Antibacterial modified polypropylene material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of synthetic materials, in particular to an antibacterial modified polypropylene material as well as a preparation method and application thereof. The antibacterial modified polypropylene material is prepared from the following components in parts by weight: 100 parts of polypropylene, 2 to 4 parts of polypropylene grafted maleic anhydride, 1 to 2 parts of polypropylene random copolymer, 0.8 to 1.2 parts of p-allylphenol-styrene copolymer, 0.2 to 0.8 part of ethylene bis stearamide, 0.5 to 1 part of calcium stearate, 0.5 to 1 part of nano titanium dioxide, 0.2 to 0.3 part of nano zinc oxide and 0.3 to 0.5 part of PP (Propene Polymer) toughening agent. The antibacterial plastic has a good antibacterial effect on staphylococcus aureus ATCC6538 and Escherichia coli ATCC25922, polypropylene crystallization is delayed by adding the polypropylene random copolymer and the p-allylphenol-styrene copolymer, the situation that the size of polypropylene crystals is too large is avoided, the product strength is enhanced, and the antibacterial plastic can be made into daily chemical product packaging bottles and daily chemical product packaging bottle caps and can be used for manufacturing daily chemical product packaging bottles and daily chemical product packaging bottle caps. And a plastic pump head accessory.

Description

Technical Field

[0001] The invention relates to the technical field of synthetic materials, in particular to an antibacterial modified polypropylene material and a preparation method and application thereof. Background Art

[0002] As one of the five general-purpose plastics, polypropylene has been widely used in modern daily necessities such as household appliances, decorative building materials, and daily textiles due to its excellent performance and low price. However, polypropylene itself does not have antibacterial properties. In order to better apply it in daily life, it can be modified by grafting antibacterial agents on polypropylene.

[0003] The Chinese invention with publication number CN103059405B discloses an antibacterial polypropylene plastic, which includes the following raw materials: polypropylene, a composite antibacterial agent, a dispersant and a compatibilizer, wherein the dispersant can be ethylene bisstearamide, and the compatibilizer can be polypropylene grafted maleic anhydride. The invention increases the compatibility of polypropylene and the composite antibacterial agent by using polypropylene grafted maleic anhydride as a bridge, but it will induce accelerated crystallization of polypropylene, resulting in defects caused by excessively large crystal size of polypropylene, thereby reducing product strength. Summary of the invention

[0004] The purpose of the present invention is to provide an antibacterial modified polypropylene material and a preparation method and application thereof, so as to solve the problems raised in the above background technology.

[0005] To achieve the above object, the present invention provides the following technical scheme: a method for preparing an antibacterial modified polypropylene material, wherein the antibacterial modified polypropylene material comprises the following components by weight: 100 parts of polypropylene, 2 to 4 parts of polypropylene grafted maleic anhydride, 1 to 2 parts of random copolymerized polypropylene, 0.8 to 1.2 parts of p-allylphenol-styrene copolymer, 0.2 to 0.8 parts of ethylene bisstearamide, 0.5 to 1 parts of calcium stearate, 0.5 to 1 parts of nano titanium dioxide, 0.2 to 0.3 parts of nano zinc oxide and 0.3 to 0.5 parts of PP toughening agent;

[0006] The preparation method of the antibacterial modified polypropylene material comprises the following steps:

[0007] S1. Weighing raw materials: accurately weigh each component according to the formula ratio, and vacuum dry the polypropylene and random copolymer polypropylene at 80-90°C;

[0008] S2, premixing: the weighed components are mixed in a high-speed mixer at 1500-1800 r / min for 10-20 min;

[0009] S3, extrusion molding: adding the premixed materials into a twin-screw extruder, melt blending, and extruding to obtain the antibacterial modified polypropylene material.

[0010] Optionally, the melt index (230°C / 2.16kg) of the polypropylene grafted maleic anhydride is 470g / 10min, and the density of the polypropylene grafted maleic anhydride is 0.90g / cm 3 .

[0011] Optionally, the p-allylphenol-styrene copolymer is prepared by the following steps: firstly dissolving p-allylphenol and styrene in toluene at a molar ratio of 1:1, then adding azobisisobutyronitrile to the toluene, and using nitrogen as a protective gas, and then heating the reaction system to 78°C and continuously stirring for 6 hours, and finally filtering to remove unreacted impurities, and washing and drying the obtained solid product to obtain the p-allylphenol-styrene copolymer; wherein the added amount of azobisisobutyronitrile accounts for 0.1% of the total mass of p-allylphenol and styrene.

[0012] Optionally, the PP toughening agent is any one of multi-component blended bidirectional graft PS510, multi-component blended bidirectional graft PS512, multi-component blended bidirectional graft PS535 and polypropylene blended bidirectional graft PS566.

