A block polymer, a preparation method thereof, an antibacterial antistatic nylon material and application thereof

Abstract

The application discloses antibacterial antistatic nylon and a preparation method and application thereof, and relates to the technical field of antibacterial materials. The preparation method of the antibacterial antistatic nylon comprises the following steps: reacting a first mixed reaction system containing hexanediamine, furan dicarboxylic acid, dibasic acid and water to prepare a terminal carboxyl pre-polymer; and reacting a second mixed reaction system containing the terminal carboxyl pre-polymer, PEG and tetrabutyl titanate in a protective atmosphere to prepare an antibacterial antistatic nylon block copolymer. The antibacterial antistatic nylon prepared through condensation polymerization can improve the antibacterial performance of a PA66 base material and also can improve the antistatic performance of the PA66 base material, and can be used for preparing antibacterial antistatic PA66 material.

Description

TECHNICAL FIELD

[0001] The present application relates to a preparation method of antibacterial nylon material, in particular to a block polymer and a preparation method thereof, an antibacterial and antistatic nylon material and application. BACKGROUND

[0002] The antibacterial and antistatic nylon is a high-performance engineering plastic with antibacterial and antistatic properties by functional modification of the traditional nylon material, and also has the basic performance of the nylon material, including high strength, wear resistance and chemical corrosion resistance of the nylon. In the prior art, the antibacterial and antistatic nylon material has been widely used in the fields of textiles, medical treatment, food packaging, such as medical field of surgical instruments, catheters, electronic industry of chip tray, circuit board shell, protective equipment of antistatic work clothes and automobile parts of fuel pipeline, gear bearing, so as to meet the composite requirements of sterility, antistatic and oil resistance in the application field.

[0003] The method commonly used for the antibacterial function of the nylon material includes blending or grafting to introduce silver ions, zinc ions, organic quaternary ammonium salt and other antibacterial agents to destroy the cell structure of microorganisms; and the antistatic function of the prior art is generally to reduce the surface resistance by adding conductive fillers such as carbon black and carbon fiber, or to graft hydrophilic groups (such as sulfonic acid groups) to adsorb environmental moisture to form a conductive layer.

[0004] Although the antibacterial and antistatic nylon obtained by the blending method has diversified functions, it still has significant technical defects.

[0005] Firstly, from the process conditions, in order to give the nylon material its antistatic property, a large amount of antistatic agent needs to be added, which directly leads to a significant reduction in the mechanical properties of the material, making it difficult to meet the performance requirements in actual applications, and the processing technology of the nylon material is relatively complex, and the dispersion of the antistatic agent needs to be accurately controlled to avoid the generation of agglomeration or interface defects; at the same time, due to the high melting point of the nylon material, which is usually between 215-225℃, the addition of the antistatic agent leads to a narrow processing window, increasing the processing difficulty.

[0006] Then, from the production cost, the conventional antibacterial agent or antistatic agent for nylon material usually selects functional additives such as nano-silver and carbon nanotubes, which leads to a significant increase in the cost of multifunctional nylon material, and the cost of antibacterial and antistatic nylon material is increased by 30-50% compared with ordinary nylon, thus limiting the wide application of antibacterial and antistatic nylon material.

[0007] Finally, from the performance of the material, although the introduction of the antistatic agent and / or the antibacterial agent provides the nylon material with antibacterial and antistatic functions, the antistatic and antibacterial properties may gradually decrease due to the migration of the functional additives, thereby affecting the long-term antibacterial effect and antistatic effect.

[0008] And the grafting method provides antibacterial and antistatic properties for nylon materials, and the preparation method also has the following disadvantages, such as complex process, the grafting reaction usually needs to accurately control the reaction conditions, such as temperature, time, reactant concentration, initiator dosage and the like. Small changes in these conditions can affect the grafting effect, resulting in unstable product performance. Moreover, the whole preparation process often involves multiple steps, which needs professional equipment and technical personnel to operate, increasing the production cost and production difficulty; the material performance changes, in the grafting process, the molecular structure of nylon has changed, which may have a negative impact on its original some excellent properties. For example, it may reduce the mechanical properties of nylon, such as strength, toughness and the like, in addition, it may also change the thermal stability, chemical corrosion resistance and the like of nylon, so that its use in a specific environment is limited; the antibacterial and antistatic properties are limited in time, although the grafted nylon has antibacterial and antistatic properties, because the grafted antibacterial agent and antistatic agent may gradually fall off or change chemically from the surface of the nylon, resulting in performance attenuation, affecting the long-term use effect of the material, or gradually reducing with the extension of use time, the increase of washing times or under specific environmental conditions.

