PC composite plastic material with antibacterial function and preparation process

Abstract

The invention relates to the technical field of plastics, and discloses a PC composite plastic material with an antibacterial function and a preparation technology, the PC composite plastic material comprises 70-80 parts by weight of polycarbonate, 20-30 parts by weight of nylon resin, and 2-7 parts by weight of a polycarbonate amide polymer; the main chain of the polycarbonate amide polymer contains a large number of quaternary ammonium salt groups, so that the completeness of bacterial cell membranes can be destroyed, the polycarbonate amide polymer has very strong bactericidal performance, and the antibacterial rate of the material to escherichia coli and staphylococcus aureus is remarkably improved. The polycarbonate amide polymer plays a role of a compatilizer, so that the compatibility between the polycarbonate and the nylon resin is improved, and the composite plastic material has better mechanical properties and higher tensile strength and bending strength.

Description

Technical Field

[0001] This invention relates to the field of plastics technology, specifically to a PC composite plastic material with antibacterial function and its preparation process. Background Technology

[0002] Polycarbonate is colorless and transparent with high light transmittance. It is also highly impact-resistant, heat-resistant, and cold-resistant, making it widely used in the automotive industry, electronics, medical supplies, and other fields. However, ordinary polycarbonate has poor antibacterial properties, which hinders its practical application in antibacterial materials such as medical supplies. Therefore, it is usually necessary to add antibacterial agents such as quaternary ammonium salts, quaternary phosphorus salts, copper, and titanium dioxide.

[0003] To improve the mechanical properties of polycarbonate, it is compounded with plastics such as nylon, polyethylene, and ABS. The resulting alloy plastic materials have better mechanical strength. However, the compatibility between polycarbonate and plastics such as nylon is poor, requiring the addition of compatibilizers such as maleic anhydride-grafted POE and glycidyl methacrylate-grafted polyethylene. Patent CN101280099B discloses a xylene-resistant polycarbonate-nylon polymer alloy and its preparation method. Using polycarbonate, polydecanoic acid decylamine, and the compatibilizer ethylene-octene copolymer grafted with glycidyl methacrylate as raw materials, the prepared polycarbonate-nylon alloy exhibits good solvent resistance and mechanical properties, but it lacks good antibacterial properties. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a PC composite plastic material with antibacterial function and a preparation process, solving problems such as poor compatibility between polycarbonate and nylon and poor antibacterial properties of polycarbonate.

[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: a PC composite plastic material with antibacterial function and a preparation process, wherein the PC composite plastic material comprises 70-80 parts by weight of polycarbonate, 20-30 parts by weight of nylon resin, and 2-7 parts by weight of polycarbonate amide polymer; the preparation process of the PC composite plastic material is as follows:

[0006] (1) Add bisphenol A chloroethyl formate and N to ethanol. 1 N 4 -Bis[3-(dimethylamino)propyl]succinamide was heated and stirred to react, filtered, washed with ethanol and ethyl acetate, and dried to obtain a polycarbonate amide polymer.

[0007] (2) Mix polycarbonate, nylon resin and polycarbonate amide polymer, then extrude them in a twin-screw extruder and granulate them to obtain PC composite plastic material with antibacterial function.

[0008] Furthermore, in (1), the reaction temperature is 70-80℃ and the reaction time is 24-36h.

[0009] Furthermore, in (1) bisphenol A chloroethyl formate, N 1 N 4 The molar ratio of bis[3-(dimethylamino)propyl]succinamide is (0.9-1.1):1.

[0010] Furthermore, in (2), the temperature of zones 1-5 of the twin-screw extruder is 180-250℃.

[0011] Furthermore, the preparation process of bisphenol A chloroethyl formate is as follows: bisphenol A, chloroethyl formate, catalyst, and acid-binding agent are added to dichloromethane. After the reaction, water is added, and the mixture is shaken and extracted. The organic phase of dichloromethane is dried with anhydrous sodium sulfate, filtered, and the filtrate is concentrated under reduced pressure. The crude product is washed with petroleum ether and then recrystallized and purified in ethyl acetate to obtain bisphenol A chloroethyl formate.

[0012] Furthermore, the molar ratio of bisphenol A, ethyl chloroformate, catalyst, and acid-binding agent is 1:(3.2-4.6):(0.8-1.2):(5.2-6).

[0013] Furthermore, the catalyst includes 4-dimethylaminopyridine, and the acid-binding agent includes pyridine.

[0014] Furthermore, in the preparation process of bisphenol A chloroethyl formate, the reaction temperature is 15-25℃ and the reaction time is 18-24h.

