix and disperse all the raw materials and then feed them into a twin-screw extruder, melt extrude, and pelletize to obtain the polyolefin composition;

[0051] Among them, the ratio of the screw length to the diameter of the twin-screw extruder is 40:1, the screw rotation speed is 450 r / min, the temperature of zone 1 is 120 °C, the temperature of zones 2-4 is 210 °C, the temperature of zones 5-6 is 235 °C, the temperature of zone 7 is 225 °C, and the temperature of zone 8 is 190 °C.

[0052] The raw material information used in the above examples and comparative examples is as follows, and unless otherwise specified, they are all commercially available raw materials. In addition, the component raw materials used in each parallel experiment are all of the same kind:

[0053] Polyolefin resin 1: Random PP, with a melt flow rate of 2 g / 10 min at a temperature of 230 °C and a load of 2.16 kg, model SM198, manufacturer Lotte Chemical;

[0054] Polyolefin resin 2: Homopolymer PP, with a melt flow rate of 1.8 g / 10 min at a temperature of 230 °C and a load of 2.16 kg, model S30S, manufacturer Zhenhai Refining & Chemical;

[0055] Polyolefin resin 3: Copolymer PP, with a melt flow rate of 60 g / 10 min at a temperature of 230 °C and a load of 2.16 kg, model EP648U, manufacturer CNOOC and Shell Petrochemicals;

[0056] Polyolefin resin 4: LLDPE, melt flow rate at 230 °C and load of 2.16 kg is 2.0 g / 10 min, model DFDA-7042, manufacturer Daqing Petrochemical;

[0057] Polyolefin resin 5: LDPE, melt flow rate at 230 °C and load of 2.16 kg is 2.4 g / 10 min, model 2426H, manufacturer Lanzhou Petrochemical;

[0058] Polyolefin resin 6: HDPE, melt flow rate at 230 °C and load of 2.16 kg is 8 g / 10 min, model DMDA8008, manufacturer Daqing Petrochemical;

[0059] Polysulfone resin 1: PSU, melt flow rate at 380 °C and load of 2.16 kg is 3 g / 10 min, model P-3500NT LCD, manufacturer Solvay;

[0060] Polysulfone resin 2: PPSU, melt flow rate at 380 °C and load of 2.16 kg is 16 g / 10 min, model R 7300, manufacturer Solvay;

[0061] Polysulfone resin 3: PESU, melt flow rate at 380 °C and load of 2.16 kg is 20 g / 10 min, model E2010, manufacturer BASF;

[0062] Antistatic agent 1: Dioctadecyl dimethyl ammonium chloride, model D1821, manufacturer Solvay;

[0063] Antistatic agent 2: Sodium dodecylbenzenesulfonate, model LAS-90, manufacturer Suyuan Chemical Industry;

[0064] Antistatic agent 3: Dodecyl imidazoline, manufacturer Sandy Fine Chemical Research Institute;

[0065] Antistatic agent 4: Polyethylene glycol fatty acid ester, model PEG600MO, manufacturer Renda Chemical Company;

[0066] Compatibilizer 1: POE-g-MAH, maleic anhydride grafting rate 1.0 wt.%, model PC-28, manufacturer Nanhai Baichen High Polymer Materials;

[0067] Compatibilizer 2: EVA-g-MAH, maleic anhydride grafting rate 1.5 wt.%, model C250, manufacturer Dow Chemical Company, USA;

[0068] Compatibilizer 3: EEA-g-MAH, maleic anhydride grafting rate 1.3 wt.%, model LOTADER 4700, manufacturer SK, South Korea;

[0069] Compatibilizer 4: PP-g-MAH, maleic anhydride grafting rate 1.5 wt.%, model 18729, manufacturer Arkema;

[0070] Compatibilizer 5: PE-g-MAH, maleic anhydride grafting rate 1.0 wt.%, model AMPLIFY TY 1352, manufacturer Dow Chemical;

[0071] Antioxidant: Antioxidant 1010, commercially available.

[0072] The following performance tests were carried out on the polyolefin compositions of the above examples and comparative examples:

[0073] (1) Surface friction coefficient: According to the ISO 8295-1995 standard, the surface friction coefficient of the material was tested.

[0074] (2) Surface resistance: A square plastic plate with a length of 100 * width of 100 * thickness of 2 mm was injection molded. According to the GB / T31838.3-2019 standard, a voltage of DC250V was applied to test the surface resistance of the material.