[0009] In summary, there is an urgent need for an intrinsic antibacterial and antistatic nylon material in the prior art to solve the technical problems of the antibacterial and antistatic nylon material in the prior art in terms of performance, processing, cost and application. SUMMARY

[0010] The main purpose of the present application is to provide a block polymer and a preparation method thereof, an antibacterial and antistatic nylon and an application, so as to overcome the deficiencies in the prior art.

[0011] As a first aspect of the application, the present application provides a block copolymer, the structural formula is as follows:

[0012]

[0013] Wherein, R is a fatty chain of 2-6 carbons; m is 5-10, n is 5-20, p is 5-20, q is 1-6, and b is 2-8.

[0014] As a second aspect of the application, the present application also provides a preparation method of the above-mentioned block copolymer, and the specific steps include:

[0015] S1. A first mixed reaction system comprising hexanediamine, furandicarboxylic acid, dibasic acid and water is subjected to a prepolymerization reaction to prepare a carboxyl-terminated prepolymer;

[0016] S2. A second mixed reaction system comprising the carboxyl-terminated prepolymer, PEG and a catalyst is subjected to a catalytic reaction in an atmosphere of a protective gas to prepare the block copolymer.

[0017] In some specific embodiments, in S1, the molar ratio of hexanediamine, the dibasic acid and furandicarboxylic acid is 2-7: 1.1-4: 1-4.

[0018] In some specific embodiments, the dibasic acid comprises any one or a combination of two or more of adipic acid, terephthalic acid and succinic acid.

[0019] In some specific embodiments, in S1, the conditions of the prepolymerization reaction comprise a first stage and a second stage.

[0020] Preferably, the first stage comprises heating the first mixed reaction system to T1 in a closed space, and the pressure rises accordingly; when the pressure rises to P1, P1 is maintained, and the temperature is raised to T2, and the reaction is maintained at T2 and P1 for 2-8 hours.

[0021] Preferably, the second stage comprises depressurizing to normal pressure state, and adjusting the temperature of the first mixed reaction system to T2, and performing normal pressure reaction under the atmosphere of the protective gas until the reaction is completed.

[0022] Preferably, T1 = 200-220°C; T2 = 220-280°C; P1 = 0.5-1 MPa.

[0023] Preferably, the temperature range of T3 is 210-250°C.

[0024] Preferably, the protective gas is an inert gas.

[0025] Preferably, the reaction time of the normal pressure reaction is 2-8 hours.

[0026] In some specific embodiments, in S2, the mass ratio of the carboxyl-terminated prepolymer and PEG is 40-90: 10-60.

[0027] In some specific embodiments, the amount of the catalyst added is 0.1-1 wt% of the sum of the carboxyl-terminated prepolymer and PEG.

[0028] In some specific embodiments, the catalyst is a titanate compound.

[0029] In some specific embodiments, the number average molecular weight of PEG is any one or a combination of two or more of 300, 800, 1000.

[0030] Preferably, the protective gas is an inert gas.

[0031] Preferably, the reaction conditions of the second mixed reaction system include 210-250℃ reaction for 2-8h under a protective gas atmosphere.

[0032] As a third aspect of the application, the application further provides the use of the block copolymer as described above in the preparation of an antibacterial antistatic nylon material.

[0033] As a fourth aspect of the application, the application further provides an antibacterial antistatic nylon material comprising at least the block copolymer as described above and a nylon matrix material.

[0034] Preferably, the mass ratio of the block copolymer and the nylon matrix material is 1-30:70-90.

[0035] Preferably, the nylon matrix material is PA66 or PA6.

