Hard polyvinyl chloride antibacterial master batch and preparation method thereof

Abstract

The invention discloses a rigid polyvinyl chloride antibacterial master batch and a preparation method thereof.The rigid polyvinyl chloride antibacterial master batch is composed of polyvinyl chloride resin, maleic anhydride, a stabilizer, polyhexamethylene biguanide hydrochloride and the like. PVC-MAH which is difficult to obtain through a common method is prepared through a mechanochemical reaction; polyhexamethyleneguanidine hydrochloride (PHMG) is screened out from numerous polymer antibacterial agents containing guanidine salt, in melt blending, anhydride groups of polyvinyl chloride grafted maleic anhydride are combined with terminal amino groups of polyhexamethyleneguanidine hydrochloride to obtain the polymer (PVC-MAH-g-PHMG) with antibacterial performance, an initiator and other solvents do not need to be additionally used, and the preparation method is simple and easy to implement. The polyhexamethylene guanidine hydrochloride is added into the polyvinyl chloride resin, so that the PHMG can be successfully grafted onto a polyvinyl chloride resin molecular chain, good dispersion of the PHMG in a system is realized, and the compatibility of the polyhexamethylene guanidine hydrochloride and the polyvinyl chloride resin is improved, so that the prepared master batch has both water resistance and antibacterial property, dissolution resistance, good antibacterial effect and stable and lasting antibacterial efficiency.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a rigid polyvinyl chloride antibacterial masterbatch and a preparation method thereof. Background Art

[0002] Polyvinyl chloride resin (PVC) is one of the five general-purpose plastics. It has the advantages of wear resistance, acid and alkali resistance, good insulation, strong stability and low production cost. It is widely used in construction, electrical appliances, medical devices and product packaging. However, polyvinyl chloride resin does not have antibacterial function. Research and preparation of polyvinyl chloride products with excellent antibacterial properties can reduce the spread and reproduction of bacteria, which is beneficial to human health and has great social and economic significance.

[0003] At present, the method for preparing polyvinyl chloride with antibacterial properties is mainly to evenly disperse the antibacterial agent in the polyvinyl chloride resin to obtain a masterbatch. The antibacterial agents used are mainly divided into natural antibacterial agents, inorganic antibacterial agents and organic synthetic antibacterial agents. Among them, natural antibacterial agents come from nature, but are limited by factors such as stability, extraction process and cost, and are not widely used in industry. Inorganic antibacterial agents such as silver-based substances have problems such as high price, easy agglomeration in the matrix resin, easy discoloration, and toxicity. Organic synthetic antibacterial agents are divided into organic small molecule antibacterial agents and organic polymer antibacterial agents. Organic small molecule antibacterial agents have the disadvantages of poor heat resistance, easy migration and precipitation, poor washing resistance, and short service life. Therefore, organic polymer antibacterial agents are currently studied more.

[0004] Among organic polymer antimicrobial agents, guanidine-containing polymer antimicrobial agents have shown great development potential due to their low toxicity and strong antimicrobial properties. They have been widely used in medical disinfection, food and other daily necessities sterilization and disinfection. However, if such antimicrobial agents are directly added to polyvinyl chloride resin to prepare antimicrobial masterbatch, there will be problems such as poor compatibility, poor antimicrobial effect, short-lasting antimicrobial effect, and inability to take into account both water resistance and antimicrobial properties. Summary of the invention

[0005] In order to solve the above technical problems, one of the purposes of the present application is to provide a rigid polyvinyl chloride antibacterial masterbatch, which includes the following components in parts by weight: 90-100 parts of polyvinyl chloride resin, 5-8 parts of maleic anhydride, 1-3 parts of stabilizer, 10-15 parts of polyhexamethylene biguanide hydrochloride, 5-8 parts of toughening agent, and 0.1-0.5 parts of lubricant.

[0006] Preferably, the toughening agent is at least one of chlorinated polyethylene and acrylic rubber (ACR401).

[0007] Preferably, the stabilizer is at least one of a calcium-zinc composite heat stabilizer and an organic tin heat stabilizer.

[0008] Preferably, the lubricant is any one of polyethylene wax, oxidized polyethylene wax and stearic acid.

