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

Abstract

The invention discloses a triazine antibacterial agent, an antibacterial halogen-free flame-retardant nylon composite material as well as a preparation method and application of the antibacterial halogen-free flame-retardant nylon composite material. The triazine antibacterial agent has a structure as shown in the following formula: # imgabs0 #, wherein R1, R2 and R3 are independently selected from an aldehyde group, a hydroxyl group, halogen, a phenyl group or an alkyl group and the like. The antibacterial halogen-free flame-retardant nylon composite material is prepared from the following raw materials in percentage by weight: 15%-85% of nylon, 0.5%-5% of a 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 invention has excellent toughness and antibacterial property; meanwhile, the preparation method of the nylon composite material is simple, convenient and easy to implement, relatively low in cost input, good in operability and practicability, and very suitable for industrial large-scale production.

Description

Technical Field

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

[0002] As one of the five major engineering plastics, nylon (PA6) has good processability, temperature resistance, chemical resistance and excellent lubrication properties, and is now widely used in home appliances, electronic and electrical fields, and automotive parts. However, nylon materials have poor flame retardancy, easy water absorption, and poor dimensional stability, which greatly limits the use of nylon in the fields of automobiles, electronic appliances, home appliances, etc. As people continue to expand the application of nylon, they have put forward higher requirements for the flame retardancy and antibacterial properties of the material.

[0003] Common antimicrobial agents used in traditional antimicrobial flame retardant nylon are divided into inorganic antimicrobial agents and organic antimicrobial agents. Inorganic antimicrobial agents are generally antimicrobial agents containing copper metal, zinc metal, silver metal, etc. This type of antimicrobial agent has good thermal stability, but it is easy to react with flame retardants, affecting the color and mechanical properties of the material, and cannot meet the needs of many products. Although organic antimicrobial agents have good compatibility with nylon, they have poor temperature resistance and are easily degraded at high temperatures, affecting the use of products.

[0004] The published patent CN102643539A discloses a method for preparing an antibacterial flame-retardant nylon composite material, which mainly improves the antibacterial properties of the alloy material by zinc pyridine sulfate, but the antibacterial agent has poor compatibility with nylon and reduces the impact performance of the material; the patent CN107447282A discloses an antibacterial flame-retardant polyamide 66, which uses a mesoporous inorganic antibacterial agent as an antibacterial agent for nylon and is added during the polymerization process of nylon. The processing technology in this solution is complicated and the cost is relatively high. Therefore, it is an urgent problem to provide an antibacterial halogen-free flame-retardant nylon composite material with low cost, simple preparation and good toughness. Summary of the invention

[0005] The main purpose of the present invention 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 object of the present invention is to provide an application of the antibacterial halogen-free flame-retardant nylon composite material.

[0007] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes:

[0008] The present invention provides a triazine antibacterial agent having a structure as shown in formula (I):

[0009]

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

[0011] The present invention also provides a method for preparing the triazine antibacterial agent, which comprises:

[0012] In a protective atmosphere, a mixed reaction system comprising melamine, furfural and / or furfural derivatives and an organic solvent is polymerized to prepare a triazine antibacterial agent.

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

[0014] The embodiment of the present invention also provides a method for preparing an antibacterial halogen-free flame-retardant nylon composite material, which comprises: uniformly mixing nylon, a 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 twin-screw extruder for granulation to obtain the antibacterial halogen-free flame-retardant nylon composite material.

[0015] Furthermore, the embodiments of the present invention also provide the use of the aforementioned antibacterial halogen-free flame-retardant nylon composite material in the preparation of electronic and electrical housings, household appliances, automobile parts or motor housings.

[0016] Compared with the prior art, the beneficial effects of the present invention include:

[0017] 1) The triazine antimicrobial agent provided by the present invention is an organic antimicrobial agent, which can be fully dispersed in the nylon matrix under the shearing of the twin screw, ensuring the excellent long-term antimicrobial and impact resistance of the composite material. When the triazine antimicrobial agent is added to the composite material, the triazine antimicrobial 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 isolate oxygen and flame retardant combustion, so that the composite material has more excellent flame retardant properties, and at the same time, the content of halogen-free flame retardant can be further reduced, thereby improving the impact performance of nylon materials;

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

[0019] In view of the limitations and shortcomings of the current technology, the inventor of this case has proposed the technical solution of the present invention after a long period of research and a lot of practice. The technical points of the present invention will be clearly described below. The above embodiments are only part of our invention and do not cover all possible situations. Among the many embodiments involved in the present invention, any other application examples derived by conventional practitioners without original efforts should be deemed to be protected by the patent of the present invention.

