An antibacterial polyvinyl chloride film and its preparation method

Abstract

This invention relates to the field of thin film materials technology and discloses an antibacterial polyvinyl chloride (PVC) film and its preparation method. The film comprises the following raw materials: polyvinyl chloride resin, plasticizer, epoxidized soybean oil, stabilizer, lubricant, and organic-inorganic composite antibacterial filler. The organic-inorganic composite antibacterial filler is prepared by a substitution reaction between a long-chain vanillin Schiff base type secondary amine modifier and a halogen-modified nano-zinc oxide. The long-chain vanillin Schiff base type secondary amine modifier modifies the surface of the halogen-modified nano-zinc oxide, and its long carbon chain can diffuse into the PVC matrix. The compatibility between the nano-zinc oxide and the PVC matrix is ​​improved, and the nano-zinc oxide has good dispersion, playing a role in dispersion reinforcement. This results in the prepared PVC film having excellent mechanical properties and antibacterial properties, meeting market demands and showing broad application prospects.

Description

Technical Field

[0001] This invention relates to the field of thin film materials technology, and in particular to an antibacterial polyvinyl chloride film and its preparation method. Background Technology

[0002] Polyvinyl chloride (PVC) is one of the most widely used polymer materials today. Its production technology is mature and its cost is low, so it is widely used in industries, daily necessities and packaging materials.

[0003] Polyvinyl chloride (PVC) molecules have few branches, and chlorine atoms are randomly arranged on the PVC main chain, resulting in low structural regularity of the PVC molecular chain. PVC molecules have a rigid chain structure with a large length of rigid chain segments, which restricts the movement of the molecular chain and leads to poor toughness of pure PVC. In the existing technology, PVC is usually toughened by adding elastomers or nanoparticles.

[0004] With the advancement of technology and the enhancement of health awareness, the market has created a demand for the antibacterial properties of polyvinyl chloride (PVC). However, since PVC itself does not possess antibacterial properties, it is easily adhered to and proliferated by bacteria during use, leading to a decline in the performance of PVC materials and adverse effects on health and safety. Therefore, modifying the antibacterial properties of PVC films while maintaining their excellent mechanical properties is of great practical significance. Summary of the Invention

[0005] This invention proposes an antibacterial polyvinyl chloride (PVC) film and its preparation method. By preparing an organic-inorganic composite antibacterial filler and adding it to PVC, the prepared PVC film has excellent mechanical and antibacterial properties, thereby solving the problems of poor antibacterial properties of PVC film and easy adhesion and growth of bacteria.

[0006] To achieve the above objectives, in a first aspect, the present invention adopts the following technical solution:

[0007] An antibacterial polyvinyl chloride film, comprising the following raw materials in parts by weight:

[0008] 80-100 parts polyvinyl chloride resin;

[0009] 25-40 parts plasticizer;

[0010] 3-6 parts epoxidized soybean oil;

[0011] 4-8 parts stabilizer;

[0012] 0.3-0.6 parts lubricant;

[0013] 3-6 parts of organic-inorganic composite antibacterial filler;

[0014] The organic-inorganic composite antibacterial filler is prepared by a substitution reaction between a long-chain vanillin Schiff base type secondary amine modifier and halogen-modified nano zinc oxide.

[0015] Furthermore, the preparation method of the long-chain vanillin Schiff base type secondary amine modifier is as follows:

[0016] One molar equivalent of the primary amine in diethylenetriamine reacts with one molar equivalent of the aldehyde group in vanillin to give a primary amine, secondary amine, vanillin, Schiff base intermediate.

[0017] Under the action of an activator, the primary amine in 1 molar equivalent of the primary amine-secondary amine vanillin Schiff base intermediate undergoes an amidation reaction with the carboxyl group in 1 molar equivalent of palmitic acid to obtain a long-chain vanillin Schiff base type secondary amine modifier.

[0018] Furthermore, the activator is N,N-dicarbonylimidazole.

[0019] Furthermore, the preparation method of the halogen-modified nano zinc oxide is as follows:

[0020] By adding nano-zinc oxide and a halogenated silane coupling agent to a mixed solution of deionized water and anhydrous ethanol, halogenated modified nano-zinc oxide is prepared through chemical bonding between the nano-zinc oxide and the halogenated silane coupling agent.

[0021] Furthermore, the halogenated silane coupling agent is any one of 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, and 3-bromopropyltrimethoxysilane.

