CN112980183A - Precipitation-resistant halogen-free flame-retardant reinforced nylon material and preparation method thereof - Google Patents
Precipitation-resistant halogen-free flame-retardant reinforced nylon material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a precipitation-resistant halogen-free flame-retardant reinforced nylon material and a preparation method thereof. The material comprises the following components in parts by weight: 30-55 parts of nylon, 25-40 parts of glass fiber, 5-10 parts of modified melamine cyanurate, 0.5-3 parts of compatilizer, 10-25 parts of flame-retardant toughening agent and 1-3 parts of other auxiliary agents. According to the invention, the surface modified melamine cyanurate is adopted to enhance the compounding of the nylon with excellent compatibility and the flame retardant toughening agent with flame retardant elements, so that the low precipitation and corrosion of the halogen-free flame retardant and the high electrical performance characteristics of the flame retardant reinforced nylon material are realized on the premise of keeping good mechanical and heat-resistant properties. The adoption of the flame-retardant toughening agent greatly reduces the use of the traditional flame retardant and effectively improves the mechanical property of the material. Meanwhile, the product has the characteristics of environmental protection, high dimensional stability and the like, and meets the key material requirements of products such as household appliances, new energy automobiles and the like.
Description
Technical Field
The invention relates to a household appliance material and a preparation method thereof, in particular to a precipitation-resistant halogen-free flame-retardant reinforced nylon material and a preparation method thereof, belonging to the technical field of materials.
Background
The key parts of the household appliance product are made of flame-retardant reinforced nylon materials. With more precise product design, the requirements on the safety, heat resistance, electrode corrosivity, precipitation performance and the like of the flame-retardant nylon material are continuously improved; and simultaneously meets the requirements of easier forming thin-walled products. Compared with halogen flame retardants, the halogen-free flame-retardant modified nylon material has a higher CTI value and lower toxicity, and gradually becomes the mainstream of the flame-retardant nylon material for household appliances. Despite the wide range of applications, there are a number of specific problems encountered during use, such as: 1. the existing halogen-free flame-retardant nylon material for household appliances mainly takes red phosphorus flame-retardant reinforced nylon as a main material, and because the red phosphorus flame-retardant reinforced nylon material has poor compatibility with a nylon system, very poor toughness, poor toughness and elasticity and the like, 2. the red phosphorus flame retardant has poor moisture and heat resistance and poor surface migration resistance, is easy to precipitate, generates a sweating phenomenon, forms phosphoric acid, corrodes an electrode or a component, and causes damage to the electrical property of a product.
Disclosure of Invention
In order to solve the technical problems, the surface modified melamine cyanurate is adopted to enhance the compatibility of nylon, and simultaneously, the surface modified melamine cyanurate is compounded with the flame retardant toughening agent with flame retardant elements, so that the flame retardant UL941.6mm reaches the V0 level on the premise of maintaining good mechanical and heat-resistant performances of the reinforced nylon, the problems of precipitation and corrosion of the flame retardant are greatly improved, and the high electrical performance characteristic of the flame retardant reinforced nylon material is realized. The adoption of the flame retardant toughening agent greatly reduces the dosage of the traditional flame retardant and effectively improves the mechanical property of the material. Meanwhile, the product has the characteristics of environmental protection, high dimensional stability and the like, and meets the key material requirements of products such as household appliances, new energy automobiles and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a precipitation-resistant halogen-free flame-retardant reinforced nylon material comprises the following components in parts by weight:
30-55 parts of nylon
25-40 parts of glass fiber
5-10 parts of modified melamine cyanurate
0.5 to 3 portions of compatilizer
10-25 parts of flame-retardant toughening agent
1-3 parts of other auxiliary agents.
