Heat-resistant plastic bottle and preparation method thereof

Abstract

The invention relates to the technical field of plastic bottles, and particularly discloses a heat-resistant plastic bottle and a preparation method thereof. The heat-resistant plastic bottle is prepared from the following raw materials in parts by weight: 60 to 80 parts of polypropylene, 10 to 15 parts of polyethylene, 20 to 30 parts of polyethylene glycol terephthalate resin, 1 to 3 parts of coloring master batch, 5 to 10 parts of zinc molybdate, 1 to 3 parts of triphenyl phosphate, 5 to 9 parts of micron aluminum oxide, 3 to 5 parts of nano aluminum oxide, 8 to 12 parts of superfine mica powder and 0.1 to 0.3 part of antioxidant. The vicat softening temperature of the heat-resistant plastic bottle is 143 DEG C, and the heat resistance of the plastic bottle is improved.

Description

Technical Field

[0001] The present application relates to the technical field of plastic bottles, and more specifically, to a heat-resistant plastic bottle and a preparation method thereof. Background Art

[0002] Plastic bottles are mostly used for liquid packaging. They are low-cost and are widely used in food, medicine, chemical and other fields. However, plastic bottles are usually produced using blow molding, which makes the bottle body thinner and more susceptible to high temperatures. Generally speaking, the heat resistance range is between -40℃ and 70℃. When poured into substances with too high a temperature or in a high temperature environment, they are very likely to soften, deform, and age, affecting normal use and even causing harmful substances to seep out.

[0003] In the related art, calcium carbonate is added to the raw materials of plastic bottles to improve the heat resistance of the plastic bottles, but the improvement effect is weak, and the use of plastic bottles is still limited. Summary of the invention

[0004] In order to improve the heat resistance of a plastic bottle, the present application provides a heat-resistant plastic bottle and a preparation method thereof.

[0005] In the first aspect, the present application provides a heat-resistant plastic bottle, which adopts the following technical solution: A heat-resistant plastic bottle comprises the following raw materials in parts by weight: 60-80 parts of polypropylene, 10-15 parts of polyethylene, 20-30 parts of polyethylene terephthalate resin, 1-3 parts of coloring masterbatch, 5-10 parts of zinc molybdate, 1-3 parts of triphenyl phosphite, 5-9 parts of micron alumina, 3-5 parts of nano alumina, 8-12 parts of ultrafine mica powder and 0.1-0.3 parts of antioxidant.

[0006] The heat-resistant plastic bottle of the present application can choose 60-80 parts of polypropylene, 10-15 parts of polyethylene, 20-30 parts of polyethylene terephthalate resin, 1-3 parts of masterbatch, 5-10 parts of zinc molybdate, 1-3 parts of triphenyl phosphite, 5-9 parts of micron alumina, 3-5 parts of nano alumina, 8-12 parts of ultrafine mica powder, and 0.1-0.3 parts of antioxidant. Any value within the respective ranges can be selected, and the heat resistance of the heat-resistant plastic bottle can be improved.

[0007] By adopting the above technical solution, polypropylene is a thermoplastic general resin with good heat resistance, can withstand high temperatures of 110 to 150°C, and will not release toxic substances, and is suitable for plastic bottles. Polyethylene terephthalate resin has excellent air permeability, gas barrier and mechanical properties, and it also has high heat resistance. Adding polyethylene terephthalate resin can improve the heat resistance of plastic bottles to varying degrees. Even if the bottle body is thin, it is not easy to produce permanent deformation and still has good hardness at high temperatures.

[0008] Zinc molybdate has high thermal conductivity. Adding zinc molybdate can block further penetration of heat and oxygen, delay thermal decomposition of the plastic matrix, disperse local heat, and reduce degradation caused by thermal stress. The lattice structure is highly stable and is not easy to phase change at high temperatures, maintaining the overall mechanical properties of the plastic bottle, thereby further improving the heat resistance of the plastic bottle.

[0009] Triphenyl phosphite is added together with zinc molybdate. On the one hand, the Mo in zinc molybdate is 6+ Partially reduced to MO 4+ On the one hand, the formation of more active low-valent molybdenum species can more efficiently terminate the free radicals produced by the thermal degradation of plastics. On the other hand, the combined addition of the two can significantly prolong the oxidation induction period of plastics, thereby further improving the heat resistance of plastic bottles.

