CN110669333A - Flame-retardant nylon material and preparation method thereof - Google Patents
Flame-retardant nylon material and preparation method thereof Download PDFInfo
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- CN110669333A CN110669333A CN201911093723.XA CN201911093723A CN110669333A CN 110669333 A CN110669333 A CN 110669333A CN 201911093723 A CN201911093723 A CN 201911093723A CN 110669333 A CN110669333 A CN 110669333A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention provides a flame-retardant nylon material which is prepared from the following raw materials in parts by weight: 40-50 parts of nylon resin, 15-30 parts of flame retardant, 0.6-1 part of antioxidant, 0.5-1.5 parts of lubricant, 1-5 parts of flexibilizer, 0.3-1.5 parts of laser etching powder, 20-40 parts of glass fiber, 10-30 parts of talcum powder and 0.5-1 part of toner. The flame-retardant nylon material provided by the invention has more excellent comprehensive performances such as flame retardance, mechanical properties and the like, and has the advantages of production safety, flexible dyeable selectivity and good appearance.
Description
Technical Field
The invention belongs to the technical field of composite materials, particularly relates to a flame-retardant nylon material and a preparation method thereof, and particularly relates to a flame-retardant nylon material which has good appearance and can be used for laser engraving and a preparation method thereof.
Background
Polyamide is commonly known as Nylon (Nylon), and is called Polyamide (PA for short) in English, and is a general name of thermoplastic resin containing repeated amide groups- [ NHCO ] -on a molecular main chain, and comprises aliphatic PA, aliphatic-aromatic PA and aromatic PA. Among them, aliphatic PA has many varieties, large yield, and wide application, and its nomenclature is determined by the specific carbon atom number of the synthetic monomer. Because polyamide has non-toxicity, light weight, excellent mechanical strength, wear resistance and better corrosion resistance, the polyamide is widely applied to the manufacture of bearings, gears, pump blades and other parts in the industries of machinery, chemical industry, instruments, automobiles and the like instead of metals such as copper, but because the polyamide has the characteristics of flammability, low notch impact and the like, the polyamide is often required to be modified so as to be suitable for wider fields.
Disclosure of Invention
The invention aims to provide a flame-retardant nylon material with good appearance and capable of being laser engraved and a preparation method thereof, and aims to solve the problems of flammability and low notch impact of the conventional nylon material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a flame-retardant nylon material, which is prepared from the following raw materials in parts by weight:
the second aspect of the invention provides a preparation method of a flame-retardant nylon material, which comprises the following steps:
providing nylon resin, toner, an antioxidant, a toughening agent, talcum powder, glass fiber, a lubricant, a flame retardant and laser etching powder according to a raw material formula of the flame-retardant nylon material;
feeding nylon resin, toner, an antioxidant, a toughening agent, talcum powder, a lubricant, a flame retardant and radium carving powder from a main feeding port, and uniformly mixing; feeding glass fiber from a side feeding port, extruding and granulating by an extruder, and carrying out water cooling, traction and grain cutting to prepare the flame-retardant nylon material with good appearance and capable of being used for laser engraving.
The flame-retardant nylon material provided by the invention adopts 15-30 parts of flame retardant, 0.6-1 part of antioxidant, 0.5-1.5 parts of lubricant, 1-5 parts of flexibilizer, 20-40 parts of glass fiber, 10-30 parts of talcum powder and 0.5-1 part of toner to carry out composite modification on 30-50 parts of nylon resin, so that the flame retardant property and notch impact property of the obtained nylon material are improved, and the appearance of the nylon material is improved. Specifically, 1-5 parts of toughening agent and 20-40 parts of glass fiber are simultaneously added into the nylon material, so that the notch impact performance of the nylon material can be obviously improved; the nylon material is endowed with good flame retardant performance by adding 5-30 parts of flame retardant into the nylon material; by adding 10-30 parts of talcum powder into the nylon material, the appearance problems of floating fibers and left marks caused by the introduction of glass fibers and flame retardants (with the problem of fluidity) can be remarkably improved, so that the appearance of the nylon material is improved. In addition, as 0.3-1.5 parts of laser etching powder is added into the composite material, the nylon material can be endowed with a clear laser etching effect, so that the nylon material can be flexibly subjected to laser printing according to the requirements of products, and if white black printing or black white printing can be realized, the nylon material can be suitable for different types of laser coding machines. In conclusion, the flame-retardant nylon material provided by the invention has more excellent comprehensive performances such as flame retardance, mechanical property and the like, and has the advantages of production safety, flexible dyeable selectivity and good appearance.