[0015] Beneficial technical effects of the present invention: Bisphenol A chloroethyl ester and N 1 N 4 -Bis[3-(dimethylamino)propyl]succinamide is polymerized to obtain a polycarbonate amide polymer containing bisphenol A type carbonate structural units and amide bonds. Then, it is blended with polycarbonate and nylon 6 resin to obtain PC composite plastic material. The main chain of the polycarbonate amide polymer contains a large number of quaternary ammonium salt groups, which can disrupt the integrity of bacterial cell membranes and have strong bactericidal properties, significantly improving the antibacterial rate of the material against Escherichia coli and Staphylococcus aureus.

[0016] The polycarbonate amide polymer of the present invention contains bisphenol A type carbonate structural units similar to polycarbonate. At the same time, the amide bonds in the main molecular chain interact with the amide bonds of nylon through hydrogen bonding, thereby making the polycarbonate amide polymer act as a compatibilizer, improving the compatibility between polycarbonate and nylon resin, and giving the composite plastic material better mechanical properties, with higher tensile strength and flexural strength. Detailed Implementation

[0017] The present invention can be better understood from the following embodiments. However, those skilled in the art will readily understand that the descriptions in the embodiments are for illustrative purposes only and should not, and will not, limit the invention as detailed in the claims.

[0018] The nylon resin is PA6 M2800, manufactured by Shanghai Hehongcheng Plastics Technology Co., Ltd. The maleic anhydride-grafted POE is XY-310, manufactured by Dongguan Xingyuan Chemical Co., Ltd. The polycarbonate is bisphenol A type polycarbonate, manufactured by Jiangsu Runfeng Synthetic Technology Co., Ltd.

[0019] According to the journal *Journal of Molecular Structure*, 1273, (2023), 134377, the literature...

[0020] N 1 N 4 -Bis[3-(dimethylamino)propyl]succinamide.

[0021] Add 10 mmol of succinic acid, 20 mmol of triethylamine, and 15 mmol of 2-(7-azabenzotriazole)-N,N,N',N'-tetramethylurea hexafluorophosphate (HATU) to 10 mL of N,N-dimethylformamide. Stir for 1 h under a nitrogen atmosphere, then add 20 mmol of N,N-dimethyl-1,3-diaminopropane and react at 25 °C for 6 h. Add ethyl acetate and water, and extract by shaking. Dry the ethyl acetate organic phase with anhydrous sodium sulfate, filter, concentrate the filtrate under reduced pressure, and dry to obtain N... 1 N 4 -Bis[3-(dimethylamino)propyl]succinamide, with the structural formula as follows:

[0022] Example 1:

[0023] (1) Add 0.5 mol of bisphenol A, 2 mol of chloroethyl chloroformate, 0.4 mol of 4-dimethylaminopyridine, and 2.6 mol of pyridine to 0.8 L of dichloromethane. React at 25 °C for 18 h. Add water, shake and extract. Dry the dichloromethane organic phase with anhydrous sodium sulfate, filter, concentrate the filtrate under reduced pressure, wash the crude product with petroleum ether, and then recrystallize and purify in ethyl acetate to obtain bisphenol A chloroethyl chloroformate. The reaction formula is:

[0024]

[0025] (2) Add 0.8 mol of bisphenol A chloroethyl formate and 0.8 mol of N to 1 L of ethanol. 1 N 4 -Bis[3-(dimethylamino)propyl]succinamide was heated to 75°C and stirred for 36 h. The mixture was refluxed during the reaction, filtered, washed with ethanol and ethyl acetate, and dried to obtain a polycarbonate amide polymer. The reaction formula is as follows:

[0026]

[0027] (3) Mix 8kg of polycarbonate, 2kg of nylon resin and 0.2kg of polycarbonate amide polymer, and then extrude them in a twin-screw extruder. The temperatures of zones 1-5 are 180℃, 230℃, 250℃, 250℃ and 240℃. Then, cut the mixture into pellets to obtain PC composite plastic material with antibacterial function.

[0028] Example 2:

[0029] (1) Add 0.5 mol of bisphenol A, 2.3 mol of chloroethyl chloroformate, 0.5 mol of 4-dimethylaminopyridine and 2.6 mol of pyridine to 1 L of dichloromethane, react at 15 °C for 24 h, add water, shake and extract, dry the organic phase of dichloromethane with anhydrous sodium sulfate, filter and concentrate the filtrate under reduced pressure, wash the crude product with petroleum ether, and then recrystallize and purify in ethyl acetate to obtain bisphenol A chloroethyl chloroformate.

