Wear-resistant PET bottle and preparation process thereof

Abstract

The application relates to the technical field of PET materials, and particularly discloses a wear-resistant PET bottle and a preparation process. The preparation raw materials of the wear-resistant PET bottle include PET resin, modified ceramic powder, glass fiber, a toughening agent, an antioxidant, a light stabilizer and a lubricant. The modified ceramic powder includes B2O3-A12O3 complex powder and a titanate coupling agent. The B2O3-A12O3 complex powder is modified through the titanate coupling agent. One end of the coupling agent molecules is connected with the B2O3-A12O3 complex powder particles through chemical action, and the other end is crosslinked with the PET resin. The compatibility of the ceramic powder and the base resin is improved, and the ceramic powder is uniformly dispersed in the PET resin, so that the wear resistance of the PET resin is effectively enhanced.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of PET materials, in particular to a wear-resistant PET bottle and a preparation process. BACKGROUND

[0002] In the packaging field, PET plastic bottles have become one of the most widely used packaging materials due to their light weight, transparency, easy recycling and other characteristics. PET plastic bottles are widely used not only in the packaging of carbonated beverages, drinking water, fruit juice, enzymes and tea beverages, but also in other packaging fields such as food, chemical industry and medicine. PET plastic bottles have many advantages, such as low production cost, chemical resistance, easy processing and molding, etc.

[0003] However, PET material itself has certain deficiencies in wear resistance. In daily use, PET plastic bottles often encounter friction and scratching, which may cause scratches or wear on the surface of the bottle, affecting its appearance and service life. Therefore, in order to improve the wear resistance of PET plastic, various fillers are usually added to the PET material to enhance the wear resistance of the material. For example, inorganic fillers such as calcium carbonate, talc powder and wollastonite powder, and organic fillers such as carbon fibers and glass fibers. These fillers can improve the hardness and rigidity of PET material, thereby improving the wear resistance. However, these methods also bring some new problems, the interface compatibility between the filler particles and the high molecular material is poor, and due to the small particle size of the filler particles, self-agglomeration phenomenon easily occurs, thereby affecting the comprehensive performance of the material. SUMMARY

[0004] In order to improve the dispersion of the filler particles and the interface compatibility between the matrix resin, and improve the wear resistance of the PET material, the application provides a wear-resistant PET bottle and a preparation process.

[0005] In a first aspect, the application provides a wear-resistant PET bottle, which adopts the following technical scheme:

[0006] A wear-resistant PET bottle is prepared from the following raw materials by weight parts:

[0007] PET resin 60-70 parts;

[0008] Modified ceramic powder 4-8 parts;

[0009] Glass fiber 8-12 parts;

[0010] Toughening agent 1-3 parts;

[0011] Antioxidant 0.1-0.3 parts;

[0012] Light stabilizer 0.3-0.5 parts;

[0013] 0.4-0.6 parts of lubricant;

[0014] The modified ceramic powder is prepared from B2O3-A12O3 composite powder and titanate coupling agent, and the weight ratio of the B2O3-A12O3 composite powder and the titanate coupling agent is 10:(0.5-0.7).

[0015] By adopting the technical scheme, the PET resin is used as the base resin, the ceramic powder is modified by the titanate coupling agent, one end of the coupling agent molecule is connected to the B2O3-A12O3 composite powder particles through chemical action, and the other end is crosslinked with the PET resin, so as to increase the compatibility of the ceramic powder and the base resin, and make the ceramic powder uniformly fill the PET resin. Since the B2O3-A12O3 composite powder has a small size and can be uniformly dispersed in the base resin, in the process of friction, on one hand, the powder particles which are detached from the surface of the material due to wear have strong surface activity, are easy to combine with the counter surface to form a thin layer, and thus form a boundary lubricating film on the surface, on the other hand, the amount of the powder particles which are re-embedded in the high polymer base almost reaches the degree of covering the whole wear surface, and thus forms a complete lubricating film on the surface of the high polymer, so that the possibility of direct wear of the PET resin base is reduced, and thus the overall wear resistance of the material is improved. In addition, the addition of the glass fiber can further improve the crystallization performance and mechanical properties of the PET material.

[0016] Preferably, the B2O3-A12O3 composite powder is prepared from micron boron oxide and nano aluminum oxide, and the weight ratio of the micron boron oxide and the nano aluminum oxide is 1:(1.8-2.2).