[0036] In some specific embodiments, the antibacterial antistatic nylon material further comprises one or more of a combination of a compatibilizer, a lubricant, and an antioxidant.

[0037] In some specific embodiments, the mass ratio of the compatibilizer and the nylon matrix material is 0.5-5:70-90.

[0038] In some specific embodiments, the mass ratio of the lubricant and the nylon matrix material is 0.5-2:70-90.

[0039] In some specific embodiments, the mass ratio of the antioxidant and the nylon matrix material is 0.5-2:70-90.

[0040] In some specific embodiments, the compatibilizer includes but is not limited to any one or a combination of two or more of maleic anhydride grafted POE, glycidyl methacrylate grafted polyethylene wax, maleic anhydride grafted PE, and maleic anhydride grafted PP.

[0041] In some specific embodiments, the antioxidant is antioxidant 1010.

[0042] In some specific embodiments, the lubricant is a fatty acid and its salts or fatty acid esters. Preferably, the lubricant includes but is not limited to any one or a combination of several of ethylene bis-stearamide (EBS), stearic acid, butyl stearate, glyceryl stearate, zinc stearate, calcium stearate, etc.

[0043] As a fifth aspect of the application, the application further provides the use of the antibacterial antistatic nylon material as described above in the fields of textiles, the automotive industry, electronics and electrical appliances, medical treatment, and food packaging.

[0044] Compared with the prior art, the application has at least the following beneficial effects:

[0045] 1) The application prepares the antibacterial antistatic nylon block copolymer by the self-condensation free radical method, the process route is simple, easy to implement, and the operability is strong, the obtained antibacterial antistatic nylon has good antibacterial performance, and can be used to prepare antibacterial antistatic nylon material.

[0046] 2) The antibacterial antistatic nylon block copolymer provided by the application has good compatibility with nylon, good physical and mechanical properties, and good antistatic and antibacterial properties, and can be spun into a shape alone or used as a high molecular permanent antistatic additive.

[0047] 3) After compounding the PA66 base material, the antibacterial antistatic nylon block copolymer, and the compatibilizer, the antistatic and antibacterial properties of the PA66 base material are improved, the inherent properties of nylon are retained, and the tensile strength, wear resistance, and impact resistance are excellent. DETAILED DESCRIPTION

[0048] In view of the deficiencies in the prior art, the present application has been proposed after long-term research and a large amount of practice, and the technical scheme of the present application is mainly to prepare an antibacterial antistatic nylon by a self-condensation free radical method, to improve the antibacterial properties of the PA66 base material while improving the antistatic properties of the PA66 base material, and to be used to prepare an antibacterial antistatic nylon material. The technical scheme, the implementation process, and the principles will be further explained as follows.

[0049] One aspect of an embodiment of the application provides a preparation method of an antibacterial antistatic nylon, which comprises:

[0050] (1) reacting a first mixed reaction system comprising hexamethylenediamine, furandicarboxylic acid, dibasic acid, and water to obtain a carboxyl-terminated prepolymer;

[0051] (2) reacting a second mixed reaction system comprising the carboxyl-terminated prepolymer, PEG, and tetrabutyl titanate in a protective atmosphere to obtain an antibacterial antistatic nylon block copolymer.

[0052] In some embodiments, step (1) specifically comprises:

[0053] A mixture comprising hexamethylenediamine, dibasic acid, furandicarboxylic acid, and water is provided and placed in a reaction kettle;

[0054] The temperature is raised to 220-280°C and the pressure is raised to 0.5-1 MPa under stirring;

[0055] The first mixed reaction system is stirred and reacted at 210-250°C for 2-8 h to obtain the carboxyl-terminated prepolymer.

[0056] In some embodiments, the molar ratio of the hexanediamine, dibasic acid and furandicarboxylic acid is (2-7):(1.1-4):(1-4).

[0057] In some embodiments, the dibasic acid includes any one or a combination of two or more of adipic acid, terephthalic acid, succinic acid, but is not limited thereto.

[0058] In some embodiments, the number average molecular weight of the PEG is any one or a combination of two or more of 300, 800, 1000.

