Triazine antibacterial agent, antibacterial halogen-free flame-retardant nylon composite material and preparation method and application thereof

Abstract

The application discloses a triazine antibacterial agent, an antibacterial halogen-free flame-retardant nylon composite material and a preparation method and application thereof. The triazine antibacterial agent has the structure shown in the following formula: wherein R1, R2 and R3 are independently selected from aldehyde group, hydroxyl group, halogen, phenyl group or alkyl group and the like. Raw materials for preparing the antibacterial halogen-free flame-retardant nylon composite material include the following components in percentage by weight: 15-85% of nylon, 0.5-5% of the triazine antibacterial agent, 6-14% of a halogen-free flame retardant, 2-5% of melamine polyphosphate, 1-8% of a toughening agent, 0.1-5% of a lubricant and 0.1-3% of a nucleating agent. The antibacterial halogen-free flame-retardant nylon composite material provided by the application has excellent toughness and antibacterial performance; meanwhile, the preparation method of the nylon composite material is simple and easy to operate, has relatively low cost investment, has good operability and practicality, and is very suitable for industrialized production.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of nylon composite materials, and particularly relates to a triazine antibacterial agent, an antibacterial halogen-free flame-retardant nylon composite material and a preparation method and application thereof. BACKGROUND

[0002] Nylon (PA6) is one of the five engineering plastics, has good processability, temperature resistance, chemical resistance and excellent lubricity, and has been widely used in the fields of household appliances, electronic appliances, automobile parts. However, the poor flame retardant performance, easy water absorption and poor dimensional stability of nylon material greatly limit the use of nylon in the fields of automobile, electronic appliances, household appliances and the like. With the continuous expansion of the application field of nylon, higher requirements for the flame retardant, antibacterial and other properties of the material are put forward.

[0003] The conventional antibacterial and flame-retardant nylon commonly uses antibacterial agents, which are divided into inorganic antibacterial agents and organic antibacterial agents. The inorganic antibacterial agent is generally an antibacterial agent containing copper metal, zinc metal, silver metal and the like. The antibacterial agent has good thermal stability, but is prone to react with the flame retardant, affecting the color and mechanical properties of the material, and cannot meet the needs of many products. The organic antibacterial agent has good compatibility with nylon, but has poor temperature resistance and is prone to degradation at high temperature, affecting the use of the product.

[0004] The preparation method of the antibacterial and flame-retardant nylon composite material disclosed in the published patent CN102643539A mainly improves the antibacterial performance of the alloy material by using zinc pyrithione, but the antibacterial agent has poor compatibility with nylon, which reduces the impact performance of the material. The patent CN107447282A discloses an antibacterial and flame-retardant polyamide 66, which uses a mesoporous inorganic antibacterial agent as the antibacterial agent of nylon and adds it in the polymerization process of nylon. The process in this scheme is complex and the cost is high. Therefore, it is an urgent problem to provide an antibacterial and halogen-free flame-retardant nylon composite material with low cost, simple preparation and good toughness. SUMMARY

[0005] The main purpose of the present application is to provide a triazine antibacterial agent, an antibacterial halogen-free flame-retardant nylon composite material and a preparation method thereof, so as to overcome the deficiencies in the prior art.

[0006] Another purpose of the present application is to provide the application of the antibacterial halogen-free flame-retardant nylon composite material.

[0007] In order to achieve the above-mentioned purposes, the technical scheme adopted by the present application comprises:

[0008] The triazine antibacterial agent provided by the embodiment of the present application has the structure as shown in formula (I):

[0009]

[0010] wherein R1, R2, R3 are independently selected from any one of aldehyde group, hydroxyl group, halogen, phenyl group or alkyl group.

[0011] The application also provides a preparation method of the triazine antibacterial agent, which comprises the following steps:

[0012] The triazine antibacterial agent is prepared by polymerization of a mixed reaction system containing melamine, furfural and / or furfural derivative and an organic solvent in a protective atmosphere.

[0013] The application also provides an antibacterial halogen-free flame-retardant nylon composite material, and raw materials for preparing the antibacterial halogen-free flame-retardant nylon composite material include the following components in percentage by weight: 15%-85% of nylon, 0.5%-5% of the triazine antibacterial agent, 6%-14% of a halogen-free flame retardant, 2%-5% of melamine polyphosphate, 1%-8% of a toughening agent, 0.1%-5% of a lubricant and 0.1%-3% of a nucleating agent; wherein the triazine antibacterial agent is the aforementioned triazine antibacterial agent.