[0017] By adopting the technical scheme, since the boron oxide has chemical inertness, it cannot form a chemical bond with the functional groups in the titanate coupling agent, therefore, the boron oxide and the aluminum oxide are prepared into a composite powder, the nano aluminum oxide is used as an intermediate, the aluminum oxide is modified, the coupling agent molecules are connected to the surface of the composite ceramic powder, and thus the composite ceramic powder can react with the base resin. In addition, the nano aluminum oxide is relatively uniformly dispersed around the micron boron oxide particles, and is not in a state of agglomeration, the agglomeration phenomenon is not obvious, the nano aluminum oxide has a certain combination and coating effect on the micron boron oxide, and thus the composite ceramic powder has a good phase.

[0018] Preferably, the titanate coupling agent includes at least one of titanium bis(dioctyl diphosphate) glycolate, dicarboxy ethylene glycol titanate, triethanolamine titanate, and amide ethylene glycol titanate.

[0019] By adopting the technical scheme, the titanate coupling agent molecule contains alkoxy and long-chain molecular structure units. When the coupling agent molecule acts on the B2O3-A12O3 composite powder, the alkoxy takes away the protons on the surface of the powder, the protons are derived from the combined water in the powder, including crystal water, chemisorption water and physical adsorption water, thereby forming a chemical bond, and covering a molecular layer of the coupling agent on the surface of the B2O3-A12O3 composite powder. The long-chain molecular structure units in the coupling agent can be chemically crosslinked or physically entangled with the PET molecules, and finally the B2O3-A12O3 composite powder and the PET molecules are well combined, thereby improving the wear resistance of the material. In addition, the action of the titanate coupling agent reduces the surface energy of the powder, improves the dispersion ability of the powder in the resin, reduces the viscosity of the filled system, increases the filling amount, and reduces the mechanical wear.

[0020] Preferably, the toughening agent adopts E-BA-GMA, and the GMA content in the toughening agent is 6-8%.

[0021] By adopting the technical scheme, the ethylene-butyl acrylate-glycidyl methacrylate block copolymer has good dispersibility and compatibility, can change the internal stress distribution of the material, disperse the concentrated stress to a larger area, reduce the local stress concentration, and thereby improve the impact resistance of the PET material.

[0022] Preferably, the light stabilizer adopts at least one of 2,2,6,6-tetramethyl-4-piperidinyl stearate and bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

[0023] By adopting the technical scheme, the light stabilizer is a free radical trapping agent, and when receiving ultraviolet irradiation, the piperidine ring in the molecular structure thereof is converted into a stable nitroxyl radical. After the PET material is irradiated by ultraviolet light, alkyl radicals, peroxyalkyl radicals and the like are generated. The appearance of these radicals will accelerate the aging of the PET material. The nitroxyl radical can capture the free radicals generated by the PET material to generate corresponding ester or peroxide ester compounds, terminate the chain reaction, achieve the effect of light stabilization, and prevent the aging of the PET material.

[0024] Preferably, the antioxidant includes at least one of pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxy)phenylpropionate and thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0025] By adopting the technical scheme, the benzene ring in the antioxidant molecule has a hydroxyl group, which can provide an efficient hydrogen donor, and the ortho or para position of the hydroxyl functional group has two substituent groups, i.e., tert-butyl groups. Due to the space obstacle, the hydrogen atom is easily separated from the original molecular structure, thereby achieving the function of providing a proton, and combining with a peroxide radical, an alkyl radical or a hydroxyl radical, etc., so as to cause the loss of original activity, reduce the source of free radicals, and terminate the oxidation reaction, thereby achieving the antioxidant effect and prolonging the service life of the PET material.

[0026] Preferably, the lubricant includes at least one of pentaerythritol stearate, solid paraffin, polyethylene wax, oxidized polyethylene wax, zinc stearate, calcium stearate, and fatty amide.

[0027] By adopting the technical scheme, the lubricant molecule structure generally has two parts, i.e., a nonpolar long chain and a polar group, which plays a role in reducing the intermolecular cohesive force in the melt system of the base resin, can reduce the internal friction of the plastic melt, increase the melting rate and melt deformation of the plastic, reduce the melt viscosity, and improve the plasticizing performance.