[0059] In some embodiments, step (2) specifically includes:

[0060] The carboxyl-terminated prepolymer and the PEG are uniformly mixed in a reaction vessel, air in the reaction vessel is excluded, and a protective atmosphere is formed by introducing a protective gas;

[0061] Tetrabutyl titanate is added to the reaction vessel as a catalyst, air in the reaction vessel is again excluded, a protective atmosphere is formed by introducing a protective gas, and then the reaction system in the reaction vessel is reacted at 210-250°C for 2-8 hours to produce the antibacterial antistatic nylon block copolymer.

[0062] In some embodiments, the mass ratio of the carboxyl-terminated prepolymer, the PEG, and the tetrabutyl titanate is (40-90):(10-60):(0.1-1).

[0063] Further, the protective gas includes an inert gas, for example, argon can be preferably used, but is not limited thereto.

[0064] In some more specific embodiments, the method for preparing the antibacterial antistatic nylon block copolymer includes the following steps:

[0065] (1) Hexanediamine, furandicarboxylic acid, dibasic acid, water, and the like are placed in a reaction kettle in proportion. First, the reaction kettle is heated to 220-280°C, and at the same time, a stirring device is started to make the pressure in the kettle rise to 0.5-1.0 MPa along with the temperature. Then, a gradient heating and needle valve joint adjustment strategy is adopted: slow heating is achieved by reducing the heating power, and water vapor is released through a needle valve to maintain a constant pressure. After 2-8 hours, the stage reaction is completed, the pressure is gradually released to normal pressure through the needle valve, argon is injected to isolate air, and the normal pressure reaction is continued for 2-8 hours under the protection of argon to obtain a carboxyl-terminated prepolymer.

[0066] (2) sequentially adding polyethylene glycol and tetrabutyl titanate in proportion, and continuing to react at 210-250 DEG C under argon atmosphere for 2-8 hours. In order to increase the molecular weight of the product, a reduced pressure reaction mechanism is started: low molecular weight by-products are removed by a vacuum pump, and at the end of the reaction, stirring is stopped, and high polymer melt is separated by gravity sedimentation. After the normal pressure is restored, nitrogen pressure is used to complete the casting strip forming and granulation. Finally, the obtained particles are rotary evaporated to remove oligomers and solvents, and dried to constant weight to obtain the antibacterial and antistatic nylon block copolymer.

[0067] Further, the molar ratio of each substance is [hexanediamine]: [furandicarboxylic acid]: [adipic acid]: [water] = (2-7): (1.1-4): (1-4): (2.1-2.5); wherein the mass ratio of each substance is [carboxyl-terminated prepolymer]: [polyethylene glycol]: [tetrabutyl titanate] = (40-90): (10-60): (0.1-1).

[0068] The prepared antibacterial and antistatic nylon block copolymer is subjected to nuclear magnetic characterization, and the chemical shift δ = 4.57-4.70 ppm corresponds to the two proton hydrogens connected with the carboxyl group on the furan ring in the main chain; δ = 8.0 ppm corresponds to the proton hydrogen on the amide bond formed by hexanediamine and furan in the main chain; δ = 7.70 ppm corresponds to the proton hydrogen on the amide bond formed by hexanediamine and adipic acid in the main chain; δ = 4.2-4.25 ppm corresponds to the proton hydrogen on the δ position involved in esterification of PEG, furan ring dicarboxylic acid and adipic acid, indicating that the obtained antibacterial and antistatic nylon block copolymer has the following structure:

[0069]

[0070] Another aspect of the embodiment of the present application also provides an antibacterial and antistatic nylon prepared by the foregoing method.

[0071] Another aspect of the embodiment of the present application also provides the use of the foregoing antibacterial and antistatic nylon in the preparation of antibacterial performance enhanced PA66 materials.

[0072] The antibacterial and antistatic nylon block copolymer prepared by the present application has good antibacterial and antistatic properties, and can be used to prepare antibacterial and antistatic nylon materials.

[0073] Another aspect of the embodiment of the present application also provides a preparation method of an antibacterial and antistatic nylon material, which comprises:

[0074] The antibacterial and antistatic nylon block copolymer, PA66, a compatibilizer, a lubricant, and an antioxidant are uniformly mixed to prepare the antibacterial and antistatic nylon material.