[0014] The application also provides a preparation method of the antibacterial halogen-free flame-retardant nylon composite material, which comprises the following steps: uniformly mixing nylon, the triazine antibacterial agent, a halogen-free flame retardant, melamine polyphosphate, a toughening agent, a lubricant and a nucleating agent, and then adding the obtained mixture into a double-screw extrusion device for granulation treatment to obtain the antibacterial halogen-free flame-retardant nylon composite material.

[0015] Further, the application also provides application of the aforementioned antibacterial halogen-free flame-retardant nylon composite material in preparation of electronic and electrical enclosures, household appliances, automobile parts or motor enclosures.

[0016] Compared with the prior art, the application has the following beneficial effects:

[0017] 1) The triazine antibacterial agent provided by the application belongs to an organic antibacterial agent, which can be fully dispersed in a nylon matrix under the shearing of a double screw, so that excellent long-acting antibacterial property and impact resistance of the composite material are ensured. When the triazine antibacterial agent is added into the composite material, the triazine antibacterial agent contains a large amount of flame-retardant element nitrogen, which can release non-combustible gases such as nitrogen and ammonia at high temperature to insulate oxygen and retard combustion, so that the composite material has more excellent flame-retardant property, and the content of the halogen-free flame retardant can be further reduced, so that the impact property of the nylon material is improved.

[0018] 2) The preparation method of the antibacterial halogen-free flame-retardant nylon composite material is simple and easy to operate, has relatively low cost investment, has good operability and practicability, and is very suitable for industrialized production. DETAILED DESCRIPTION

[0019] In view of the limitations and deficiencies of the current technology, the present inventors have developed the present application after long-term research and a large number of practices. The technical points of the present application will be described clearly below. The above examples are only a part of our invention and do not cover all possible cases. In the embodiments of the present application, any other application examples derived by conventional practitioners without original efforts should be considered as falling within the scope of the present application.

[0020] The technical solution, implementation process and principles will be further explained as follows.

[0021] Specifically, as one aspect of the technical solution of the present application, the triazine antibacterial agent has a structure as shown in formula (I):

[0022]

[0023] wherein R1, R2, R3 can be independently selected from any one of aldehyde group, hydroxyl group, halogen, phenyl group, or other alkyl groups.

[0024] As another aspect of the technical solution of the present application, the present application also relates to a preparation method of the aforementioned triazine antibacterial agent, which comprises: performing a polymerization reaction on a mixed reaction system comprising melamine, furfural and / or furfural derivatives, and an organic solvent in a protective atmosphere to obtain the triazine antibacterial agent.

[0025] In some embodiments, the furfural derivative has a structure as shown in formula (II):

[0026]

[0027] wherein R is independently selected from any one of aldehyde group, hydroxyl group, halogen, phenyl group, or other alkyl groups.

[0028] In some preferred embodiments, the furfural derivative can include any one or a combination of 2,5-furandicarboxaldehyde, 5-hydroxymethyl-2-furfuraldehyde, 5-iodo-2 furfuraldehyde, 7-hydroxy-1-benzofuran-4-carboxaldehyde, furano[2,3-b]pyridine-3-carboxaldehyde, 5-methoxymethyl-2-furfuraldehyde, 5-benzyl-furan-2-carboxaldehyde, etc., but not limited thereto.

[0029] Further, the organic solvent can include any one or a combination of DMSO, ethanol, water (e.g., deionized water), DMF, etc., but not limited thereto.

[0030] In some preferred embodiments, the molar ratio of melamine to furfural and / or furfural derivative is 1:3-8.

[0031] In some embodiments, the temperature of the polymerization reaction is 50-80℃ and the time is 4-12h.

[0032] In some more specific embodiments, the method for preparing the triazine antibacterial agent comprises:

[0033] Melamine (0.1 mol), 5-methyl-2-furfuraldehyde (0.4 mol), and ethanol (100 ml) are added to a round bottom flask, stirred to form a uniform solution, and sealed. The flask is then placed in a 120℃ oil bath to maintain a constant temperature and sealed polymerization. After the polymerization reaction is completed, the product is precipitated with a poor solvent, filtered, and vacuum dried to a constant weight to obtain the polymerized triazine antibacterial agent.