[0028] In a second aspect, the application provides a preparation process of a wear-resistant PET bottle, which adopts the following technical scheme:

[0029] A preparation method of a wear-resistant PET bottle includes the following steps:

[0030] The raw materials are weighed according to the component allocation ratio, and the PET resin, modified ceramic powder, toughening agent, antioxidant, light stabilizer and lubricant are stirred and mixed, placed in an extruder, then the glass fiber is added and uniformly mixed, and then melted and extruded at 170-190°C. After granulation, the PET material is obtained, then the PET material is heated to 210-220°C to form a melt, and the bottle embryo is injection molded, and finally the bottle embryo is stretched and blown into a bottle body, thereby obtaining a wear-resistant PET bottle.

[0031] By adopting the technical scheme, by adding the modified ceramic powder and glass fiber, the wear resistance of the PET bottle is significantly improved, the bottle is more durable during use, and the risk of wear and damage is reduced. The addition of glass fiber enhances the mechanical strength of the PET material, so that the finished bottle can withstand greater pressure and impact. The addition of the antioxidant and the light stabilizer improves the thermal stability and light resistance of the PET material, prolongs the service life of the bottle, especially in high-temperature or direct sunlight environments. The addition of the toughening agent and the lubricant improves the processing performance of the PET material, making the extrusion, injection molding and blowing process more smooth, reducing the energy consumption and material loss during the production process.

[0032] Preferably, the preparation method of the modified ceramic powder is as follows:

[0033] ① Put the B2O3-A12O3 composite powder into NaOH solution, stir at 50-60℃ for 3-4h, then wash with deionized water and alcohol alternately, remove excess water by vacuum filtration, and dry to obtain pretreated B2O3-A12O3 composite powder;

[0034] ② Add titanate coupling agent into ethanol solution, adjust pH to 6.5-7.5, and stir for 1-2h to obtain hydrolyzed coupling agent solution, then add pretreated B2O3-A12O3 composite powder into the hydrolyzed coupling agent solution, stir at 50-60℃ for 2-3h, ultrasonic dispersion for 30-40min, and after the reaction is completed, perform filtration separation, wash with acetone for 2-3 times, and dry at 40-50℃ for 2-4h to obtain modified ceramic powder.

[0035] By using the above technical solution, the B2O3-A12O3 composite powder is pretreated to increase the content of surface hydroxyl groups. The hydrolysis of the titanate coupling agent can form an active layer on the surface of the powder, which helps to improve the bonding force of the powder with PET resin. The ultrasonic dispersion step helps to uniformly disperse the powder in the PET resin, avoids agglomeration, and ensures the uniformity and consistency of the composite material.

[0036] Preferably, the preparation method of the B2O3-A12O3 composite powder is as follows:

[0037] Add micron-sized boron oxide and nano-sized aluminum oxide into ethanol, mix uniformly, perform ball milling for 50-70min, then perform ultrasonic, filtration, and drying to obtain the B2O3-A12O3 composite powder.

[0038] By using the above technical solution, the ball milling method has certain promoting effect on the dispersion of particles. The boron oxide particles are dispersed among each other, and many aluminum oxide particles surround the boron oxide particles. The boron oxide particles and the aluminum oxide particles are in contact with each other, so that the B2O3-A12O3 composite powder is well dispersed and does not have obvious agglomeration phenomenon.

[0039] In summary, the present application at least has the following beneficial technical effects:

[0040] In the application, the PET resin is used as the base resin, the ceramic powder is modified by titanate coupling agent, one end of the coupling agent molecule is connected with the B2O3-A12O3 composite powder particles through chemical action, and the other end is crosslinked with the PET resin, so as to increase the compatibility of the ceramic powder and the base resin, and make the ceramic powder uniformly fill the PET resin. Since the size of the B2O3-A12O3 composite powder is small, it can be uniformly dispersed in the base resin. In the process of friction, on the one hand, the debonded powder particles in the material surface wear have strong surface activity, and are easy to combine with the opposite surface to form a thin layer, thereby forming a boundary lubricating film on the friction surface, on the other hand, the powder particles can be re-embedded in the polymer matrix, and the amount of the powder particles almost reaches the degree of covering the entire wear surface, so as to form a complete lubricating film on the polymer surface, and the possibility of direct wear of the PET resin base cup is reduced, thereby improving the overall wear resistance of the material. In addition, the addition of glass fiber can further improve the crystallization performance and mechanical properties of the PET material. DETAILED DESCRIPTION