Wherein the surface modified melamine cyanurate is prepared by the following method: firstly, dissolving a surface modifier in absolute ethyl alcohol to obtain a mixed solution; adding melamine cyanurate into a high-speed mixer at the temperature of 40-100 ℃, adding the surface modifier solution obtained in the step, raising the temperature to 190 ℃ and continuously mixing for 5-35min until the absolute ethanol is completely volatilized; obtaining the surface modified melamine cyanurate. Wherein the surface modifier is one of epoxy resin, tetrahydrophthalic anhydride, polyamide polyamine epichlorohydrin, adipic acid dihydrazide and N-aminoethyl piperazine, and preferably the polyamide polyamine epichlorohydrin.
In a further aspect, the nylon is one of nylon 6 and nylon 66, preferably nylon 66.
Further scheme, the glass fiber is alkali-free glass fiber with the diameter of 10-20um, and alkali-free glass fiber with the diameter of 12um is preferred.
Further, the melamine cyanurate is melamine cyanurate with the particle size of less than or equal to 1um and the preferred diameter of 0.5 um.
In a further scheme, the flame-retardant toughening agent is one of phosphorus-containing monomer graft modified polyolefin, phosphorus-containing monomer graft modified ethylene-alpha olefin copolymer, phosphorus-containing monomer graft modified ethylene-propylene rubber and phosphorus-containing monomer graft modified SEBS, wherein the phosphorus-containing monomer is one of 2-hydroxyethyl aminomethyl phosphonate, trihydroxymethyl phosphine oxide, oxyphosphate cyclohexane phosphonate, butylated triphenyl thiophosphate and diphenyl thiophosphate, and preferably the butylated triphenyl thiophosphate graft ethylene-alpha olefin copolymer;
the flame retardant toughening agent is prepared by the following method: firstly, 10 to 25 parts of phosphorus-containing monomer and 0.1 to 1 part of initiator are blended in a high-speed mixer and then dissolved in acetone; and adding the mixed solution into a medium mixer containing 75-90 parts of the toughening agent and at the temperature of 40-120 ℃, fully mixing until acetone is volatilized, respectively recovering acetone and the solid mixed material, adding the mixed material into an extruder at the temperature of 100-200 ℃, and performing extrusion granulation to obtain the phosphorus-containing monomer grafted toughening agent. Wherein, the rotating speed of the high-speed mixer is 200-. Wherein the initiator is one of cumyl peroxide, potassium persulfate, sodium bisulfite, N-dimethylaniline and cerium sulfate, and sodium bisulfite is preferred.
In a further embodiment, the compatibilizer is one of oxazoline, acrylate, epoxy, and maleic anhydride grafted polyolefin, and preferably acrylate grafted polyolefin.
In a further scheme, the other auxiliary agents are an antioxidant, a lubricant and black master batch, wherein the antioxidant is one of 1010, 168, 624, 1098 and H10, preferably 1098; the lubricant is one of TAF, EBS, PTFE, polyethylene wax and silicone powder, and the silicone powder is preferred; the black master batch is carbon black master batch.
A preparation method of precipitation-resistant halogen-free flame-retardant reinforced nylon material is characterized by comprising the following steps: the method comprises the following steps:
(1) firstly, dissolving a surface modifier in absolute ethyl alcohol to obtain a mixed solution; adding melamine cyanurate into a high-speed mixer at the temperature of 40-100 ℃, adding the surface modifier solution obtained in the step, raising the temperature to 190 ℃ and continuously mixing for 5-35min until the absolute ethanol is completely volatilized; obtaining the surface modified melamine cyanurate.