[0034] The present application prepares an organic triazine antibacterial agent by a free radical reaction method. The polymer is compatible with the nylon matrix and can be fully dispersed under the shear of a twin screw, thereby improving the antibacterial performance and toughness of the nylon composite material. On the other hand, the triazine antibacterial agent contains a large number of nitrogen atoms, which can reduce the use of halogen-free flame retardants in the material, thereby improving the strength and toughness of the nylon.

[0035] Specifically, as another aspect of the technical solution of the present application, the raw materials for preparing an antibacterial halogen-free flame-retardant nylon composite material include the following components in terms of weight percentage: nylon 15%-85%, triazine antibacterial agent 0.5%-5%, halogen-free flame retardant 6%-14%, melamine polyphosphate 2%-5%, toughening agent 1%-8%, lubricant 0.1%-5%, and nucleating agent 0.1%-3%; wherein the triazine antibacterial agent has a structure as shown in formula (I):

[0036]

[0037] wherein R1, R2, and R3 can each be independently selected from any one of an aldehyde group, a hydroxyl group, a halogen, a phenyl group, or other alkyl groups, and are not limited thereto.

[0038] The triazine antibacterial agent used in the present application is an organic antibacterial agent, which can be fully dispersed in the matrix, thereby improving the antibacterial performance and toughness of the material.

[0039] In some preferred embodiments, the raw materials for preparing the antibacterial halogen-free flame-retardant nylon composite material include the following components in terms of weight percentage: nylon 45%-65%, triazine antibacterial agent 1%-5%, halogen-free flame retardant 6%-14%, melamine polyphosphate 2%-5%, toughening agent 2%-7%, lubricant 0.1%-5%, and nucleating agent 0.5%-3%.

[0040] In some more preferred embodiments, the raw materials for preparing the antibacterial halogen-free flame-retardant nylon composite material include the following components in percentage by weight: nylon 45%-65%, triazine antibacterial agent 1%-3%, halogen-free flame retardant 6%-14%, melamine polyphosphate 2%-4%, toughening agent 2%-5%, lubricant 0.1%-5%, and nucleating agent 0.5%-2%.

[0041] In the present application, the nylon can be the commonly used PA6 type available on the market.

[0042] In some preferred embodiments, the halogen-free flame retardant includes aluminum diethyl phosphite (Clariant, OP1230), and is not limited thereto.

[0043] In some preferred embodiments, the toughening agent includes a combination of any one or more of ethylene-methyl acrylate copolymer (EMA), POE-MAH modifier (MBS), POE, and the like, and is not limited thereto.

[0044] In some preferred embodiments, the lubricant includes a combination of any one or more of OP wax, calcium stearate, silicone, and the like, and is not limited thereto.

[0045] In some preferred embodiments, the nucleating agent includes a combination of any one or more of nano-talc powder, calcium carboxylate, nano-silicon dioxide, and the like, and is not limited thereto.

[0046] As another aspect of the technical solution of the present application, it relates to a method for preparing the antibacterial halogen-free flame-retardant nylon composite material, which includes:

[0047] The nylon, triazine antibacterial agent, halogen-free flame retardant, melamine polyphosphate, toughening agent, lubricant, and nucleating agent are uniformly mixed, and then the obtained mixture is added to a double-screw extrusion device for granulation treatment to prepare the antibacterial halogen-free flame-retardant nylon composite material.

[0048] The triazine antibacterial agent used in the present application can be fully dispersed in the nylon matrix under the shearing of the double screw, ensuring excellent long-term antibacterial property and impact resistance of the composite material. When the triazine antibacterial agent is added to the composite material, the triazine antibacterial agent contains a large amount of flame-retardant element nitrogen, which can release non-combustible gases such as nitrogen and ammonia at high temperatures to insulate oxygen and retard combustion, so that the composite material has more excellent flame-retardant property, and the content of the halogen-free flame retardant can be further reduced, thereby improving the impact resistance of the nylon material.

[0049] In some preferred embodiments, the preparation method specifically comprises: placing nylon, triazine antibacterial agent, halogen-free flame retardant, melamine polyphosphate, toughening agent, lubricant and nucleating agent into a high-speed kneading device, and stirring and mixing under the condition of a rotation speed of 50-400 rpm / min for 5-25 min; then adding the mixed material into a twin-screw extrusion device, and after cutting by a traction machine, an antibacterial halogen-free flame-retardant nylon composite material is obtained; wherein the temperature of each zone of the twin-screw extrusion device from the feeding port to the die head comprises: a first zone temperature of 190-210°C, a second zone temperature of 260-275°C, a third zone temperature of 260-275°C, a fourth zone temperature of 260-275°C, a fifth zone temperature of 260-265°C, a sixth zone temperature of 245-255°C, a seventh zone temperature of 240-255°C, and a die head temperature of 260-270°C, and the rotation speed is 300-450 rpm / min.