[0075] The mass ratio of the antibacterial and antistatic nylon, PA66, compatibilizer, lubricant and antioxidant is (1-30):(70-90):(0.5-5):(0.5-2):(0.5-2).

[0076] The compatibilizer includes any one or a combination of two or more of maleic anhydride-grafted POE, glycidyl methacrylate-grafted polyethylene wax, maleic anhydride-grafted PE, and maleic anhydride-grafted PP, but is not limited thereto.

[0077] The main antibacterial mechanism of the antibacterial and antistatic nylon block compound prepared in this invention lies in the fact that furan derivatives, under specific temperature ranges, humidity levels, and chemical concentrations, easily produce acidic substances, leading to a decrease in pH. This severely disrupts the normal operation of many intracellular physiological processes, resulting in significant damage to the overall structure and function of bacterial cells. The rigid furan ring structure can alter the permeability of the bacterial cell membrane. The cell membrane, as a crucial barrier for bacterial cells, normally exerts strict control over intracellular substances, maintaining a balance in the exchange of substances between the inside and outside of the cell. However, when the rigid furan ring structure intervenes and alters its permeability, this balance is disrupted, ultimately achieving a significant antibacterial effect.

[0078] The main antistatic mechanism of antibacterial and antistatic nylon block compounds lies in the characteristics of the ether segments contained within the material. These ether segments can effectively bind with moisture in the environment through hydrogen bonds, forming conductive pathways. This process helps the material to conduct and disperse static charge in a timely manner, thereby achieving its antistatic function.

[0079] The invention will be more fully understood by referring to the following detailed description and accompanying drawings. Detailed embodiments of the invention are disclosed herein; however, it should be understood that the disclosed embodiments are merely exemplary and the invention can be embodied in various forms. Therefore, the specific functional details disclosed herein should not be construed as limiting, but rather as the basis for the claims and as intended to teach those skilled in the art to employ the representative basis of the invention in different ways in any suitable detailed embodiment.

[0080] Example 1

[0081] The method for preparing antibacterial and antistatic nylon provided in this embodiment consists of two stages, specifically including the following steps:

[0082] (1) Add hexamethylenediamine, furanyl dicarboxylic acid, adipic acid and water in a molar ratio of 3.5:2:2:5 to the reaction vessel.

[0083] The reactor was heated to 220℃ and then slowly heated to 280℃, while the stirring device was started, and the pressure in the reactor was increased to 0.6 MPa as the temperature rose.

[0084] Subsequently, a carboxyl-terminated prepolymer was prepared by a staged reaction, specifically including the following steps:

[0085] The temperature was slowly increased by reducing the heating power, and the needle valve was adjusted to release water vapor to maintain a constant pressure in the system. The first stage reaction was completed after 2 hours. The pressure was gradually released to normal pressure by the needle valve, and argon was injected to isolate air. The second stage reaction was continued under argon protection for 2 hours to obtain the carboxyl-terminated prepolymer.

[0086] (2) In the reaction kettle, polyethylene glycol and tetrabutyl titanate were added in sequence, and the mass ratio of carboxyl-terminated prepolymer, polyethylene glycol and tetrabutyl titanate was 60.5:40:0.5.

[0087] At 210-250℃, the pressure was maintained at normal pressure, and the reaction was continued for 4 hours in an argon protective atmosphere. Then, the pressure regulation started the decompression reaction mechanism, and the low molecular weight by-products were removed by vacuum pumping (vacuum degree 0.08 MPa). At the end of the reaction, the stirring was stopped, and the polymer melt was separated by gravity sedimentation. The decompression reaction mechanism can improve the molecular weight of the product.

[0088] (3) After the reaction was completed, the system returned to normal pressure, and nitrogen pressure was used to complete the casting and granulation. Finally, the obtained particles were rotary evaporated to remove oligomers and solvents, and dried to constant weight to obtain a block copolymer with a number average molecular weight of 19804.