[0022] Further, the plasticizer is any one of diisononyl 1,2-cyclohexanedicarboxylate, di(2-ethylhexyl) phthalate, and dioctyl phthalate.

[0023] Furthermore, the stabilizer is dibutyltin dilaurate or calcium-zinc stabilizer.

[0024] Furthermore, the lubricant is any one of calcium stearate, zinc stearate, stearic acid, and liquid paraffin.

[0025] Secondly, the present invention provides a method for preparing an antibacterial polyvinyl chloride film, comprising the following steps:

[0026] Step 1: Mix polyvinyl chloride resin with organic-inorganic composite antibacterial filler at high speed for 5-15 minutes, then add plasticizer, epoxidized soybean oil, stabilizer, and lubricant, and knead at high speed. Set the temperature to 115-125℃ and knead for 10-30 minutes. Then stop heating, keep stirring, and unload the mixture when the temperature cools to 45-55℃ to obtain the mixture.

[0027] Step 2: The mixture is extruded and blown into a film. The extruder barrel temperature is 80-100℃ in zone 1, 135-160℃ in zone 2, 145-180℃ in zone 3, 160-170℃ in zone 4, 170-185℃ in zone 5, and 190-200℃ in zone 6. The die temperature is 180-200℃, the screw speed is 60-70 r / min, and the blow-up ratio is 2.3-2.8, to obtain an antibacterial polyvinyl chloride film.

[0028] The beneficial effects of this invention are as follows:

[0029] This invention prepares an organic-inorganic composite antibacterial filler by reacting a long-chain vanillin Schiff base-type secondary amine modifier with halogen-modified nano zinc oxide through a substitution reaction.

[0030] Long-chain vanillin Schiff base type secondary amine modifier is used to modify the surface of halogen-modified nano zinc oxide. Its long carbon chain can diffuse into polyvinyl chloride matrix, which improves the compatibility between nano zinc oxide and polyvinyl chloride matrix. The nano zinc oxide has good dispersion and plays a role in dispersion strengthening. The prepared polyvinyl chloride film has excellent mechanical properties and antibacterial properties, which meets market demand and has broad application prospects.

[0031] The test results show that the polyvinyl chloride film prepared by this invention has excellent tensile strength and tear resistance, and the antibacterial rate reaches more than 97%, demonstrating excellent antibacterial performance. Detailed Implementation

[0032] The mechanism for preparing organic-inorganic composite antibacterial fillers is as follows:

[0033] The primary amine group in 1 molar equivalent of diethylenetriamine reacts with the aldehyde group in 1 molar equivalent of vanillin to form a Schiff base reaction, yielding a primary amine, secondary amine, vanillin, Schiff base intermediate.

[0034] Under the action of N,N-dicarbonyl imidazole, the primary amine in 1 molar equivalent of the primary amine-secondary amine vanillin Schiff base intermediate undergoes an amidation reaction with the carboxyl group in 1 molar equivalent of palmitic acid to obtain a long-chain vanillin Schiff base type secondary amine modifier.

[0035] 3-Chloropropyltrimethoxysilane (3-Chloropropyltriethoxysilane or 3-bromopropyltrimethoxysilane) was used to modify the surface of nano zinc oxide to obtain halogen-modified nano zinc oxide.

[0036] An organic-inorganic composite antibacterial filler was obtained by substituting a long-chain vanillin Schiff base-type secondary amine modifier with halogen-modified nano zinc oxide.

[0037] In this experimental example, 3-chloropropyltrimethoxysilane was used to modify the surface of nano-zinc oxide. The specific steps for preparing the organic-inorganic composite antibacterial filler are as follows:

[0038] 1.6 g of vanillin was added to 30 mL of anhydrous ethanol and stirred until dissolved to form a vanillin solution. 1.1 g of diethylenetriamine was added to 30 mL of anhydrous ethanol and stirred until dissolved to form a diethylenetriamine solution. In a constant temperature water bath at 80 °C, the diethylenetriamine solution was slowly added to the vanillin solution under electromagnetic stirring. The addition was completed in 30 min. The reaction was stirred for 4 h. After cooling to room temperature, the solution was concentrated under reduced pressure, the precipitate was filtered off, washed with diethyl ether, and dried under vacuum to obtain the primary and secondary amine vanillin Schiff base intermediate.

