CN107189321A - TPE/PVAC composite fresh-keeping box cover and preparation method thereof - Google Patents

Abstract

The invention discloses a TPE/PVAC composite fresh-keeping box cover and a preparation method thereof, the preparation method comprising: 1) mixing soluble aluminum salt, soluble magnesium salt, soluble zirconium salt, urea and water to form a salt solution, and then performing a hydrothermal reaction to obtain a hydrothermal product; 2) ball-milling the hydrothermal product in a silane coupling agent to obtain a modified hydrothermal product; 3) mixing and molding TPE (thermoplastic rubber), PVAC (polyvinyl acetate), talcum powder, stearic acid, paraffin oil, diisononyl phthalate, silicon powder, the modified hydrothermal product and oleic acid to obtain the TPE/PVAC composite fresh-keeping box cover. The TPE/PVAC composite fresh-keeping box cover has excellent high temperature resistance, and the preparation method has the advantages of simple process and easy availability of raw materials.

Description

TPE/PVAC composite fresh-keeping box cover and preparation method thereof

technical field

The invention relates to a fresh-keeping box cover, in particular to a TPE/PVAC composite fresh-keeping box cover and a preparation method thereof.

Background technique

The lid of the crisper is an important component of the crisper, which not only determines the sealing performance of the crisper, but also directly affects the freshness of the crisper. At present, the lid of the crisper is mainly made of polymer, which can basically meet the market demand, but in the process of use, it is often found that the crisper cannot be sealed immediately after filling the high-temperature food, otherwise it will cause the deformation of the crisper Therefore, it can be seen that there is still a certain deficiency in the high temperature resistance of the current crisper lid.

Contents of the invention

The object of the present invention is to provide a TPE/PVAC composite fresh-keeping box cover and a preparation method thereof. The TPE/PVAC composite fresh-keeping box cover has excellent high temperature resistance, and the preparation method has the advantages of simple procedures and readily available raw materials.

In order to achieve the above object, the invention provides a method for preparing a TPE/PVAC composite fresh-keeping box cover, comprising:

1) mixing soluble aluminum salt, soluble magnesium salt, soluble zirconium salt, urea and water to make a salt solution, and then performing a hydrothermal reaction to obtain a hydrothermal product;

2) ball milling the hydrothermal product in a silane coupling agent to obtain a modified hydrothermal product;

3) Mix TPE (thermoplastic rubber), PVAC (polyethyl acetate), talcum powder, stearic acid, paraffin oil, diisononyl phthalate, silicon micropowder, modified hydrothermal product and oleic acid , Molding to make TPE/PVAC composite crisper lid.

The present invention also provides a TPE/PVAC composite fresh-keeping box cover, and the TPE/PVAC composite fresh-keeping box cover is prepared by the above preparation method.

In the above-mentioned technical scheme, the present invention first generates aluminum hydroxide/magnesium-zirconium compound through the hydrothermal reaction of soluble aluminum salt, soluble magnesium salt, soluble zirconium salt, urea and water; Activation produces free radicals or ions, so as to better couple with the silane coupling agent and improve its lipophilic and hydrophobic properties; finally, the modified hydrothermal product is used as a flame retardant to improve the high temperature resistance of the prepared fresh-keeping box cover. Simultaneously, the preparation method has the advantages of simple procedure and readily available raw materials.

Other features and advantages of the present invention will be described in detail in the following detailed description.

detailed description

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

The invention provides a method for preparing a TPE/PVAC composite fresh-keeping box cover, comprising:

1) mixing soluble aluminum salt, soluble magnesium salt, soluble zirconium salt, urea and water to make a salt solution, and then performing a hydrothermal reaction to obtain a hydrothermal product;

2) ball milling the hydrothermal product in a silane coupling agent to obtain a modified hydrothermal product;

3) Mix TPE (thermoplastic rubber), PVAC (polyethyl acetate), talcum powder, stearic acid, paraffin oil, diisononyl phthalate, silicon micropowder, modified hydrothermal product and oleic acid , Molding to make TPE/PVAC composite crisper lid.

