Process for the preparation of modified antibacterial polypropylene materials

Abstract

The application relates to the technical field of polypropylene, and discloses a preparation method of modified antibacterial polypropylene material; polypropylene resin, butadiene styrene rubber powder, quaternary ammonium salt phenyl polypropylene and an antioxidant are mixed in a proportion of 100g:(2-10)g:(3-15)g:(0.3-0.4)g, melt extrusion is carried out, and granulation is carried out to obtain the modified antibacterial polypropylene material. The quaternary ammonium salt phenyl polypropylene improves the compatibility between the polypropylene and the butadiene styrene rubber, the butadiene styrene rubber powder has good toughening effect, and the bending strength and the impact strength of the polypropylene material are remarkably improved. The quaternary ammonium salt phenyl polypropylene contains antibacterial quaternary ammonium salt groups, can effectively kill bacteria and microorganisms, and enhances the sterilization rate and the antibacterial performance of the polypropylene material.

Description

Technical Field

[0001] This invention relates to the field of polypropylene technology, specifically to a method for preparing a modified antibacterial polypropylene material. Background Technology

[0002] Antibacterial materials possess excellent bactericidal properties and are widely used across various industries. Adding antibacterial agents such as quaternary ammonium salts and haloamines to polypropylene produces antibacterial polypropylene materials with high transparency, high strength, and good heat resistance. These materials can be used to manufacture antibacterial plastics, antibacterial fibers, and other products, with a wide range of applications.

[0003] Styrene-butadiene rubber (SBR) powder has good toughness and excellent processability, making it suitable for toughening materials such as polypropylene and polycarbonate. However, SBR powder has poor compatibility with polypropylene, resulting in a poor toughening effect, usually requiring the addition of a compatibilizer. Chinese patent CN114940788B discloses a modified polypropylene masterbatch and its preparation method, which involves blending polypropylene resin, a nucleating agent, and vulcanized SBR powder to obtain modified polypropylene with properties such as low-temperature impact strength and toughness. However, this patent also improves the antibacterial properties of polypropylene. This invention aims to utilize polypropylene containing quaternary ammonium salts and benzene rings to improve the antibacterial and toughness properties of SBR-polypropylene materials. Summary of the Invention

[0004] In view of the shortcomings of the existing technology, the present invention solves the problems of poor toughness and antibacterial properties of polypropylene materials.

[0005] Technical solution: A method for preparing a modified antibacterial polypropylene material:

[0006] (1) Add maleic anhydride-grafted polypropylene to toluene, heat and stir, then add 4-(chloromethyl)benzyl alcohol and p-toluenesulfonic acid, heat to 60-70℃, stir and react for 6-10h, then add more 4-(chloromethyl)benzyl alcohol, then heat to 85-95℃, react for 12-18h, cool and pour the solution into acetone, filter and extract the product with acetone in a Soxhlet extractor, dry the product to obtain 4-(chloromethyl)phenyl ester polypropylene.

[0007] (2) Add 4-(chloromethyl)phenyl ester polypropylene to N,N-dimethylformamide, heat and stir, then add N,N-dimethylbenzylamine, stir the reaction, cool, pour the solution into acetone, filter, extract the product with acetone in a Soxhlet extractor, and dry the product to obtain quaternary ammonium phenyl polypropylene. The reaction formula is:

[0008]

[0009] (3) Mix polypropylene resin, styrene-butadiene rubber powder, quaternary ammonium salt phenyl polypropylene and antioxidant in a ratio of 100g:(2-10)g:(3-15)g:(0.3-0.4)g, then melt extrude and granulate in a twin-screw extruder to obtain modified antibacterial polypropylene material.

[0010] Furthermore, in (1), the ratio of maleic anhydride-grafted polypropylene, 4-(chloromethyl)benzyl alcohol, and p-toluenesulfonic acid is 100g:(15-40):(0.2-0.5).

