Wear-resistant high-toughness polypropylene material and preparation method thereof

Abstract

The application relates to the technical field of materials, and discloses a wear-resistant high-toughness polypropylene material and a preparation method thereof. The polypropylene material is prepared through a mixing and melt extrusion process by taking polypropylene as a base material and taking a compatibilizer, an ethylene-octene block copolymer and a mullite functional agent as auxiliary materials. The mullite functional agent is prepared by connecting a branched macromolecular polymer to the surface of the mullite through an ester bond. The presence of the macromolecular polymer can improve the compatibility between the mullite and the polypropylene matrix, is beneficial to the efficient exertion of the reinforcing effect of the mullite, improves the stress deformation resistance of the material, and helps the material to have high strength and high toughness. In addition, the macromolecular polymer can be crosslinked with the polypropylene molecular chain, helps to improve the structural density of the material, makes the material have higher hardness, and further reduces the width of the wear mark of the material on the film surface, and improves the wear resistance of the material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of materials, in particular to a wear-resistant high-toughness polypropylene material and a preparation method thereof. BACKGROUND

[0002] Polypropylene (PP for short) is the second largest general synthetic resin in the world in terms of production, and its density is only 0.90-0.91 g / cm 3 , which is one of the lightest varieties of plastics. This characteristic makes it the first choice for lightweight daily use. For example, plastic pots, storage boxes and other products made of polypropylene have a weight reduction of more than 30% compared with traditional materials while maintaining sufficient strength, significantly improving user experience. It is the light weight, heat resistance, chemical corrosion resistance and other characteristics that make polypropylene an irreplaceable advantage in the field of daily use plastic products.

[0003] However, as the application continues to deepen, the poor wear resistance and toughness of polypropylene gradually expose the defects, which has a great negative impact on the service life of polypropylene plastic products. In the prior art, the wear resistance and other comprehensive properties of polypropylene are generally improved by adding inorganic reinforcing agents. However, there is a natural interface incompatibility problem between the inorganic reinforcing agent and the polypropylene matrix. Adding a small amount will result in ineffective improvement, and adding a large amount will cause agglomeration, which has a negative impact on the performance of the material. Based on this, the present application provides a polypropylene composite material with good wear resistance, high toughness and other comprehensive properties, which can be used to manufacture daily use plastic products. SUMMARY

[0004] In order to solve the problems mentioned in the background art, the purpose of the present application is to provide a wear-resistant high-toughness polypropylene material and a preparation method thereof.

[0005] The purpose of the present application can be achieved by the following technical solutions:

[0006] A wear-resistant high-toughness polypropylene material, according to weight parts, comprises the following raw materials:

[0007] Polypropylene 65-85 parts, compatibilizer 5-15 parts, ethylene-octene block copolymer 5-10 parts, mullite functional agent 2-6.5 parts, lubricant 0.5-1.5 parts, antioxidant 0.5-1 part, initiator 0.1-0.4 part.

[0008] As a further scheme of the present application, the compatibilizer is maleic anhydride grafted polyethylene or maleic anhydride grafted polypropylene.

[0009] As a further scheme of the present application, the mullite functional agent is prepared by the following method:

[0010] Step one, the epoxy silane coupling agent is added to the sulfuric acid solution, the mixture is stirred and mixed uniformly, then the temperature is raised to 90-100 DEG C, and the temperature is kept for 30-60 min, then the temperature is reduced to 40-50 DEG C, and the mullite is continuously added, and the temperature is controlled to 80-90 DEG C after ultrasonic dispersion, and the stirring is continued for 3-6 h, and the temperature is reduced to discharge, and the activated mullite is obtained after post-processing.

[0011] Step two, the activated mullite is dispersed in N,N-dimethylformamide, and nitrogen is introduced for protection, then the triphenylene-2,6,10-tricarboxylic acid, catalyst and condensing agent are added to the formed dispersion, the mechanical stirring is uniform after addition, then the temperature is raised to 100-120 DEG C, and the stirring is kept for 4-8 h, then the allyl pentaerythritol is continuously added, and the stirring is continuously kept for 12-24 h after addition, the heating is stopped, the solid material is separated by centrifugation, and the mullite functional agent is obtained after washing and vacuum drying treatment.

[0012] As a further scheme of the application, in step one, the epoxy silane coupling agent is selected from 3-glycidyloxypropyltrimethylsilane or 3-glycidyloxypropyltriethylsilane.

[0013] As a further scheme of the application, in step one, the pH of the sulfuric acid solution is 2-3.

[0014] As a further scheme of the application, in step two, the catalyst is any one of 4-dimethylaminopyridine, N-hydroxysuccinimide or 1-hydroxybenzotriazole.