[0050] For example, the high-speed kneading device can be a high-speed kneader.

[0051] In some more specific embodiments, the preparation method of the antibacterial halogen-free flame-retardant nylon composite material comprises:

[0052] (1) uniformly mixing nylon, triazine antibacterial agent, toughening agent, halogen-free flame retardant, nucleating agent, lubricant and melamine polyphosphate to obtain a mixed material;

[0053] (2) adding the mixed material into a twin-screw extruder, and after cutting by a traction machine, an antibacterial halogen-free flame-retardant nylon composite material is obtained.

[0054] Further, in step (1), the uniform mixing condition is that each component is placed in a high-speed kneader, the rotation speed is maintained at 100-200 rpm / min, and the high-speed stirring time is 5-20 min.

[0055] Further, in step (2), the temperature of each zone of the twin-screw extrusion device from the feeding port to the die head comprises: a first zone temperature of 190-210°C, a second zone temperature of 265-275°C, a third zone temperature of 265-275°C, a fourth zone temperature of 265-275°C, a fifth zone temperature of 260-265°C, a sixth zone temperature of 245-250°C, a seventh zone temperature of 240-250°C, and a die head temperature of 260-265°C, and the rotation speed is 300-450 rpm / min.

[0056] In summary, the preparation method of the antibacterial halogen-free flame-retardant nylon composite material provided by the application is simple and easy to operate, has relatively low cost investment, has good operability and practicability, and is very suitable for industrialized large-scale production.

[0057] As another aspect of the technical scheme of the present application, it also relates to the use of the aforementioned antibacterial halogen-free flame-retardant nylon composite material.

[0058] Specifically, the antibacterial halogen-free flame-retardant nylon composite material has excellent toughness and antibacterial performance, and can be used for the preparation of automobile parts, motor housings, electronic and electrical housings, or household appliances.

[0059] The technical scheme of the present application will be further described in detail below in combination with several preferred embodiments. The embodiments are implemented on the premise of the technical scheme of the present application, and give detailed implementation modes and specific operation processes, but the protection scope of the present application is not limited to the following embodiments.

[0060] In the following examples, the experimental materials used are commercially available from conventional biochemical reagent companies, unless otherwise specified.

[0061] Example 1

[0062] The preparation of a triazine antibacterial agent specifically includes the following steps:

[0063] Melamine (0.1 mol), 5-methyl-2-furfuraldehyde (0.4 mol), and ethanol (100 ml) were added to a round-bottom flask, stirred to form a uniform solution, and sealed. Then the flask was placed in a 120℃ oil bath for constant temperature sealed polymerization reaction for 10 hours. After the completion of the polymerization reaction, the product was precipitated with a poor solvent, filtered, and vacuum dried to constant weight to obtain the polymerized triazine antibacterial agent.

[0064] The prepared triazine antibacterial agent was characterized by nuclear magnetic resonance. The chemical shift δδ=7.96-8.1 ppm corresponds to the hydrogen element on the double bond carbon of -HC=N- on the 2nd position of furan, the chemical shift δ=6.83-6.86 ppm corresponds to the hydrogen atom on the 3rd position of furan, and the chemical shift δ=2.36-2.37 ppm corresponds to the three hydrogen atoms on the methyl group on the 5th position of furan, indicating that the antibacterial group 5-methyl-2-furfuraldehyde has been polymerized on the triazine antibacterial agent, proving the successful preparation of the triazine antibacterial agent. The obtained triazine antibacterial agent has the following structure:

[0065]

[0066] Example 2

[0067] The preparation of a triazine antibacterial agent specifically includes the following steps:

[0068] Melamine (0.1 mol), 5-methyl-2-furaldehyde (0.7 mol), and ethanol (100 ml) were added to a round-bottom flask, stirred to a uniform solution, and sealed. The flask was then placed in a 110°C oil bath and sealed for polymerization for 8 hours. After the polymerization reaction was complete, the product was precipitated with a poor solvent, filtered, and vacuum-dried to a constant weight to obtain a polymerized triazine antimicrobial agent.

