Composite additive for polypropylene film and preparation method of composite additive

Abstract

The invention provides a composite additive for a polypropylene film. The composite additive is prepared from the following components in parts by weight: 5 to 10 parts of an antioxidant 1010, 7 to 12 parts of an antioxidant 168, 4 to 8 parts of an antioxidant 1330, 2 to 4 parts of hydrotalcite DHT-4A, 1 to 3 parts of AC-207 and 1 to 3 parts of sodium diphenylacetate serving as a nucleating agent. The plastic is prepared from the following components in parts by weight: 3-8 parts of a plasticizer, 2-4 parts of an antibacterial agent, 1-3 parts of an antistatic agent, 0.5-1.5 parts of glass fibers, 1.5-2.5 parts of butyl stearate, 0.3-0.8 part of a silane coupling agent KH550 and 0.5-1 part of dicumyl peroxide. By rechecking the auxiliaries, the problems of product instability, synergistic benefit damage, much dust pollution and the like caused by independently adding the auxiliaries are reduced, and finally the composite auxiliary with good stability and good effect is prepared.

Description

Technical Field

[0001] The invention belongs to the technical field of auxiliary agent preparation, and specifically relates to a composite auxiliary agent for polypropylene film and a preparation method thereof. Background Art

[0002] Polypropylene (PP) is a thermoplastic prepared by polymerization of propylene monomers, with excellent physical properties, chemical stability and cost-effectiveness. Polypropylene can be divided into the following main types: Isotactic Polypropylene (iPP): The methyl groups of the propylene monomers are located on the same side, forming a highly regular molecular chain. Isotactic polypropylene has high crystallinity and mechanical strength and is the most common type of polypropylene. Syndiotactic Polypropylene (sPP): The methyl groups of the propylene monomers are arranged alternately on both sides of the molecular chain to form a symmetrical structure. Syndiotactic polypropylene has a high glass transition temperature (Tg) and heat resistance, but its output is low and its application is limited. Atactic Polypropylene (aPP): The methyl groups of the propylene monomers are randomly arranged, the molecular chain is irregular, and the crystallinity is low. It is usually used as a modifier or blended with other polymers.

[0003] Polypropylene films are used for various purposes such as packaging, mold release, tape, cable winding, and electrical applications such as capacitors due to their excellent transparency, mechanical properties, and electrical properties. In particular, polypropylene films are suitable for use as mold release films and process films for various components such as plastic products, building materials, and optical components due to their excellent surface release properties and mechanical properties.

[0004] With the expansion of the application field of domestic polypropylene products and the improvement of the performance of special polypropylene film products, the antioxidant properties and other physical properties of its additives are becoming more and more stringent. At present, domestic manufacturers are gradually switching from the earliest imported additives to domestic additives due to the high prices of imported additives. At present, most domestic additives are often added separately according to different physical properties to achieve performance indicators, which can easily cause the destruction of the synergistic effect between additives, inaccurate addition, unstable product quality, and dust pollution caused by separate addition, which is harmful to health and prone to dangerous factors caused by dust static electricity. Summary of the invention

[0005] The purpose of the present invention is to provide a composite auxiliary agent for polypropylene film and a preparation method thereof. By reviewing each auxiliary agent, the problems of product instability, destruction of synergistic benefits, excessive dust pollution, etc. caused by adding auxiliary agents alone are reduced, and the composite auxiliary agent finally obtained has good stability and good effect.

[0006] In order to achieve the above object, the present invention provides the following technical solutions: A composite auxiliary agent for polypropylene film comprises the following components in parts by weight: 5-10 parts of antioxidant 1010, 7-12 parts of antioxidant 168, 4-8 parts of antioxidant 1330, 2-4 parts of hydrotalcite DHT-4A, 1-3 parts of AC-207 and 1-3 parts of nucleating agent sodium diphenylacetate.

