Wear-resistant and impact-resistant PP (polypropylene) composite material and preparation process thereof

Abstract

The invention relates to the technical field of polypropylene, and discloses a wear-resistant and impact-resistant PP composite material and a preparation process thereof.The preparation method comprises the steps that polybutadiene and 4-mercapto ethylene dibenzoate react to obtain ethylene dibenzoate polybutadiene, then the ethylene dibenzoate polybutadiene is mixed with polypropylene resin, polyethylene glycol terephthalate and the like, and the wear-resistant and impact-resistant PP composite material is obtained. And carrying out melt blending in a double-screw extruder, extruding and pelletizing to obtain the wear-resistant and impact-resistant PP composite material. Ethylene dibenzoate polybutadiene can play a role in compatibilizing PET and PP, the processability of the PP composite material is improved, the interfacial properties of PET and PP are excellent, the mechanical properties of the composite material are improved, and the composite material has higher impact strength and bending strength, and is low in abrasion loss and good in wear resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of polypropylene, in particular to a wear-resistant and impact-resistant PP composite material and a preparation process thereof. Background Art

[0002] Polypropylene (PP) is a common thermoplastic polymer. To improve its toughness, impact strength, and wear resistance, it is often blended with high-performance resins to create alloys with enhanced mechanical properties. Polyethylene terephthalate (PET) boasts high strength, excellent wear resistance, and high-temperature resistance, making it widely used in plastics such as polypropylene, nylon, and polycarbonate. However, PP and PET are thermodynamically incompatible, which can affect the processability and mechanical properties of the composite material. Therefore, a compatibilizer is required to improve the compatibility of PP and PET.

[0003] Patent application with publication number CN116814001A discloses that a compatibilizer prepared using POE, PP, maleic anhydride and other first grafting monomers and styrene and other second monomers as raw materials improves the impact performance and compatibility of PP-PET alloy. However, the impact strength of the PP-PET alloy material disclosed in the patent application is low, and the flexural strength and wear resistance of the PP-PET material are not improved, resulting in poor mechanical properties. Summary of the Invention

[0004] (1) Technical problems solved by the present invention: In view of the deficiencies of the prior art, the present invention solves the problems of poor compatibility, wear resistance and impact resistance of PET / PP composite materials.

[0005] (2) The technical solution of the present invention: a wear-resistant and impact-resistant PP composite material and a preparation process thereof, wherein the PP composite material comprises a polypropylene resin, polyethylene terephthalate, polyethylene dibenzoate-based polybutadiene, and an antioxidant in a ratio of (60-90) g: (10-40) g: (3-10) g: (0.2-0.4) g.

[0006] The preparation process of PP composite materials is:

[0007] (1) Toluene and polybutadiene are added to a reaction flask, heated and stirred, and then cooled. 4-Mercaptodibenzoate and benzoin dimethyl ether are added. The reaction flask is irradiated under an ultraviolet lamp for reaction. A large amount of precipitate is precipitated by vacuum distillation. The product is filtered, washed with ethanol, and dried to obtain dibenzoate-based polybutadiene.

[0008] (2) Polypropylene resin, polyethylene terephthalate, polyethylene dibenzoate-based polybutadiene, and an antioxidant are mixed, melt-blended in a twin-screw extruder, and extruded and pelletized to obtain a wear-resistant and impact-resistant PP composite material.

[0009] Preferably, the ratio of polybutadiene, 4-mercaptobenzene sulfonic acid ethylene ester and benzo pinacol in (1) is 100g:(20-50)g:(0.6-1)g.

[0010] Preferably, the power of the ultraviolet lamp in (1) is 30-80W, and the wavelength range is 320-380nm.

[0011] Preferably, the irradiation reaction time in (1) is 1-2h.

[0012] Preferably, the temperature of each section of the twin-screw extruder in (2) is 180-270℃, and the screw rotation speed is 30-50r / min.

[0013] Preferably, the preparation process of 4-mercaptobenzene sulfonic acid ethylene ester comprises: adding toluene, 4-mercaptobenzoic acid, 2-hydroxyethyl benzoate and p-toluenesulfonic acid with a ratio of 100g:(220-340)g:(14-20)g into a reaction bottle equipped with a condenser reflux tube, heating to 80-90℃, reacting for 7-12h, washing the crude product with petroleum ether after rotary evaporation, and then adding to ethyl acetate for recrystallization to obtain 4-mercaptobenzene sulfonic acid ethylene ester.