[0089] The prepared antibacterial and antistatic nylon block copolymer was characterized by nuclear magnetic resonance. The chemical shift δ=4.57-4.70 ppm corresponds to the two proton hydrogens connected to the carboxyl group on the furan ring in the main chain; δ=8.0 ppm corresponds to the proton hydrogen on the amide bond formed by hexanediamine and furan in the main chain; δ=7.70 ppm corresponds to the proton hydrogen on the amide bond formed by hexanediamine and adipic acid in the main chain; δ=4.2-4.25 ppm corresponds to the proton hydrogen on the δ position of PEG participating in esterification with furan dicarboxylic acid and adipic acid, indicating that the block copolymer synthesis is successful.

[0090] Example 2

[0091] The preparation method of the antibacterial and antistatic nylon provided in this embodiment is divided into two stages, specifically including the following steps:

[0092] (1) Put adipic acid, furandicarboxylic acid, hexanediamine, water and the like into the reaction kettle according to the proportion. First, heat the reaction kettle to 220°C, then slowly heat to 280°C, and at the same time, start the stirring device, so that the pressure in the kettle rises to 0.6 MPa with the temperature. Then, adopt the gradient heating and needle valve joint adjustment strategy: slowly heat by reducing the heating power, and at the same time, adjust the needle valve to release water vapor to maintain constant pressure. After 2 hours, complete the stage reaction, gradually release the pressure to normal pressure state through the needle valve, reduce the temperature to 210°C, and at the same time, inject argon to isolate air. Continue to carry out the normal pressure reaction under argon protection for 2 hours to obtain the carboxyl-terminated prepolymer;

[0093] (2) Add polyethylene glycol and tetrabutyl titanate in turn according to the proportion, and continue to react at 210°C under the condition of constant pressure and argon protection environment for 4 hours. In order to improve the molecular weight of the product, the reduced pressure reaction mechanism needs to be started: the low molecular weight by-product is removed by vacuum pump, and at the end of the reaction, the stirring is stopped, and the high polymer melt is separated by gravity sedimentation. Finally, after the pressure is restored to normal pressure, the nitrogen pressure feeding method is used to complete the casting strip forming and granulation. Finally, the obtained particles are rotary evaporated to remove oligomers and solvents, dried to constant weight, and the antibacterial and antistatic nylon block copolymer with a number average molecular weight of 25401 is obtained.

[0094] The molar ratio of each substance is: [hexanediamine]: [furandicarboxylic acid]: [diacid]: [water] = 3:2.5:1:2.5. The mass ratio of each substance is: [carboxyl-terminated prepolymer]: [polyethylene glycol]: [tetrabutyl titanate] = 60.5:40:0.5.

[0095] Example 3

[0096] The preparation method of the antibacterial and antistatic nylon provided in this embodiment is divided into two stages, which specifically includes the following steps:

[0097] (1) Put adipic acid, furandicarboxylic acid, diacid, water and the like into the reaction kettle according to the proportion. First, heat the reaction kettle to 220°C, then slowly heat to 280°C, and at the same time, start the stirring device, so that the pressure in the kettle rises to 0.6 MPa with the temperature. Then, adopt the gradient heating and needle valve joint adjustment strategy: slowly heat by reducing the heating power, and at the same time, adjust the needle valve to release water vapor to maintain constant pressure. After 2 hours, complete the stage reaction, gradually release the pressure to normal pressure state through the needle valve, reduce the temperature to 250°C, and at the same time, inject argon to isolate air. Continue to carry out the normal pressure reaction under argon protection for 2 hours to obtain the carboxyl-terminated prepolymer;

[0098] (2) The polyethylene glycol and tetrabutyl titanate are added in turn in proportion, and the reaction is continued at 250°C under normal pressure and in an argon protection environment for 4 hours. To increase the molecular weight of the product, a reduced pressure reaction mechanism is started: low molecular weight by-products are removed by a vacuum pump, and at the end of the reaction, stirring is stopped and the high polymer melt is separated by gravity sedimentation. After the normal pressure is restored, nitrogen pressure is used to complete the casting strip forming and granulation. Finally, the obtained particles are rotary evaporated to remove oligomers and solvents, dried to constant weight, and an antibacterial and antistatic nylon block copolymer with a number average molecular weight of 21040 is obtained.