[0030] (2) Add 0.88 mol of bisphenol A chloroethyl formate and 0.8 mol of N to 1.2 L of ethanol. 1 N 4 -Bis[3-(dimethylamino)propyl]succinamide was heated to 70°C and stirred for 36 h. The mixture was refluxed during the reaction, filtered, washed with ethanol and ethyl acetate, and dried to obtain a polycarbonate amide polymer.

[0031] (3) Mix 7.5kg polycarbonate, 2.5kg nylon resin and 0.45kg polycarbonate amide polymer, and then extrude them in a twin-screw extruder. The temperatures of zones 1-5 are 180℃, 230℃, 250℃, 250℃ and 240℃. Then, cut the mixture into pellets to obtain PC composite plastic material with antibacterial function.

[0032] Example 3:

[0033] (1) Add 0.5 mol bisphenol A, 1.6 mol chloroethyl chloroformate, 0.6 mol 4-dimethylaminopyridine and 3 mol pyridine to 1 L of dichloromethane, react at 25 °C for 18 h, add water, shake and extract, dry the organic phase of dichloromethane with anhydrous sodium sulfate, filter and concentrate the filtrate under reduced pressure, wash the crude product with petroleum ether, and then recrystallize and purify in ethyl acetate to obtain bisphenol A chloroethyl chloroformate.

[0034] (2) Add 0.72 mol of bisphenol A chloroethyl formate and 0.8 mol of N to 1 L of ethanol. 1 N 4 -Bis[3-(dimethylamino)propyl]succinamide was heated to 80°C and stirred for 24 h. The mixture was refluxed during the reaction, filtered, washed with ethanol and ethyl acetate, and dried to obtain a polycarbonate amide polymer.

[0035] (3) Mix 7kg of polycarbonate, 3kg of nylon resin and 0.7kg of polycarbonate amide polymer, and then extrude them in a twin-screw extruder. The temperatures of zones 1-5 are 180℃, 230℃, 250℃, 250℃ and 240℃. Then, cut the mixture into pellets to obtain PC composite plastic material with antibacterial function.

[0036] Comparative Example 1

[0037] (1) Mix 8kg of polycarbonate and 2kg of nylon resin, then extrude them in a twin-screw extruder. The temperatures in zones 1-5 are 180℃, 230℃, 250℃, 250℃, and 240℃. The mixture is then granulated to obtain PC composite plastic material.

[0038] Comparative Example 2

[0039] (1) Add 0.8 mol of 1,4-dichlorobenzyl (CAS No. 623-25-6) and 0.8 mol of N to 1 L of ethanol. 1 N 4 -Bis[3-(dimethylamino)propyl]succinamide was heated to 75°C and stirred for 36 h. The mixture was refluxed during the reaction, filtered, washed with ethanol and ethyl acetate, and dried to obtain the polyamide polymer.

[0040] (2) Mix 8kg of polycarbonate, 2kg of nylon resin and 0.2kg of polyamide polymer, and then extrude them in a twin-screw extruder. The temperatures of zones 1-5 are 180℃, 230℃, 250℃, 250℃ and 240℃. Then, cut the mixture into pellets to obtain PC composite plastic material.

[0041] Comparative Example 3:

[0042] (1) Add 0.8 mol of bisphenol A chloroethyl formate and 0.8 mol of N,N,N',N'-tetramethyl-1,4-butanediamine (CAS No. 111-51-3) to 1L of ethanol, heat to 75℃, stir and react for 36h, reflux during the reaction, filter, wash with ethanol and ethyl acetate, and dry to obtain polycarbonate polymer.

[0043] (2) Mix 8kg of polycarbonate, 2kg of nylon resin and 0.2kg of polycarbonate polymer, and then extrude them in a twin-screw extruder. The temperatures in zones 1-5 are 180℃, 230℃, 250℃, 250℃ and 240℃. Then, cut the mixture into pellets to obtain PC composite plastic material.

[0044] Comparative Example 4:

[0045] (1) Mix 8kg of polycarbonate, 2kg of nylon resin and 0.2kg of maleic anhydride-grafted POE, and then extrude them in a twin-screw extruder. The temperatures of zones 1-5 are 180℃, 230℃, 250℃, 250℃ and 240℃. Then, cut the mixture into pellets to obtain PC composite plastic material.

[0046] The antibacterial properties of PC composite plastic materials were tested according to standard QB / T2591-2003. The experimental bacteria were Escherichia coli and Staphylococcus aureus. The PC composite plastic material in Comparative Example 1 was used as a blank control sample.

[0047] Tensile strength was tested according to standard GB / T 1040.1-2018. Flexural strength was tested according to standard GB / T 9341-2008.