[0015] As a further scheme of the application, in step two, the condensing agent is dicyclohexyl carbodiimide or 1-ethyl-(3-dimethylaminopropyl) carbonyldiimidazole hydrochloride.

[0016] As a further scheme of the application, in step two, the mass ratio of the activated mullite, triphenylene-2,6,10-tricarboxylic acid and allyl pentaerythritol is 1:1.5-2.5:0.8-1.5.

[0017] By using the above technical scheme, the epoxy substituent in the structure of the epoxy silane coupling agent is first opened by sulfuric acid to form two equivalent hydroxyl substituents, then the surface of the mullite is modified to form a large number of active hydroxyl substituents on the surface of the mullite to obtain the activated mullite, then the active hydroxyl substituent is used as an initiation site, and the triphenylene-2,6,10-tricarboxylic acid and the allyl pentaerythritol are in-situ branched polymerized on the surface of the mullite under the combined action of the catalyst and the condensing agent under high temperature conditions, so that the branched macromolecule connected by ester bonds is modified on the surface of the mullite, that is, the mullite functional agent.

[0018] As a further scheme of the present application, the lubricant is polyethylene wax or liquid paraffin; the antioxidant is any one of hindered phenol antioxidant or phosphite antioxidant; and the initiator is benzoyl peroxide or dicumyl peroxide.

[0019] A preparation method of a wear-resistant high-toughness polypropylene material, comprising the following steps:

[0020] In the first step, the prepared raw materials are weighed and added into a high-speed mixer, the rotation speed is set to 1000-2000 r / min, the temperature is set to 80-100 DEG C, and the mixture is mechanically stirred for 20-40 min, then the temperature is lowered and the mixture is discharged to form a premix;

[0021] In the second step, the premix is fed into a double-screw extruder through a feeding port, the temperature is controlled to be 180-230 DEG C, and the screw rotation speed is controlled to be 300-400 r / min, and then the melting extrusion is performed.

[0022] The present application has the following advantages:

[0023] In the present application, the branched macromolecular polymer connected by ester bond is modified on the surface of mullite to obtain a mullite functional agent, which is used as an additive, and the branched structure of the macromolecular polymer contains unsaturated alkenyl substituent groups, which can interact with the polypropylene molecular chain under the action of initiator during the melting extrusion process, and then form a crosslinked network between each other, thereby greatly improving the compatibility between the mullite and the polypropylene matrix, and the mullite can act as a rigid support point in the form of a crosslinked core, which can not only bear and transfer the load, but also improve the stress deformation resistance of the material, and produce toughening and strengthening effects.

[0024] Of course, it is not necessary for any product implementing the present application to achieve all the advantages mentioned above. DETAILED DESCRIPTION

[0025] The technical solutions of the present application will be described clearly and completely below with reference to the embodiments, and obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0026] Embodiment 1

[0027] A kind of wear-resistant high toughness polypropylene material, according to weight fraction, including following raw materials:

[0028] Polypropylene 65 parts, maleic anhydride grafted polyethylene 5 parts, ethylene-octene block copolymer 5 parts, mullite functional agent 2 parts, polyethylene wax 0.5 parts, antioxidant 1010 0.5 parts, benzoyl peroxide 0.1 parts.

[0029] The preparation method of the polypropylene material includes the following steps:

[0030] First step, the each raw material according to weight fraction is called and added to high-speed mixer, sets the speed to 1000r / min, temperature is 80 DEG C, after mechanical stirring mixing 40 min, temperature is lowered and is discharged, forms premix;

[0031] Second step, premix is fed into double-screw extruder through feeding port, temperature is controlled to be 220 DEG C, screw rotation speed is 300 / min, melt extrusion is carried out, namely.

[0032] Example 2

[0033] A kind of wear-resistant high toughness polypropylene material, according to weight fraction, including following raw materials:

[0034] Polypropylene 70 parts, maleic anhydride grafted polyethylene 10 parts, ethylene-octene block copolymer 6 parts, mullite functional agent 6 parts, polyethylene wax 1 part, antioxidant 1010 0.6 parts, benzoyl peroxide 0.3 parts.

[0035] The preparation method of the polypropylene material includes the following steps:

[0036] First step, the each raw material according to weight fraction is called and added to high-speed mixer, sets the speed to 1500r / min, temperature is 100 DEG C, after mechanical stirring mixing 30 min, temperature is lowered and is discharged, forms premix;

[0037] Second step, premix is fed into double-screw extruder through feeding port, temperature is controlled to be 220 DEG C, screw rotation speed is 350r / min, melt extrusion is carried out, namely.