[0009] Another object of the present application is to provide a method for preparing the above-mentioned rigid polyvinyl chloride antibacterial masterbatch, comprising the following steps:

[0010] The polyvinyl chloride resin, maleic anhydride and stabilizer are mixed according to the above weight proportions to obtain a material to be ground, the material to be ground is added to a vibration mill, and the mixture is vibrated for 6 to 8 hours at 15 to 35° C. in a nitrogen atmosphere to obtain a mixture a;

[0011] Add the mixture a, the polyhexamethylene biguanide hydrochloride, the toughening agent and the lubricant in the above weight parts into a mixer, and mix them uniformly at 40-50° C. to obtain a mixture b;

[0012] The above mixture b is melt-blended, tableted, and crushed into pellets to obtain polyvinyl chloride resin antibacterial masterbatch.

[0013] Preferably, in the vibration mill, the mass ratio of the steel balls to the material to be ground is 10 to 100:1.

[0014] Preferably, the diameter of the steel ball is 5 to 10 mm.

[0015] Preferably, the rotation speed of the steel balls in the vibration mill is 500 to 1500 r / min.

[0016] Preferably, the amplitude of the vibration mill is 9 to 11 mm.

[0017] Preferably, the melting temperature is 175-185°C and the blending time is 5-15 minutes.

[0018] The principle of this application is:

[0019] The polyvinyl chloride resin breaks the molecular chain through physical force in the vibration mill to form large molecular free radicals, that is, PVC→PVC·+PVC·;

[0020] Maleic anhydride can react with polyvinyl chloride free radicals to form copolymers. As a comonomer, maleic anhydride can react with polyvinyl chloride free radicals and insert into the polyvinyl chloride chain to form a copolymer containing maleic anhydride groups, that is, PVC·+MAH→PVC-MAH;

[0021] In melt blending, the anhydride groups of polyvinyl chloride grafted with maleic anhydride (PVC-MAH) were combined with the terminal amine groups of polyhexamethyleneguanidine hydrochloride (PHMG) to obtain a polymer with antibacterial properties (PVC-MAH-g-PHMG), that is, PVC-MA·+PHMG→PVC-MA-g-PHMG.

[0022] The beneficial effect is that: the present application prepares PVC-MAH which is difficult to obtain by general methods through mechanochemical reaction, and screens out polyhexamethyleneguanidine hydrochloride (PHMG) from many guanidine salt-containing polymer antibacterial agents. In melt blending, the anhydride group of polyvinyl chloride grafted with maleic anhydride is combined with the terminal amine group of polyhexamethyleneguanidine hydrochloride to obtain a polymer (PVC-MAH-g-PHMG) with antibacterial properties. Without the need for additional initiators and other solvents, PHMG can be successfully grafted onto the molecular chain of polyvinyl chloride resin, thereby achieving good dispersion of PHMG in the system, improving the compatibility of polyhexamethyleneguanidine hydrochloride with polyvinyl chloride resin, and enabling the prepared masterbatch to take into account both water resistance and antibacterial properties, with good anti-dissolution and antibacterial effects, and stable and long-lasting antibacterial efficacy. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

[0024] Figure 1 These are photos of the antibacterial performance test results of the embodiments and comparative examples of the present application after 50°C / 24h anti-dissolution treatment. DETAILED DESCRIPTION

[0025] The present invention is further described in detail below in conjunction with specific embodiments so that those skilled in the art can understand the present invention more clearly.

[0026] The following embodiments are only used to illustrate the present invention, but are not limited to the scope of the present invention. Based on the specific embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without creative work belong to the protection scope of the present invention.

[0027] In the examples of the present invention, unless otherwise specified, all raw material components are commercially available products well known to those skilled in the art; in the examples of the present invention, unless otherwise specified, the technical means used are conventional means well known to those skilled in the art.