(2) Blending phosphorus-containing monomers and an initiator in a high-speed mixer, and then dissolving the mixture in acetone; adding the mixed solution into a medium mixer containing a toughening agent and having a temperature of 40-120 ℃, then fully mixing until acetone is volatilized, respectively recovering acetone and solid mixed materials, adding the mixed materials into an extruder at the temperature of 100-200 ℃, and carrying out extrusion granulation to obtain a phosphorus-containing monomer grafted toughening agent, namely the flame retardant toughening agent; wherein the rotating speed of the high-speed mixer is 200-;
(3) 30-55 parts of nylon, 0.5-3 parts of compatilizer, 25-40 parts of glass fiber, 5-10 parts of modified melamine cyanurate, 10-25 parts of flame-retardant toughening agent and 1-3 parts of other auxiliary agents are put into a high-speed mixer for mixing, the mixture is added into a double-screw extruder through a hopper, 25-40 parts of glass fiber are accurately weighed through a weightlessness scale, are introduced into the extruder through a side feeder according to certain weight parts, and are subjected to meshing plasticization, mixing, extrusion, bracing, air drying and granulation to obtain the precipitation-resistant halogen-free flame-retardant reinforced nylon composite material; wherein, the extruder temperature sets up a district to the aircraft nose: 230 ℃ and 320 ℃.
Advantageous effects
1. The surface-modified melamine cyanurate is adopted to enhance the compatibility of the flame retardant and nylon, and meanwhile, the flame retardant toughening agent with flame retardant elements is compounded, so that the flame retardant UL941.6 mm reaches the V0 level on the premise of keeping good mechanical and heat-resistant performances of the reinforced nylon, meanwhile, the problems of precipitation and acid corrosion of the flame retardant of household appliance products are effectively solved, the high electrical performance characteristics of the flame retardant reinforced nylon material are realized, and the CTI value exceeds 600V. The flame retardant toughening agent greatly reduces the consumption of the traditional flame retardant, and effectively improves the mechanical properties of the material, particularly the toughness and the impact strength of the material. Meanwhile, the product has the characteristics of environmental protection, high dimensional stability and the like, and meets the key material requirements of products such as household appliances, new energy automobiles and the like.
2. The material has the characteristic of high fluidity, and can meet the requirements of the processing and forming performance of thin-wall household electrical appliances with complex structures; in addition, short-period rapid injection molding can be realized, and the production efficiency is improved;
3. the preparation method of the material has the advantages of economic process, easy operation, high production efficiency and easy realization of industrialization.
Drawings
FIG. 1 is a graph showing the results of a precipitation resistance test in comparative example 1;
FIG. 2 is a graph showing the results of the precipitation resistance test in example 1;
FIG. 3 is a graph showing the results of the corrosion resistance test of the copper sheet for an electrode of comparative example 1;
FIG. 4 is a graph showing the results of the corrosion resistance test of the electrode copper sheet of example 1.
Detailed Description
The present invention will be described in further detail with reference to examples.
Examples
A preparation method of a precipitation-resistant halogen-free flame-retardant reinforced nylon material comprises the following steps:
(1) firstly, dissolving a surface modifier in absolute ethyl alcohol to obtain a mixed solution; adding melamine cyanurate into a high-speed mixer at the temperature of 40-100 ℃, adding the surface modifier solution obtained in the step, raising the temperature to 190 ℃ and continuously mixing for 5-35min until the absolute ethanol is completely volatilized; obtaining the surface modified melamine cyanurate. Wherein the surface modifier is one of epoxy resin, tetrahydrophthalic anhydride, polyamide polyamine epichlorohydrin, adipic dihydrazide and N-aminoethyl piperazine, preferably polyamide polyamine epichlorohydrin
(2) Blending phosphorus-containing monomers and an initiator in a high-speed mixer, and then dissolving the mixture in acetone; adding the mixed solution into a medium mixer containing a toughening agent and having a temperature of 40-120 ℃, then fully mixing until acetone is volatilized, respectively recovering acetone and solid mixed materials, adding the mixed materials into an extruder at the temperature of 100-200 ℃, and carrying out extrusion granulation to obtain a phosphorus-containing monomer grafted toughening agent, namely the flame retardant toughening agent; wherein the rotating speed is 200-800 r/min; wherein the initiator is one of cumyl peroxide, potassium persulfate, sodium bisulfite, N-dimethylaniline and cerium sulfate, and sodium bisulfite is preferred.