[0038] Example 3

[0039] A kind of wear-resistant high toughness polypropylene material, according to weight fraction, including following raw materials:

[0040] Polypropylene 85 parts, maleic anhydride grafted polyethylene 15 parts, ethylene-octene block copolymer 10 parts, mullite functional agent 6.5 parts, polyethylene wax 1.5 parts, antioxidant 1010 1 part, benzoyl peroxide 0.4 parts.

[0041] The preparation method of the polypropylene material comprises the following steps:

[0042] In the first step, the prepared raw materials are weighed by weight fraction and added to a high-speed mixer, the rotating speed is set to 2000 r / min, the temperature is set to 100 DEG C, and after mechanical stirring and mixing for 20 min, the temperature is lowered and the material is discharged to form a premix;

[0043] In the second step, the premix is fed into a double-screw extruder through a feeding port, the temperature is controlled to be 220 DEG C, and the screw rotating speed is 400 r / min, and then the melting extrusion is performed.

[0044] The mullite functional agent in the above examples is prepared by the following method:

[0045] In step one, 1 g of 3-glycidyloxypropyltriethylsilane is added to 2 mL of sulfuric acid solution with pH of 2, and stirred and mixed uniformly, then the temperature is raised to 100 DEG C, and the temperature is maintained for 40 min, then the temperature is lowered to 40 DEG C, and 1.5 h of mullite is continuously added, and after ultrasonic dispersion, the temperature is controlled to be 90 DEG C, and the stirring is continued for 4 h, and then the temperature is lowered and the material is discharged, and after post-treatment, the activated mullite is prepared;

[0046] In step two, 1.2 g of the activated mullite is dispersed in N,N-dimethylformamide, and nitrogen is introduced for protection, then 2.5 g of triphenylene-2,6,10-tricarboxylic acid, 0.1 g of 4-dimethylamino pyridine and 0.3 g of dicyclohexyl carbodiimide are added to the formed dispersion, and after the addition is completed, the mechanical stirring is uniform, then the temperature is raised to 120 DEG C, and the temperature is maintained and stirred for 6 h, then 1.6 g of allyl pentaerythritol is continuously added, and after the addition is completed, the temperature is maintained and stirred for 18 h, then the heating is stopped, the solid material is separated by centrifugation, and after washing and vacuum drying treatment, the mullite functional agent is prepared.

[0047] The ester group content of the mullite functional agent is titrated by using the soap back titration method, and the result shows that the ester group content is 4.697 mmol / g.

[0048] Comparative Example 1

[0049] A kind of wear-resistant high-toughness polypropylene material, according to weight fraction, comprising the following raw materials:

[0050] Polypropylene 70 parts, maleic anhydride grafted polyethylene 10 parts, ethylene-octene block copolymer 6 parts, mullite 6 parts, polyethylene wax 1 part, antioxidant 1010 0.6 parts, benzoyl peroxide 0.3 parts.

[0051] The preparation method of the polypropylene material comprises the following steps:

[0052] The first step, the various raw materials are weighed according to the weight fraction, and are added to a high-speed mixer, the rotation speed is set to 1500r / min, the temperature is 100℃, and mechanical stirring is mixed for 30min, then the temperature is lowered and the material is discharged, forming a premix;

[0053] The second step, the premix is fed into a double-screw extruder through a feeding port, the temperature is controlled to be 220℃, and the screw rotation speed is 350r / min, and then the material is melt-extruded.

[0054] Example 2

[0055] A kind of wear-resistant high-toughness polypropylene material, according to weight fraction, includes the following raw materials:

[0056] Polypropylene 70 parts, maleic anhydride grafted polyethylene 10 parts, ethylene-octene block copolymer 6 parts, polyethylene wax 1 part, antioxidant 1010 0.6 parts, and benzoyl peroxide 0.3 parts.

[0057] The preparation method of the polypropylene material includes the following steps:

[0058] The first step, the various raw materials are weighed according to the weight fraction, and are added to a high-speed mixer, the rotation speed is set to 1500r / min, the temperature is 100℃, and mechanical stirring is mixed for 30min, then the temperature is lowered and the material is discharged, forming a premix;

[0059] The second step, the premix is fed into a double-screw extruder through a feeding port, the temperature is controlled to be 220℃, and the screw rotation speed is 350r / min, and then the material is melt-extruded.