[0010] The chemical properties of micron alumina and nano alumina are stable. Adding micron alumina and nano alumina at the same time can not only improve the hardness and stability of plastic bottles, but also improve their heat resistance. When adding micron alumina and nano alumina at the same time, nano alumina can fill the gaps between micron alumina particles to form a multi-scale dense structure, further restricting the movement of molecular chains. Micron alumina provides a fast heat conduction path, and nano alumina disperses heat evenly through the interface effect. Adding both at the same time can avoid local overheating. It can be seen that there is a synergistic effect between nano alumina and micron alumina, which is more conducive to improving the heat resistance of plastic bottles. Ultrafine mica powder itself has high heat resistance and dispersibility. Adding ultrafine mica powder can further improve the heat resistance of plastic bottles.

[0011] Preferably, a heat-resistant plastic bottle comprises the following raw materials in parts by weight: 65-75 parts of polypropylene, 12-14 parts of polyethylene, 25-28 parts of polyethylene terephthalate resin, 1.5-2.5 parts of masterbatch, 7-9 parts of zinc molybdate, 1.5-2.5 parts of triphenyl phosphite, 6-8 parts of micron alumina, 3.5-4.5 parts of nano alumina, 9-11 parts of ultrafine mica powder, and 0.15-0.25 parts of antioxidant.

[0012] The heat-resistant plastic bottle of the present application can choose 65-75 parts of polypropylene, 12-14 parts of polyethylene, 25-28 parts of polyethylene terephthalate resin, 1.5-2.5 parts of masterbatch, 7-9 parts of zinc molybdate, 1.5-2.5 parts of triphenyl phosphite, 6-8 parts of micron alumina, 3.5-4.5 parts of nano alumina, 9-11 parts of ultrafine mica powder, and 0.15-0.25 parts of antioxidant. Any value within the respective ranges can be selected, and the heat resistance of the plastic bottle can be improved.

[0013] Preferably, the weight ratio of the nano-alumina to the micron-alumina is 1:(1-3).

[0014] By adopting the above technical solution and adjusting the weight ratio of micron alumina to nano alumina, the heat resistance of the plastic bottle can be further improved.

[0015] Preferably, the ultrafine mica powder is prepared by modification, specifically: S1, drying the ultrafine mica powder at 100-110°C for 2h, ultrasonically treating the ultrafine mica powder in an ethanol solution at 300W for 20-30min, filtering, and then soaking in 5% dilute hydrochloric acid to obtain pretreated ultrafine mica powder; S2, mixing the silane coupling agent, the titanate coupling agent and the ethanol solution, adjusting the pH to 3.5-4.5, stirring at 100-110° C., atomizing, adding to the pretreated ultrafine mica powder, stirring, cooling, discharging, washing, and drying to obtain modified ultrafine mica powder; The mass ratio of the silane coupling agent to the titanate coupling agent is 1:(1-2).

[0016] By adopting the above technical scheme, the titanate coupling agent and the silane coupling agent are compositely coated on the surface of the ultrafine mica powder, which can improve the polar and non-polar interface and improve the dispersibility of the ultrafine mica powder in the plastic bottle raw material, thereby further improving the heat resistance of the plastic bottle.

[0017] In addition, by drying the ultrafine mica powder at 100-110°C for 2 hours, the moisture consumption of silane active groups can be reduced. The ultrafine mica powder is then placed in an ethanol solution for ultrasonic treatment to destroy the ultrafine mica powder agglomerates. The mica is soaked in 5% dilute hydrochloric acid for 1 hour to increase the surface hydroxyl density and the silane grafting rate, thereby improving the dispersibility of the ultrafine mica powder in the heat-resistant plastic bottle raw material, thereby further improving the heat resistance of the plastic bottle.

[0018] Preferably, the weight ratio of the silane coupling agent to the ultrafine mica powder is 1: (70-80).

[0019] By adopting the above technical solution and adjusting the weight ratio of the silane coupling agent and the ultrafine mica powder, the dispersibility of the ultrafine mica powder in the plastic bottle raw material can be further improved, thereby further improving the heat resistance of the plastic bottle.

[0020] Preferably, the heat-resistant plastic bottle further comprises the following raw materials in parts by weight: 5-7 parts of polyphenylsiloxane microspheres.

[0021] By adopting the above technical solution, polyphenylsiloxane microspheres are a kind of organic silicon material with the characteristics of high temperature resistance and chemical stability. Adding polyphenylsiloxane microspheres can increase the thermal deformation temperature of plastic bottles, thereby further improving the heat resistance of plastic bottles.