[0011] Furthermore, in (2), the ratio of 4-(chloromethyl)phenyl ester polypropylene to N,N-dimethylbenzylamine is 100:(18-50).

[0012] Furthermore, in (2), the reaction temperature is 80-110℃ and the reaction time is 48-72h.

[0013] Furthermore, in (3), the temperature of zones 1-6 of the twin-screw extruder is 160-200℃, and the screw speed is 200-400r / min.

[0014] The beneficial technical effects of this invention are as follows: 4-(chloromethyl)benzyl alcohol containing a benzene ring is used to perform an esterification reaction with maleic anhydride-grafted polypropylene, and then N,N-dimethylbenzylamine containing a benzene ring structure is used to perform a quaternization reaction to obtain quaternary ammonium salt phenyl polypropylene. This quaternary ammonium salt is then melt-granulated with polypropylene, styrene-butadiene rubber powder, etc., to obtain a modified antibacterial polypropylene material.

[0015] The quaternary ammonium salt phenyl polypropylene of the present invention has a large number of benzene ring structures in its side chains, which are highly similar to the structure of styrene-butadiene rubber and have good interfacial compatibility. In addition, it contains the main chain of polypropylene molecules, so that the quaternary ammonium salt phenyl polypropylene can act as a compatibilizer for polypropylene and styrene-butadiene rubber powder, improve the compatibility between polypropylene and styrene-butadiene rubber, give styrene-butadiene rubber powder a good toughening effect, and significantly improve the flexural strength and impact strength of polypropylene materials.

[0016] The quaternary ammonium salt phenyl polypropylene of the present invention contains antibacterial quaternary ammonium salt groups, which can effectively kill bacteria and microorganisms, and enhance the bactericidal rate and antibacterial properties of polypropylene materials. Detailed Implementation

[0017] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0018] Polypropylene resin, grade Lotte H4540, Dongguan Mingyuan Plastics Co., Ltd. Maleic anhydride-grafted polypropylene, model OP-1020, Dongguan Mingyuan Plastics Co., Ltd. Styrene-butadiene rubber powder, average particle size 200 mesh, Dongguan Shenghao Plastic Raw Materials Co., Ltd.

[0019] Example 1:

[0020] (1) Add 100g of maleic anhydride-grafted polypropylene to 2L of toluene, heat and stir, then add 11g of 4-(chloromethyl)benzyl alcohol and 0.32g of p-toluenesulfonic acid, heat to 70℃, stir and react for 6h, then add 13g of 4-(chloromethyl)benzyl alcohol, heat to 90℃, react for 18h, cool and pour the solution into acetone, filter and extract the product with acetone in a Soxhlet extractor, dry the product to obtain 4-(chloromethyl)phenyl ester polypropylene.

[0021] (2) Add 120g of 4-(chloromethyl)phenyl ester polypropylene to 1.5L of N,N-dimethylformamide, heat and stir, then add 46.6g of N,N-dimethylbenzylamine, heat to 90℃, stir and react for 72h, cool and pour the solution into acetone, filter and extract the product with acetone in a Soxhlet extractor, dry the product to obtain quaternary ammonium salt phenyl polypropylene.

[0022] (3) Mix 2kg of polypropylene resin, 40g of styrene-butadiene rubber powder, 60g of quaternary ammonium salt phenyl polypropylene and 7.2g of antioxidant 1010, and then melt-extrude and granulate the mixture in a twin-screw extruder with the temperatures of zones 1-6 being 160℃, 180℃, 190℃, 200℃, 200℃ and 195℃, and the screw speed being 300r / min to obtain modified antibacterial polypropylene material.

[0023] Example 2:

[0024] (1) Add 100g of maleic anhydride-grafted polypropylene to 2.5L of toluene, heat and stir, then add 18g of 4-(chloromethyl)benzyl alcohol and 0.5g of p-toluenesulfonic acid, heat to 60℃, stir and react for 10h, then add 22g of 4-(chloromethyl)benzyl alcohol, heat to 95℃, react for 12h, cool and pour the solution into acetone, filter and extract the product with acetone in a Soxhlet extractor, dry the product to obtain 4-(chloromethyl)phenyl ester polypropylene.