[0007] Preferably, the invention also includes 3-8 parts of plasticizer, 2-4 parts of antibacterial agent, 1-3 parts of antistatic agent, 0.5-1.5 parts of glass fiber, 1.5-2.5 parts of butyl stearate, 0.3-0.8 parts of silane coupling agent KH550 and 0.5-1 parts of diisopropylbenzene peroxide.

[0008] Preferably, the plasticizer is prepared by mixing 7-10 parts of polyisobutylene, 1-4 parts of 2-aminocyclohexanol and 2-6 parts of N-dodecylalanine.

[0009] Preferably, the antibacterial agent is prepared by chitosan loaded with nanosilver.

[0010] Preferably, the antistatic agent comprises 60-80 parts of high-density polyethylene, 35-45 parts of conductive carbon black, 1-4 parts of tetraisopropyl titanate and 2-5 parts of 2-tert-butyl-4,6-dimethylphenol; the average particle size of the conductive carbon black is 10-50nm, the oil absorption value is greater than 200ml / 100g, and the ash content is less than 1.0%.

[0011] Preferably, the glass fiber is alkali-free chopped glass fiber, with a single fiber diameter of 3-5 um and a length of 1-3 mm.

[0012] A method for preparing a composite auxiliary agent for a polypropylene film comprises the following steps: S1: prepare plasticizer, antibacterial agent and antistatic agent respectively; S2: 5-10 parts of antioxidant 1010, 7-12 parts of antioxidant 168, 4-8 parts of antioxidant 1330, 2-4 parts of hydrotalcite DHT-4A, 2-4 parts of antibacterial agent, 1-3 parts of antistatic agent and 0.5-1.5 parts of glass fiber are mixed, and stirred at a temperature of 60-80°C for 50-80 minutes to obtain material A; S3: 3-8 parts of plasticizer, 1.5-2.5 parts of butyl stearate, 1-3 parts of AC-207, and 1-3 parts of nucleating agent sodium diphenylacetate are mixed, stirred at a temperature of 140-160° C. for 40-60 minutes, and then the material A described in step S2, 0.3-0.8 parts of silane coupling agent KH550 and 0.5-1 parts of diisopropylbenzene peroxide are added, and the mixture is put into an extruder, and the extruder is controlled to include a first zone, a second zone, and a third zone connected in sequence from the feed port to the die; the temperature of the first zone is 180-200° C., the temperature of the second zone is 210-220° C., and the temperature of the third zone is 225-235° C.; the screw speed of the twin-screw extruder is 600-800 r / min, the extruder stays for 5-8 minutes, and the composite auxiliary agent for the polypropylene film is obtained after cooling.

[0013] Preferably, the preparation process of the plasticizer in step S1 is: 7-10 parts of polyisobutylene, 1-4 parts of 2-aminocyclohexanol and 2-6 parts of N-dodecylalanine are mixed, and stirred at a temperature of 100-120° C. for 30-50 minutes to obtain the plasticizer.

[0014] Preferably, the preparation process of the antibacterial agent in step S1 is: dissolving chitosan in a 3% by mass acetic acid aqueous solution according to a solid-liquid ratio of 1g:8-10ml; adding 5% by mass of silver nitrate of the total mass of the chitosan solution while stirring, and stirring evenly to obtain the antibacterial agent.

[0015] Preferably, the preparation process of the antistatic agent in step S1 is: mix 60-80 parts of high-density polyethylene, 35-45 parts of conductive carbon black, 1-4 parts of tetraisopropyl titanate and 2-5 parts of 2-tert-butyl-4,6-dimethylphenol, and stir at a temperature of 140-160° C. for 50-70 minutes to obtain the antistatic agent.