[0022] Preferably, 6 parts by weight of polyphenylsiloxane microspheres are added to the heat-resistant plastic bottle raw material.

[0023] By adopting the above technical solution and adjusting the dosage of polyphenylsiloxane microspheres in the raw material of heat-resistant plastic bottles, the heat resistance of the plastic bottles can be further improved.

[0024] In a second aspect, the present application provides a method for preparing any of the above-mentioned heat-resistant plastic bottles.

[0025] A method for preparing a heat-resistant plastic bottle comprises the following steps: mixing various raw materials, heating and melting, stirring and plasticizing, preparing embryos, forming films, blowing and molding, demoulding, and sterilizing to obtain a heat-resistant plastic bottle.

[0026] In summary, the present application includes at least one of the following beneficial technical effects: (1) This application controls the type and dosage of each raw material in the heat-resistant plastic bottle so that the Vicat softening temperature of the plastic bottle is 135°C, thereby improving the heat resistance of the plastic bottle; (2) In this application, the surface of ultrafine mica powder is modified by coating a titanate coupling agent and a silane coupling agent in a composite manner, and the weight ratio of the silane coupling agent to the ultrafine mica powder is adjusted, so that the Vicat softening temperature of the plastic bottle is 136-137°C, thereby further improving the heat resistance of the plastic bottle; (3) The present application further improves the heat resistance of the plastic bottle by adding polyphenylsiloxane microspheres to the plastic bottle raw material and controlling the dosage thereof so that the Vicat softening temperature of the plastic bottle is 143°C. DETAILED DESCRIPTION

[0027] The present application is further described in detail below in conjunction with specific embodiments.

[0028] The following raw materials in this application are all commercially available products, and are intended to make the raw materials of this application fully disclosed, and should not be understood as limiting the source of the raw materials. Specifically: polypropylene, brand SK, grade R372Y; polyethylene, grade LB560410; color masterbatch, yellow, moisture 0.2%; polyethylene terephthalate resin, effective content 99%; micron alumina, particle size 50μm; nano alumina, particle size 50nm; ultrafine mica powder, particle size 1250 mesh; silane coupling agent, model KH-550; ethanol solution, effective substance content 70%; polyphenylsiloxane microspheres, effective substance content 98%; antioxidant, model HP-136.

[0029] The following is an example of the preparation of modified ultrafine mica powder Preparation Example 1 The modified ultrafine mica powder of Preparation Example 1 is prepared by the following steps: S1, drying 70kg of ultrafine mica powder at 105°C for 2h, ultrasonically treating in an ethanol solution (300W, 30min), filtering, and then soaking in 5% dilute hydrochloric acid to obtain pretreated ultrafine mica powder; S2. Evenly mix 1 kg of silane coupling agent, 1 kg of titanate coupling agent and 10 L of 70% ethanol solution, adjust the pH to 4, stir at 105°C for 30 min, atomize, add to 60 kg of ultrafine mica powder, stir evenly, cool to room temperature, discharge, wash, and dry to obtain modified ultrafine mica powder.

[0030] Preparation Example 2-5 The preparation methods of the modified ultrafine mica powders of Preparation Examples 2-5 are the same as those of Preparation Example 1, except that the amounts of ultrafine mica powder used are 70kg, 75kg, 80kg and 90kg respectively, and the types and amounts of other raw materials are the same as those of Preparation Example 1.

[0031] Example 1

[0032] The heat-resistant plastic bottle of Example 1 is prepared by the following preparation method: According to the dosage in Table 1, the raw materials were mixed, heated to 180°C, heated for 25 minutes, melted, stirred and plasticized to make embryos, the injection molding pressure was 2 MPa, the film was closed, and the blowing pressure was 1 MPa and the blowing temperature was 80°C for 2 seconds to form, cooled to 10°C, demolded after cooling for 4 seconds, and sterilized with ozone for 15 minutes to obtain a heat-resistant plastic bottle.