[0039] 2.6 g of palmitic acid and 1.6 g of N,N-dicarbonyl imidazole were added to 80 mL of tetrahydrofuran. After stirring and mixing evenly, nitrogen gas was introduced, and 2.4 g of primary amine-secondary amine vanillin Schiff base intermediate was added. After mixing evenly, the mixture was refluxed for 10 h and cooled to room temperature. The tetrahydrofuran phase was washed with sodium chloride aqueous solution, dried with anhydrous sodium sulfate, filtered, and the tetrahydrofuran was evaporated to remove it. After vacuum drying, a long-chain vanillin Schiff base type secondary amine modifier was obtained.

[0040] The chemical structural formula of the long-chain vanillin Schiff base type secondary amine modifier is as follows:

[0041] ;

[0042] The 1H NMR characterization results of the long-chain vanillin Schiff base type secondary amine modifier are as follows:

[0043] 1 H NMR (400MHz, DMSO-D6, δ, ppm): 0.88-0.90 (t, 3H), 1.24-1.34 (m, 24H), 1.55-1.61 (m, 2H), 2.13-2.17 (t, 2H), 2.79-2.85 (m, 3 H), 2.90-2.93(m, 2H), 3.27-3.30(m, 2H), 3.59-3.62(t, 2H), 3.84(s, 3H), 6.79-6.84(m, 2H), 7.15-7.23(m, 3H), 8.30(s, 1H);

[0044] 2g of nano zinc oxide (particle size 50nm) was added to a mixed solution of 10mL deionized water and 90mL anhydrous ethanol. The mixture was magnetically stirred for 30min at room temperature and ultrasonically dispersed for 20min. 0.3g of 3-chloropropyltrimethoxysilane was added, and the mixture was refluxed for 6h. After centrifugation, the mixture was washed with anhydrous ethanol and deionized water, respectively, and then vacuum dried to obtain chlorine-modified nano zinc oxide.

[0045] 3g of chlorine-modified nano zinc oxide was added to 100mL of N,N-dimethylformamide and ultrasonically dispersed for 20min. Then, 1g of long-chain vanillin Schiff base type secondary amine modifier and 0.2g of potassium hydroxide were added. The temperature was raised to 80℃ and stirred for 8h. After cooling to room temperature, the mixture was filtered, washed with methanol, and vacuum dried to obtain an organic-inorganic composite antibacterial filler.

[0046] Example 1: An antibacterial polyvinyl chloride film, comprising the following raw materials in parts by weight:

[0047] 100 parts of polyvinyl chloride resin (SG-3 type, purchased from Hubei Xindongyi New Material Technology Co., Ltd.);

[0048] 35 parts dioctyl phthalate;

[0049] 5 parts epoxidized soybean oil;

[0050] 5 parts dibutyltin dilaurate;

[0051] 0.5 parts calcium stearate;

[0052] Three organic-inorganic composite antibacterial fillers;

[0053] An antibacterial polyvinyl chloride film, the specific preparation steps of which are as follows:

[0054] Step 1: After passing the polyvinyl chloride resin through a 60-mesh sieve, add the organic-inorganic composite antibacterial filler and mix at high speed for 10 minutes. Then add dioctyl phthalate, epoxidized soybean oil, dibutyltin dilaurate, and calcium stearate and knead at high speed. Set the temperature to 120℃ and knead for 20 minutes. Then stop heating and keep stirring. When the temperature cools down to 50℃, unload the mixture to obtain the final product.

[0055] Step 2: Add the mixture to a single-screw extruder blown film mill and form a film by extrusion blow molding. The extruder barrel temperature is 90℃ in zone 1, 150℃ in zone 2, 160℃ in zone 3, 165℃ in zone 4, 180℃ in zone 5, and 195℃ in zone 6. The die temperature is 195℃, the screw speed is 65r / min, and the blow-up ratio is 2.5 to obtain an antibacterial polyvinyl chloride film.

[0056] Example 2: An antibacterial polyvinyl chloride film, comprising the following raw materials in parts by weight:

[0057] 100 parts of polyvinyl chloride resin (SG-3 type, purchased from Hubei Xindongyi New Material Technology Co., Ltd.);

[0058] 35 parts dioctyl phthalate;

[0059] 5 parts epoxidized soybean oil;

[0060] 5 parts dibutyltin dilaurate;

[0061] 0.5 parts calcium stearate;

[0062] Four organic-inorganic composite antibacterial fillers;

[0063] An antibacterial polyvinyl chloride film, the specific preparation steps of which are as follows:

[0064] Step 1: After passing the polyvinyl chloride resin through a 60-mesh sieve, add the organic-inorganic composite antibacterial filler and mix at high speed for 10 minutes. Then add dioctyl phthalate, epoxidized soybean oil, dibutyltin dilaurate, and calcium stearate and knead at high speed. Set the temperature to 120℃ and knead for 20 minutes. Then stop heating and keep stirring. When the temperature cools down to 50℃, unload the mixture to obtain the final product.