[0069] Example 3

[0070] The preparation of a triazine antibacterial agent specifically comprises the following steps:

[0071] Melamine (0.1 mol), furfural (0.4 mol), and ethanol (100 ml) were added to a round-bottom flask, stirred to a uniform solution, and sealed. The flask was then placed in a 140°C oil bath and sealed for polymerization for 10 hours. After the polymerization was complete, the product was precipitated with a poor solvent, filtered, and vacuum-dried to a constant weight to obtain a polymerized triazine antimicrobial agent.

[0072] Example 4

[0073] Weigh the components according to Table 1 below:

[0074] Table 1

[0075]

[0076] (1) According to the weight percentage formula, the dried nylon, the prepared triazine antibacterial agent, the toughening agent, the calcium stearate, the nucleating agent, the diethyl aluminum hypophosphite, and the melamine polyphosphate are weighed;

[0077] (2) Place the weighed components in a high-speed mixer at a speed of 350 rpm / min for 20 min;

[0078] (3) adding the mixture obtained in step (2) into the feeding funnel of a twin-screw extruder, wherein the parameters of the twin-screw extruder are as follows: the temperature of zone 1 is 195°C, the temperature of zone 2 is 260°C, the temperature of zone 3 is 260°C, the temperature of zone 4 is 260°C, the temperature of zone 5 is 260°C, the temperature of zone 6 is 250°C, the temperature of zone 7 is 250°C, the head temperature is 270°C, the rotation speed is 300 rpm / min, and after being pulled and pelletized by a traction machine, an antibacterial halogen-free flame-retardant nylon composite material is obtained.

[0079] Example 5

[0080] Weigh the components according to Table 2 below:

[0081] Table 2

[0082]

[0083] (1) According to the weight percentage formula, the dried nylon, prepared triazine antibacterial agent, toughening agent, OP wax, nucleating agent, aluminum diethyl phosphite, melamine polyphosphate were weighed;

[0084] (2) The weighed components were placed in a high-speed mixer, the rotating speed was 350 rpm / min, and the stirring time was 20 min;

[0085] (3) The mixture obtained in step (2) was added to the feeding hopper of the twin-screw extruder, and the parameters of the twin-screw extruder were as follows: the temperature of the first zone was 195°C, the temperature of the second zone was 260°C, the temperature of the third zone was 260°C, the temperature of the fourth zone was 260°C, the temperature of the fifth zone was 260°C, the temperature of the sixth zone was 250°C, the temperature of the seventh zone was 250°C, the temperature of the die head was 270°C, the rotating speed was 300 rpm / min, and after being cut by a traction machine, an antibacterial halogen-free flame-retardant nylon composite material was obtained.

[0086] Example 6

[0087] The components were weighed according to the following Table 3:

[0088] Table 3

[0089]

[0090]

[0091] (1) According to the weight percentage formula, the dried nylon, prepared triazine antibacterial agent, toughening agent, silicone, nano-silicon dioxide, aluminum diethyl phosphite, melamine polyphosphate were weighed;

[0092] (2) The weighed components were placed in a high-speed mixer, the rotating speed was 350 rpm / min, and the stirring time was 20 min;

[0093] (3) The mixture obtained in step (2) was added to the feeding hopper of the twin-screw extruder, and the parameters of the twin-screw extruder were as follows: the temperature of the first zone was 195°C, the temperature of the second zone was 260°C, the temperature of the third zone was 260°C, the temperature of the fourth zone was 260°C, the temperature of the fifth zone was 260°C, the temperature of the sixth zone was 250°C, the temperature of the seventh zone was 250°C, the temperature of the die head was 270°C, the rotating speed was 300 rpm / min, and after being cut by a traction machine, an antibacterial halogen-free flame-retardant nylon composite material was obtained.