[0041] Preparation Example

[0042] Preparation Example 1

[0043] The preparation method of the modified ceramic powder is as follows:

[0044] ① 2 kg of micron boron oxide and 3.6 kg of nano aluminum oxide are added to ethanol, uniformly mixed, subjected to ball milling for 50 min, then subjected to ultrasonic treatment, suction filtration and drying to obtain B2O3-A12O3 composite powder;

[0045] ② 4 kg of the B2O3-A12O3 composite powder is placed in a NaOH solution, stirred at 50°C for 3 h, then washed with deionized water and alcohol alternately for 3 times, suction filtered under reduced pressure to remove excess water, and dried to obtain pretreated B2O3-A12O3 composite powder;

[0046] ③ 0.2 kg of di(octyl diphosphate) titanium glycolate is added to an ethanol solution, the pH is adjusted to 6.5, and the solution is stirred for 1 h to obtain a hydrolyzed coupling agent solution, then the pretreated B2O3-A12O3 composite powder is added to the hydrolyzed coupling agent solution, stirred at 50°C for 2 h, ultrasonically dispersed for 30 min, and after the reaction is completed, suction filtration separation is performed, and the powder is washed with acetone for 2 times, and dried at 40°C for 2 h to obtain the modified ceramic powder.

[0047] Preparation Example 2

[0048] The preparation method of the modified ceramic powder is as follows:

[0049] ① 3 kg micron boron oxide and 6 kg nano alumina are added into ethanol, mixed uniformly, treated by grinding ball for 60 min, then treated by ultrasonic, suction filtration, and drying to obtain B2O3-A12O3 composite powder;

[0050] ② 6 kg B2O3-A12O3 composite powder is placed in NaOH solution, stirred at 55℃ for 3.5 h, then washed with deionized water and alcohol alternately for 3 times, suction filtered under reduced pressure to remove excess water, and dried to obtain pretreated B2O3-A12O3 composite powder; ③ 0.36 kg dicarboxyl titanate is added into ethanol solution, the pH is adjusted to 7.0, and hydrolysis coupling agent solution is obtained by stirring for 2 h, then the pretreated B2O3-A12O3 composite powder is added into the hydrolysis coupling agent solution, stirred at 55℃ for 2.5 h, ultrasonic dispersed for 35 min, after the reaction is completed, suction filtration separation is performed, and washed with acetone for 3 times, and dried at 45℃ for 3 h to obtain modified ceramic powder.

[0051] Preparation Example 3

[0052] The preparation method of the modified ceramic powder is as follows:

[0053] ① 4 kg micron boron oxide and 8.8 kg nano alumina are added into ethanol, mixed uniformly, treated by grinding ball for 70 min, then treated by ultrasonic, suction filtration, and drying to obtain B2O3-A12O3 composite powder;

[0054] ② 8 kg B2O3-A12O3 composite powder is placed in NaOH solution, stirred at 60℃ for 4 h, then washed with deionized water and alcohol alternately for 3 times, suction filtered under reduced pressure to remove excess water, and dried to obtain pretreated B2O3-A12O3 composite powder;

[0055] ③ 0.56 kg triethanolamine titanate is added into ethanol solution, the pH is adjusted to 7.5, and hydrolysis coupling agent solution is obtained by stirring for 2 h, then the pretreated B2O3-A12O3 composite powder is added into the hydrolysis coupling agent solution, stirred at 60℃ for 3 h, ultrasonic dispersed for 40 min, after the reaction is completed, suction filtration separation is performed, and washed with acetone for 3 times, and dried at 50℃ for 4 h to obtain modified ceramic powder.

[0056] Example

[0057] Example 1

[0058] A wear-resistant PET bottle, comprising the following raw materials:

[0059] 60 kg of PET resin (DuPont FG530 NC011), 4 kg of modified ceramic powder (prepared in Preparation Example 1), 8 kg of glass fiber, 1 kg of E-MA-GMA (GMA content of 6%), 0.1 kg of pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxy) phenylpropionate, 0.3 kg of 2,2,6,6-tetramethyl-4-piperidinyl stearate, 0.2 kg of solid paraffin, and 0.2 kg of pentaerythritol stearate.