[0016] Compared with the prior art, the advantages and beneficial effects of the present invention are: The invention combines various auxiliary agents in the preparation of polypropylene film, such as antioxidant 1010, antioxidant 168, antioxidant 1330, hydrotalcite DHT-4A, AC-207 and nucleating agent sodium diphenylacetate and other basic auxiliary agents, with improvement auxiliary agents such as plasticizer, antibacterial agent, antistatic agent, glass fiber and the like, and simultaneously adds silane coupling agent KH550 and diisopropylbenzene peroxide to improve the interface relationship between organic resin and inorganic material, enhance the bonding force, and better form a unified whole. The prepared composite auxiliary agent has the characteristics of stability, good auxiliary agent efficacy and the like, and is applied to the production process of polypropylene film to improve its production efficiency. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] The raw materials used in the present invention are as follows: Polyisobutylene (Shanghai Yuanye Biotechnology Co., Ltd., S22214); chitosan (Shanghai Yuanye Biotechnology Co., Ltd., S11064); high-density polyethylene (Shanghai Pengyue New Materials Co., Ltd., HYA-600); conductive carbon black (Zhejiang Yamei Nanotechnology Co., Ltd., 331); tetraisopropyl titanate (Huzhou Haipu Chemical Co., Ltd., 56); antioxidant 1010 (Shanghai Yuanye Biotechnology Co., Ltd., S67391); antioxidant 168 (Shanghai Yuanye Biotechnology Co., Ltd., S31114); antioxidant 1330 (Shanghai Yuanye Biotechnology Co., Ltd., S43553); hydrotalcite DHT-4A (Shanghai Yuanye Biotechnology Co., Ltd., T22944); butyl stearate (Hubei Wande Chemical Co., Ltd., WD1138); AC-207 (Daoer Chemical, 135); sodium diphenylacetate (Shanghai Yuanye Biotechnology Co., Ltd., S62426); silane coupling agent KH550 (Shanghai Yuanye Biotechnology Co., Ltd., S15028).

[0019] Example 1 This embodiment provides a method for preparing a composite auxiliary agent for a polypropylene film, comprising the following steps: S1: 7 g of polyisobutylene, 1 g of 2-aminocyclohexanol and 2 g of N-dodecylalanine were mixed, and stirred at 100° C. and 300 r / min for 30 min to obtain a plasticizer; Dissolve chitosan in a 3% by mass acetic acid aqueous solution according to a solid-liquid ratio of 1g:8ml; add 5% by mass of silver nitrate of the total mass of the chitosan solution while stirring, and stir evenly to obtain an antibacterial agent; 60g of high-density polyethylene, 35g of conductive carbon black, 1g of tetraisopropyl titanate and 2g of 2-tert-butyl-4,6-dimethylphenol were mixed, and stirred at a temperature of 140°C and a speed of 400r / min for 50min to obtain an antistatic agent; the conductive carbon black had an average particle size of 10-20nm, an oil absorption value of 300ml / 100g, and an ash content of 0.6%; S2: 5g of antioxidant 1010, 7g of antioxidant 168, 4g of antioxidant 1330, 2g of hydrotalcite DHT-4A, 2g of antibacterial agent, 1g of antistatic agent and 0.5g of glass fiber (the glass fiber is alkali-free chopped glass fiber, the monofilament diameter is 3-5um, and the length is 1-3mm) are mixed, and stirred at a temperature of 60°C and a speed of 400r / min for 50min to obtain material A; S3: 3g of plasticizer, 1.5g of butyl stearate, 1g of AC-207, and 1g of nucleating agent sodium diphenylacetate are mixed, stirred at a temperature of 140°C and a speed of 500r / min for 40min, and then the material A described in step S2, 0.3g of silane coupling agent KH550 and 0.5g of diisopropylbenzene peroxide are added, and the mixture is put into an extruder, and the extruder is controlled to include a first zone, a second zone, and a third zone connected in sequence from the feed port to the die; the temperature of the first zone is 180°C, the temperature of the second zone is 210°C, and the temperature of the third zone is 225°C; the screw speed of the twin-screw extruder is 600 r / min, the extruder stays for 5min, and the composite auxiliary agent for the polypropylene film is obtained after cooling.