[0025] (2) Add 120g of 4-(chloromethyl)phenyl ester polypropylene to 2L of N,N-dimethylformamide, heat and stir, then add 60g of N,N-dimethylbenzylamine, heat to 90℃, stir and react for 72h, cool and pour the solution into acetone, filter and extract the product with acetone in a Soxhlet extractor, dry the product to obtain quaternary ammonium salt phenyl polypropylene.

[0026] (3) Mix 2kg of polypropylene resin, 100g of styrene-butadiene rubber powder, 140g of quaternary ammonium salt phenyl polypropylene and 6g of antioxidant 1010, and then melt-extrude and granulate the mixture in a twin-screw extruder with the temperatures of zones 1-6 being 160℃, 180℃, 190℃, 200℃, 200℃ and 195℃, and the screw speed being 200r / min to obtain modified antibacterial polypropylene material.

[0027] Example 3:

[0028] (1) Add 100g of maleic anhydride-grafted polypropylene to 2L of toluene, heat and stir, then add 7g of 4-(chloromethyl)benzyl alcohol and 0.2g of p-toluenesulfonic acid, heat to 70℃, stir and react for 8h, then add 8g of 4-(chloromethyl)benzyl alcohol, heat to 85℃, react for 18h, cool and pour the solution into acetone, filter and extract the product with acetone in a Soxhlet extractor, dry the product to obtain 4-(chloromethyl)phenyl ester polypropylene.

[0029] (2) Add 120g of 4-(chloromethyl)phenyl ester polypropylene to 1.5L of N,N-dimethylformamide, heat and stir, then add 21.6g of N,N-dimethylbenzylamine, heat to 80℃, stir and react for 60h, cool and pour the solution into acetone, filter and extract the product with acetone in a Soxhlet extractor, dry the product to obtain quaternary ammonium salt phenyl polypropylene.

[0030] (3) Mix 2kg of polypropylene resin, 150g of styrene-butadiene rubber powder, 220g of quaternary ammonium salt phenyl polypropylene and 6g of antioxidant 1010, and then melt-extrude and granulate the mixture in a twin-screw extruder with the temperatures of zones 1-6 being 160℃, 180℃, 190℃, 200℃, 200℃ and 195℃, and the screw speed being 400r / min to obtain modified antibacterial polypropylene material.

[0031] Example 4:

[0032] (1) Add 100g of maleic anhydride-grafted polypropylene to 2.5L of toluene, heat and stir, then add 14g of 4-(chloromethyl)benzyl alcohol and 0.43g of p-toluenesulfonic acid, heat to 60℃, stir and react for 10h, then add 18g of 4-(chloromethyl)benzyl alcohol, heat to 90℃, react for 18h, cool and pour the solution into acetone, filter and extract the product with acetone in a Soxhlet extractor, dry the product to obtain 4-(chloromethyl)phenyl ester polypropylene.

[0033] (2) Add 120g of 4-(chloromethyl)phenyl ester polypropylene to 2L of N,N-dimethylformamide, heat and stir, then add 33.6g of N,N-dimethylbenzylamine, heat to 110℃, stir and react for 48h, cool and pour the solution into acetone, filter and extract the product with acetone in a Soxhlet extractor, dry the product to obtain quaternary ammonium salt phenyl polypropylene.

[0034] (3) Mix 2kg of polypropylene resin, 200g of styrene-butadiene rubber powder, 300g of quaternary ammonium salt phenyl polypropylene and 8g of antioxidant 1010, and then melt-extrude and granulate the mixture in a twin-screw extruder with the temperatures of zones 1-6 being 160℃, 180℃, 190℃, 200℃, 200℃ and 195℃, and the screw speed being 400r / min to obtain modified antibacterial polypropylene material.