[0014] (Three) Beneficial technical effects: The thiol group of 4-mercaptobenzene sulfonic acid ethylene ester and the alkenyl group of polybutadiene are subjected to addition reaction to obtain benzene sulfonic acid ethylene ester-based polybutadiene, which is then blended with polypropylene PP, polyethylene terephthalate PET and the like to obtain wear-resistant and impact-resistant PP composite material. The polybutadiene main chain of the benzene sulfonic acid ethylene ester-based polybutadiene is similar to the molecular chain of polypropylene, the solubility parameter difference is small, the compatibility is excellent, and the benzene sulfonic acid ethylene ester-based structure similar to PET is introduced into the polybutadiene side chain, so that the benzene sulfonic acid ethylene ester-based polybutadiene can play a role in compatibilizing PET and PP, improving the processability of the PP composite material, the interface performance of the two is excellent, the mechanical properties of the composite material are improved, the impact strength and the bending strength are higher, the wear amount is low, and the wear resistance is good. DETAILED DESCRIPTION

[0015] In order to make the purpose, technical scheme and advantages of the present application more clear, the embodiments of the present application will be described in detail below. It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other arbitrarily without conflict.

[0016] Example 1:

[0017] (1) Into a reaction flask equipped with a condenser reflux tube, 100 mL of toluene, 4 g of 4-mercaptobenzoic acid (CAS No. 1074-36-8), 13.6 g of 2-hydroxyethyl benzoate (CAS No. 94-33-7), 0.56 g of p-toluenesulfonic acid were added, heated to 90°C, reacted for 8 h, and after rotary evaporation, the crude product was washed with petroleum ether and then recrystallized in ethyl acetate to obtain 4-mercaptodiethyl benzoate. The reaction formula is as follows:

[0018]

[0019] (2) Into a reaction flask, 0.7 L of toluene, 50 g of polybutadiene were added, heated and stirred, then cooled, 10 g of 4-mercaptodiethyl benzoate, 0.3 g of benzoine dimethyl ether were added, and the reaction flask was irradiated under a UV lamp with a power of 80 W for 1 h, a large amount of precipitate was precipitated by distillation under reduced pressure, and the product was washed with ethanol after filtration and dried to obtain diethyl benzoate-based polybutadiene.

[0020] (3) 9 kg of polypropylene resin, 1 kg of polyethylene terephthalate, 0.3 kg of diethyl benzoate-based polybutadiene, 27 g of antioxidant 1076 were mixed and melt blended in a double screw extruder, the temperature of each section was 180°C, 230°C, 250°C, 265°C, 270°C, and the screw rotation speed was 50 r / min; extrusion and granulation were carried out to obtain a wear-resistant and impact-resistant PP composite material.

[0021] Example 2:

[0022] (1) Into a reaction flask equipped with a condenser reflux tube, 80 mL of toluene, 4 g of 4-mercaptobenzoic acid, 8.8 g of 2-hydroxyethyl benzoate, 0.8 g of p-toluenesulfonic acid were added, heated to 80°C, reacted for 12 h, and after rotary evaporation, the crude product was washed with petroleum ether and then recrystallized in ethyl acetate to obtain 4-mercaptodiethyl benzoate.

[0023] (2) Into a reaction flask, 1 L of toluene, 50 g of polybutadiene were added, heated and stirred, then cooled, 18 g of 4-mercaptodiethyl benzoate, 0.4 g of benzoine dimethyl ether were added, and the reaction flask was irradiated under a UV lamp with a power of 30 W for 2 h, a large amount of precipitate was precipitated by distillation under reduced pressure, and the product was washed with ethanol after filtration and dried to obtain diethyl benzoate-based polybutadiene.

[0024] (3) 7.5 kg of polypropylene resin, 2.5 kg of polyethylene terephthalate, 0.6 kg of diethyl benzoate-based polybutadiene, 40 g of antioxidant 1076 were mixed and melt blended in a double screw extruder, the temperature of each section was 180°C, 230°C, 250°C, 265°C, 270°C, and the screw rotation speed was 50 r / min; extrusion and granulation were carried out to obtain a wear-resistant and impact-resistant PP composite material.

[0025] Example 3:

[0026] (1) To a reaction flask equipped with a reflux tube, 100 mL of toluene, 4 g of 4-mercaptobenzoic acid, 11.2 g of 2-hydroxyethyl benzoate, and 0.7 g of p-toluenesulfonic acid were added, heated to 90° C., and reacted for 7 h. After rotary evaporation, the crude product was washed with petroleum ether and then added to ethyl acetate for recrystallization to obtain 4-mercaptodibenzoic acid ethylene glycol.