[0060] Performance test

[0061] The polypropylene materials in the examples and comparative examples are made into various test bars, and various performance tests are performed, and the results are recorded in the following table:

[0062] Wear amount / g Tensile strength / MPa Elongation at break / % Example 1 0.05 32.6 458.9 Example 2 0.03 33.1 459.7 Example 3 0.04 33.0 459.4 Comparative Example 1 0.11 29.9 381.2 Comparative Example 2 0.12 23.8 338.5

[0063] The test method for the abrasion amount is as follows: according to the standard ASTM D3884, a sample of 10cm×10cm×8mm is placed on a grinding rotary test table, the rotation speed is set to 60r / min, the test sample is rubbed, the load is 1000g, the grinding wheel is selected as SC10, and the abrasion amount of the test sample is tested after 5000 revolutions.

[0064] According to GB / T 1040.1-2006, the tensile properties of the test sample are tested.

[0065] According to the test result analysis, the wear resistance and toughness of the polypropylene material prepared by using the unmodified mullite as the additive alone are poor, because the unmodified mullite has compatibility problems with the polypropylene matrix, cannot efficiently play its own performance, is difficult to play the reinforcing and toughening effect, and also cannot utilize the crosslinking network and rigidity brought by the macromolecular polymer, resulting in that the wear resistance of the material is also poor.

[0066] The principles and implementations of the present application are described herein with specific examples. The above examples are only used to help understand the method of the present application and its core idea, including the best mode, and also enable any person skilled in the art to practice the present application, including manufacturing and using any device or system, and implementing any combined method. It should be noted that, for those skilled in the art, some improvements and modifications can be made to the present application without departing from the principles of the present application, and these improvements and modifications also fall within the protection scope of the claims of the present application. The scope of the patent protection of the present application is defined by the claims, and can include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements similar to the literal expression of the claims, or if they include equivalent structural elements that are not substantially different from the literal expression of the claims, then these other embodiments should also be included in the scope of the claims.

[0067] The above examples are only used to illustrate the technical solutions of the present application, rather than limit them; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for some technical features thereof; and these modifications or replacements will not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A wear resistant, high toughness polypropylene material, characterized in that, According to the weight parts, the following raw materials are included: Polypropylene 65-85 parts, compatibilizer 5-15 parts, ethylene-octene block copolymer 5-10 parts, mullite functional agent 2-6.5 parts, lubricant 0.5-1.5 parts, antioxidant 0.5-1 part, initiator 0.1-0.4 parts; The mullite functional agent is prepared by the following method: Step one, add the epoxy silane coupling agent to the sulfuric acid solution, stir and mix uniformly, then raise the temperature to 90-100℃, keep warm for 30-60min, then reduce the temperature to 40-50℃, continue to add mullite, ultrasonic dispersion is uniform, then control the temperature at 80-90℃, continue to stir for 3-6h, cool down and discharge, after treatment, the activated mullite is obtained; Step two, disperse the activated mullite in N,N-dimethylformamide, protect with nitrogen, then add triphenylene-2,6,10-tricarboxylic acid, catalyst and condensing agent to the formed dispersion, after adding, mechanically stir uniformly, then raise the temperature to 100-120℃, keep warm and stir for 4-8h, then continue to add allyl pentaerythritol, after adding, continue to keep warm and stir for 12-24h, stop heating, centrifugal separation of solid material, after washing, vacuum drying treatment, the mullite functional agent is obtained; The epoxy silane coupling agent is selected from 3-glycidyloxypropyltrimethylsilane or 3-glycidyloxypropyltriethylsilane; The pH of the sulfuric acid solution is 2-3; The catalyst is any one of 4-dimethylaminopyridine, N-hydroxysuccinimide or 1-hydroxybenzotriazole; The condensing agent is dicyclohexyl carbodiimide or 1-ethyl-(3-dimethylaminopropyl) carbonyl diimide hydrochloride.

2. The wear resistant, high toughness polypropylene material of claim 1, wherein, The compatibilizer is maleic anhydride grafted polyethylene or maleic anhydride grafted polypropylene.

3. The wear resistant high toughness polypropylene material according to claim 1, characterized in that, In step two, the mass ratio of the activated mullite, triphenylene-2,6,10-tricarboxylic acid and allyl pentaerythritol is 1:1.5-2.5:0.8-1.

5.

4. The wear resistant, high toughness polypropylene material of claim 1, wherein, The lubricant is polyethylene wax or liquid paraffin; the antioxidant is any one of hindered phenolic antioxidant or phosphite antioxidant; the initiator is benzoyl peroxide or dicumyl peroxide.

5. A process for the production of the wear resistant, high toughness polypropylene material according to claim 1, characterized in that The following steps are included: First step, add the weighed raw materials to the high-speed mixer, set the rotation speed to 1000-2000r / min and the temperature to 80-100℃, mechanically stir and mix for 20-40min, then cool down and discharge, forming the premix; Second step, feed the premix into the twin-screw extruder through the feeding port for melt extrusion.