[0075] (3) Linear thermal expansion coefficient test: An 80 mm * 10 mm * 4 mm spline was injection molded, and then a 10 mm * 10 mm * 4 mm sample was cut. Referring to ISO 11359-2-2021, the linear expansion coefficient (CLTE) in the range of -40 to 60 °C was tested.

[0076] The test results are shown in Table 3.

[0077] Table 1

[0078]

[0079] Table 2

[0080]

[0081]

[0082] Table 3

[0083]

[0084]

[0085] From the above data, it can be seen that the polyolefin compositions of the examples of this application have both a high surface friction coefficient and good antistatic properties and dimensional stability. For example, the surface friction coefficient is above 0.46, the surface resistance is below 1.8×10 13 Ω, and the linear thermal expansion coefficient is below 128 μm / (m·°C).

[0086] Compared with Example 1, in Comparative Example 1, the polysulfone resin was not added, and the resulting polyolefin composition had a low surface friction coefficient and poor dimensional stability; in Comparative Example 2, the antistatic agent was not added, and the resulting polyolefin composition had a low surface friction coefficient and poor antistatic property; in Comparative Examples 3 to 5, the content of the polysulfone resin was excessive. When the polyolefin resin was mixed with the polysulfone resin, a relatively high processing temperature (>300 °C) was required. The composite material gradually shifted to the polysulfone type, and the components of the polyolefin and the antistatic agent would degrade and fail, and the surface friction coefficient and the surface resistance would decrease significantly.

[0087] Comparing Examples 1, 9 to 12, it can be seen that compared with PP-g-MAH and PE-g-MAH, POE-g-MAH, EVA-g-MAH, and EEA-g-MAH make the surface friction coefficient of the material higher, the anti-slip property better, and at the same time, the linear thermal expansion coefficient is lower and the dimensional stability is better.

[0088] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application rather than to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present application can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A polyolefin composition, characterized in that, Comprising the following components in parts by weight:

2. The polyolefin composition according to claim 1, wherein The polysulfone resin includes at least one of bisphenol A polysulfone, polyphenylene sulfone, and polyethersulfone.

3. The polyolefin composition according to claim 1, characterized in that, The melt flow rate of the polysulfone resin at a temperature of 380 °C and a load of 2.16 kg is 1 - 30 g / 10 min.

4. The polyolefin composition according to claim 1, characterized in that, The surfactant-type antistatic agent includes at least one of cationic antistatic agents, anionic antistatic agents, zwitterionic antistatic agents, and nonionic antistatic agents.

5. The polyolefin composition according to claim 1, characterized in that, The surfactant-type antistatic agent includes at least one of quaternary ammonium salts, quaternary sulfonium salts, alkyl amino acid salts, alkyl sulfonates, sulfates, phosphates, carboxylates, higher fatty acid salts, quaternary ammonium carboxylate inner salts, imidazoline metal salts, polyethylene glycol esters, polyethylene glycol ethers, polyol fatty acid esters, fatty acid alkanolamides, and fatty amine ethoxyethers.

6. The polyolefin composition according to claim 1, characterized in that, The compatibilizer is a polymer grafted with a polar monomer.

7. The polyolefin composition according to claim 6, wherein The polymer in the polymer grafted with a polar monomer includes at least one of polyethylene, polypropylene, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer. Preferably, the polymer in the polymer grafted with a polar monomer includes at least one of ethylene-octene copolymer, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer. More preferably, the polymer in the polymer grafted with a polar monomer includes ethylene-octene copolymer; and / or The polar monomer in the polymer grafted with a polar monomer includes at least one of maleic anhydride and maleic anhydride derivatives.

8. The polyolefin composition according to claim 1, characterized in that, Meeting at least one of the following conditions: S1. The polyolefin resin includes at least one of polyethylene and polypropylene, where polyethylene includes at least one of high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, and polypropylene includes at least one of atactic polypropylene, homopolypropylene, and copolymerized polypropylene; S2. The melt flow rate of the polyolefin resin at a temperature of 230 °C and a load of 2.16 kg is 1 - 60 g / min; S3. The polyolefin composition further comprises the following components in parts by weight: 0.5 - 2 parts of other additives, and the other additives include at least one of antioxidants, light stabilizers, and lubricants.

9. The preparation method of the polyolefin composition according to any one of claims 1 to 8, characterized in that, Mix and disperse all raw materials, melt extrude, and pelletize to obtain the polyolefin composition.

10. A workpiece, characterized in that, It is formed by using the polyolefin composition as described in any one of claims 1 - 8.

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