[0060] The preparation process of the wear-resistant PET bottle of the present embodiment includes the following steps:

[0061] The raw materials were weighed according to the component allocation ratio, and the PET resin, modified ceramic powder, E-MA-GMA, pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxy) phenylpropionate, 2,2,6,6-tetramethyl-4-piperidinyl stearate, solid paraffin, and pentaerythritol stearate were stirred and mixed, placed in an extruder, then the glass fiber was added, uniformly mixed, and melt-extruded at 170°C. After granulation, the PET material was obtained. Then the PET material was heated to 210°C to form a melt, and the bottle blank was injection molded. Finally, the bottle blank was stretch blow molded into a bottle body, and the wear-resistant PET bottle was obtained.

[0062] Example 2

[0063] A wear-resistant PET bottle includes the following raw materials:

[0064] 65 kg of PET resin (DuPont FG530 NC011), 6 kg of modified ceramic powder (prepared in Preparation Example 1), 10 kg of glass fiber, 2 kg of E-MA-GMA (GMA content of 7%), 0.2 kg of thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 0.4 kg of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 0.2 kg of zinc stearate, and 0.2 kg of calcium stearate.

[0065] The preparation process of the wear-resistant PET bottle of the present embodiment includes the following steps:

[0066] The raw materials were weighed according to the component allocation ratio, and the PET resin, modified ceramic powder, E-MA-GMA, pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxy) phenylpropionate, 2,2,6,6-tetramethyl-4-piperidinyl stearate, solid paraffin, and pentaerythritol stearate were stirred and mixed, placed in an extruder, then the glass fiber was added, uniformly mixed, and melt-extruded at 170°C. After granulation, the PET material was obtained. Then the PET material was heated to 210°C to form a melt, and the bottle blank was injection molded. Finally, the bottle blank was stretch blow molded into a bottle body, and the wear-resistant PET bottle was obtained.

[0067] Example 3

[0068] A wear-resistant PET bottle, comprising the following raw materials:

[0069] 70 kg of PET resin (DuPont FG530 NC011), 8 kg of modified ceramic powder (prepared in Preparation Example 1), 12 kg of glass fiber, 3 kg of E-MA-GMA (GMA content of 8%), 0.3 kg of pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxy) phenylpropionate, 0.5 kg of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 0.2 kg of oxidized polyethylene wax, and 0.2 kg of fatty amide.

[0070] In this embodiment, the preparation process of the wear-resistant PET bottle includes the following steps:

[0071] The raw materials are weighed according to the component allocation ratio, and the PET resin, modified ceramic powder, E-MA-GMA, pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxy) phenylpropionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, oxidized polyethylene wax, and fatty amide are stirred and mixed, placed in an extruder, then the glass fiber is added, mixed uniformly, and then melted and extruded at 190°C. After granulation, the PET material is obtained, then the PET material is heated to 220°C to form a melt, and the bottle blank is injection molded, and finally the bottle blank is stretched and blown into a bottle body, and the wear-resistant PET bottle is obtained.

[0072] Example 4

[0073] The difference between this embodiment and Example 2 is that the modified ceramic powder is replaced by an equal amount of the modified ceramic powder prepared in Preparation Example 2.

[0074] Example 5

[0075] The difference between this embodiment and Example 2 is that the modified ceramic powder is replaced by an equal amount of the modified ceramic powder prepared in Preparation Example 3.

[0076] Comparative Example

[0077] Comparative Example 1

[0078] A wear-resistant PET bottle, which is different from Example 2 in that the modified ceramic powder is replaced by an equal amount of B2O3-A12O3 complex powder.

[0079] Comparative Example 2

[0080] A wear-resistant PET bottle, which is different from Example 2 in that the B2O3-A12O3 complex powder in the preparation raw materials of the modified ceramic powder is replaced by an equal amount of micron boron oxide.

[0081] Comparative Example 3

[0082] A wear-resistant PET bottle, which is different from example 2 in that the B2O3-A12O3 complex powder in the raw material for preparing the modified ceramic powder is replaced with an equal amount of nano-aluminum oxide.

[0083] Comparative example 4

[0084] A wear-resistant PET bottle, which is different from example 2 in that the modified ceramic powder is replaced with an equal amount of glass fiber.