(3) 30-55 parts of nylon, 0.5-3 parts of compatilizer, 25-40 parts of glass fiber, 5-10 parts of modified Melamine Cyanurate (MCA), 10-25 parts of flame retardant toughening agent and 1-3 parts of other auxiliary agents are put into a high-speed mixer to be mixed, the mixture is added into a double-screw extruder through a hopper, 25-40 parts of glass fiber are accurately weighed through a weightless scale, are introduced into the extruder through a side feeder according to certain weight parts, and are subjected to meshing plasticization, mixing, extrusion, bracing, air drying and granulation to obtain the precipitation-resistant halogen-free flame retardant reinforced nylon composite material; wherein, the extruder temperature sets up a district to the aircraft nose: 230 ℃ and 320 ℃.
The nylon is one of nylon 6 and nylon 66, preferably nylon 66.
The glass fiber is alkali-free glass fiber with the diameter of 10-20um, and preferably alkali-free glass fiber with the diameter of 12 um.
The melamine cyanurate is melamine cyanurate with the particle size of less than or equal to 1um and the preferred diameter of 0.5 um.
The flame-retardant toughening agent is one of phosphorus-containing monomer graft modified polyolefin, phosphorus-containing monomer graft modified ethylene-alpha olefin copolymer, phosphorus-containing monomer graft modified ethylene-propylene rubber and phosphorus-containing monomer graft modified SEBS, wherein the phosphorus-containing monomer is one of 2-hydroxyethyl aminomethylphosphonate, trihydroxymethyl phosphine oxide, oxyphosphate cyclohexane phosphonate, butylated triphenyl thiophosphate and diphenyl thiophosphate, and the butylated triphenyl thiophosphate graft ethylene-alpha olefin copolymer is preferred;
the compatilizer is one of oxazoline, acrylate, epoxy and maleic anhydride grafted polyolefin, and acrylate grafted polyolefin is preferred.
The other auxiliary agents are an antioxidant, a lubricant and black master batch, wherein the antioxidant is one of 1010, 168, 624, 1098 and H10, and 1098 is preferable; the lubricant is one of TAF, EBS, PTFE, polyethylene wax and silicone powder, and the silicone powder is preferred; the black master batch is carbon black master batch.
According to the method, 3 precipitation-resistant halogen-free flame-retardant reinforced nylon materials and comparative examples are prepared by adjusting the specific components and parts, and the specific formula is shown in the following table 1.
Table 1 comparative and 3 example formulations
Comparative example 1 | Example 1 | Example 2 | Example 3 | |
Nylon 6 | 50 | |||
Nylon 66 | 56 | 55 | 30 | |
Glass fiber | 25 | 30 | 25 | 40 |
Red phosphorus master batch | 18 | |||
Modified MCA | 5 | 8 | 10 | |
Oxazoline grafted polyethylene | 0.5 | |||
Acrylate grafted polyethylene | 1 | |||
Maleic anhydride grafted polyethylene | 3 | |||
Oxaphosphorocyclohexane phosphonate grafted polyethylene | 10 | |||
Butylated triphenyl phosphorothioate grafted ethylene-alpha olefin copolymer | 15 | |||
Diphenyl thiophosphate grafted ethylene-propylene rubber | 25 | |||
Antioxidant H10 | 0.5 | 0.5 | ||
Antioxidant 1098 | 0.1 | 0.4 | ||
Silicone powder | 0.5 | 0.5 | ||
TAF | 0.2 | 0.6 | ||
Black masterbatch | 0.7 | 1 | 2 |
The performance results of the above comparative and examples are shown in the following table:
table 2 table of properties of examples of products according to the invention
Through the tables, the material obviously has higher strength, modulus, heat distortion temperature and impact property when V0-grade flame retardance is realized, and the material is derived from the maintenance of the good performance of the material on the reinforced material, and the characteristics enable the material to meet the requirements of electronic and electrical use.