[0099] The molar ratio of each substance is: [hexanediamine]: [furandicarboxylic acid]: [diacid]: [water] = 3:2.5:1:3.25. The mass ratio of each substance is: [carboxyl-terminated prepolymer]: [polyethylene glycol]: [tetrabutyl titanate] = 50:50:0.5.

[0100] Example 4

[0101] The preparation of the antibacterial and antistatic nylon material provided in this example specifically includes the following steps:

[0102] The block copolymer prepared in Example 3 is used as an antibacterial and antistatic additive, which is mixed uniformly with the base material and functional additives such as compatibilizers, lubricants and antioxidants, to prepare an antibacterial and antistatic nylon material.

[0103] Table 1 Composition of each raw material for preparing the antibacterial and antistatic nylon material in the example

[0104]

[0105] Example 5

[0106] Compared with Example 4, the difference is that the added block copolymer is the antibacterial and antistatic nylon prepared in Example 2.

[0107] Table 2 Composition of each raw material for preparing the antibacterial and antistatic nylon material in the comparative example 1

[0108]

[0109] Example 6

[0110] Compared with Example 4, the difference is that the added block copolymer is the antibacterial and antistatic nylon prepared in Example 1.

[0111] Table 3 Composition of each raw material for preparing the antibacterial and antistatic nylon material in the comparative example 1

[0112]

[0113]

[0114] Example 7

[0115] The difference between this example and Example 4 is only that the addition amount of the block copolymer is 10wt%, and other steps are the same.

[0116] Example 8

[0117] The difference between this example and Example 4 is only that the addition amount of the block copolymer is 30wt%, and other steps are the same.

[0118] Comparative Example 1

[0119] The difference between this comparative example and Example 4 is that the antibacterial antistatic nylon prepared in Example 3 is not added, but the Akema (MV1074 SA 01) antistatic agent is added as a substitute, and the addition amount is the same. The raw material composition is shown in Table 4.

[0120] Table 4 Raw material composition of antibacterial antistatic nylon material prepared in Comparative Example 1

[0121]

[0122] Comparative Example 2

[0123] The difference between this comparative example and Example 4 is that the antibacterial antistatic nylon prepared in Example 3 is not added, but the LD 904 antibacterial agent is added as a substitute, and the addition amount is the same. The raw material composition is shown in Table 5.

[0124] Table 5 Raw material composition of antibacterial antistatic nylon material prepared in Comparative Example 2

[0125]

[0126] Comparative Example 3

[0127] The difference between this comparative example and Example 4 is that the addition amount of the block copolymer is 1wt%, and other steps are the same.

[0128] Table 6 Comparison of test results of examples and comparative examples

[0129]

[0130] From the results in Table 6, it can be seen that the PA66 / antibacterial antistatic nylon alloy of the present application has good toughness and meets the requirements of antibacterial performance.

[0131] In addition, the present application also refers to the foregoing examples, and tests are carried out with other raw materials, process operations and process conditions described in the specification, and ideal results are obtained.

[0132] While the application has been described with reference to the illustrative embodiments, those skilled in the art will understand that various other changes, omissions, and / or additions can be made without departing from the spirit and scope of the application. Further, many modifications can be made to adapt a particular situation or material to the teachings of the application without departing from its scope. Therefore, it is intended that the application not be limited to the disclosed embodiments, but will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated otherwise, any use of the terms first, second, etc., does not denote any ordinal, or importance, but merely distinguishes one element from another.

Claims

1. A block copolymer, characterized in that, The structural formula is as follows: ； Where R is an aliphatic chain of 2 to 6 carbons; m is 5 to 10, n is 5 to 20, p is 5 to 20, q is 1 to 6, and b is 2 to 8.

2. A method for preparing the block copolymer as described in claim 1, characterized in that, include: S1. A prepolymerization reaction is carried out on a first mixed reaction system containing hexamethylenediamine, furanyl dicarboxylic acid, diacid and water to prepare a carboxyl-terminated prepolymer; S2. In a protective gas atmosphere, a second mixed reaction system containing the terminal carboxyl prepolymer, PEG, and catalyst is subjected to a catalytic reaction to prepare the block copolymer; The dicarboxylic acid is any one or both of adipic acid and succinic acid.