[0033] Example 2-3 The preparation method of the heat-resistant plastic bottle of Example 2-3 is the same as that of Example 1, except that the dosage of each raw material is different, as shown in Table 1. Table 1 Amount of each raw material in Examples 1-3 heat-resistant plastic bottles (kg)

[0034] Embodiment 4-7 The preparation method of the heat-resistant plastic bottle of Examples 4-7 is the same as that of Example 2, except that the dosage of each raw material is different, as shown in Table 2. Table 2 Amount of each raw material in Example 4-7 heat-resistant plastic bottle (kg)

[0035] Examples 8-12 The preparation method of the heat-resistant plastic bottles of Examples 8-12 is the same as that of Example 5, except that the ultrafine mica powder in the raw material of the heat-resistant plastic bottles is the modified ultrafine mica powder prepared in Preparation Examples 1-5, and the other raw material types and dosages are the same as those in Example 5.

[0036] Example 13

[0037] The preparation method of the heat-resistant plastic bottle of Example 13 is the same as that of Example 10, except that it further includes 4 kg of polyphenylsiloxane microspheres, and the other raw material types and dosages are the same as those of Example 10.

[0038] Examples 14-17 The preparation method of the heat-resistant plastic bottle of Examples 14-17 is the same as that of Example 13, except that the dosage of polyphenylsiloxane microspheres is 5kg, 6kg, 7kg and 8kg respectively, and the types and dosages of other raw materials are the same as those of Example 13.

[0039] Comparative Example 1 The preparation method of the heat-resistant plastic bottle of Comparative Example 1 is the same as that of Example 1, except that an equal amount of micron alumina in the heat-resistant plastic bottle is replaced by nano alumina, and the other raw material types and dosages are the same as those of Example 1.

[0040] Comparative Example 2 The preparation method of the heat-resistant plastic bottle of Comparative Example 2 is the same as that of Example 1, except that an equal amount of nano-alumina in the heat-resistant plastic bottle is replaced by micron-alumina, and the other raw material types and dosages are the same as those of Example 1.

[0041] Comparative Example 3 The preparation method of the heat-resistant plastic bottle of Comparative Example 3 is the same as that of Example 1, except that no ultrafine mica powder is added to the raw materials of the plastic bottle, and the types and amounts of other raw materials are the same as those of Example 1.

[0042] Comparative Example 4 The preparation method of the heat-resistant plastic bottle of Comparative Example 4 is the same as that of Example 1, except that an equal amount of zinc molybdate in the heat-resistant plastic bottle is replaced by triphenyl phosphite, and the other raw material types and dosages are the same as those of Example 1.

[0043] Comparative Example 5 The preparation method of the heat-resistant plastic bottle of Comparative Example 5 is the same as that of Example 1, except that an equal amount of triphenyl phosphite in the heat-resistant plastic bottle is replaced by zinc molybdate, and the other raw material types and dosages are the same as those of Example 1.

[0044] Performance Testing The performance of the plastic bottles obtained in different Examples 1-17 and Comparative Examples 1-5 was tested respectively. The test results are shown in Table 3.

[0045] Impact strength: The impact strength of plastic bottles was tested according to GB / T 1843-2008, see Table 3 for details; Tensile strength: The tensile strength of plastic bottles was tested according to GB / T 1040.2-2006, see Table 3 for details; Heat resistance: According to QBT 1633-2000, the heat resistance of plastic bottles was tested and the Vicat softening temperature was tested. See Table 3 for details. Table 3 Performance test results of different plastic bottles

[0046] The test results in Table 3 show that the impact strength and tensile strength of the plastic bottle obtained in this application can reach up to 7.0KJ / m 2 , 40.0Mpa, with high mechanical properties, and the Vicat softening temperature reaches 143°C, which greatly improves the heat resistance of plastic bottles.

[0047] Combining the performance test data of the plastic bottles in Examples 1-3, it can be seen that the Vicat softening temperature of the plastic bottle in Example 2 is 135°C, which is higher than that in Examples 1 and 3, indicating that the dosage of zinc molybdate and triphenyl phosphite in the raw materials of the plastic bottle in Example 2 is more appropriate, which improves the heat resistance of the plastic bottle. It may be that the addition of triphenyl phosphite together with zinc molybdate can, on the one hand, reduce the Mo in zinc molybdate to 100% at high temperature. 6+ Partially reduced to MO 4+ On the one hand, the formation of more active low-valent molybdenum species can more efficiently terminate the free radicals produced by the thermal degradation of plastics. On the other hand, the combined addition of the two can significantly prolong the oxidation induction period of plastics, thereby further improving the heat resistance of plastic bottles.