[0020] Example 2 This embodiment provides a method for preparing a composite auxiliary agent for a polypropylene film, comprising the following steps: S1: 10 g polyisobutylene, 4 g 2-aminocyclohexanol and 6 g N-dodecylalanine were mixed, and stirred at 120° C. and 600 r / min for 50 min to obtain a plasticizer; Dissolve chitosan in a 3% by mass acetic acid aqueous solution according to a solid-liquid ratio of 1g:10ml; add 5% by mass of silver nitrate of the total mass of the chitosan solution while stirring, and stir evenly to obtain an antibacterial agent; 80g of high-density polyethylene, 45g of conductive carbon black, 4g of tetraisopropyl titanate and 5g of 2-tert-butyl-4,6-dimethylphenol were mixed, and stirred at a temperature of 160°C and a speed of 500r / min for 70min to obtain an antistatic agent; the conductive carbon black had an average particle size of 40-50nm, an oil absorption value of 350ml / 100g, and an ash content of 0.8%; S2: 10g antioxidant 1010, 12g antioxidant 168, 8g antioxidant 1330, 4g hydrotalcite DHT-4A, 4g antibacterial agent, 3g antistatic agent and 1.5g glass fiber (the glass fiber is alkali-free chopped glass fiber, the monofilament diameter is 3-5um, and the length is 1-3mm) are mixed, and stirred at a temperature of 80°C and a speed of 500r / min for 80min to obtain material A; S3: 8g of plasticizer, 2.5g of butyl stearate, 3g of AC-207, and 3g of nucleating agent sodium diphenylacetate are mixed, stirred at a temperature of 160°C and a speed of 500r / min for 60min, and then the material A described in step S2, 0.8g of silane coupling agent KH550 and 1g of diisopropylbenzene peroxide are added, and the mixture is put into an extruder, and the extruder is controlled to include a first zone, a second zone, and a third zone connected in sequence from the feed port to the die; the temperature of the first zone is 200°C, the temperature of the second zone is 220°C, and the temperature of the third zone is 235°C; the screw speed of the twin-screw extruder is 800 r / min, the extruder stays for 8 min, and the composite additive for the polypropylene film is obtained after cooling.

[0021] Example 3 This embodiment provides a method for preparing a composite auxiliary agent for a polypropylene film, comprising the following steps: S1: 8 g of polyisobutylene, 3 g of 2-aminocyclohexanol and 4 g of N-dodecylalanine were mixed, and stirred at 110° C. and 500 r / min for 45 min to obtain a plasticizer; Dissolve chitosan in a 3% by mass acetic acid aqueous solution according to a solid-liquid ratio of 1g:9ml; add 5% by mass of silver nitrate of the total mass of the chitosan solution while stirring, and stir evenly to obtain an antibacterial agent; 70g of high-density polyethylene, 40g of conductive carbon black, 3g of tetraisopropyl titanate and 4g of 2-tert-butyl-4,6-dimethylphenol were mixed, and stirred at a temperature of 150°C and a speed of 600r / min for 60min to obtain an antistatic agent; the conductive carbon black had an average particle size of 20-30nm, an oil absorption value of 300ml / 100g, and an ash content of 0.3%; S2: 7g of antioxidant 1010, 10g of antioxidant 168, 6g of antioxidant 1330, 3g of hydrotalcite DHT-4A, 3g of antibacterial agent, 2g of antistatic agent and 1g of glass fiber (the glass fiber is alkali-free chopped glass fiber, the monofilament diameter is 3-5um, and the length is 1-3mm) are mixed, and stirred at a temperature of 70°C and a speed of 500r / min for 65min to obtain material A; S3: 6g of plasticizer, 2g of butyl stearate, 2g of AC-207, and 2g of nucleating agent sodium diphenylacetate are mixed, stirred at a temperature of 155°C and a speed of 600r / min for 50min, and then the material A described in step S2, 0.6g of silane coupling agent KH550 and 0.7g of diisopropylbenzene peroxide are added, and the mixture is put into an extruder, and the extruder is controlled to include a first zone, a second zone, and a third zone connected in sequence from the feed port to the die head; the temperature of the first zone is 190°C, the temperature of the second zone is 215°C, and the temperature of the third zone is 230°C; the screw speed of the twin-screw extruder is 750 r / min, the extruder stays for 7min, and the composite additive for the polypropylene film is obtained after cooling.