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

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

[0022]

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

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

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

[0026]

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

[0028] In some preferred embodiments, the furan carboxaldehyde derivatives may include any one or more combinations of 2,5-furandicarboxaldehyde, 5-hydroxymethyl-2-furaldehyde, 5-iodo-2-furaldehyde, 7-hydroxy-1-benzofuran-4-carboxaldehyde, furano[2,3-b]pyridine-3-carboxaldehyde, 5-methoxymethyl-2-furaldehyde, 5-benzyl-furan-2-carboxaldehyde, etc., but are not limited thereto.

[0029] Furthermore, the organic solvent may include any one or more combinations of DMSO, ethanol, water (such as deionized water), DMF, etc., but is not limited thereto.

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

[0031] In some embodiments, the polymerization reaction is carried out at a temperature of 50 to 80° C. and for a time of 4 to 12 hours.

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

[0033] Melamine (0.1 mol), 5-methyl-2-furancarboxaldehyde (0.4 mol) and ethanol (100 ml) were added to a round-bottom flask, stirred to make a uniform solution and sealed. The flask was then placed in a 120°C oil bath for constant temperature and sealed polymerization. After the polymerization reaction was completed, a poor solvent was used for precipitation, filtration, and vacuum drying to constant weight to obtain a polymerized triazine antibacterial agent.

[0034] The present invention prepares an organic triazine antibacterial agent by a free radical reaction method. The polymer has good compatibility with a nylon matrix and can be fully dispersed under the shearing 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 amount of nitrogen atoms, which can reduce the use of halogen-free flame retardants in the material, thereby improving the strength and toughness of nylon.

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

[0036]

[0037] Among them, R1, R2, and R3 can be independently selected from any one of aldehyde, hydroxyl, halogen, phenyl, or other alkyl groups, but are not limited thereto.

[0038] The triazine antibacterial agent used in the present invention is an organic antibacterial agent and can be fully dispersed in the matrix, thereby improving the antibacterial property 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 calculated by weight percentage: 45%-65% nylon, 1%-5% triazine antibacterial agent, 6%-14% halogen-free flame retardant, 2%-5% melamine polyphosphate, 2%-7% toughening agent, 0.1%-5% lubricant and 0.5%-3% nucleating agent.

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

[0041] The nylon in the present invention can be a commercially available PA6 type.

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

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

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

[0045] In some preferred embodiments, the nucleating agent includes any one or more combinations of nano-talc, calcium carboxylate, nano-silicon dioxide, etc., but is not limited thereto.

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

[0047] 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 into a twin-screw extruder for granulation to obtain the antibacterial halogen-free flame retardant nylon composite material.

[0048] The triazine antimicrobial agent used in the present invention can be fully dispersed in the nylon matrix under the shearing of the twin screw, thereby ensuring the excellent long-term antimicrobial and impact resistance of the composite material. When the triazine antimicrobial agent is added to the composite material, the triazine antimicrobial 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 isolate oxygen and flame retardant combustion, so that the composite material has more excellent flame retardant properties, and at the same time, the content of the halogen-free flame retardant can be further reduced, thereby improving the impact performance of the nylon material.

[0049] In some preferred embodiments, the preparation method specifically includes: placing nylon, triazine antibacterial agent, halogen-free flame retardant, melamine polyphosphate, toughening agent, lubricant and nucleating agent in a high-speed kneading device, and stirring and mixing for 5 to 25 minutes at a rotation speed of 50 to 400 rpm / min; then adding the mixed material to a twin-screw extruder, and after pelletizing 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 extruder from the feed port to the die includes: the temperature of zone 1 is 190 to 210°C, the temperature of zone 2 is 260 to 275°C, the temperature of zone 3 is 260 to 275°C, the temperature of zone 4 is 260 to 275°C, the temperature of zone 5 is 260 to 265°C, the temperature of zone 6 is 245 to 255°C, the temperature of zone 7 is 240 to 255°C, the temperature of the die is 260 to 270°C, and the rotation speed is 300 to 450 rpm / min.

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

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

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

[0053] (2) The mixed material is added into a twin-screw extruder and pelletized by a tractor to obtain an antibacterial halogen-free flame-retardant nylon composite material.

[0054] Furthermore, in step (1), the conditions for uniform mixing are as follows: each component is placed in a high-speed kneader, the rotation speed is maintained at 100 to 200 rpm / min, and the high-speed stirring time is 5 to 20 minutes.