[0048] Combining the performance test data of the plastic bottles in Examples 2 and 4-7, it can be seen that the Vicat softening temperature of the plastic bottles in Examples 4-6 is 136-137°C, which is higher than that in Examples 2 and 7, indicating that when the weight ratio of nano-alumina to micron-alumina is 1: (1-3), it is more appropriate, which improves the heat resistance of the plastic bottles.

[0049] Combined with the performance test data of the plastic bottles in Examples 8-12, it can be seen that the Vicat softening temperature of the plastic bottles in Examples 4-6 is 139-140°C, which is higher than that in Example 8 and Example 12, indicating that when modifying the ultrafine mica powder, it is more appropriate to use the weight ratio of silane coupling agent to ultrafine mica powder of 1: (70-80), which can further improve the dispersibility of the ultrafine mica powder in the raw materials, thereby improving the heat resistance of the plastic bottle.

[0050] Combined with the performance test data of the plastic bottles in Examples 13-17, it can be seen that the Vicat softening temperature of the plastic bottle in Example 15 is 143°C, which is higher than that of Examples 13-14 and Examples 16-17, indicating that it is more appropriate to add 6 parts by weight of polyphenylsiloxane microspheres to the raw material of the heat-resistant plastic bottle, which improves the heat resistance of the plastic bottle.

[0051] In addition, based on the performance test data of the plastic bottles of Comparative Examples 1-3 and Example 1, it was found that adding zinc molybdate, triphenyl phosphite, micron alumina and nano alumina to the plastic bottle raw materials can improve the heat resistance of the plastic bottles to varying degrees.

[0052] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A heat-resistant plastic bottle, characterized in that: The invention comprises the following raw materials in parts by weight: 60-80 parts of polypropylene, 10-15 parts of polyethylene, 20-30 parts of polyethylene terephthalate resin, 1-3 parts of coloring masterbatch, 5-10 parts of zinc molybdate, 1-3 parts of triphenyl phosphite, 5-9 parts of micron alumina, 3-5 parts of nano alumina, 8-12 parts of superfine mica powder and 0.1-0.3 parts of antioxidant.

2. The heat-resistant plastic bottle according to claim 1, characterized in that: The invention comprises the following raw materials in parts by weight: 65-75 parts of polypropylene, 12-14 parts of polyethylene, 25-28 parts of polyethylene terephthalate resin, 1.5-2.5 parts of coloring masterbatch, 7-9 parts of zinc molybdate, 1.5-2.5 parts of triphenyl phosphite, 6-8 parts of micron alumina, 3.5-4.5 parts of nano alumina, 9-11 parts of superfine mica powder and 0.15-0.25 parts of antioxidant.

3. The heat-resistant plastic bottle according to claim 1, characterized in that: The weight ratio of the nano-alumina to the micron-alumina is 1:(1-3).

4. The heat-resistant plastic bottle according to claim 1, characterized in that: The ultrafine mica powders are prepared by modification, specifically: S1, drying the ultrafine mica powder at 100-110°C for 2h, ultrasonically treating it in an ethanol solution at 300W for 20-30min, filtering it, and then soaking it in 5% dilute hydrochloric acid to obtain the pretreated ultrafine mica powder; S2, mixing the silane coupling agent, the titanate coupling agent and the ethanol solution, adjusting the pH to 3.5-4.5, stirring at 100-110° C., atomizing, adding to the pretreated ultrafine mica powder, stirring, cooling, discharging, washing, and drying to obtain modified ultrafine mica powder; The mass ratio of the silane coupling agent to the titanate coupling agent is 1:(1-2).

5. The heat-resistant plastic bottle according to claim 4, characterized in that: The weight ratio of the silane coupling agent to the ultrafine mica powder is 1: (70-80).

6. The heat-resistant plastic bottle according to claim 1, characterized in that: The heat-resistant plastic bottle further comprises the following raw materials in parts by weight: 5-7 parts of polyphenylsiloxane microspheres.

7. The heat-resistant plastic bottle according to claim 6, characterized in that: 6 parts by weight of polyphenylsiloxane microspheres are added to the heat-resistant plastic bottle raw material.

8. A method for preparing a heat-resistant plastic bottle according to any one of claims 1 to 7, characterized in that: The method comprises the following operating steps: mixing various raw materials, heating and melting, stirring and plasticizing, preparing embryos, combining films, blowing and forming, demoulding, and sterilizing to obtain heat-resistant plastic bottles.

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