High-antibacterial petg composite material, preparation method and application thereof

Abstract

The application relates to a high-antibacterial PETG composite material and a preparation method and application thereof, which comprises the following raw materials in parts by mass: 100 parts of PETG, 2-5 parts of a composite antibacterial agent, 3-10 parts of a silane coupling agent and 0.1-0.3 parts of an initiator; wherein the composite antibacterial agent is a combination of propyl gallate, hexamidine diisethionate and polyhexamethylene biguanide hydrochloride. The composite antibacterial agent can be stably combined with the PETG matrix through the action of the coupling agent and the initiator. The PETG composite material has both processing feasibility and long-acting antibacterial property through the synergistic action of the composite antibacterial agent, the coupling agent and the initiator.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of PETG composite materials, and in particular to a high-antibacterial PETG composite material and a preparation method and application thereof. BACKGROUND

[0002] In the process of compounding the antibacterial agent with PETG, there are a series of significant drawbacks. First, the compatibility problem is particularly prominent: part of the inorganic antibacterial agent, such as silver ions, is easy to agglomerate due to the significant difference in polarity with PETG, thereby causing local concentration to be too high or forming an antibacterial blind area; at the same time, the processing temperature (about 220-250℃) of PETG may damage the structure of the organic antibacterial agent (such as quaternary ammonium salt), causing discoloration or decomposition phenomenon; in addition, the low compatibility antibacterial agent is also easy to migrate from the PETG matrix to the surface, not only causing waste of the antibacterial agent, but also possibly polluting the contacted objects, such as the exudation of silver ions in food packaging. Second, there are obvious defects in long-acting antibacterial: antibacterial agents relying on the dissolution mechanism (such as nano-silver) release too fast in the early stage, and the concentration is insufficient in the later stage, which is difficult to cope with long-term microbial challenges; the light / oxygen sensitive antibacterial agent (such as titanium dioxide) is easy to be inactivated in outdoor application, and its long-acting nature is limited to laboratory conditions; the sprayed antibacterial layer quickly falls off under mechanical friction, and cannot realize the persistent antibacterial of the material body, such as the failure of medical devices after repeated disinfection. More troublesome is that safety and regulatory restrictions make some high-efficiency antibacterial agents (such as triclosan) be banned for use in food contact grade PETG due to potential toxicity, forcing manufacturers to use low-efficiency substitutes. Finally, the balance between cost and performance also becomes a big problem: high-load antibacterial agents can improve the antibacterial effect, but significantly increase the brittleness of the material (such as the elongation at break of PETG decreases by more than 30%), which seriously restricts its application in high-toughness demand scenarios. SUMMARY

[0003] The purpose of the present application is to overcome the deficiencies of the prior art and provide a high-antibacterial PETG composite material and a preparation method and application thereof.

[0004] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0005] In the first aspect, the present application provides a high-antibacterial PETG composite material, comprising the following raw materials in parts by mass:

[0006] PETG 100 parts, composite antibacterial agent 2-5 parts, silane coupling agent 3-10 parts and initiator 0.1-0.3 parts; wherein the composite antibacterial agent is a combination of propyl gallate, hexamidine diisethionate and polyhexamethylene biguanide hydrochloride.

[0007] The composite antibacterial agent of the present application is all organic antibacterial agent, which avoids the reduction of free movement space of polymer molecular chain due to the addition of a large amount of inorganic antibacterial agent particles (such as silver, zinc), limits the deformation ability of the material, and causes the occurrence of the situation that the elongation at break decreases, so the PETG composite material of the present application can maintain good mechanical properties. Polyhexamethylene biguanide hydrochloride (PHMB) is a high molecular guanidine salt antibacterial agent, a large number of amino groups in the molecular chain of which are combined with the ester groups of PETG through hydrogen bond action, and the introduction of silane coupling agent can further improve the interfacial compatibility. Propyl gallate and hexamidine diisethionate are low molecular organic antibacterial agents, which can be stably combined in the PETG matrix through the action of coupling agent and initiator. PHMB belongs to a non- elution type antibacterial agent (kills bacteria by contact), and the antibacterial groups are fixed on the surface of the material by chemical bonds and are resistant to washing and rubbing, so the long-term antibacterial effect is stable. Propyl gallate and hexamidine diisethionate are elution type antibacterial agents, so PHMB in the composite antibacterial agent provides a long-acting antibacterial base, and propyl gallate and hexamidine diisethionate supplement short-term rapid sterilization. At the same time, the silane coupling agent can effectively prevent the loss of propyl gallate and hexamidine diisethionate, and prolong the overall antibacterial life.