[0028] Source of raw materials:

[0029] Polyvinyl chloride resin, model S700, purchased from Shandong Chisheng Chemical Technology Co., Ltd.;

[0030] Maleic anhydride, purchased from Dongguan Yingxiang Plastic Raw Materials Co., Ltd.;

[0031] Polyhexamethylene biguanide hydrochloride was purchased from Jinan Yuanfang Chemical Co., Ltd.;

[0032] Calcium zinc composite heat stabilizer, product model German Bear brand BAEROPAN MC 9875KA, purchased from Shanghai Kaiyin Chemical Co., Ltd.;

[0033] Organic tin heat stabilizer, product model Rohm and Haas TM-181FS, purchased from Dongguan Baojulai Plastic Raw Materials Co., Ltd.;

[0034] Chlorinated polyethylene, purchased from Shijiazhuang Qiushi Chemical Co., Ltd.;

[0035] Acrylate rubber, ACR401, was purchased from Jiangsu Pules Biotechnology Co., Ltd.;

[0036] Polyethylene wax was purchased from Wuhan Xindongyi Chemical Co., Ltd.

[0037] Oxidized polyethylene wax was purchased from Shanghai Xingsi Chemical Co., Ltd.;

[0038] Stearic acid (octadecanoic acid), purchased from Shanghai Better Chemical Co., Ltd.;

[0039] The remaining reagents are commercially available.

[0040] Example 1

[0041] A rigid polyvinyl chloride antibacterial masterbatch comprises the following components in parts by weight: 90 parts of polyvinyl chloride resin, 8 parts of maleic anhydride, 3 parts of stabilizer, 15 parts of polyhexamethylene biguanide hydrochloride, 8 parts of toughening agent, and 0.5 parts of lubricant; wherein the toughening agent is chlorinated polyethylene, the stabilizer is a calcium-zinc composite heat stabilizer, and the lubricant is polyethylene wax.

[0042] A method for preparing rigid polyvinyl chloride antibacterial masterbatch comprises the following steps:

[0043] 90 parts of polyvinyl chloride resin, 8 parts of maleic anhydride and 3 parts of stabilizer are mixed to obtain a material to be ground, and the material to be ground is added into a vibration mill, and the mixture is ground for 6 hours at 15° C. and in a nitrogen atmosphere to obtain a mixture a; wherein the amplitude of the vibration mill is 9 mm, the mass ratio of the steel ball to the material to be ground is 10:1, the diameter of the steel ball is 5 mm, and the rotation speed of the steel ball is 500 r / min;

[0044] The mixture a, 15 parts of polyhexamethylene biguanide hydrochloride, 8 parts of toughening agent and 0.5 parts of lubricant were added into a mixer, and mixed uniformly at 40° C. to obtain a mixture b;

[0045] The mixture b was put into an internal mixer and melt-blended at 175° C. for 15 minutes, and then pressed into sheets by double rollers. The sheets were crushed into pellets in a crusher to obtain polyvinyl chloride resin antibacterial masterbatch.

[0046] Example 2

[0047] A rigid polyvinyl chloride antibacterial masterbatch comprises the following components in parts by weight: 95 parts of polyvinyl chloride resin, 6 parts of maleic anhydride, 2 parts of stabilizer, 13 parts of polyhexamethylene biguanide hydrochloride, 7 parts of toughening agent, and 0.3 parts of lubricant; wherein the toughening agent is acrylic rubber (ACR401), the stabilizer is an organic tin heat stabilizer, and the lubricant is oxidized polyethylene wax.

[0048] A method for preparing rigid polyvinyl chloride antibacterial masterbatch comprises the following steps:

[0049] 95 parts of polyvinyl chloride resin, 6 parts of maleic anhydride and 2 parts of stabilizer are mixed to obtain a material to be ground, and the material to be ground is added into a vibration mill, and the mixture is vibrated for 7 hours at 25° C. in a nitrogen atmosphere to obtain a mixture a; wherein the amplitude of the vibration mill is 10 mm, the mass ratio of the steel ball to the material to be ground is 50:1, the diameter of the steel ball is 8 mm, and the rotation speed of the steel ball is 1000 r / min;

[0050] The mixture a, 13 parts of polyhexamethylene biguanide hydrochloride, 7 parts of toughening agent and 0.3 parts of lubricant were added into a mixer, and mixed uniformly at 45° C. to obtain a mixture b;

[0051] The mixture b was put into an internal mixer and melt-blended at 180° C. for 10 minutes, and then pressed into sheets by double rollers. The sheets were crushed into pellets in a crusher to obtain polyvinyl chloride resin antibacterial masterbatch.