[0055] Furthermore, in step (2), the temperatures of the zones of the twin-screw extruder from the feed port to the die include: the temperature of zone 1 is 190-210°C, the temperature of zone 2 is 265-275°C, the temperature of zone 3 is 265-275°C, the temperature of zone 4 is 265-275°C, the temperature of zone 5 is 260-265°C, the temperature of zone 6 is 245-250°C, the temperature of zone 7 is 240-250°C, the temperature of the die is 260-265°C, and the rotation speed is 300-450rpm / min.

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

[0057] As another aspect of the technical solution of the present invention, 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 properties, and can be used to prepare automotive parts, motor housings, electronic and electrical housings or household appliances, etc.

[0059] The technical solution of the present invention is further described in detail below in conjunction with several preferred embodiments. This embodiment is implemented on the premise of the technical solution of the invention, and provides a detailed implementation method and a specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0060] Unless otherwise specified, the experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.

[0061] Example 1

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

[0063] Melamine (0.1 mol), 5-methyl-2-furan carboxaldehyde (0.4 mol), and ethanol (100 ml) were added to a round-bottom flask, stirred to make a uniform solution, and sealed. The flask was then placed in a 120°C oil bath and sealed for polymerization for 10 hours. After the polymerization reaction was completed, a poor solvent was used for precipitation, filtration, and vacuum drying to constant weight to obtain a polymerized triazine antibacterial agent.

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

[0065]

[0066] Example 2

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

[0068] Melamine (0.1 mol), 5-methyl-2-furancarboxaldehyde (0.7 mol), and ethanol (100 ml) were added to a round-bottom flask, stirred to make a uniform solution, and sealed. The flask was then placed in a 110°C oil bath and sealed for constant temperature polymerization for 8 hours. After the polymerization reaction was completed, a poor solvent was used for precipitation, filtration, and vacuum drying to constant weight to obtain a polymerized triazine antibacterial agent.

[0069] Example 3

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

[0071] Melamine (0.1 mol), furan formaldehyde (0.4 mol), and ethanol (100 ml) were added to a round-bottom flask, stirred to make a uniform solution, and sealed. The flask was then placed in a 140°C oil bath and sealed for polymerization reaction for 10 hours. After the polymerization reaction was completed, a poor solvent was used for precipitation, filtration, and vacuum drying to constant weight to obtain a polymerized triazine antibacterial 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, weigh the dried nylon, the prepared triazine antibacterial agent, the toughening agent, calcium stearate, the nucleating agent, diethyl aluminum hypophosphite, and melamine polyphosphate;

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

[0078] (3) adding the mixed material obtained in step (2) into the feeding funnel of a twin-screw extruder, wherein the parameters of the twin-screw extruder are: 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, weigh the dried nylon, the prepared triazine antibacterial agent, the toughening agent, the OP wax, the nucleating agent, the diethyl aluminum hypophosphite, and the melamine polyphosphate;

[0084] (2) The weighed components were placed in a high-speed mixer at a speed of 350 rpm / min for 20 min;

[0085] (3) adding the mixed material obtained in step (2) into the feeding funnel of a twin-screw extruder, wherein the parameters of the twin-screw extruder are: 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.

[0086] Example 6

[0087] Weigh the components according to Table 3 below:

[0088] Table 3

[0089]

[0090]

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

[0092] (2) The weighed components were placed in a high-speed mixer at a speed of 350 rpm / min for 20 min;

[0093] (3) adding the mixed material obtained in step (2) into the feeding funnel of a twin-screw extruder, wherein the parameters of the twin-screw extruder are: 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.

[0094] Example 7

[0095] Weigh the components according to Table 4 below:

[0096] Table 4

[0097]

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

[0099] (2) The weighed components were placed in a high-speed mixer at a speed of 350 rpm / min for 20 min;

[0100] (3) adding the mixed material obtained in step (2) into the feeding funnel of a twin-screw extruder, wherein the parameters of the twin-screw extruder are: 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.

[0101] Example 8

[0102] Weigh the components according to Table 5 below:

[0103] Table 5

[0104]

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

[0106] (2) The weighed components were placed in a high-speed mixer at a speed of 350 rpm / min for 20 min;

[0107] (3) adding the mixed material obtained in step (2) into the feeding funnel of a twin-screw extruder, wherein the parameters of the twin-screw extruder are: 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.