In step 1) of the above-mentioned preparation method, the consumption of each material can be selected in a wide range, but in order to further improve the high temperature resistance of the prepared fresh-keeping box cover, preferably, in step 1), relative to 1 mmol The amount of soluble aluminum salt and soluble magnesium salt is 0.5-0.8mmol, the amount of soluble zirconium salt is 0.1-0.3mmol, the amount of urea is 3-5mmol, and the amount of water is 5-10mL.

In step 1) of the above-mentioned preparation method, the specific types of soluble aluminum salt, soluble magnesium salt, and soluble zirconium salt can be selected in a wide range, but in order to further improve the high temperature resistance of the prepared fresh-keeping box cover, preferably, In step 1), the soluble aluminum salt is selected from at least one of aluminum chloride, aluminum nitrate or aluminum sulfate, the soluble magnesium salt is selected from magnesium chloride and/or magnesium nitrate, and the soluble zirconium salt is selected from zirconium chloride and/or Zirconium nitrate.

In step 1) of the above-mentioned preparation method, the specific conditions of the hydrothermal reaction can be selected in a wide range, but in order to further improve the high temperature resistance of the prepared fresh-keeping box cover, preferably, in step 1), hydrothermal reaction The reaction at least satisfies the following conditions: it is carried out in a closed environment, the reaction temperature is 170-200°C, and the reaction time is 12-20h.

In step 2) of the above-mentioned preparation method, the consumption of each material can be selected in a wide range, but in order to further improve the high temperature resistance of the prepared fresh-keeping box cover, preferably, in step 2), the hydrothermal product and The molar ratio of silane coupling agent is 1:0.1-0.2.

In step 2) of the above preparation method, the specific type of silane coupling agent can be selected in a wide range, but in order to further improve the high temperature resistance of the prepared fresh-keeping box cover, preferably, in step 2), silane The coupling agent is selected from at least one of silane coupling agent Kh550, silane coupling agent Kh560 and silane coupling agent Kh570.

In step 2) of the above-mentioned preparation method, the specific conditions of ball milling can be selected in a wide range, but in order to further improve the high temperature resistance of the prepared fresh-keeping box cover, preferably, in step 2), the ball milling at least satisfies the following Conditions: The number ratio of large balls to small balls is 2:0.8-1.2, the mass ratio of grinding balls to materials is 10:2-2.5, the rotation speed is 800-1000rpm, and the ball milling time is 40-60min.

In step 3) of the above-mentioned preparation method, the consumption of each material can be selected in a wide range, but in order to further improve the high temperature resistance of the prepared fresh-keeping box cover, preferably, in step 3), TPE, PVAC, The weight ratio of talc powder, stearic acid, paraffin oil, diisononyl phthalate, silicon micropowder, modified hydrothermal product and oleic acid is 100:40-60:10-14:25-36:7- 18:22-37:4-7:3-5:30-38.

In step 3) of the above-mentioned preparation method, the conditions of mixing and molding can be selected in a wide range, but in order to further improve the high temperature resistance of the prepared fresh-keeping box cover, preferably, in step 3), mixing At least the following conditions are met: the mixing temperature is 200-215° C., and the mixing time is 4-6 hours; the molding is carried out by extrusion molding.

In step 3) of the above-mentioned preparation method, the specific type of TPE can be selected in a wide range, but in order to further improve the high temperature resistance of the fresh-keeping box cover made, TPE is selected from SBS (styrene-butadiene copolymer ), TPU (thermoplastic polyurethane), TEO (polyolefin thermoplastic elastomer) and TES (styrene thermoplastic elastomer).

The present invention also provides a TPE/PVAC composite fresh-keeping box cover, and the TPE/PVAC composite fresh-keeping box cover is prepared by the above preparation method.