According to the preparation method of the flame-retardant nylon material, the raw material components except the glass fiber in the formula amount are mixed, the glass fiber is fed from a side feeding port, the glass fiber is extruded and granulated by an extruder, and the flame-retardant nylon material with good appearance and capable of being laser engraved can be prepared through water cooling, traction and grain cutting.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The first aspect of the embodiment of the invention provides a flame-retardant nylon material, which is prepared from the following raw materials in parts by weight:
the flame-retardant nylon material provided by the embodiment of the invention adopts 15-30 parts of flame retardant, 0.6-1 part of antioxidant, 0.5-1.5 parts of lubricant, 1-5 parts of toughening agent, 20-40 parts of glass fiber, 10-30 parts of talcum powder and 0.5-1 part of toner to carry out composite modification on 30-50 parts of nylon resin, so that the flame retardant property and notch impact property of the obtained nylon material are improved, and the appearance of the nylon material is improved. Specifically, 1-5 parts of toughening agent and 20-40 parts of glass fiber are simultaneously added into the nylon material, so that the notch impact performance of the nylon material can be obviously improved; the nylon material is endowed with good flame retardant performance by adding 5-30 parts of flame retardant into the nylon material; by adding 10-30 parts of talcum powder into the nylon material, the appearance problems of floating fibers and left marks caused by the introduction of glass fibers and flame retardants (with the problem of fluidity) can be remarkably improved, so that the appearance of the nylon material is improved. In addition, as 0.3-1.5 parts of laser etching powder is added into the composite material, the nylon material can be endowed with a clear laser etching effect, so that the nylon material can be flexibly subjected to laser printing according to the requirements of products, and if white black printing or black white printing can be realized, the nylon material can be suitable for different types of laser coding machines. In conclusion, the flame-retardant nylon material provided by the invention has more excellent comprehensive performances such as flame retardance, mechanical property and the like, and has the advantages of production safety, flexible dyeable selectivity and good appearance.
The nylon resin is used as a matrix component of the nylon material, is light and nontoxic, and endows the nylon material with excellent mechanical strength, wear resistance and better corrosion resistance. In some embodiments, the nylon resin is selected from one or more of PA6, PA66, MXD 6. When preparing nylon products, the specific nylon material can be selected according to different use conditions, for example, when preparing high temperature resistant nylon products, MXD6 is preferably used. In the examples of the present application, the addition amount of each component is based on the content of the nylon resin, and in some specific examples, the content of the nylon resin may be 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, and other specific parts by weight.
The antioxidant is used for improving the oxidation resistance of a nylon material, particularly nylon resin, so that the service life and the service performance of the nylon material are improved. In some embodiments, the antioxidant is selected from a complex antioxidant consisting of a hindered phenol antioxidant and a phosphite antioxidant, and the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant in the complex antioxidant is 1: 0.5-2. In some embodiments, the antioxidant may be present in an amount of 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 part, etc. by weight.
The flame retardant is used as a functional component of the nylon material and endows the nylon material with flame retardant property. In some embodiments, the flame retardant is a composite flame retardant formed by compounding decabromodiphenylethane and antimony trioxide. Decabromodiphenylethane (BPS) and antimony trioxide (Sb)2O3) The formed composite flame retardant not only meets the environmental protection requirement specified by Rohs, but also more importantly, the two flame retardants with different properties play a synergistic effect, and the flame retardant efficiency can be obviously improved. In addition, the composite flame retardant formed by compounding decabromodiphenylethane and antimony trioxide can reduce the addition of the flame retardant, thereby reducing the influence of the flame retardant on the physical properties of nylon products and improving the physical properties of the nylon products. In some embodiments, the flame retardant may be present in an amount of 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, etc. by weight.
The lubricant is added into the nylon material in order to improve the processing performance of the nylon material because more materials are compounded in the nylon resin. In some embodiments, the lubricant is selected from one or more of oxidized polyethylene wax, silicone, hyperbranched polymer, calcium stearate, which can allow smoother processing, reduce material decomposition by shear heat, and provide a smoother particle appearance. In some embodiments, the lubricant may be present in an amount of 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, etc. by weight.
The function of adding the toughening agent into the nylon material is used for improving the mechanical property of the material. In some embodiments, the toughening agent is selected from polyoctene-maleic anhydride grafts and/or ethylene-ethyl acrylate copolymers. The polyoctene-maleic anhydride graft and/or the ethylene-ethyl acrylate copolymer are used as toughening agents, so that the impact resistance of the product can be improved. In some embodiments, the toughening agent may be present in an amount of 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, and the like, by weight.