[0035] Comparative Example 1 differs from Example 1 in that it does not contain quaternary ammonium salt phenyl polypropylene.

[0036] (1) Mix 2kg of polypropylene resin, 40g of styrene-butadiene rubber powder and 7.2g of antioxidant 1010, and then melt-extrude and granulate the mixture in a twin-screw extruder with the temperatures of zones 1-6 being 160℃, 180℃, 190℃, 200℃, 200℃ and 195℃, and the screw speed being 300r / min to obtain modified antibacterial polypropylene material.

[0037] Comparative Example 2 differs from Example 1 in that 4-(chloromethyl)benzyl alcohol is replaced with 8-chloro-1-octanol, which does not contain a benzene ring.

[0038] (1) Add 100g of maleic anhydride-grafted polypropylene to 2L of toluene, heat and stir, then add 11g of 8-chloro-1-octanol and 0.32g of p-toluenesulfonic acid, heat to 70℃, stir and react for 6h, then add 13g of 8-chloro-1-octanol, heat to 90℃, react for 18h, cool and pour the solution into acetone, filter and extract the product with acetone in a Soxhlet extractor, dry the product to obtain 4-(chloromethyl)phenyl ester polypropylene.

[0039] (2) Add 120g of 4-(chloromethyl)phenyl ester polypropylene to 1.5L of N,N-dimethylformamide, heat and stir, then add 46.6g of N,N-dimethylbenzylamine, heat to 90℃, stir and react for 72h, cool and pour the solution into acetone, filter and extract the product with acetone in a Soxhlet extractor, dry the product to obtain quaternary ammonium salt polypropylene.

[0040] (3) Mix 2kg of polypropylene resin, 40g of styrene-butadiene rubber powder, 60g of quaternary ammonium salt-based polypropylene and 7.2g of antioxidant 1010, and then melt-extrude and granulate the mixture in a twin-screw extruder with the temperatures of zones 1-6 being 160℃, 180℃, 190℃, 200℃, 200℃ and 195℃, and the screw speed being 300r / min to obtain modified polypropylene material.

[0041] Comparative Example 3 differs from Example 1 in that N,N-dimethylbenzylamine is replaced with N,N-dimethyloctylamine, which does not contain a benzene ring.

[0042] (1) Add 100g of maleic anhydride-grafted polypropylene to 2L of toluene, heat and stir, then add 11g of 4-(chloromethyl)benzyl alcohol and 0.32g of p-toluenesulfonic acid, heat to 70℃, stir and react for 6h, then add 13g of 4-(chloromethyl)benzyl alcohol, heat to 90℃, react for 18h, cool and pour the solution into acetone, filter and extract the product with acetone in a Soxhlet extractor, dry the product to obtain 4-(chloromethyl)phenyl ester polypropylene.

[0043] (2) Add 120g of 4-(chloromethyl)phenyl ester polypropylene to 1.5L N,N-dimethylformamide, heat and stir, then add 46.6g of N,N-dimethyloctylamine, heat to 90℃, stir and react for 72h, cool and pour the solution into acetone, filter and extract the product with acetone in a Soxhlet extractor, dry the product to obtain quaternary ammonium salt polypropylene.

[0044] (3) Mix 2kg of polypropylene resin, 40g of styrene-butadiene rubber powder, 60g of quaternary ammonium salt-based polypropylene and 7.2g of antioxidant 1010, and then melt-extrude and granulate the mixture in a twin-screw extruder with the temperatures of zones 1-6 being 160℃, 180℃, 190℃, 200℃, 200℃ and 195℃, and the screw speed being 300r / min to obtain modified polypropylene material.

[0045] Comparative Example 4 differs from Example 1 in that conventional maleic anhydride-grafted polypropylene is used instead of quaternary ammonium phenyl polypropylene.