[0065] Step 2: Add the mixture to a single-screw extruder blown film mill and form a film by extrusion blow molding. The extruder barrel temperature is 90℃ in zone 1, 150℃ in zone 2, 160℃ in zone 3, 165℃ in zone 4, 180℃ in zone 5, and 195℃ in zone 6. The die temperature is 195℃, the screw speed is 65r / min, and the blow-up ratio is 2.5 to obtain an antibacterial polyvinyl chloride film.

[0066] Example 3: An antibacterial polyvinyl chloride film, comprising the following raw materials in parts by weight:

[0067] 100 parts of polyvinyl chloride resin (SG-3 type, purchased from Hubei Xindongyi New Material Technology Co., Ltd.);

[0068] 35 parts dioctyl phthalate;

[0069] 5 parts epoxidized soybean oil;

[0070] 5 parts dibutyltin dilaurate;

[0071] 0.5 parts calcium stearate;

[0072] 5 parts of organic-inorganic composite antibacterial filler;

[0073] An antibacterial polyvinyl chloride film, the specific preparation steps of which are as follows:

[0074] Step 1: After passing the polyvinyl chloride resin through a 60-mesh sieve, add the organic-inorganic composite antibacterial filler and mix at high speed for 10 minutes. Then add dioctyl phthalate, epoxidized soybean oil, dibutyltin dilaurate, and calcium stearate and knead at high speed. Set the temperature to 120℃ and knead for 20 minutes. Then stop heating and keep stirring. When the temperature cools down to 50℃, unload the mixture to obtain the final product.

[0075] Step 2: Add the mixture to a single-screw extruder blown film mill and form a film by extrusion blow molding. The extruder barrel temperature is 90℃ in zone 1, 150℃ in zone 2, 160℃ in zone 3, 165℃ in zone 4, 180℃ in zone 5, and 195℃ in zone 6. The die temperature is 195℃, the screw speed is 65r / min, and the blow-up ratio is 2.5 to obtain an antibacterial polyvinyl chloride film.

[0076] Example 4: An antibacterial polyvinyl chloride film, comprising the following raw materials in parts by weight:

[0077] 100 parts of polyvinyl chloride resin (SG-3 type, purchased from Hubei Xindongyi New Material Technology Co., Ltd.);

[0078] 35 parts dioctyl phthalate;

[0079] 5 parts epoxidized soybean oil;

[0080] 5 parts dibutyltin dilaurate;

[0081] 0.5 parts calcium stearate;

[0082] Six organic-inorganic composite antibacterial fillers;

[0083] An antibacterial polyvinyl chloride film, the specific preparation steps of which are as follows:

[0084] Step 1: After passing the polyvinyl chloride resin through a 60-mesh sieve, add the organic-inorganic composite antibacterial filler and mix at high speed for 10 minutes. Then add dioctyl phthalate, epoxidized soybean oil, dibutyltin dilaurate, and calcium stearate and knead at high speed. Set the temperature to 120℃ and knead for 20 minutes. Then stop heating and keep stirring. When the temperature cools down to 50℃, unload the mixture to obtain the final product.

[0085] Step 2: Add the mixture to a single-screw extruder blown film mill and form a film by extrusion blow molding. The extruder barrel temperature is 90℃ in zone 1, 150℃ in zone 2, 160℃ in zone 3, 165℃ in zone 4, 180℃ in zone 5, and 195℃ in zone 6. The die temperature is 195℃, the screw speed is 65r / min, and the blow-up ratio is 2.5 to obtain an antibacterial polyvinyl chloride film.

[0086] Performance testing:

[0087] 1. The tensile strength of the antibacterial polyvinyl chloride (PVC) films prepared in Examples 1-4 was tested using a universal testing machine according to the method in standard GB / T 1040.3-2006, and the tear resistance of the antibacterial PVC films prepared in Examples 1-4 was tested according to the method in standard GB / T 16578.1-2008. The mechanical properties of the antibacterial PVC films were evaluated, and the results are shown in Table 1.