[0108] Example 9

[0109] Weigh the components according to Table 6 below:

[0110] Table 6

[0111]

[0112]

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

[0114] (2) Place the weighed components in a high-speed mixer at a speed of 50 rpm / min and a stirring time of 25 min;

[0115] (3) adding the mixed material obtained in step (2) into the feeding funnel of a twin-screw extruder, wherein the parameters of the twin-screw extruder are: the temperature of zone 1 is 190° C., the temperature of zone 2 is 265° C., the temperature of zone 3 is 265° C., the temperature of zone 4 is 265° C., the temperature of zone 5 is 265° C., the temperature of zone 6 is 245° C., the temperature of zone 7 is 240° C., the head temperature is 260° C., the rotation speed is 350 rpm / min, and after being pulled and pelletized by a traction machine, an antibacterial halogen-free flame-retardant nylon composite material is obtained.

[0116] Example 10

[0117] Weigh the components according to Table 7 below:

[0118] Table 7

[0119]

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

[0121] (2) The weighed components were placed in a high-speed mixer at a speed of 400 rpm / min for 5 min;

[0122] (3) adding the mixed material obtained in step (2) into the feeding funnel of a twin-screw extruder, wherein the parameters of the twin-screw extruder are: the temperature of zone 1 is 210° C., the temperature of zone 2 is 275° C., the temperature of zone 3 is 275° C., the temperature of zone 4 is 275° C., the temperature of zone 5 is 265° C., the temperature of zone 6 is 255° C., the temperature of zone 7 is 255° C., the head temperature is 265° C., the rotation speed is 450 rpm / min, and after being pulled and pelletized by a traction machine, an antibacterial halogen-free flame-retardant nylon composite material is obtained.

[0123] Comparative Example 1

[0124] Weigh the components according to Table 8 below:

[0125] Table 8

[0126]

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

[0128] (2) The weighed components were placed in a high-speed mixer at a speed of 350 rpm / min for 20 min;

[0129] (3) adding the mixed material obtained in step (2) into a feeding hopper of a twin-screw extruder, wherein the parameters of the twin-screw extruder are: 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, a nylon composite material is obtained.

[0130] Comparative Example 2

[0131] Weigh the components according to Table 9 below:

[0132] Table 9

[0133]

[0134]

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

[0136] (2) The weighed components were placed in a high-speed mixer at a speed of 350 rpm / min for 20 min;

[0137] (3) Adding the mixed material obtained in step (2) into the feeding funnel of a twin-screw extruder. The parameters of the twin-screw extruder are: 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, a nylon composite material is obtained.

[0138] Comparative Example 3

[0139] Weigh the components according to Table 10 below:

[0140] Table 10

[0141]

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

[0143] (2) The weighed components were placed in a high-speed mixer at a speed of 350 rpm / min for 20 min;

[0144] (3) Adding the mixed material obtained in step (2) into the feeding funnel of a twin-screw extruder. The parameters of the twin-screw extruder are: 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, a nylon composite material is obtained.

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

[0146] Table 11

[0147]

[0148] From the data effect of Table 11, the nylon composite material prepared by the present invention has high impact, and the antibacterial and flame retardant properties meet the requirements. Examples 5-8 have a higher antibacterial rate than Example 1. It can be seen that in the present invention, when the triazine antibacterial agent is added, the antibacterial property of the resin can be improved. It can be seen from Comparative Examples 1, 2 and 3 that the flame retardant property of the composite material without the addition of the triazine antibacterial agent is poor. It can be seen from Examples 6-8 that under the synergistic effect of the triazine antibacterial agent and the 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 temperature to isolate oxygen from flame retardant combustion, so that the composite material has more excellent flame retardant properties, and at the same time, the content of the halogen-free flame retardant can be further reduced, thereby improving the impact performance of the nylon material.

[0149] In addition, the inventors of this case also drew on the aforementioned implementation cases and conducted in-depth research and experiments on other raw materials, process flow control and process parameters mentioned in this specification, and achieved good results.

[0150] The technical solution of the present invention is not limited to the above-mentioned specific implementation cases. Any technical adjustments made in strict accordance with the technical essentials of the present invention without departing from the spirit of the present invention and the scope protected by the claims shall fall within the protection scope of the present invention.

Claims

1. A triazine antibacterial agent, characterized in that: The triazine antibacterial agent has a structure as shown in formula (I): Wherein, R1, R2, and R3 are independently selected from any one of aldehyde, hydroxyl, halogen, phenyl or alkyl.

2. The method for preparing a triazine antibacterial agent according to claim 1, characterized in that: include: In a protective atmosphere, a mixed reaction system comprising melamine, furfural and / or furfural derivatives and an organic solvent is polymerized to prepare a triazine antibacterial agent.