[0027] (2) Add 1 L of toluene and 50 g of polybutadiene to a reaction flask, heat and stir, then cool, add 25 g of 4-mercaptodibenzoate and 0.5 g of benzoin dimethyl ether, irradiate the reaction flask under an 80 W ultraviolet lamp for 1.5 h, and precipitate a large amount of precipitate by vacuum distillation. After filtering, wash the product with ethanol and dry it to obtain dibenzoate-based polybutadiene.

[0028] (3) 6 kg of polypropylene resin, 4 kg of polyethylene terephthalate, 1 kg of dibenzoate-based polybutadiene, and 20 g of antioxidant 1076 were mixed and melt-blended in a twin-screw extruder with the temperatures of each section being 180°C, 230°C, 250°C, 265°C, and 270°C and the screw speed being 30 r / min; extrusion and pelletizing were performed to obtain a wear-resistant and impact-resistant PP composite material.

[0029] Comparative Example 1

[0030] (1) 9 kg of polypropylene resin, 1 kg of polyethylene terephthalate, and 27 g of antioxidant 1076 were mixed and melt-blended in a twin-screw extruder at temperatures of 180°C, 230°C, 250°C, 265°C, and 270°C, with a screw speed of 50 r / min; the mixture was extruded and pelletized to obtain a PP composite material.

[0031] Comparative Example 2

[0032] (1) 9 kg of polypropylene resin, 1 kg of polyethylene terephthalate, 0.3 kg of polybutadiene, and 27 g of antioxidant 1076 were mixed and melt-blended in a twin-screw extruder at temperatures of 180°C, 230°C, 250°C, 265°C, and 270°C, with a screw speed of 50 r / min; the mixture was extruded and pelletized to obtain a PP composite material.

[0033] Comparative Example 3

[0034] (1) Add 0.7 L of toluene and 50 g of polybutadiene to a reaction flask, heat and stir, then cool, add 10 g of ethyl mercaptoacetate (CAS No. 623-51-8) and 0.3 g of dimethyl benzoate, irradiate the reaction flask under an 80 W ultraviolet lamp for 1 h, and distill under reduced pressure to precipitate a large amount of precipitate. After filtering, wash the product with ethanol, and dry it to obtain ethyl mercaptoacetate-based polybutadiene.

[0035] (2) 9 kg of polypropylene resin, 1 kg of polyethylene terephthalate, 0.3 kg of mercaptoacetic acid ethyl-based polybutadiene, and 27 g of antioxidant 1076 were mixed and melt blended in a twin-screw extruder, with the temperature of each section being 180°C, 230°C, 250°C, 265°C, and 270°C, and the screw rotation speed being 50 r / min; extrusion and granulation were performed to obtain a PP composite material.

[0036] Comparative Example 4

[0037] (1) 0.7 L of toluene and 50 g of polybutadiene were added to a reaction bottle, heated and stirred, and then cooled. 10 g of 4-mercapto methyl benzoate (CAS No. 6302-65-4) and 0.3 g of benzoic acid dimethyl ether were added, and the reaction bottle was irradiated under a UV lamp with a power of 80 W for 1 h. A large amount of precipitate was distilled off under reduced pressure, and the product was washed with ethanol after filtration and dried to obtain methyl benzoate-based polybutadiene.

[0038] (2) 9 kg of polypropylene resin, 1 kg of polyethylene terephthalate, 0.3 kg of methyl benzoate-based polybutadiene, and 27 g of antioxidant 1076 were mixed and melt blended in a twin-screw extruder, with the temperature of each section being 180°C, 230°C, 250°C, 265°C, and 270°C, and the screw rotation speed being 50 r / min; extrusion and granulation were performed to obtain a PP composite material.

[0039] Comparative Example 5

[0040] (1) 9 kg of polypropylene resin, 1 kg of polyethylene terephthalate, 0.3 kg of maleic anhydride grafted polypropylene, and 27 g of antioxidant 1076 were mixed and melt blended in a twin-screw extruder, with the temperature of each section being 180°C, 230°C, 250°C, 265°C, and 270°C, and the screw rotation speed being 50 r / min; extrusion and granulation were performed to obtain a PP composite material.

[0041] The PP composite material was injection molded into a test sample by an injection molding machine at a temperature of 260°C and a pressure of 50 MPa. The Izod impact strength of the test sample was tested according to the standard GB / T 1843-2008. The bending strength was tested according to the standard GB / T 9341-2008. The wear resistance was tested according to the standard GB T 3960-2016.