[0022] Comparative Example 1 The difference from Example 1 is that no plasticizer is prepared in step S1, and the other steps remain unchanged.

[0023] Comparative Example 2 The difference from Example 1 is that no antibacterial agent is prepared in step S1, and the other steps remain unchanged.

[0024] Comparative Example 3 The difference from Example 1 is that no antistatic agent is prepared in step S1, and the other steps remain unchanged.

[0025] Comparative Example 4 The difference from Example 1 is that glass fiber is not added in step S2, and the other steps remain unchanged.

[0026] Comparative Example 5 The difference from Example 1 is that the silane coupling agent KH550 and dicumyl peroxide are not added in step S3, and the other steps remain unchanged.

[0027] Select a polypropylene raw material with an isotacticity of more than 99%, an ash content of 10ppm, a melt index of 3.5g / 10min, and a molecular weight distribution coefficient of 5; take 70g of polypropylene and 5g of the composite auxiliary agent of each embodiment and comparative example, put them into an extruder, and melt and plasticize them through a feeding section with a temperature of 220°C, a melting section at 250°C, and a homogenization section at 255°C to obtain a melt; the extruded melt is led to a chilled roller at 90°C for cooling and forming. The diameter of the chilled roller is 4.0 meters, and the speed of the chilled roller is 38m / min. The air knife heating device attached to the chilled roller blows air to the chilled roller to make the melt adhere and adhere to the chilled roller to achieve melt cooling. The heating temperature of the air knife is 83°C. After the melt is cooled on the chilled roller, a cast polypropylene film with a thickness of 80um is obtained. The performance of the polypropylene film obtained by applying the composite auxiliary agent of each embodiment and comparative example is tested. The results are as shown in the following table.

[0028] Performance Test: According to GB / T1040.1-2006, the tensile strength was tested; GB / T 23257-2009, the elongation at break was tested; GB12027-2004, the thermal shrinkage was tested; GB / T 2591-2003, the antibacterial property was tested; GB∕T 11210-2014, the antistatic property was tested. The results are shown in the following table.

[0029] Table 1

[0030] From the above performance test results, it can be seen that the products prepared in Examples 1-3 have excellent tensile strength, elongation at break, heat shrinkage resistance, antibacterial, antistatic and other properties. In particular, the comprehensive performance of Example 3 is the most outstanding. However, since Comparative Examples 1-5 do not adopt the necessary technical solutions, their corresponding performance tests are significantly worse than those of the Examples. The above experimental results further prove the importance of the technical solutions defined in the present invention for its technical effects.

[0031] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A composite auxiliary agent for polypropylene film, characterized in that: The invention comprises the following components in parts by weight: 5-10 parts of antioxidant 1010, 7-12 parts of antioxidant 168, 4-8 parts of antioxidant 1330, 2-4 parts of hydrotalcite DHT-4A, 1-3 parts of AC-207 and 1-3 parts of nucleating agent sodium diphenylacetate.

2. A composite auxiliary agent for polypropylene film according to claim 1, characterized in that: The invention also comprises 3-8 parts of plasticizer, 2-4 parts of antibacterial agent, 1-3 parts of antistatic agent, 0.5-1.5 parts of glass fiber, 1.5-2.5 parts of butyl stearate, 0.3-0.8 parts of silane coupling agent KH550 and 0.5-1 parts of diisopropylbenzene peroxide.