[0013] Optionally, the temperature zones of the twin-screw extruder are controlled as follows: zone one 160-170°C, zone two 170-180°C, zone three 180-190°C, zone four 180-190°C, zone five 180-190°C, zone six 180-190°C, zone seven 180-190°C, zone eight 180-190°C, zone nine 170-180°C, zone ten 170-180°C, die head 170-180°C, and the rotation speed of the twin-screw extruder is 140r / min.

[0014] On the other hand, the present invention further discloses an antibacterial modified polypropylene material, which is prepared by the preparation method of the antibacterial modified polypropylene material of the present invention.

[0015] In addition, the present invention also aims to provide the application of the antibacterial modified polypropylene material.

[0016] Optionally, the antibacterial modified polypropylene material is used in the field of daily chemical product packaging materials.

[0017] Compared with the prior art, the present invention has the following beneficial effects: the present invention has a good antibacterial effect on Staphylococcus aureus ATCC6538 and Escherichia coli ATCC25922, delays the crystallization of polypropylene by adding random copolymerized polypropylene and p-allylphenol-styrene copolymer, avoids excessive size of polypropylene crystals, enhances product strength, and can be made into daily chemical product packaging bottles, daily chemical product packaging bottle caps, and plastic pump head accessories. DETAILED DESCRIPTION

[0018] 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 the embodiments. 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.

[0019] Embodiment 1: The present invention provides a method for preparing an antibacterial modified polypropylene material, wherein the antibacterial modified polypropylene material comprises the following components by weight: 100 parts of polypropylene, 2 parts of polypropylene grafted maleic anhydride, 1 part of random copolymerized polypropylene, 0.8 parts of p-allylphenol-styrene copolymer, 0.2 parts of ethylene bisstearamide, 0.5 parts of calcium stearate, 0.5 parts of nano titanium dioxide, 0.2 parts of nano zinc oxide and 0.3 parts of PP toughening agent;

[0020] The preparation method of the antibacterial modified polypropylene material comprises the following steps:

[0021] S1. Weighing raw materials: accurately weigh each component according to the formula ratio, and vacuum dry the polypropylene and random copolymer polypropylene at 80°C;

[0022] S2, premixing: the weighed components were mixed in a high-speed mixer at 1500 r / min for 10 min;

[0023] S3, extrusion molding: adding the premixed materials into a twin-screw extruder, melt blending, and extruding to obtain an antibacterial modified polypropylene material.

[0024] Embodiment 2: The present invention provides a method for preparing an antibacterial modified polypropylene material, wherein the antibacterial modified polypropylene material comprises the following components by weight: 100 parts of polypropylene, 3 parts of polypropylene grafted maleic anhydride, 1.2 parts of random copolymerized polypropylene, 1.0 parts of p-allylphenol-styrene copolymer, 0.4 parts of ethylene stearamide, 0.7 parts of calcium stearate, 0.6 parts of nano titanium dioxide, 0.2 parts of nano zinc oxide and 0.4 parts of PP toughening agent;

[0025] The preparation method of the antibacterial modified polypropylene material comprises the following steps:

[0026] S1. Weighing raw materials: accurately weigh each component according to the formula ratio, and vacuum dry the polypropylene and random copolymer polypropylene at 84°C;

[0027] S2, premixing: the weighed components were mixed in a high-speed mixer at 1600 r / min for 15 min;

[0028] S3, extrusion molding: adding the premixed materials into a twin-screw extruder, melt blending, and extruding to obtain an antibacterial modified polypropylene material.

[0029] Embodiment 3: The present invention provides a method for preparing an antibacterial modified polypropylene material, wherein the antibacterial modified polypropylene material comprises the following components by weight: 100 parts of polypropylene, 3 parts of polypropylene grafted maleic anhydride, 1.8 parts of random copolymerized polypropylene, 1.2 parts of p-allylphenol-styrene copolymer, 0.6 parts of ethylene bisstearamide, 0.9 parts of calcium stearate, 0.4 parts of nano titanium dioxide, 0.3 parts of nano zinc oxide and 0.4 parts of PP toughening agent;

[0030] The preparation method of the antibacterial modified polypropylene material comprises the following steps:

[0031] S1. Weighing raw materials: accurately weigh each component according to the formula ratio, and vacuum dry the polypropylene and random copolymer polypropylene at 88°C;

[0032] S2, premixing: the weighed components were mixed in a high-speed mixer at 1700 r / min for 18 min;

[0033] S3, extrusion molding: adding the premixed materials into a twin-screw extruder, melt blending, and extruding to obtain an antibacterial modified polypropylene material.