[0094] Example 7

[0095] The components were weighed according to the following Table 4:

[0096] Table 4

[0097]

[0098] (1) According to the weight percentage formula, the dried nylon, prepared triazine antibacterial agent, toughening agent, calcium stearate, antibacterial agent, aluminum diethyl hypophosphite, melamine polyphosphate were weighed;

[0099] (2) The weighed components were placed in a high-speed mixer, the rotation speed was 350 rpm / min, and the stirring time was 20 min;

[0100] (3) The mixture obtained in step (2) was added to the feeding hopper of the twin-screw extruder, and the parameters of the twin-screw extruder were as follows: the temperature of the first zone was 195°C, the temperature of the second zone was 260°C, the temperature of the third zone was 260°C, the temperature of the fourth zone was 260°C, the temperature of the fifth zone was 260°C, the temperature of the sixth zone was 250°C, the temperature of the seventh zone was 250°C, the temperature of the die head was 270°C, the rotation speed was 300 rpm / min, and after being pulled by a traction machine and cut into particles, an antibacterial halogen-free flame-retardant nylon composite material was obtained.

[0101] Example 8

[0102] The components were weighed according to the following Table 5:

[0103] Table 5

[0104]

[0105] (1) According to the weight percentage formula, the dried nylon, prepared triazine antibacterial agent, toughening agent, nucleating agent, calcium stearate, antibacterial agent, aluminum diethyl hypophosphite, melamine polyphosphate were weighed;

[0106] (2) The weighed components were placed in a high-speed mixer, the rotation speed was 350 rpm / min, and the stirring time was 20 min;

[0107] (3) The mixture obtained in step (2) was added to the feeding hopper of the twin-screw extruder, and the parameters of the twin-screw extruder were as follows: the temperature of the first zone was 195°C, the temperature of the second zone was 260°C, the temperature of the third zone was 260°C, the temperature of the fourth zone was 260°C, the temperature of the fifth zone was 260°C, the temperature of the sixth zone was 250°C, the temperature of the seventh zone was 250°C, the temperature of the die head was 270°C, the rotation speed was 300 rpm / min, and after being pulled by a traction machine and cut into particles, an antibacterial halogen-free flame-retardant nylon composite material was obtained.

[0108] Example 9

[0109] The components were weighed according to the following Table 6:

[0110] Table 6

[0111]

[0112]

[0113] (1) According to the weight percentage formula, the dried nylon, prepared triazine antibacterial agent, toughening agent, nucleating agent, calcium stearate, antibacterial agent, aluminum diethyl hypophosphite, melamine polyphosphate were weighed;

[0114] (2) The weighed components were placed in a high-speed mixer, the rotation speed was 50 rpm / min, and the stirring time was 25 min;

[0115] (3) The mixture obtained in step (2) was added to the feeding hopper of the twin-screw extruder, and the parameters of the twin-screw extruder were as follows: the temperature of the first zone was 190°C, the temperature of the second zone was 265°C, the temperature of the third zone was 265°C, the temperature of the fourth zone was 265°C, the temperature of the fifth zone was 265°C, the temperature of the sixth zone was 245°C, the temperature of the seventh zone was 240°C, the temperature of the die head was 260°C, and the rotation speed was 350 rpm / min. After being cut by a traction machine, an antibacterial halogen-free flame-retardant nylon composite material was obtained.

[0116] Example 10

[0117] The components were weighed according to the following Table 7:

[0118] Table 7

[0119]

[0120] (1) According to the weight percentage formula, the dried nylon, prepared triazine antibacterial agent, toughening agent, nucleating agent, calcium stearate, antibacterial agent, aluminum diethyl hypophosphite, melamine polyphosphate were weighed;

[0121] (2) The weighed components were placed in a high-speed mixer, the rotation speed was 400 rpm / min, and the stirring time was 5 min;

[0122] (3) The mixture obtained in step (2) was added to the feeding hopper of the twin-screw extruder, and the parameters of the twin-screw extruder were as follows: the temperature of the first zone was 210°C, the temperature of the second zone was 275°C, the temperature of the third zone was 275°C, the temperature of the fourth zone was 275°C, the temperature of the fifth zone was 265°C, the temperature of the sixth zone was 255°C, the temperature of the seventh zone was 255°C, the temperature of the die head was 265°C, and the rotation speed was 450 rpm / min. After being cut by a traction machine, an antibacterial halogen-free flame-retardant nylon composite material was obtained.