3. A composite auxiliary agent for polypropylene film according to claim 2, characterized in that: The plasticizer is prepared by compounding 7-10 parts of polyisobutylene, 1-4 parts of 2-aminocyclohexanol and 2-6 parts of N-dodecyl alanine.

4. The composite auxiliary agent for polypropylene film according to claim 2, characterized in that: The antibacterial agent is prepared by chitosan loaded with nanosilver.

5. The composite auxiliary agent for polypropylene film according to claim 2, characterized in that: The antistatic agent comprises 60-80 parts of high-density polyethylene, 35-45 parts of conductive carbon black, 1-4 parts of tetraisopropyl titanate and 2-5 parts of 2-tert-butyl-4,6-dimethylphenol; the conductive carbon black has an average particle size of 10-50nm, an oil absorption value of more than 200ml / 100g, and an ash content of less than 1.0%.

6. A composite auxiliary agent for polypropylene film according to claim 2, characterized in that: The glass fiber is alkali-free chopped glass fiber, with a single fiber diameter of 3-5um and a length of 1-3mm.

7. A method for preparing a composite auxiliary agent for polypropylene film, characterized in that: The steps include: S1: prepare plasticizer, antibacterial agent and antistatic agent respectively; S2: 5-10 parts of antioxidant 1010, 7-12 parts of antioxidant 168, 4-8 parts of antioxidant 1330, 2-4 parts of hydrotalcite DHT-4A, 2-4 parts of antibacterial agent, 1-3 parts of antistatic agent and 0.5-1.5 parts of glass fiber are mixed, and stirred at a temperature of 60-80°C for 50-80 minutes to obtain material A; S3: 3-8 parts of plasticizer, 1.5-2.5 parts of butyl stearate, 1-3 parts of AC-207, and 1-3 parts of nucleating agent sodium diphenylacetate are mixed, stirred at a temperature of 140-160° C. for 40-60 minutes, and then the material A described in step S2, 0.3-0.8 parts of silane coupling agent KH550 and 0.5-1 parts of diisopropylbenzene peroxide are added, and the mixture is put into an extruder, and the extruder is controlled to include a first zone, a second zone, and a third zone connected in sequence from the feed port to the die; the temperature of the first zone is 180-200° C., the temperature of the second zone is 210-220° C., and the temperature of the third zone is 225-235° C.; the screw speed of the twin-screw extruder is 600-800 r / min, the extruder stays for 5-8 minutes, and the composite auxiliary agent for the polypropylene film is obtained after cooling.

8. The method for preparing a composite auxiliary agent for polypropylene film according to claim 7, characterized in that: The preparation process of the plasticizer in step S1 is: 7-10 parts of polyisobutylene, 1-4 parts of 2-aminocyclohexanol and 2-6 parts of N-dodecylalanine are mixed, and stirred at a temperature of 100-120° C. for 30-50 minutes to obtain the plasticizer.

9. The method for preparing a composite auxiliary agent for polypropylene film according to claim 7, characterized in that: The preparation process of the antibacterial agent in step S1 is as follows: dissolve chitosan in a 3% by mass acetic acid aqueous solution according to a solid-liquid ratio of 1g:8-10ml; add 5% by mass of silver nitrate of the total mass of the chitosan solution while stirring, and stir evenly to obtain the antibacterial agent.

10. The method for preparing a composite auxiliary agent for polypropylene film according to claim 7, characterized in that: The preparation process of the antistatic agent in step S1 is as follows: 60-80 parts of high-density polyethylene, 35-45 parts of conductive carbon black, 1-4 parts of tetraisopropyl titanate and 2-5 parts of 2-tert-butyl-4,6-dimethylphenol are mixed, and stirred at a temperature of 140-160° C. for 50-70 minutes to obtain the antistatic agent.

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