[0052] Example 3

[0053] A rigid polyvinyl chloride antibacterial masterbatch comprises the following components in parts by weight: 100 parts of polyvinyl chloride resin, 5 parts of maleic anhydride, 1 part of stabilizer, 10 parts of polyhexamethylene biguanide hydrochloride, 5 parts of toughening agent, and 0.1 part of lubricant; wherein the toughening agent is composed of chlorinated polyethylene and acrylic rubber (ACR401) in a weight ratio of 1:1, the stabilizer is composed of a calcium-zinc composite heat stabilizer and an organic tin heat stabilizer in a weight ratio of 1:1, and the lubricant is composed of oxidized polyethylene wax and stearic acid in a weight ratio of 1:1.

[0054] A method for preparing rigid polyvinyl chloride antibacterial masterbatch comprises the following steps:

[0055] 100 parts of polyvinyl chloride resin, 5 parts of maleic anhydride and 1 part of stabilizer are mixed to obtain a material to be ground, and the material to be ground is added into a vibration mill, and is vibrated for 8 hours at 35° C. in a nitrogen atmosphere to obtain a mixture a; wherein the amplitude of the vibration mill is 11 mm, the mass ratio of the steel ball to the material to be ground is 100:1, the diameter of the steel ball is 10 mm, and the rotation speed of the steel ball is 1500 r / min;

[0056] The mixture a, 10 parts of polyhexamethylene biguanide hydrochloride, 5 parts of toughening agent and 0.1 parts of lubricant were added into a mixer, and mixed uniformly at 50° C. to obtain a mixture b;

[0057] The mixture b was put into an internal mixer and melt-blended at 185° C. for 5 minutes, and then pressed into sheets by double rollers. The sheets were crushed into pellets in a crusher to obtain polyvinyl chloride resin antibacterial masterbatch.

[0058] Comparative Example 1

[0059] The difference between this comparative example and Example 2 is that the polyvinyl chloride resin is increased from 95 parts to 108 parts, and polyhexamethylene biguanide hydrochloride is not added. The other ingredients and experimental steps are the same as those in Example 2.

[0060] Comparative Example 2

[0061] The difference between this comparative example and Example 2 is that 13 parts of polyhexamethylene biguanide hydrochloride are replaced by 13 parts of cuprous oxide, and the other ingredients and experimental steps are the same as those in Example 2.

[0062] Comparative Example 3

[0063] This comparative example is different from Example 2 in that the polyvinyl chloride resin, maleic anhydride and stabilizer are not ground but directly mixed with other components and then directly put into an internal mixer for melt blending at 180°C for 10 minutes, then pressed into sheets by double rollers, and the sheets are crushed in a grinder to obtain master batches.

[0064] The antibacterial properties and anti-dissolution properties of the polyvinyl chloride resin antibacterial masterbatches prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were tested respectively.

[0065] Test method:

[0066] The antibacterial properties were tested in accordance with GB / T 31402-2015 "Plastics - Test Method for Antibacterial Properties of Plastic Surfaces", using Staphylococcus aureus ATCC 6538P and Escherichia coli ATCC 8739;

[0067] The anti-dissolution performance was tested according to GB / T 21510-2008 "Dissolution test method for plastic antimicrobial agents". The samples were immersed in distilled water at a constant temperature of 50±2℃ for 24h.

[0068] The test results are shown in Table 1.

[0069] Table 1 Antibacterial performance test results of each embodiment and comparative example

[0070]

[0071] From the experimental data in Table 1, the antibacterial rate of the polyvinyl chloride resin antibacterial masterbatch prepared in each embodiment of the present application against Staphylococcus aureus can reach more than 98%, and the antibacterial rate against Escherichia coli can reach more than 99.9%. After the anti-dissolution treatment at 50°C / 24 hours, although the antibacterial rate of each embodiment against Staphylococcus aureus is slightly reduced, it still remains above 98%, and the antibacterial rate against Escherichia coli is still maintained at more than 99.9%. It can be seen that the polyvinyl chloride resin antibacterial masterbatch prepared in each embodiment of the present application exhibits good antibacterial performance and anti-dissolution performance.