[0034] Embodiment 4: The present invention provides a method for preparing an antibacterial modified polypropylene material, wherein the antibacterial modified polypropylene material comprises the following components by weight: 100 parts of polypropylene, 4 parts of polypropylene grafted maleic anhydride, 2 parts of random copolymerized polypropylene, 1.2 parts of p-allylphenol-styrene copolymer, 0.8 parts of ethylene bisstearamide, 1 part of calcium stearate, 1 part of nano titanium dioxide, 0.3 parts of nano zinc oxide and 0.5 parts of PP toughening agent;

[0035] The preparation method of the antibacterial modified polypropylene material comprises the following steps:

[0036] S1. Weighing raw materials: accurately weigh each component according to the formula ratio, and vacuum dry the polypropylene and random copolymer polypropylene at 90°C;

[0037] S2, premixing: the weighed components are mixed in a high-speed mixer at 1800 r / min for 20 min;

[0038] S3, extrusion molding: adding the premixed materials into a twin-screw extruder, melt blending, and extruding to obtain an antibacterial modified polypropylene material.

[0039] In Examples 1 to 4, the melt index (230°C / 2.16kg) of the polypropylene grafted maleic anhydride is 470 g / 10 min, and the density of the polypropylene grafted maleic anhydride is 0.90 g / cm 3 .

[0040] In Examples 1 to 4, the p-allylphenol-styrene copolymer is prepared by the following steps: the p-allylphenol-styrene copolymer is prepared by the following steps: firstly, p-allylphenol and styrene are dissolved in toluene at a molar ratio of 1:1, then azobisisobutyronitrile is added to the toluene, and nitrogen is used as a protective gas, then the reaction system is heated to 78°C and stirred for 6 hours, and finally, unreacted impurities are removed by filtration, and the obtained solid product is washed and dried to obtain the p-allylphenol-styrene copolymer. Wherein, the amount of azobisisobutyronitrile added accounts for 0.1% of the total mass of p-allylphenol and styrene.

[0041] In Examples 1 to 4, the temperature zones of the twin-screw extruder are controlled as follows: 160-170°C in zone one, 170-180°C in zone two, 180-190°C in zone three, 180-190°C in zone four, 180-190°C in zone five, 180-190°C in zone six, 180-190°C in zone seven, 180-190°C in zone eight, 170-180°C in zone nine, 170-180°C in zone ten, 170-180°C at the die head, and the speed of the twin-screw extruder is 140r / min.

[0042] The PP toughening agents in Examples 1 to 4 are respectively multi-component blended bidirectional graft PS510, multi-component blended bidirectional graft PS512, multi-component blended bidirectional graft PS535 and polypropylene blended bidirectional graft PS566.

[0043] On the other hand, the present invention also discloses an antibacterial modified polypropylene material, which can be prepared by the preparation method of the antibacterial modified polypropylene material disclosed in Examples 1 to 4. In addition, the purpose of the present invention is to provide an application of the antibacterial modified polypropylene material, which can be applied to the field of daily chemical packaging materials, and the antibacterial modified polypropylene material can be made into daily chemical packaging bottles, daily chemical packaging bottle caps, and plastic pump head accessories.

[0044] Test Example 1

[0045] Test content: The antibacterial modified polypropylene material prepared in Examples 1 to 4 was biaxially stretched by a plastic film tenter, and the longitudinal stretching ratio was set to 5 times and the transverse stretching ratio was set to 7 times to obtain a film, and then the film was cut into 50mm×50mm samples. The test method disclosed in QB / T2591-2003 was adopted, wherein Staphylococcus aureus ATCC6538 (A bacteria) and Escherichia coli ATCC25922 (B bacteria) were used for detection bacteria, and the blank control sample was a polypropylene cast film produced by Sinopec with a model number of F800E. The antibacterial rate was statistically analyzed and the results are recorded in Table 1.

[0046] Table 1 Antibacterial test results

[0047] Antibacterial rate (A bacteria) / % Antibacterial rate (B bacteria) / % Example 1 84.2 81.1 Example 2 85.9 82.9 Example 3 88.2 83.5 Example 4 86.0 82.3

[0048] As can be seen from Table 1, the films obtained from the antibacterial modified polypropylene materials prepared in Examples 1 to 4 have an antibacterial rate of >81% against Staphylococcus aureus ATCC6538 and Escherichia coli ATCC25922, among which Example 3 has the highest antibacterial rate and is worthy of promotion and use.