[0088] Table 1 Test results of mechanical properties of antibacterial polyvinyl chloride film

[0089]

[0090] 2. The antibacterial properties of the antibacterial polyvinyl chloride films prepared in Examples 1-4 were tested according to the method in standard GB / T 31402-2023, using Staphylococcus aureus (ACTT6538) as the test strain to evaluate the antibacterial properties of the antibacterial polyvinyl chloride films. The results are shown in Table 2.

[0091] Table 2 Test results of antibacterial properties of antibacterial polyvinyl chloride film

[0092]

Claims

1. An antibacterial polyvinyl chloride film, characterized by, The raw materials include the following weight parts: 80-100 parts of polyvinyl chloride resin; 25-40 parts of plasticizer; 3-6 parts of epoxy soybean oil; 4-8 parts of stabilizer; 0.3-0.6 parts of lubricant; 3-6 parts of organic-inorganic composite antibacterial filler; The organic-inorganic composite antibacterial filler is prepared by substitution reaction of long carbon chain vanillin Schiff base type secondary amine modifier and halogen modified nano zinc oxide; The chemical structural formula of the long carbon chain vanillin Schiff base type secondary amine modifier is as follows: ； The halogen modified nano zinc oxide is prepared by chemical bonding of nano zinc oxide and halogen silane coupling agent, and the halogen silane coupling agent is one of 3-chloropropyl trimethoxysilane, 3-chloropropyl triethoxysilane and 3-bromopropyl trimethoxysilane.

2. The antibacterial polyvinyl chloride film according to claim 1, wherein The preparation method of the long carbon chain vanillin Schiff base type secondary amine modifier is as follows: 1 mole equivalent of primary amine in diethylenetriamine and 1 mole equivalent of aldehyde group in vanillin undergo Schiff base reaction to obtain a primary amine secondary amine vanillin Schiff base intermediate; Under the action of an activating agent, 1 mole equivalent of primary amine in the primary amine secondary amine vanillin Schiff base intermediate and 1 mole equivalent of carboxyl in palmitic acid undergo amide reaction to obtain the long carbon chain vanillin Schiff base type secondary amine modifier.

3. The antibacterial polyvinyl chloride film according to claim 2, wherein The activating agent is N,N-dicarbonylimidazole.

4. The antibacterial polyvinyl chloride film according to claim 1, wherein The preparation method of the halogen modified nano zinc oxide is as follows: Nano zinc oxide and halogen silane coupling agent are added to a mixed solution composed of deionized water and anhydrous ethanol to prepare halogen modified nano zinc oxide through chemical bonding of nano zinc oxide and halogen silane coupling agent.

5. The antibacterial polyvinyl chloride film according to claim 1, wherein The plasticizer is any one of 1,2-cyclohexane dicarboxylic acid diisononyl ester, phthalic acid di(2-ethylhexyl) ester and dioctyl phthalate.

6. The antibacterial polyvinyl chloride film according to claim 1, wherein The stabilizer is dibutyltin dilaurate or calcium-zinc stabilizer.

7. The antibacterial polyvinyl chloride film according to claim 1, wherein The lubricant is any one of calcium stearate, zinc stearate, stearic acid and liquid paraffin.

8. A process for the preparation of an antibacterial polyvinyl chloride film as claimed in any one of claims 1 to 7, characterized in that, The method includes the following steps: Step one, polyvinyl chloride resin and organic-inorganic composite antibacterial filler are mixed at high speed for 5-15 min, then plasticizer, epoxy soybean oil, stabilizer and lubricant are added and kneaded at high speed, the temperature is set to 115-125 DEG C, and kneading is performed for 10-30 min, then heating is stopped, stirring is maintained, and the temperature is cooled to 45-55 DEG C, then the material is unloaded to obtain a mixture; Step two, the mixture is formed into a film by extrusion blow molding, the temperature of the extruder barrel is 80-100 DEG C in the first zone, 135-160 DEG C in the second zone, 145-180 DEG C in the third zone, 160-170 DEG C in the fourth zone, 170-185 DEG C in the fifth zone, 190-200 DEG C in the sixth zone, the die temperature is 180-200 DEG C, the screw rotation speed is 60-70 r / min, and the blow ratio is 2.3-2.8 to obtain an antibacterial polyvinyl chloride film.

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