3. The method for preparing the block copolymer according to claim 2, characterized in that, In S1, the molar ratio of hexamethylenediamine, the dicarboxylic acid (excluding furanyldicarboxylic acid), and furanyldicarboxylic acid is 2~7:1.1~4:1~4.

4. The method for preparing the block copolymer according to claim 2, characterized in that, In S1, the conditions for the prepolymerization reaction include a first stage and a second stage; The first stage includes heating the first mixed reaction system to T1 in a closed space, and the pressure is increased accordingly; when the pressure increases to P1, P1 is maintained, and the temperature is increased to T2, and the reaction is maintained at T2 and P1 for 2 to 8 hours. The second stage includes depressurizing to atmospheric pressure and adjusting the temperature of the first mixed reaction system to T3. Under the atmosphere of the protective gas, the reaction is carried out at atmospheric pressure for 2 to 8 hours.

5. The method for preparing the block copolymer according to claim 4, characterized in that, T1=200~220℃; T2=220~280℃; P1=0.5~1Mpa.

6. The method for preparing the block copolymer according to claim 4, characterized in that, T3=210~250℃。 7. The method for preparing the block copolymer according to claim 4, characterized in that, The protective gas is an inert gas.

8. The method for preparing the block copolymer according to claim 2, characterized in that, In S2, the mass ratio of the carboxyl-terminated prepolymer to PEG is (40~90):(10~60).

9. The method for preparing the block copolymer according to claim 2, characterized in that, The amount of catalyst added is 0.1 to 1 wt% of the sum of the mass of the carboxyl-terminated prepolymer and PEG.

10. The method for preparing the block copolymer according to claim 2, characterized in that, The catalyst is a titanate compound.

11. The method for preparing the block copolymer according to claim 2, characterized in that, PEG has a number average molecular weight of 300, 800, 1000 or a combination of two or more of these.

12. The method for preparing the block copolymer according to claim 2, characterized in that, The reaction conditions for the second mixed reaction system include reacting at 210~250℃ for 2~8 hours under a protective gas atmosphere.

13. The application of the block copolymer as described in claim 1 in the preparation of antibacterial and antistatic nylon materials.

14. An antibacterial and antistatic nylon material, characterized in that, It includes at least the block copolymer and nylon matrix material as described in claim 1.

15. The antibacterial and antistatic nylon material according to claim 14, characterized in that, The mass ratio of the block copolymer to the nylon matrix material is (1~30):(70~90).

16. The antibacterial and antistatic nylon material according to claim 14, characterized in that, The nylon matrix material is PA66 or PA6.

17. The antibacterial and antistatic nylon material according to any one of claims 14-16, characterized in that, It also includes one or more combinations of compatibilizers, lubricants, and antioxidants.

18. The antibacterial and antistatic nylon material according to claim 17, characterized in that, The mass ratio of the compatibilizer to the nylon matrix material is (0.5~5):(70~90).

19. The antibacterial and antistatic nylon material according to claim 17, characterized in that, The mass ratio of the lubricant to the nylon matrix material is (0.5~2):(70~90).

20. The antibacterial and antistatic nylon material according to claim 17, characterized in that, The mass ratio of the antioxidant to the nylon matrix material is (0.5~2):(70~90).

21. The antibacterial and antistatic nylon material according to claim 17, characterized in that, The compatibilizer includes any one or a combination of two or more of the following: maleic anhydride-grafted POE, glycidyl methacrylate-grafted polyethylene wax, maleic anhydride-grafted PE, and maleic anhydride-grafted PP.

22. The antibacterial and antistatic nylon material according to claim 17, characterized in that, The antioxidant is antioxidant 1010.

23. The antibacterial and antistatic nylon material according to claim 17, characterized in that, The lubricant is a fatty acid and its salts or a fatty acid ester.

24. The application of an antibacterial and antistatic nylon material as described in any one of claims 14-23 in the fields of textiles, automotive industry, electronics and electrical engineering, medical, and food packaging.

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