[0049] Test Example 2

[0050] Test content: Take the formula of antibacterial modified polypropylene material in Example 3 as the test group, and take the test group without adding random copolymerized polypropylene and p-allylphenol-styrene copolymer as the control group. First, heat the test group and the control group to a molten state by a heater, and then control the temperature of the heater to 130°C, record the time when crystallization occurs in the test group and the control group, and the results are recorded in Table 2.

[0051] Table 2 Crystallization test results

[0052] Crystallization time / min Experimental Group 138 Control group 102

[0053] It can be seen from Table 1 that the crystallization time of the test group is shorter than that of the control group. Therefore, the addition of random copolymer polypropylene and p-allylphenol-styrene copolymer can delay the crystallization of the antibacterial modified polypropylene material.

[0054] Test Example 3

[0055] Test content: The test group and control group in Test Example 2 were subjected to biaxial stretching by a plastic film tenter, with the longitudinal stretching ratio set to 5 times and the transverse stretching ratio set to 7 times to obtain a film, and then the film was cut into 50mm×50mm specimens, referred to as the test group. According to the test method disclosed in GB / T 1040, the tensile strength of the test group and the control group was measured respectively, and according to the test method disclosed in GB / T 16578, the tear strength of the test group and the control group was measured respectively, and the results are recorded in Table 3.

[0056] Table 3 Strength test results

[0057] Tensile strength / MPa Tear strength / MPa Experimental Group 40.74 1.72 Control group 32.07 1.30

[0058] It can be seen from Table 2 that the tensile strength and tear strength of the test group are better than those of the control group. Therefore, adding random copolymer polypropylene and p-allylphenol-styrene copolymer can improve the strength of the antibacterial modified polypropylene material.

[0059] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing an antibacterial modified polypropylene material, characterized in that: The antibacterial modified polypropylene material comprises the following components by weight: 100 parts of polypropylene, 2 to 4 parts of polypropylene grafted maleic anhydride, 1 to 2 parts of random copolymerized polypropylene, 0.8 to 1.2 parts of p-allylphenol-styrene copolymer, 0.2 to 0.8 parts of ethylene bisstearamide, 0.5 to 1 parts of calcium stearate, 0.5 to 1 parts of nano titanium dioxide, 0.2 to 0.3 parts of nano zinc oxide and 0.3 to 0.5 parts of PP toughening agent; The preparation method of the antibacterial modified polypropylene material comprises the following steps: S1. Weighing raw materials: accurately weigh each component according to the formula ratio, and vacuum dry the polypropylene and random copolymer polypropylene at 80-90°C; S2, premixing: the weighed components are mixed in a high-speed mixer at 1500-1800 r / min for 10-20 min; S3, extrusion molding: adding the premixed materials into a twin-screw extruder, melt blending, and extruding to obtain the antibacterial modified polypropylene material.

2. The method for preparing an antibacterial modified polypropylene material according to claim 1, characterized in that: The melt index (230°C / 2.16kg) of the polypropylene grafted maleic anhydride is 470g / 10min, and the density of the polypropylene grafted maleic anhydride is 0.90g / cm 3 .

3. The method for preparing an antibacterial modified polypropylene material according to claim 1, characterized in that: The p-allylphenol-styrene copolymer is prepared by the following steps: firstly dissolving p-allylphenol and styrene in toluene at a molar ratio of 1:1, then adding azobisisobutyronitrile to the toluene, using nitrogen as a protective gas, then heating the reaction system to 78°C, and continuously stirring for 6 hours, finally filtering to remove unreacted impurities, and washing and drying the obtained solid product to obtain the p-allylphenol-styrene copolymer; wherein the added amount of azobisisobutyronitrile accounts for 0.1% of the total mass of p-allylphenol and styrene.

4. The method for preparing an antibacterial modified polypropylene material according to claim 1, characterized in that: The PP toughening agent is any one of multi-component blended bidirectional graft PS510, multi-component blended bidirectional graft PS512, multi-component blended bidirectional graft PS535 and polypropylene blended bidirectional graft PS566.

5. The method for preparing an antibacterial modified polypropylene material according to claim 1, characterized in that: The temperature zones of the twin-screw extruder are controlled as follows: zone one 160-170°C, zone two 170-180°C, zone three 180-190°C, zone four 180-190°C, zone five 180-190°C, zone six 180-190°C, zone seven 180-190°C, zone eight 180-190°C, zone nine 170-180°C, zone ten 170-180°C, die head 170-180°C, and the rotation speed of the twin-screw extruder is 140r / min.

6. An antibacterial modified polypropylene material, characterized in that: The antibacterial modified polypropylene material is prepared by the preparation method of any one of claims 1 to 5.

7. Application of the antibacterial modified polypropylene material as claimed in claim 6 in the field of daily chemical product packaging materials.