[0123] Comparative Example 1

[0124] The components were weighed according to the following Table 8:

[0125] Table 8

[0126]

[0127] (1) According to the weight percentage formula, the dried nylon, toughening agent, silicone, nucleating agent, aluminum diethyl phosphinate, melamine polyphosphate were weighed;

[0128] (2) The weighed components were placed in a high-speed mixer, the rotating speed was 350 rpm / min, and the stirring time was 20 min;

[0129] (3) The mixture obtained in step (2) was added to the feeding hopper of the twin-screw extruder, and the parameters of the twin-screw extruder were as follows: the temperature of the first zone was 195°C, the temperature of the second zone was 260°C, the temperature of the third zone was 260°C, the temperature of the fourth zone was 260°C, the temperature of the fifth zone was 260°C, the temperature of the sixth zone was 250°C, the temperature of the seventh zone was 250°C, the temperature of the die head was 270°C, and the rotating speed was 300 rpm / min. After being cut by a traction machine, a nylon composite material was obtained.

[0130] Comparative Example 2

[0131] The components were weighed according to the following Table 9:

[0132] Table 9

[0133]

[0134]

[0135] (1) According to the weight percentage formula, the dried nylon, silver ion antibacterial agent, toughening agent, silicone, nano-silicon dioxide, aluminum diethyl phosphinate, melamine polyphosphate were weighed;

[0136] (2) The weighed components were placed in a high-speed mixer, the rotating speed was 350 rpm / min, and the stirring time was 20 min;

[0137] (3) The mixture obtained in step (2) was added to the feeding hopper of the twin-screw extruder, and the parameters of the twin-screw extruder were as follows: the temperature of the first zone was 195°C, the temperature of the second zone was 260°C, the temperature of the third zone was 260°C, the temperature of the fourth zone was 260°C, the temperature of the fifth zone was 260°C, the temperature of the sixth zone was 250°C, the temperature of the seventh zone was 250°C, the temperature of the die head was 270°C, and the rotating speed was 300 rpm / min. After being cut by a traction machine, a nylon composite material was obtained.

[0138] Comparative Example 3

[0139] The components were weighed according to the following Table 10:

[0140] Table 10

[0141]

[0142] (1) According to the weight percentage formula, the dry nylon, zinc ion antibacterial agent, toughening agent, silicone, nano-silicon dioxide, aluminum diethyl hypophosphite, melamine polyphosphate are weighed;

[0143] (2) The weighed components are placed in a high-speed mixer, the rotating speed is 350 rpm / min, and the stirring time is 20 min;

[0144] (3) The mixture obtained in step (2) is added to the feeding hopper of the double screw extruder, and the parameters of the double screw extruder are as follows: the temperature of the first zone is 195℃, the temperature of the second zone is 260℃, the temperature of the third zone is 260℃, the temperature of the fourth zone is 260℃, the temperature of the fifth zone is 260℃, the temperature of the sixth zone is 250℃, the temperature of the seventh zone is 250℃, the temperature of the die head is 270℃, and the rotating speed is 300 rpm / min; after being pulled by the traction machine and cut into particles, the nylon composite material is obtained.

[0145] The nylon composite materials prepared in Examples 4-8 and Comparative Examples 1-3 are tested, and the results are shown in Table 11:

[0146] Table 11

[0147]

[0148] From the data in Table 11, it can be seen that the impact resistance, antibacterial and flame retardant properties of the nylon composite material prepared by the present application meet the requirements. Examples 5-8 have higher antibacterial rates than Example 1. It can be seen that the antibacterial performance of the resin can be improved when the triazine antibacterial agent is added in the present application. From Comparative Example 1, Comparative Example 2 and Comparative Example 3, it can be seen that the flame retardant performance of the composite material without the addition of triazine antibacterial agent is poor. From Examples 6-8, it can be seen that under the synergistic effect of triazine antibacterial agent and halogen-free flame retardant, the composite material has more excellent glow wire performance and more excellent mechanical properties. This is because when the triazine antibacterial agent is added to the composite material, the triazine antibacterial agent contains a large amount of flame-retardant element nitrogen, which can release non-combustible gases such as nitrogen and ammonia at high temperatures to isolate oxygen and retard combustion, so that the composite material has more excellent flame retardant performance, and the content of halogen-free flame retardant can be further reduced, thereby improving the impact performance of the nylon material.

[0149] In addition, the present inventors have also learned from the foregoing implementation cases, and have conducted in-depth research and experiments on other raw materials, process flow control and process parameters mentioned in the present specification, and good results have been achieved.

[0150] The technical solutions of the present application are not limited to the specific implementation cases described above, and any technical adjustment that strictly follows the technical principles of the present application while maintaining the scope of the present application and the protection scope of the claims is within the protection scope of the present application.