The product of comparative example 1 above, example 1 of the present invention, was tested for resistance to precipitation by the following method: the two products were left alone in an environment of 85 ℃ and 95% humidity for 10 days, and the precipitation resistance of the product surface was observed after 10 days, and the results are shown in fig. 1 and fig. 2, where the comparison shows that: the product of example 1 had no sweating on the surface, while the product of comparative example 1 had sweating on the surface, and it can be seen that the product of example 1 had a significantly better precipitation resistance than the product of comparative example 1
The product of the comparative example 1 and the embodiment 1 of the invention is subjected to an electrode copper sheet corrosion resistance test, and the method comprises the following steps: the two products are respectively placed in an environment with 100 ℃ and 85% humidity for 5 days, and the corrosion condition of the surface of the product is observed after 5 days, and the results are shown in fig. 3 and fig. 4, the comparison shows that the sheet electrode of the example 1 has no corrosion, while the sheet electrode of the comparative example 1 has quite serious corrosion, and the corrosion resistance of the product of the example 1 is obviously better than that of the comparative example 1.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any equivalent changes or modifications made by those skilled in the art according to the spirit of the present invention should be covered within the scope of the present invention.
Claims (13)
1. The precipitation-resistant halogen-free flame-retardant reinforced nylon material is characterized by comprising the following components in parts by weight:
30-55 parts of nylon
25-40 parts of glass fiber
5-10 parts of modified melamine cyanurate
0.5 to 3 portions of compatilizer
10-25 parts of flame-retardant toughening agent
1-3 parts of other auxiliary agents.
2. The precipitation-resistant halogen-free flame-retardant reinforced nylon material as claimed in claim 1, wherein: the surface-modified melamine cyanurate is prepared by the following method: firstly, dissolving 1-10 parts of surface modifier in absolute ethyl alcohol to obtain a surface modifier solution; then adding 90-99 parts of melamine cyanurate into a high-speed mixer at 40-100 ℃, adding the surface modifier solution obtained in the above step until the absolute ethyl alcohol is completely volatilized, raising the temperature to 190 ℃ and continuously mixing for 5-35 min; obtaining the surface modified melamine cyanurate.
3. The precipitation-resistant halogen-free flame-retardant reinforced nylon material as claimed in claim 2, wherein:
the surface modifier is one of epoxy resin, tetrahydrophthalic anhydride, polyamide polyamine epichlorohydrin, adipic acid dihydrazide and N-aminoethyl piperazine.
4. The precipitation-resistant halogen-free flame-retardant reinforced nylon material as claimed in claim 3, wherein:
the surface modifier is polyamide polyamine epichlorohydrin.
5. The precipitation-resistant halogen-free flame-retardant reinforced nylon material as claimed in claim 1, wherein: the nylon is one of nylon 6 and nylon 66;
the glass fiber is alkali-free glass fiber with the diameter of 10-20 um;
the particle size of the melamine cyanurate salt is less than or equal to 1 um;
the compatilizer is one of oxazoline, acrylate, epoxy and maleic anhydride grafted polyolefin.
6. The precipitation-resistant halogen-free flame-retardant reinforced nylon material as claimed in claim 5, wherein: the nylon is nylon 66;
the glass fiber is alkali-free glass fiber with the diameter of 12 um;
the particle size of the melamine cyanurate salt is 0.5 um;
the compatilizer is acrylate grafted polyolefin.
7. The precipitation-resistant halogen-free flame-retardant reinforced nylon material as claimed in claim 1, wherein: the flame-retardant toughening agent is one of phosphorus-containing monomer graft modified polyolefin, phosphorus-containing monomer graft modified ethylene-alpha olefin copolymer, phosphorus-containing monomer graft modified ethylene propylene rubber and phosphorus-containing monomer graft modified SEBS; wherein the phosphorus-containing monomer is one of 2-hydroxyethyl aminomethyl phosphonate, trihydroxymethyl phosphine oxide, oxyphosphate cyclohexane phosphonate, butylated triphenyl thiophosphate and diphenyl thiophosphate.