In the embodiment of this application, add radium carving powder in the nylon materials for the nylon materials has clear radium carving effect, and can print in a flexible way according to the needs of nylon products, if can go black by white, also can go white by black, and the nylon materials after adding radium carving powder can be applicable to the laser of different grade type and beat the sign indicating number ware moreover. In some embodiments, the laser etching powder is selected from one or both of merck black and white 8835 and black and white 8208. In some embodiments, the laser etching agent can be present in an amount of 0.3 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, etc. by weight.
The glass fiber is added into the nylon material, so that the mechanical strength, particularly the notch impact strength, of the nylon material can be enhanced. In some embodiments, the glass fibers are chopped glass fibers. The chopped glass fiber is more beneficial to processing, and meanwhile, the comprehensive performance of the product is more excellent. Preferably, the chopped glass fiber is selected from one or more of a boulder 568H type, a Mount Taishan T435TM type and Chongqing Compound International 301CL type. In some embodiments, the glass fibers can be present in an amount of 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, etc. by weight.
Since glass fibers and flame retardants having poor flowability are added to nylon materials, problems such as fiber floating and marking are easily caused when nylon is manufactured into products, and the appearance of the nylon products is affected. According to the embodiment of the application, the talcum powder is introduced into the nylon material, so that the appearance problems of floating fibers, left marks and the like caused by the flowability problems of the glass fibers and the flame retardant are improved, and the nylon product is endowed with an excellent appearance. In some embodiments, the talc is selected from talc having a mesh size of 1000 mesh to 3000 mesh. The talcum powder with the particle size within the range is more beneficial to improving appearance problems such as fiber floating and trace caused by fluidity problems of glass fiber and flame retardant, and improving appearance of the nylon product. Specifically, the mesh number of the talcum powder can be 1000 meshes, 1500 meshes, 2000 meshes, 2500 meshes and 3000 meshes. In some embodiments, the talc powder may be present in an amount of 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, and the like, by weight.
The toner is added into the nylon according to the requirement of the nylon material product. In some embodiments, the toner may be present in an amount of 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, etc. by weight.
In a preferred embodiment, the flame-retardant nylon material is prepared from the following raw materials in parts by weight:
in the best embodiment, the flame-retardant nylon material is prepared from the following raw materials in parts by weight:
the flame-retardant nylon material provided by the embodiment of the invention can be prepared by the following method.
The second aspect of the embodiment of the invention provides a preparation method of a flame-retardant nylon material, which comprises the following steps:
s01, providing nylon resin, toner, an antioxidant, a toughening agent, talcum powder, glass fiber, a lubricant, a flame retardant and laser etching powder according to a raw material formula of the flame-retardant nylon material;
s02, feeding nylon resin, toner, an antioxidant, a toughening agent, talcum powder, a lubricant, a flame retardant and laser etching powder from a main feeding port, and uniformly mixing; feeding glass fiber from a side feeding port, extruding and granulating by an extruder, and carrying out water cooling, traction and grain cutting to prepare the flame-retardant nylon material with good appearance and capable of being used for laser engraving.
According to the preparation method of the flame-retardant nylon material provided by the embodiment of the invention, the raw material components except the glass fiber with the formula amount are mixed, the glass fiber is fed from the side feeding port, the extruder extrudes and granulates, and the flame-retardant nylon material with good appearance and capable of being laser engraved can be prepared through water cooling, traction and grain cutting.
Specifically, in the step S01, the raw material formulation of the flame retardant nylon material and the preferred situation thereof are as described above, and are not described herein again for saving space.
In the step S02, the nylon resin, the toner, the antioxidant, the toughening agent, the talcum powder, the lubricant, the flame retardant and the laser etching powder are fed from the main feeding port and are uniformly mixed. In some embodiments, the high-speed mixer is set to be 800rpm to 1200rpm, and the mixing treatment is carried out for 1min to 5 min. In the specific embodiment, the rotation speed of the high-speed mixer is set to be 1000rpm, and the mixing treatment is carried out for 3 min. Glass fibers have poor flowability and are difficult to disperse when added together with other components. Particularly, on the premise that the mixed material already contains a flame retardant with poor fluidity, the dispersion difficulty of the glass fiber is further increased. Thus, the glass fibers are fed from a side feed port.