Claims

1. A triazine-based antibacterial agent, characterized by, The triazine antibacterial agent has a structure as shown in formula (I): ； Wherein, R1, R2, R3 are methyl.

2. The method for preparing a triazine antibacterial agent according to claim 1, wherein: Comprise: In a protective atmosphere, a mixed reaction system comprising melamine, 5-methyl-2-furfural, organic solvent is reacted to prepare a triazine antibacterial agent.

3. The method of claim 2, wherein: The organic solvent comprises any one or a combination of DMSO, ethanol, water, DMF; And / or, the molar ratio of melamine to 5-methyl-2-furfural is 1:3-8; And / or, the reaction temperature is 50-80℃, and the time is 4-12h.

4. An antimicrobial, halogen-free, flame-retardant nylon composite material, characterized by, The raw materials for preparing the antibacterial halogen-free flame-retardant nylon composite material comprise, by weight percentage, the following components: nylon 65%, triazine antibacterial agent 1%-5%, halogen-free flame retardant 6%-14%, melamine polyphosphate 2%-5%, toughening agent 2%-7%, lubricant 0.1%-5%, and nucleating agent 0.5%-3%; wherein the triazine antibacterial agent is the triazine antibacterial agent of claim 1.

5. The antimicrobial, halogen-free, flame-retardant nylon composite of claim 4, wherein, The raw materials for preparing the antibacterial halogen-free flame-retardant nylon composite material comprise, by weight percentage, the following components: nylon 65%, triazine antibacterial agent 1%-3%, halogen-free flame retardant 6%-14%, melamine polyphosphate 2%-4%, toughening agent 2%-5%, lubricant 0.1%-5%, and nucleating agent 0.5%-2%.

6. The antimicrobial, halogen-free, flame-retardant nylon composite of claim 4, wherein: The halogen-free flame retardant comprises aluminum diethyl phosphinate; And / or, the toughening agent comprises any one or a combination of ethylene-methyl acrylate copolymer, POE-g-MAH modifier, and POE; And / or, the lubricant comprises any one or a combination of OP wax, calcium stearate, and silicone; And / or, the nucleating agent comprises any one or a combination of nanoscale talc, calcium carboxylate, and nanosilica.

7. The method for preparing the antibacterial halogen-free flame-retardant nylon composite material according to any one of claims 4 to 6, characterized in that: Comprise: The nylon, triazine antibacterial agent, halogen-free flame retardant, melamine polyphosphate, toughening agent, lubricant, and nucleating agent are uniformly mixed, and then the obtained mixture is added to a double-screw extrusion device for granulation treatment to prepare the antibacterial halogen-free flame-retardant nylon composite material.

8. The production method according to claim 7, characterized by, Specifically comprise: The nylon, triazine antibacterial agent, halogen-free flame retardant, melamine polyphosphate, toughening agent, lubricant, and nucleating agent are placed in a high-speed kneading device and stirred and mixed at a speed of 50-400 rpm / min for 5-25 min; then the mixture is added to a double-screw extrusion device, and after being cut by a traction machine, the antibacterial halogen-free flame-retardant nylon composite material is obtained; Wherein, the temperature of each zone of the double-screw extrusion device from the feeding port to the die head comprises: the temperature of the first zone is 190-210℃, the temperature of the second zone is 260-275℃, the temperature of the third zone is 260-275℃, the temperature of the fourth zone is 260-275℃, the temperature of the fifth zone is 260-265℃, the temperature of the sixth zone is 245-255℃, the temperature of the seventh zone is 240-255℃, the temperature of the die head is 260-270℃, and the speed is 300-450 rpm / min.

9. The method of claim 8, wherein: The speed in the high-speed kneading device is 100-200 rpm / min, and the stirring time is 5-20 min; And / or, the temperature of each zone of the twin-screw extrusion device from the feeding port to the die head includes: the temperature of the first zone is 190-210℃, the temperature of the second zone is 265-275℃, the temperature of the third zone is 265-275℃, the temperature of the fourth zone is 265-275℃, the temperature of the fifth zone is 260-265℃, the temperature of the sixth zone is 245-250℃, the temperature of the seventh zone is 240-250℃, the temperature of the die head is 260-265℃, and the rotation speed is 300-450 rpm / min.

10. Use of the antimicrobial halogen-free flame-retardant nylon composite material according to any one of claims 4-6 for preparing an electronic and electrical appliance shell, a household appliance, an automobile part, or a motor shell.

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