[0008] In addition, propyl gallate has certain antioxidant properties, which can prevent the degradation reaction of PETG material due to oxidation to a certain extent during processing, storage or use, and maintain the integrity of the polymer chain, which is beneficial to maintaining the original mechanical properties of the material. The sulfonic acid group of hexamidine diisethionate can form an ion pair with the silane coupling agent to construct a three-dimensional cross-linked network and improve the mechanical properties. The polyhexamethylene biguanide hydrochloride molecular chain is long and contains guanidine groups, and the guanidine group has strong polarity. On the one hand, it can form hydrogen bonds and other weak interactions with the PETG molecular chain to enhance the interaction between the molecular chains and improve the tensile strength; on the other hand, the long chain structure can play a buffering role when the material is stretched to prevent stress concentration and avoid premature rupture of the material, thereby having a beneficial effect on the elongation at break.

[0009] In summary, the PETG composite material has both processing feasibility and long-acting antibacterial property through the synergistic effect of the composite antibacterial agent and the coupling agent and the initiator.

[0010] Preferably, the mass ratio of propyl gallate, hexamidine diisethionate and polyhexamethylene biguanide hydrochloride is 1: (2-3): (2-3).

[0011] Preferably, the composite material comprises the following raw materials in parts by mass: PETG 100 parts, composite antibacterial agent 4-5 parts, silane coupling agent 6-10 parts and initiator 0.1-0.2 parts.

[0012] Preferably, the silane coupling agent comprises at least one of KH550, KH560, KH570, KH792, DL602.

[0013] Preferably, the initiator is an azo initiator.

[0014] In a second aspect, the present application provides a method for preparing the high-antibacterial PETG composite material, comprising the following steps:

[0015] S1, mixing the composite antibacterial agent with the silane coupling agent, then adding the initiator, and reacting at 70-80℃ for 2-3h to obtain a mixture;

[0016] S2, mixing the PETG with the mixture, and granulating at 210-240℃ to obtain the high-antibacterial PETG composite material.

[0017] Preferably, in the step S1, the mixing speed is 800-1000rpm, and the mixing time is 30-60min.

[0018] In a third aspect, the present application provides the use of the high-antibacterial PETG composite material in the preparation of medical packaging materials.

[0019] Compared with the prior art, the present application has the following beneficial effects:

[0020] The composite antibacterial agent in the PETG composite material of the present application is a composition of polyhexamethylene biguanide hydrochloride, propyl gallate and hexamidine diisethionate. The composite antibacterial agent can be stably combined with the PETG matrix through the action of the coupling agent and the initiator. Among them, PHMB is a non-dissolved antibacterial agent, which has stable long-term antibacterial effect. Propyl gallate and hexamidine diisethionate are dissolved antibacterial agents, which supplement short-term rapid sterilization in the composite antibacterial agent. At the same time, the silane coupling agent can effectively prevent the loss of propyl gallate and hexamidine diisethionate, and prolong the overall antibacterial life. The PETG composite material has both processing feasibility and long-term antibacterial property through the synergistic effect of the composite antibacterial agent, the coupling agent and the initiator. DETAILED DESCRIPTION

[0021] In order to better illustrate the purpose, technical scheme and advantages of the present application, the present application will be further described below in combination with specific examples.

[0022] The raw materials used in the following examples and comparative examples are as follows:

[0023] PETG: manufacturer is SK company of South Korea, brand is K2012;

[0024] Propyl gallate: the manufacturer is Guangdong Wengjiang Chemical Reagent Co., Ltd., and the model is PA01812;

[0025] Hexamidine diisethionate: the manufacturer is Guangzhou Weishi Biological Technology Co., Ltd., and the model is 988;

[0026] Polyhexamethylene biguanide hydrochloride: the manufacturer is Guangdong Wengjiang Chemical Reagent Co., Ltd., and the model is PC97458;

[0027] Silane coupling agent: KH550, KH560, and KH570 are all purchased from Shanghai Yuan Ye Biological Technology Co., Ltd.;

[0028] Azo initiator: azobisisobutyronitrile, the manufacturer is Guangdong Wengjiang Chemical Reagent Co., Ltd., and the model is WA01724;

[0029] Other materials, reagents, etc. used in the examples can be obtained from commercial channels if there is no special instruction.