[0085] Performance detection test

[0086] 1. Wear resistance test: MM-200 friction and wear tester was used for friction and wear test. The size of the sample was 6mm x 7mm x 30mm. Before each experiment, the friction surface of the sample and the counter part were polished smooth with 1200# water sandpaper, the roughness was about Ra=0.4μm, and cleaned with acetone. The friction counter part was 45# steel, the counter wheel radius was 20mm, the hardness was HRC42-45, the load was 98N, the linear velocity was 0.42m / s, and the dry friction was 2h. The test results are shown in Table 1.

[0087] Determination of friction coefficient: During the friction and wear test, the friction torque of material wear can be directly read from the MM-200 friction and wear tester. The friction coefficient was calculated from the friction torque by formula (1). The average value of three repeated experiments was taken as the final result.

[0088] μ=T / (RP)(1)

[0089] In the formula, T is the friction torque, R is the diameter of the steel wheel (40mm), and P is the load.

[0090] Determination of wear mass loss: The mass of PET composite material was weighed before and after wear test by 0.1mg sensitive electronic balance, and the wear mass loss was calculated. The average value of three repeated experiments was taken as the final result.

[0091] 2. Impact resistance test: The impact test was carried out according to GB / T 1043.1-2008. The impact test was carried out on the XJ-300A impact tester, and the impact sample was made by injection molding. The sample was a standard sample with a cross-sectional size of 1.5cm x 0.7cm. The notch type was C type, the notch width was 2mm, and the notch depth was 3mm. The test results are shown in Table 1.

[0092] 3. Tensile property test: The tensile test was carried out according to GB / T 1040.2-2022. The tensile test was carried out on the CMT5105 type SANS microcomputer control electronic universal tensile testing machine. The sample was dumbbell-shaped with a gauge length of 8cm, a width of 0.7cm and a thickness of 0.2cm. The test results are shown in Table 1.

[0093] Table 1

[0094]

[0095] According to the comparison between Example 2 and Comparative Example 1 and the data in Table 1, it can be seen that when the ceramic powder is directly added to the raw material without modification, the powder and the base resin cannot be well combined due to poor compatibility, and thus the improvement of the wear resistance of the PET material is not obvious. The modification of the surface of the ceramic powder can effectively improve the dispersion performance of the B2O3-A12O3 composite powder in the PET base resin, thereby improving the wear resistance of the PET bottle.

[0096] According to the comparison between Example 2 and Comparative Example 2 and the data in Table 1, it can be seen that the use of a single-phase powder filled in the base resin cannot ideally improve the wear resistance of the material. The reason can be that the boron oxide is inert in chemical reaction and cannot be combined with the functional groups in the titanate coupling agent, and the micron-sized boron oxide particles detached and retained in the friction interface can easily cause serious abrasive wear. The combination of micron-sized boron oxide and nano-sized aluminum oxide to prepare the B2O3-A12O3 composite powder,

[0097] The nano-sized aluminum oxide has a small size effect, and the nano-sized aluminum oxide detached during the wear of the material surface has strong surface activity and is easy to combine with the counterpart to form a thin layer, thereby slowing down the wear of the PET material and improving the wear resistance of the material. In addition, the aluminum oxide particles absorb impact energy, effectively delay and prevent the damage of the PET material, and produce a toughening effect.

[0098] According to the comparison between Example 2 and Comparative Example 3 and the data in Table 1, it can be seen that the use of nano-sized aluminum oxide powder alone filled in the base resin cannot ideally improve the wear resistance of the material. The reason can be that the nano-sized aluminum oxide particles have a blurred interface and serious agglomeration phenomenon, and are not easy to disperse in the high-viscosity base resin melting system. The combination of micron-sized boron oxide and nano-sized aluminum oxide to prepare the B2O3-A12O3 composite powder, the nano-sized aluminum oxide is relatively uniformly dispersed around the micron-sized boron oxide particles rather than in a clustered state, and the agglomeration phenomenon is not obvious. The nano-sized aluminum oxide forms a certain combination and coating effect on the micron-sized boron oxide, so that the composite ceramic powder has a good phase, thereby achieving the purpose of improving the wear resistance of the PET material. In addition, the aluminum oxide particles absorb impact energy, effectively delay and prevent the damage of the PET material, and produce a toughening effect.