The present invention will be described in detail below by way of examples.

Example 1

1) Mix soluble aluminum salt (aluminum chloride), soluble magnesium salt (magnesium chloride), soluble zirconium salt (zirconium chloride), urea and water according to the dosage ratio of 1mmol: 0.6mmol: 0.2mmol: 4mmol: 8mL Salt solution, followed by hydrothermal reaction at 180°C for 16h to obtain a hydrothermal product;

2) Ball mill the hydrothermal product and silane coupling agent (silane coupling agent Kh550) at a molar ratio of 1:0.15 (the number ratio of large balls to small balls is 2:1, and the mass ratio of grinding balls to materials is 10:2.3, the rotating speed is 900rpm, the ball milling time is 50min) to obtain the modified hydrothermal product;

3) Mix TPE (SBS), PVAC, talcum powder, stearic acid, paraffin oil, diisononyl phthalate, silicon micropowder, modified hydrothermal product and oleic acid according to the ratio of 100:50:12:29:12 : 29: 6: 4: 34 weight ratio, kneading at 210°C for 5 hours, extrusion molding to obtain TPE/PVAC composite fresh-keeping box cover A1.

Example 2

1) Mix soluble aluminum salt (aluminum nitrate), soluble magnesium salt (magnesium nitrate), soluble zirconium salt (zirconium nitrate), urea and water according to the dosage ratio of 1mmol: 0.5mmol: 0.1mmol: 3mmol: 5mL to make salt solution, followed by a hydrothermal reaction at 170°C for 12 hours to obtain a hydrothermal product;

2) Ball mill the hydrothermal product and silane coupling agent (silane coupling agent Kh560) at a molar ratio of 1:0.1 (the number ratio of large balls to small balls is 2:0.8, and the mass ratio of grinding balls to materials is 10:2, rotating speed is 800rpm, ball milling time is 40min) to obtain modified hydrothermal product;

3) Mix TPE (TEO), PVAC, talc, stearic acid, paraffin oil, diisononyl phthalate, silicon micropowder, modified hydrothermal product and oleic acid according to the ratio of 100:40:10:25:7 : 22:4:3:30 weight ratio, kneading at 200°C for 4 hours, extrusion molding to prepare TPE/PVAC composite crisper lid A2.

Example 3

1) Mix soluble aluminum salt (aluminum sulfate), soluble magnesium salt (magnesium nitrate), soluble zirconium salt (zirconium nitrate), urea and water according to the dosage ratio of 1mmol: 0.8mmol: 0.3mmol: 5mmol: 10mL to make salt solution, followed by a hydrothermal reaction at 200°C for 20h to obtain a hydrothermal product;

2) Ball mill the hydrothermal product and silane coupling agent (silane coupling agent Kh570) according to the molar ratio of 1:0.2 (the number ratio of large balls to small balls is 2:1.2, and the mass ratio of grinding balls to materials is 10:2.5, the rotation speed is 1000rpm, the ball milling time is 60min) to obtain the modified hydrothermal product;

3) Mix TPE (TES), PVAC, talc, stearic acid, paraffin oil, diisononyl phthalate, silicon micropowder, modified hydrothermal product and oleic acid according to the ratio of 100:60:14:36:18 : 37: 7: 5: 38 weight ratio, kneading at 215°C for 6 hours, extrusion molding to obtain TPE/PVAC composite crisper lid A3.

Comparative example 1

The fresh-keeping box lid B1 was prepared according to the method of Example 1, except that no soluble aluminum salt was used in step 1).

Comparative example 2

The fresh-keeping box lid B2 was prepared according to the method of Example 1, except that no soluble magnesium salt was used in step 1).

Comparative example 3

The fresh-keeping box lid B3 was prepared according to the method of Example 1, except that no soluble zirconium salt was used in step 1).