[0030] Example 1

[0031] A high-antibacterial PETG composite material includes the following raw materials in parts by mass:

[0032] PETG 100 parts, composite antibacterial agent 4 parts, silane coupling agent 6 parts, and initiator 0.2 parts; wherein the composite antibacterial agent is a composition of propyl gallate, hexamidine diisethionate, and polyhexamethylene biguanide hydrochloride in a mass ratio of 1:3:2; the silane coupling agent is KH560; and the initiator is an azo initiator.

[0033] A method for preparing a high-antibacterial PETG composite material includes the following steps:

[0034] S1, mixing the composite antibacterial agent and the silane coupling agent at 850 rpm for 40 min, then adding the initiator, and reacting at 75°C for 3 h to obtain a mixture;

[0035] S2, mixing PETG and the mixture, and granulating at 230°C to obtain the high-antibacterial PETG composite material.

[0036] Example 2

[0037] A high-antibacterial PETG composite material includes the following raw materials in parts by mass:

[0038] PETG 100 parts, composite antibacterial agent 2 parts, silane coupling agent 3 parts, and initiator 0.1 parts; wherein the composite antibacterial agent is a composition of propyl gallate, hexamidine diisethionate, and polyhexamethylene biguanide hydrochloride in a mass ratio of 1:2:2; the silane coupling agent is KH550; and the initiator is an azo initiator.

[0039] The application discloses a preparation method of a high-antibacterial PETG composite material.

[0040] S1, mixing the composite antibacterial agent and the silane coupling agent at 800 rpm for 60 min, then adding an initiator and reacting at 70 DEG C for 3 h to obtain a mixture;

[0041] S2, mixing the PETG and the mixture, and granulating at 210 DEG C to obtain the high-antibacterial PETG composite material.

[0042] Example 3

[0043] The application discloses a high-antibacterial PETG composite material.

[0044] The application discloses a high-antibacterial PETG composite material.

[0045] The application discloses a preparation method of a high-antibacterial PETG composite material.

[0046] S1, mixing the composite antibacterial agent and the silane coupling agent at 1000 rpm for 30 min, then adding an initiator and reacting at 80 DEG C for 2 h to obtain a mixture;

[0047] S2, mixing the PETG and the mixture, and granulating at 240 DEG C to obtain the high-antibacterial PETG composite material.

[0048] Example 4

[0049] The application discloses a high-antibacterial PETG composite material.

[0050] Example 5

[0051] The application discloses a high-antibacterial PETG composite material.

[0052] Comparative Example 1

[0053] The application discloses a high-antibacterial PETG composite material.

[0054] Comparative Example 2

[0055] Comparative Example 2 differs from Example 1 in that no propyl gallate is added to the composite antibacterial agent, and the missing amount is made up by hexamidinium dihydroxyethyl sulfate and polyhexamethylene biguanide hydrochloride in a mass ratio of 3:2.

[0056] Comparative Example 3

[0057] Comparative Example 3 differs from Example 1 in that no hexamidinium dihydroxyethyl sulfate is added to the composite antibacterial agent, and the missing amount is made up by propyl gallate and polyhexamethylene biguanide hydrochloride in a mass ratio of 1:2.

[0058] Comparative Example 4

[0059] Comparative Example 4 differs from Example 1 in that no polyhexamethylene biguanide hydrochloride is added to the composite antibacterial agent, and the missing amount is made up by propyl gallate and hexamidinium dihydroxyethyl sulfate in a mass ratio of 1:3.

[0060] Performance Test

[0061] 1. Mechanical Performance Test

[0062] According to GB / T 1040.2-2006 “Plastics-Determination of tensile properties”, the tensile strength and elongation at break of the samples made of the high-antibacterial PETG composite material of Examples 1-5 and Comparative Examples 1-4 were determined. The tensile speed was 50 mm / min. To ensure the accuracy of the experiment, 5 samples were taken for each group, and the data was processed using the average value method. The test results are shown in Table 1.