[0099] According to the comparison between the embodiment 2 and the comparative example 4 and the data in the table 1, it can be seen that the wear resistance of the PET resin is poor without adding the modified ceramic powder. On the contrary, after adding the modified ceramic powder, when the material surface is worn, the debonded powder particles have strong surface activity, are easy to combine with the counter surface to form a fine thin layer, so as to form a boundary lubrication film on the counter surface, so that the possibility of direct wear of the PET resin matrix is reduced, thereby improving the overall wear resistance of the material.

[0100] The specific embodiment is only an explanation of the present application, which is not a limitation of the present application. Those skilled in the art can make modifications to the specific embodiment without creative contribution after reading the specification, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A wear resistant PET bottle characterized in that, By weight parts, comprising the following raw materials: PET resin 60-70 parts; Modified ceramic powder 4-8 parts; Glass fiber 8-12 parts; Toughening agent 1-3 parts; Antioxidant 0.1-0.3 parts; Light stabilizer 0.3-0.5 parts; Lubricant 0.4-0.6 parts; The modified ceramic powder is prepared from B2O3-A12O3 complex powder and titanate coupling agent, and the weight ratio of the B2O3-A12O3 complex powder and the titanate coupling agent is 10: (0.5-0.7).

2. A wear resistant PET bottle according to claim 1, characterized in that, The B2O3-A12O3 complex powder is prepared from micron boron oxide and nano aluminum oxide, and the weight ratio of the micron boron oxide and the nano aluminum oxide is 1: (1.8-2.2).

3. A wear resistant PET bottle according to claim 1, wherein, The titanate coupling agent includes at least one of di (dioctyl phosphite) glycolate titanate, dicarboxy ethylene glycol titanate, triethanolamine titanate, amide ethylene glycol titanate.

4. A wear resistant PET bottle according to claim 1, wherein, The toughening agent uses E-BA-GMA, and the GMA content in the toughening agent is 6-8%.

5. A wear resistant PET bottle according to claim 1, wherein, The light stabilizer uses at least one of 2, 2, 6, 6-tetramethyl-4-piperidine stearate, bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.

6. A wear resistant PET bottle according to claim 1, wherein, The antioxidant includes at least one of tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionic acid pentaerythritol ester, thiodiethylenyl bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate].

7. A wear resistant PET bottle according to claim 1, wherein The lubricant includes at least one of pentaerythritol stearate, solid paraffin, polyethylene wax, oxidized polyethylene wax, zinc stearate, calcium stearate, fatty amide.

8. A process for the production of a wear resistant PET bottle as claimed in any one of claims 1 to 7, wherein, The method comprises the following steps: The raw materials are weighed according to the component allocation ratio, the PET resin, the modified ceramic powder, the toughening agent, the antioxidant, the light stabilizer and the lubricant are stirred and mixed, placed in an extruder, then the glass fiber is added, mixed uniformly, and then melted and extruded at 170-190℃, and then granulated to obtain a PET material, then the PET material is heated to 210-220℃ to form a melt, and then injection molded into a bottle embryo, and finally the bottle embryo is stretched and blown into a bottle body to obtain a wear-resistant PET bottle.

9. A process for the preparation of a wear resistant PET bottle as claimed in claim 8, wherein, The preparation method of the modified ceramic powder is: ①The B2O3-A12O3 complex powder is placed in a NaOH solution, stirred at 50-60℃ for 3-4h, then washed with deionized water and alcohol alternately, vacuum filtered to remove excess water, and dried to obtain pretreated B2O3-A12O3 complex powder; ②The titanate coupling agent is added to an ethanol solution, the pH is adjusted to 6.5-7.5, and the hydrolysis coupling agent solution is obtained by stirring for 1-2h, then the pretreated B2O3-A12O3 complex powder is added to the hydrolysis coupling agent solution, stirred at 50-60℃ for 2-3h, ultrasonic dispersed for 30-40min, and then filtered and separated after the reaction is completed, washed with acetone for 2-3 times, and dried at 40-50℃ for 2-4h to obtain the modified ceramic powder.

10. A process for the preparation of a wear resistant PET bottle as claimed in claim 9, wherein, The preparation method of the B2O3-A12O3 complex powder is: Micron boron oxide and nano alumina are added into ethanol, mixed uniformly, treated by grinding ball for 50-70 min, then treated by ultrasonic, suction filtration and drying, and B2O3-A12O3 composite powder is obtained.

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