[0042] Table 1 Performance Test

[0043]

[0044] The impact strength and bending strength of the PET / PP composite material of Comparative Example 1 are low, and the wear amount is large, and the wear resistance is poor, mainly because the compatibility of PET and PP is poor, which affects the processability of the composite material, and reduces the mechanical strength and performance of the material.

[0045] In Example 1-Example 3, ethylenedioxybenzoic acid-based polybutadiene is added, the polybutadiene has similar molecular chains to polypropylene, the difference in solubility parameter is small, the compatibility is excellent, and the ethylenedioxybenzoic acid-based structure is introduced into the side chain of polybutadiene The ethylenedioxybenzoic acid-based polybutadiene can play a role in compatibilizing PET and PP, improving the processability of the PP composite material, the interface performance of the two is excellent, and the composite material has better mechanical properties, high impact strength and bending strength, low wear amount, and good wear resistance.

[0046] In Comparative Example 2, polybutadiene is added, which plays a role in compatibilizing PET and PP, and the mechanical properties of the composite material are poor. In Comparative Example 3, polybutadiene grafted with mercaptoethyl acetate is used as a compatibilizer, in Comparative Example 4, polybutadiene grafted with mercaptomethyl benzoate is used as a compatibilizer, and in Comparative Example 5, conventional maleic anhydride grafted polypropylene is used as a compatibilizer. The compatibilization of the three is lower than that of the ethylenedioxybenzoic acid-based polybutadiene of Example 1, and the impact strength and other properties of the composite material are lower than those of Example 1.

[0047] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limiting the present application, and those skilled in the art can make changes, modifications, replacements and variations to the above embodiments within the scope of the present application.

Claims

1. A wear-resistant and impact-resistant PP composite material, characterized in that: The wear-resistant and impact-resistant PP composite material comprises polypropylene resin, polyethylene terephthalate, polyethylene dibenzoate-based polybutadiene, and an antioxidant in a ratio of (60-90) g: (10-40) g: (3-10) g: (0.2-0.4) g; The preparation process of the ethylene dibenzoate-based polybutadiene comprises: adding toluene and polybutadiene into a reaction flask, heating and stirring, and then cooling, adding 4-mercaptoethylene dibenzoate and benzoin dimethyl ether, irradiating the reaction flask under an ultraviolet lamp for reaction, performing reduced pressure distillation, filtering, washing the product, and drying to obtain the ethylene dibenzoate-based polybutadiene.

2. The wear-resistant and impact-resistant PP composite material according to claim 1, characterized in that: The ratio of the polybutadiene, 4-mercaptodibenzoic acid ethylene glycol and benzoin dimethyl ether is 100g: (20-50)g: (0.6-1)g.

3. The wear-resistant and impact-resistant PP composite material according to claim 1, characterized in that: The power of the ultraviolet lamp is 30-80W, and the wavelength range is 320-380nm.

4. The wear-resistant and impact-resistant PP composite material according to claim 1, characterized in that: The irradiation reaction time is 1-2 hours.

5. The wear-resistant and impact-resistant PP composite material according to claim 1, characterized in that: The preparation process of 4-mercaptodibenzoic acid ethylene glycol comprises: adding toluene, 4-mercaptobenzoic acid, 2-hydroxyethyl benzoate and p-toluenesulfonic acid into a reaction bottle, performing rotary evaporation after the reaction, washing the crude product, and recrystallizing to obtain 4-mercaptodibenzoic acid ethylene glycol.

6. The wear-resistant and impact-resistant PP composite material according to claim 5, characterized in that: The ratio of the 4-mercaptobenzoic acid, 2-hydroxyethyl benzoate and p-toluenesulfonic acid is 100g:(220-340)g:(14-20)g.

7. The wear-resistant and impact-resistant PP composite material according to claim 5, characterized in that: In the preparation process of 4-mercaptodibenzoic acid ethylene glycol, the reaction temperature is 80-90° C. and the reaction time is 7-12 hours.

8. A process for preparing the wear-resistant and impact-resistant PP composite material according to any one of claims 1 to 7, characterized in that: The preparation process comprises: mixing polypropylene resin, polyethylene terephthalate, diethylene glycol-based polybutadiene and an antioxidant, melting and blending the mixture in a twin-screw extruder, and extruding and pelletizing the mixture to obtain a wear-resistant and impact-resistant PP composite material.

9. The preparation process of the wear-resistant and impact-resistant PP composite material according to claim 8, characterized in that: The temperature of each section of the twin-screw extruder is 180-270° C., and the screw speed is 30-50 r / min.

Images