[0063] 2. Long-acting Antibacterial Performance Test

[0064] The high-antibacterial PETG composite material prepared in Examples 1-5 and Comparative Examples 1-4 was subjected to antibacterial performance determination according to QB / T 2591-2003 “Test method for antibacterial performance of antibacterial plastics and antibacterial effect”. The antibacterial performance and the antibacterial performance after being placed at a temperature of 50°C and a humidity of 80% for 80 days were determined, respectively. The test results are shown in Table 1.

[0065] Table 1: Mechanical performance and long-acting antibacterial performance data of each group of samples

[0066] Group Tensile strength / MPa Elongation at break / % Antibacterial rate after 80 days / % Example 1 74.9 215 99.7 Example 2 72.8 208 99.1 Example 3 74.0 213 99.6 Example 4 68.5 186 96.1 Example 5 69.8 183 96.4 Comparative Example 1 42.1 112 62.0 Comparative Example 2 55.8 164 74.2 Comparative Example 3 56.6 168 74.9 Comparative Example 4 52.8 155 72.1

[0067] As can be seen from Table 1, in combination with the data of Example 1 and Examples 4-5, when the mass ratio of propyl gallate, hexamidinium dihydroxyethyl sulfate and polyhexamethylene biguanide hydrochloride is 1:(2-3):(2-3), the long-acting antibacterial effect and the mechanical performance of the composite material are better.

[0068] According to the data of example 1 and comparative example 1, the mechanical properties and antibacterial rate of comparative example 1 are obviously decreased compared with example 1, which shows that the composite antibacterial agent realizes stable combination in the PETG matrix through the action of coupling agent and initiator.

[0069] According to the data of example 1 and comparative examples 2-4, the 80-day antibacterial rate, tensile strength and breaking elongation of example 1 are all improved, which shows that polyhexamethylene biguanide hydrochloride, propyl gallate and hexamidine diisethionate can synergistically improve the long-acting antibacterial performance of PETG composite material, and the three can also synergistically improve the mechanical properties of PETG composite material through the good compatibility of silane coupling agent with PETG.

[0070] In summary, the application selects a specific composite antibacterial agent to realize the synergistic improvement of antibacterial rate and mechanical properties through the bridging action of silane and the free radical grafting reaction of initiator, which is particularly suitable for medical packaging and other scenarios that require both antibacterial and flexibility.

[0071] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the application and not to limit the protection scope of the application. Although the application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the application.

Claims

1. A highly antibacterial PETG composite material, characterized in that, Including the following raw materials by weight: The mixture comprises 100 parts PETG, 2-5 parts composite antibacterial agent, 3-10 parts silane coupling agent, and 0.1-0.3 parts initiator; wherein the composite antibacterial agent is a composition of propyl gallate, hexamidine dihydroxyethyl sulfonate, and polyhexamethylene biguanide hydrochloride, and the mass ratio of propyl gallate, hexamidine dihydroxyethyl sulfonate, and polyhexamethylene biguanide hydrochloride is 1:(2-3):(2-3).

2. The highly antibacterial PETG composite material as described in claim 1, characterized in that, The raw materials include the following parts by weight: 100 parts PETG, 4-5 parts compound antibacterial agent, 6-10 parts silane coupling agent and 0.1-0.2 parts initiator.

3. The highly antibacterial PETG composite material as described in claim 1, characterized in that, The silane coupling agent includes at least one of KH550, KH560, KH570, KH792, and DL602.

4. The highly antibacterial PETG composite material as described in claim 1, characterized in that, The initiator is an azo initiator.

5. A method for preparing the highly antibacterial PETG composite material according to any one of claims 1-4, characterized in that, Includes the following steps: S1. Mix the composite antibacterial agent with the silane coupling agent, then add the initiator, and react at 70-80℃ for 2-3 hours to obtain a mixture; S2. Mix PETG and the mixture, and granulate at 210-240°C to obtain the highly antibacterial PETG composite material.

6. The method for preparing the highly antibacterial PETG composite material as described in claim 5, characterized in that, In step S1, the mixing speed is 800-1000 rpm and the mixing time is 30-60 min.

7. The use of the highly antibacterial PETG composite material according to any one of claims 1-4 in the preparation of medical packaging materials.