And extruding and granulating at the working temperature of 200-290 ℃, and carrying out water cooling, traction and grain cutting to prepare the flame-retardant nylon material with good appearance and capable of being laser engraved.
The following description will be given with reference to specific examples.
Example 1
A flame-retardant nylon material is prepared from the following raw materials in parts by weight shown in example 1 of Table 1.
The preparation method of the flame-retardant nylon material comprises the following steps of uniformly mixing nylon resin, toner, an antioxidant, talcum powder, a lubricant, a flame retardant and radium carving powder in a high-speed mixer according to the weight part ratio, wherein the rotating speed of the high-speed mixer is 1000rpm, and the mixing time is 3 min; and feeding glass fiber from a side feeding port, extruding and granulating, and then carrying out water cooling, traction and grain cutting to obtain the flame-retardant nylon material with good appearance and capable of being laser engraved.
Examples 2-6 and comparative examples 1, 2 each provide a flame retardant nylon material, differing from example 1 in that: the raw material formulations are different, and are specifically shown in the following table 1, examples 2-6 and comparative examples 1-2.
TABLE 1 (Unit: parts by weight)
The flame retardant nylon materials provided in examples 1 to 6 and comparative examples 1 and 2 were subjected to a performance test. The test method comprises the following steps: the obtained nylon material is subjected to injection molding according to the same method to form an ISO sample strip (standing for 48h) and a color plate with the thickness of 2mm, and the color plate is used for testing mechanical properties; appearance evaluation A2 mm light plate was injection molded by the same process with visual observation to compare floating fibers. The specific test methods are shown in table 2 below.
TABLE 2
The test results are shown in table 3 below:
TABLE 3
As can be seen from table 3 above, the nylon product made of the nylon material provided by the embodiment of the present invention has a better appearance, and can maintain a higher comprehensive mechanical property. Specifically, the talcum powder and MXD6 obviously improve the appearance of the system, and the notch impact and the tensile strength of the system are weakened to some extent after the flame retardant is added. The nylon material provided by the embodiment of the invention has good mechanical property and laser etching property, has good appearance and excellent flame retardant property, and meets the requirements of high-strength automobile parts and electronic communication industries.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The flame-retardant nylon material is characterized by being prepared from the following raw materials in parts by weight:
2. the flame-retardant nylon material of claim 1, wherein the antioxidant is selected from a composite antioxidant consisting of a hindered phenol antioxidant and a phosphite antioxidant, and the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant in the composite antioxidant is 1: 0.5-2.
3. The flame-retardant nylon material of claim 1, wherein the flame retardant is a composite flame retardant formed by compounding decabromodiphenylethane and antimony trioxide.
4. The flame retardant nylon material of any one of claims 1 to 3, wherein the talc is selected from talc having a mesh size of 1000 mesh to 3000 mesh.
5. The flame retardant nylon material of any one of claims 1 to 3, wherein the toughening agent is selected from polyoctene-maleic anhydride grafts and/or ethylene-ethyl acrylate copolymers.
6. The flame retardant nylon material of any one of claims 1 to 3 wherein the glass fibers are chopped glass fibers.
7. The flame retardant nylon material of claim 6, wherein the chopped glass fiber is selected from one or more of boulder 568H, Mount Taishan T435TM, Chongqing composite International 301 CL.
8. The flame retardant nylon material of any one of claims 1 to 3, wherein the laser etching powder is selected from one or two of Merck black and white 8835 and black and white 8208; and/or
The nylon resin is selected from one or more of PA6, PA66 and MXD 6; and/or
The lubricant is selected from one or more of oxidized polyethylene wax, silicone, hyperbranched polymer and calcium stearate.
9. The flame retardant nylon material of any one of claims 1 to 3, wherein the lubricant is selected from one or more of oxidized polyethylene wax, silicone, hyperbranched polymer, and calcium stearate.
10. The preparation method of the flame-retardant nylon material is characterized by comprising the following steps:
providing nylon resin, toner, an antioxidant, a toughening agent, talcum powder, glass fiber, a lubricant, a flame retardant and laser etching powder according to a raw material formula of the flame-retardant nylon material;
feeding nylon resin, toner, an antioxidant, a toughening agent, talcum powder, a lubricant, a flame retardant and radium carving powder from a main feeding port, and uniformly mixing; feeding glass fiber from a side feeding port, extruding and granulating by an extruder, and carrying out water cooling, traction and grain cutting to prepare the flame-retardant nylon material with good appearance and capable of being used for laser engraving.
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Application publication date: 20200110 |