Comparative example 4

The fresh-keeping box lid B4 was prepared according to the method of Example 1, except that no silane coupling agent was used in step 2).

Comparative example 5

The fresh-keeping box lid B5 was prepared according to the method of Example 1, except that no modified hydrothermal product was used in step 3).

Test example 1

According to the method recorded in GB1035-70, the heat distortion temperature of the above-mentioned fresh-keeping box cover was detected, and the specific results are shown in Table 1.

Table 1

Heat distortion temperature/℃ A1 277 A2 276 A3 279 B1 220 B2 210 B3 207 B4 244 B5 185

It can be seen from the above examples, comparative examples and test examples that the fresh-keeping box cover provided by the present invention has excellent high temperature resistance.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (10)

1. A preparation method for a TPE/PVAC composite fresh-keeping box cover, characterized in that, comprising: 1) mixing soluble aluminum salt, soluble magnesium salt, soluble zirconium salt, urea and water to make a salt solution, and then performing a hydrothermal reaction to obtain a hydrothermal product; 2) ball milling the hydrothermal product in a silane coupling agent to obtain a modified hydrothermal product; 3) Mix TPE (thermoplastic rubber), PVAC (polyethyl acetate), talcum powder, stearic acid, paraffin oil, diisononyl phthalate, silicon micropowder, modified hydrothermal product and oleic acid , molding to make the TPE/PVAC composite fresh-keeping box cover. 2. The preparation method according to claim 1, wherein, in step 1), with respect to the described soluble aluminum salt of 1mmol, the consumption of described soluble magnesium salt is 0.5-0.8mmol, the consumption of described soluble zirconium salt 0.1-0.3mmol, the amount of urea is 3-5mmol, and the amount of water is 5-10mL. 3. The preparation method according to claim 1, wherein, in step 1), the soluble aluminum salt is selected from at least one of aluminum chloride, aluminum nitrate or aluminum sulfate, and the soluble magnesium salt is selected from magnesium chloride and/or magnesium nitrate, the soluble zirconium salt is selected from zirconium chloride and/or zirconium nitrate. 4. The preparation method according to claim 1, wherein, in step 1), the hydrothermal reaction at least meets the following conditions: carried out in a closed environment, the reaction temperature is 170-200°C, and the reaction time is 12-20h . 5. The preparation method according to any one of claims 1-4, wherein, in step 2), the molar ratio of the hydrothermal product to the silane coupling agent is 1:0.1-0.2. 6. The preparation method according to claim 5, wherein, in step 2), the silane coupling agent is selected from at least one of silane coupling agent Kh550, silane coupling agent Kh560 and silane coupling agent Kh570 . 7. The preparation method according to claim 5, wherein, in step 2), the ball mill at least satisfies the following conditions: the number ratio of large balls to small balls is 2:0.8-1.2, the quality of the balls and the material The ratio is 10:2-2.5, the rotation speed is 800-1000rpm, and the ball milling time is 40-60min. 8. The preparation method according to claim 6 or 7, wherein, in step 3), the TPE, PVAC, talcum powder, stearic acid, paraffin oil, diisononyl phthalate, silicon micropowder, The weight ratio of the modified hydrothermal product to oleic acid is 100:40-60:10-14:25-36:7-18:22-37:4-7:3-5:30-38. 9. The preparation method according to claim 8, wherein, in step 3), the mixing at least satisfies the following conditions: the mixing temperature is 200-215°C, and the mixing time is 4-6h; Carried out by extrusion molding; Preferably, the TPE is selected from at least one of SBS (styrene-butadiene copolymer), TPU (thermoplastic polyurethane), TEO (polyolefin thermoplastic elastomer) and TES (styrene thermoplastic elastomer). 10. A TPE/PVAC composite fresh-keeping box cover, characterized in that, the TPE/PVAC composite fresh-keeping box cover is prepared by the preparation method described in any one of claims 1-9.