3. The preparation method according to claim 2, characterized in that: The furanaldehyde derivative has a structure as shown in formula (II): Wherein, R is independently selected from any one of aldehyde, hydroxyl, halogen, phenyl, and alkyl; Preferably, the furan carboxaldehyde derivatives include any one or more combinations of 2,5-furandicarboxaldehyde, 5-hydroxymethyl-2-furaldehyde, 5-iodo-2-furaldehyde, 7-hydroxy-1-benzofuran-4-carboxaldehyde, furano[2,3-b]pyridine-3-carboxaldehyde, 5-methoxymethyl-2-furaldehyde, and 5-benzyl-furan-2-carboxaldehyde; And / or, the organic solvent includes any one or more combinations of DMSO, ethanol, water, and DMF; and / or, the molar ratio of melamine to furfural and / or furfural derivatives is 1:3-8; And / or, the polymerization reaction temperature is 50-80° C. and the reaction time is 4-12 hours.

4. An antibacterial halogen-free flame-retardant nylon composite material, characterized in that: The raw materials for preparing the antibacterial halogen-free flame-retardant nylon composite material include the following components calculated by weight percentage: nylon 15% N85%, triazine antibacterial agent 0.5% N5%, halogen-free flame retardant 6% to 14%, melamine polyphosphate 2% to 5%, toughening agent 1% to 8%, lubricant 0.1% to 5% and nucleating agent 0.1% to 3%; wherein the triazine antibacterial agent is the triazine antibacterial agent described in claim 1.

5. The antibacterial halogen-free flame-retardant nylon composite material according to claim 4, characterized in that: The raw materials for preparing the antibacterial halogen-free flame-retardant nylon composite material include the following components calculated by weight percentage: 45% to 65% nylon, 1% to 5% triazine antibacterial agent, 6% to 14% halogen-free flame retardant, 2% to 5% melamine polyphosphate, 2% to 7% toughening agent, 0.1% to 5% lubricant and 0.5% to 3% nucleating agent; Preferably, the raw materials for preparing the antibacterial halogen-free flame-retardant nylon composite material include the following components calculated by weight percentage: 45% to 65% nylon, 1% to 3% triazine antibacterial agent, 6% to 14% halogen-free flame retardant, 2% to 4% melamine polyphosphate, 2% to 5% toughening agent, 0.1% to 5% lubricant and 0.5% to 2% nucleating agent.

6. The antibacterial halogen-free flame-retardant nylon composite material according to claim 4 or 5, characterized in that: The halogen-free flame retardant includes diethyl aluminum hypophosphite; And / or, the toughening agent includes any one or more combinations of ethylene-methyl acrylate copolymer, POE-g-MAH modifier, and POE; And / or, the lubricant includes any one or more combinations of OP wax, calcium stearate, and silicone; And / or, the nucleating agent includes any one or more combinations of nano-sized talc, calcium carboxylate, and nano-silicon dioxide.

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: include: 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 into a twin-screw extruder for granulation to obtain the antibacterial halogen-free flame retardant nylon composite material.

8. The preparation method according to claim 7, characterized in that: Specifically include: 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 for 5 to 25 minutes at a speed of 50 to 400 rpm / min; then the mixture is added to a twin-screw extruder, and pelletized by a tractor to obtain an antibacterial halogen-free flame-retardant nylon composite material; Among them, the temperatures of each zone of the twin-screw extruder from the feeding port to the die include: the temperature of zone one is 190-210°C, the temperature of zone two is 260-275°C, the temperature of zone three is 260-275°C, the temperature of zone four is 260-275°C, the temperature of zone five is 260-265°C, the temperature of zone six is ​​245-255°C, the temperature of zone seven is 240-255°C, the temperature of the die head is 260-270°C, and the rotation speed is 300-450rpm / min.

9. The preparation method according to claim 8, characterized in that: The rotation speed of the high-speed kneading device is 100-200 rpm / min, and the stirring time is 5-20 min; And / or, the temperatures of each zone of the twin-screw extruder from the feeding port to the die include: the temperature of zone one is 190-210°C, the temperature of zone two is 265-275°C, the temperature of zone three is 265-275°C, the temperature of zone four is 265-275°C, the temperature of zone five is 260-265°C, the temperature of zone six is ​​245-250°C, the temperature of zone seven is 240-250°C, the temperature of the die head is 260-265°C, and the rotation speed is 300-450rpm / min.

10. Use of the antibacterial halogen-free flame-retardant nylon composite material according to any one of claims 4 to 6 in the preparation of electronic and electrical appliance housings, household appliances, automobile parts or motor housings.

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