8. The precipitation-resistant halogen-free flame-retardant reinforced nylon material as claimed in claim 7, wherein: the flame-retardant toughening agent is a butylated triphenyl thiophosphate grafted ethylene-alpha olefin copolymer.
9. The precipitation-resistant halogen-free flame-retardant reinforced nylon material as claimed in claim 1, 7 or 8, wherein: the flame retardant toughening agent is prepared by the following method: firstly, 10 to 25 parts of phosphorus-containing monomer and 0.1 to 1 part of initiator are blended in a high-speed mixer and then dissolved in acetone; adding the mixed solution into a medium mixer containing 75-90 parts of toughening agent and at the temperature of 40-120 ℃, then fully mixing until acetone is volatilized, respectively recovering acetone and solid mixed materials, adding the mixed materials into an extruder at the temperature of 100-200 ℃, and carrying out extrusion granulation to obtain the phosphorus-containing monomer grafted toughening agent, namely the flame-retardant toughening agent; wherein, the rotating speed of the high-speed mixer is 200-.
10. The precipitation-resistant halogen-free flame-retardant reinforced nylon material as claimed in claim 9, wherein: the initiator is one of cumyl peroxide, potassium persulfate, sodium bisulfite, N-dimethylaniline and cerium sulfate.
11. The precipitation-resistant halogen-free flame-retardant reinforced nylon material as claimed in claim 1, wherein: the other auxiliary agents are an antioxidant, a lubricant and black master batch, wherein the antioxidant is one of 1010, 168, 624, 1098 and H10; the lubricant is one of TAF, EBS, PTFE, polyethylene wax and silicone powder; the black master batch is carbon black master batch.
12. The precipitation-resistant halogen-free flame-retardant reinforced nylon material as claimed in claim 1, wherein: the antioxidant is an antioxidant 1098;
the lubricant is silicone powder.
13. The preparation method of the precipitation-resistant halogen-free flame-retardant reinforced nylon material as recited in any one of claims 1 to 12, characterized in that: the method comprises the following steps:
(1) firstly, dissolving 1-10 parts of surface modifier in absolute ethyl alcohol to obtain a surface modifier solution; then adding 90-99 parts of melamine cyanurate into a high-speed mixer at 40-100 ℃, adding the surface modifier solution obtained in the above step until the absolute ethyl alcohol is completely volatilized, raising the temperature to 190 ℃ and continuously mixing for 5-35 min; obtaining surface modified melamine cyanurate;
(2) blending phosphorus-containing monomers and an initiator in a high-speed mixer, and then dissolving the mixture in acetone; adding the mixed solution into a medium mixer containing a toughening agent and having a temperature of 40-120 ℃, then fully mixing until acetone is volatilized, respectively recovering acetone and solid mixed materials, adding the mixed materials into an extruder at the temperature of 100-200 ℃, and carrying out extrusion granulation to obtain a phosphorus-containing monomer grafted toughening agent, namely the flame retardant toughening agent; wherein the rotating speed of the high-speed mixer is 200-;
(3) 30-55 parts of nylon, 0.5-3 parts of compatilizer, 25-40 parts of glass fiber, 5-10 parts of modified melamine cyanurate, 10-25 parts of flame-retardant toughening agent and 1-3 parts of other auxiliary agents are put into a high-speed mixer for mixing, the mixture is added into a double-screw extruder through a hopper, 25-40 parts of glass fiber are accurately weighed through a weightlessness scale, are introduced into the extruder through a side feeder according to certain weight parts, and are subjected to meshing plasticization, mixing, extrusion, bracing, air drying and granulation to obtain the precipitation-resistant halogen-free flame-retardant reinforced nylon composite material; wherein, the extruder temperature sets up a district to the aircraft nose: 230 ℃ and 320 ℃.
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CN114806164A (en) * | 2022-05-25 | 2022-07-29 | 南京聚隆科技股份有限公司 | Halogen-free flame-retardant PA66 and preparation method thereof |
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