[0048] Table 1 Properties of PC Composite Plastic Materials

[0049]

[0050] The poor compatibility between polycarbonate and nylon in Comparative Example 1 resulted in lower tensile and flexural strength of the composite plastic material, as well as poor antibacterial properties.

[0051] The PC composite plastic materials in Examples 1-3 incorporate polycarbonate amide polymers. These polymers contain a large number of quaternary ammonium salt groups in their main molecular chain, which can disrupt the integrity of bacterial cell membranes, exhibiting strong bactericidal properties and significantly improving the antibacterial rate against *Escherichia coli* and *Staphylococcus aureus*. Furthermore, the polycarbonate amide polymer contains bisphenol A-type carbonate structural units similar to polycarbonate. Meanwhile, the amide bonds in the main molecular chain interact with the amide bonds in nylon through hydrogen bonding, thereby making the polycarbonate amide polymer act as a compatibilizer, improving the compatibility between polycarbonate and nylon resin, and giving the composite plastic material better mechanical properties, with higher tensile strength and flexural strength.

[0052] Comparative Example 2: 1,4-dichlorobenzyl (CAS No. 623-25-6) and N... 1 N 4 The reaction of bis[3-(dimethylamino)propyl]succinamide yields a polyamide polymer that does not contain bisphenol A type carbonate structural units. This results in poor compatibility with polycarbonate, preventing it from acting as a compatibilizer and failing to improve the compatibility between polycarbonate and nylon resin. Consequently, the tensile and flexural strength of the composite plastic material is low.

[0053] Comparative Example 3 involved reacting bisphenol A chloroethyl formate with N,N,N',N'-tetramethyl-1,4-butanediamine. The resulting polycarbonate polymer did not contain amide bonds and had low interaction forces such as hydrogen bonds with nylon resin. It could not act as a compatibilizer and could not improve the compatibility between polycarbonate and nylon resin, resulting in low tensile and flexural strength of the composite plastic material.

[0054] Comparative Example 4 used conventional maleic anhydride-grafted POE as a compatibilizer. The tensile strength and flexural strength of the material were higher than those of Comparative Example 1, but it had almost no antibacterial properties.

[0055] The discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the invention is limited to these examples; within the framework of the invention, the technical features of the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.

Claims

1. A PC composite plastic material with antibacterial function, characterized in that, The PC composite plastic material with antibacterial function includes 70-80 parts by weight of polycarbonate, 20-30 parts by weight of nylon resin, and 2-7 parts by weight of polycarbonate amide polymer; The preparation process of the polycarbonate amide polymer includes: adding bisphenol A chloroethyl formate, N to ethanol. 1 N 4 -Bis[3-(dimethylamino)propyl]succinamide was heated and stirred to react, filtered, washed, and dried to obtain a polycarbonate amide polymer.

2. The PC composite plastic material with antibacterial function according to claim 1, characterized in that, The reaction temperature is 70-80℃, and the reaction time is 24-36h.

3. The PC composite plastic material with antibacterial function according to claim 1, characterized in that, The bisphenol A chloroethyl formate, N 1 N 4 The molar ratio of bis[3-(dimethylamino)propyl]succinamide is (0.9-1.1):

1.

4. The PC composite plastic material with antibacterial function according to claim 1, characterized in that, The preparation process of the bisphenol A chloroethyl formate is as follows: bisphenol A, chloroethyl formate, catalyst, and acid-binding agent are added to dichloromethane. After the reaction, water is added, and the mixture is shaken and extracted. The crude product is washed and then recrystallized for purification to obtain bisphenol A chloroethyl formate.

5. The PC composite plastic material with antibacterial function according to claim 1, characterized in that, The molar ratio of bisphenol A, ethyl chloroformate, catalyst, and acid-binding agent is 1:(3.2-4.6):(0.8-1.2):(5.2-6).

6. The PC composite plastic material with antibacterial function according to claim 1, characterized in that, The catalyst includes 4-dimethylaminopyridine, and the acid-binding agent includes pyridine.

7. The PC composite plastic material with antibacterial function according to claim 1, characterized in that, In the preparation process of the bisphenol A chloroethyl formate, the reaction temperature is 15-25℃ and the reaction time is 18-24h.

8. A PC composite plastic material with antibacterial function as described in any one of claims 1-7 and a preparation process thereof, characterized in that, The preparation process includes: mixing polycarbonate, nylon resin, and polycarbonate amide polymer, then extruding them in a twin-screw extruder, and pelletizing them to obtain a PC composite plastic material with antibacterial function.

9. The PC composite plastic material with antibacterial function and its preparation process according to claim 8, characterized in that, The temperature of zones 1-5 of the twin-screw extruder is 180-250℃.

Images