[0072] By comparing and analyzing the data of Example 2 with those of Comparative Example 1, it is found that when Comparative Example 1 does not add polyhexamethylene biguanide hydrochloride, the antibacterial performance and anti-dissolution performance of the prepared masterbatch are very poor; and by comparing and analyzing the data of Example 2 with those of Comparative Example 2, it is found that when Comparative Example 2 replaces polyhexamethylene biguanide hydrochloride with cuprous oxide, the antibacterial performance and anti-dissolution performance of the prepared masterbatch are better than those of Comparative Example 1, but far inferior to the effects of the various embodiments of the present application. This may be because after Comparative Example 2 replaces polyhexamethylene biguanide hydrochloride with cuprous oxide, cuprous oxide has poor compatibility with polyvinyl chloride resin and cannot be grafted to polyvinyl chloride resin, and cuprous oxide cannot be achieved in the system. The good dispersion in the masterbatch leads to poor anti-dissolution and antibacterial effects, unstable and non-lasting antibacterial effects; the data of Example 2 and Comparative Example 3 are further compared and analyzed to find that when the polyvinyl chloride resin, maleic anhydride and stabilizer are not ground but directly mixed with other components in Comparative Example 3 and then directly put into the internal mixer for melt blending to obtain the masterbatch, its antibacterial performance and anti-dissolution performance are better than those of the other two comparative examples, but its antibacterial performance and anti-dissolution performance have a significant downward trend, which may be because the polyvinyl chloride resin, maleic anhydride and stabilizer are not ground, which may be because the polyhexamethylene biguanide hydrochloride cannot be well grafted onto the polyvinyl chloride resin.

[0073] The above is only an embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.

Claims

1. A rigid polyvinyl chloride antibacterial masterbatch, characterized in that: The composition comprises the following components in parts by weight: 90-100 parts of polyvinyl chloride resin, 5-8 parts of maleic anhydride, 1-3 parts of stabilizer, 10-15 parts of polyhexamethylene biguanide hydrochloride, 5-8 parts of toughening agent and 0.1-0.5 parts of lubricant.

2. The rigid polyvinyl chloride antibacterial masterbatch according to claim 1, characterized in that: The toughening agent is selected from at least one of chlorinated polyethylene and acrylic rubber (ACR401).

3. The rigid polyvinyl chloride antibacterial masterbatch according to claim 1, characterized in that: The stabilizer is selected from at least one of a calcium-zinc composite heat stabilizer and an organic tin heat stabilizer.

4. The rigid polyvinyl chloride antibacterial masterbatch according to claim 1, characterized in that: The lubricant is selected from any one of polyethylene wax, oxidized polyethylene wax and stearic acid.

5. A method for preparing the rigid polyvinyl chloride antibacterial masterbatch according to any one of claims 1 to 4, characterized in that: The following steps are involved: Mixing polyvinyl chloride resin, maleic anhydride and stabilizer according to the weight proportions to obtain a material to be ground, adding the material to be ground into a vibration mill, and performing vibration grinding for 6 to 8 hours at 15 to 35° C. in a nitrogen atmosphere to obtain a mixture a; Add the mixture a and the weight proportions of polyhexamethylene biguanide hydrochloride, toughening agent and lubricant into a mixer, and mix them uniformly at 40-50° C. to obtain a mixture b; The above mixture b is melt-blended, tableted, and crushed into pellets to obtain polyvinyl chloride resin antibacterial masterbatch.

6. The method for preparing rigid polyvinyl chloride antibacterial masterbatch according to claim 5, characterized in that: In the vibration mill, the mass ratio of the steel balls to the material to be ground is 10-100:

1.

7. The method for preparing rigid polyvinyl chloride antibacterial masterbatch according to claim 6, characterized in that: The steel ball has a diameter of 5 to 10 mm.

8. The method for preparing rigid polyvinyl chloride antibacterial masterbatch according to claim 6, characterized in that: The rotation speed of the steel balls in the vibration mill is 500-1500 r / min.

9. The method for preparing rigid polyvinyl chloride antibacterial masterbatch according to claim 5, characterized in that: The amplitude of the vibration mill is 9-11 mm.

10. The method for preparing rigid polyvinyl chloride antibacterial masterbatch according to claim 5, characterized in that: The melting temperature is 175-185° C., and the blending is 5-15 minutes.

Images