[0046] (1) Mix 2kg of polypropylene resin, 40g of styrene-butadiene rubber powder, 60g of maleic anhydride-grafted polypropylene, and 7.2g of antioxidant 1010. Then, in a twin-screw extruder, the temperatures of zones 1-6 are 160℃, 180℃, 190℃, 200℃, 200℃, and 195℃, and the screw speed is 300r / min. The mixture is melt-extruded and granulated to obtain the modified polypropylene material.

[0047] Polypropylene material was injection molded in an injection molding machine at a temperature of 200℃ and a pressure of 50MPa to form specimens for performance testing.

[0048] Table 1 Performance Tests

[0049]

[0050]

[0051] Compared to Comparative Examples 1-4, Examples 1-4 involved reacting 4-(chloromethyl)benzyl alcohol containing benzene rings and N,N-dimethylbenzylamine with maleic anhydride-grafted polypropylene to obtain quaternary ammonium phenyl polypropylene. Its side chains contain numerous benzene ring structures, exhibiting high structural similarity to styrene-butadiene rubber (SBR) and good interfacial compatibility. Furthermore, it contains the polypropylene molecular backbone, allowing the quaternary ammonium phenyl polypropylene to act as a compatibilizer for both polypropylene and SBR, improving their compatibility and giving SBR a superior toughening effect. This significantly enhances the flexural strength and impact strength of the polypropylene material. Additionally, the quaternary ammonium phenyl polypropylene contains antibacterial quaternary ammonium salt groups, effectively killing bacteria and microorganisms, thus enhancing the bactericidal rate and antibacterial properties of the polypropylene material.

Claims

1. A method for preparing a modified antibacterial polypropylene material, characterized in that, The preparation method includes the following steps: (1) Add 4-(chloromethyl)phenyl ester polypropylene to N,N-dimethylformamide, heat and stir, then add N,N-dimethylbenzylamine, stir to react, cool and pour the solution into acetone, filter and extract the product in a Soxhlet extractor, then dry the product to obtain quaternary ammonium salt phenyl polypropylene. (2) Mix polypropylene resin, styrene-butadiene rubber powder, quaternary ammonium salt phenyl polypropylene and antioxidant, then melt extrude and granulate in a twin-screw extruder to obtain modified antibacterial polypropylene material; The preparation method of the 4-(chloromethyl)phenyl ester polypropylene includes the following steps: adding maleic anhydride-grafted polypropylene to toluene, heating and stirring, then adding 4-(chloromethyl)phenylmethyl alcohol and p-toluenesulfonic acid, stirring and reacting, then adding more 4-(chloromethyl)phenylmethyl alcohol, continuing the reaction, cooling and pouring the solution into acetone, filtering and extracting the product in a Soxhlet extractor, drying the product to obtain 4-(chloromethyl)phenyl ester polypropylene; The ratio of maleic anhydride-grafted polypropylene, 4-(chloromethyl)benzyl alcohol, and p-toluenesulfonic acid is 100:(15-40):(0.2-0.5). The ratio of polypropylene resin, styrene-butadiene rubber powder, quaternary ammonium salt phenyl polypropylene, and antioxidant in (2) is 100g:(2-10)g:(3-15)g:(0.3-0.4)g.

2. The method for preparing the modified antibacterial polypropylene material according to claim 1, characterized in that, The ratio of 4-(chloromethyl)phenyl ester polypropylene and N,N-dimethylbenzylamine in (1) is 100:(18-50).

3. The method for preparing the modified antibacterial polypropylene material according to claim 1, characterized in that, The reaction temperature in (1) is 80-110℃ and the reaction time is 48-72h.

4. The method for preparing the modified antibacterial polypropylene material according to claim 1, characterized in that, The temperature of zones 1-6 of the twin-screw extruder in (2) is 160-200℃, and the screw speed is 200-400r / min.

5. The method for preparing the modified antibacterial polypropylene material according to claim 1, characterized in that, In the preparation method of the 4-(chloromethyl)phenyl ester polypropylene, the temperature during the stirring reaction is 60-70℃ and the reaction time is 6-10h; the temperature during the continued reaction is 85-95℃ and the reaction time is 12-18h.

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