CN111004445B - Low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material and preparation method thereof - Google Patents
Low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material which is prepared from the following components in parts by mass: PP resin: 45-55 parts of ammonium polyphosphate flame-retardant master batch: 40-50 parts of whisker: 0.5-5 parts of ethylene-octene elastomer: 5-10 parts of main antioxidant 1073: 0.1-0.2 parts of auxiliary antioxidant 168: 0.2-0.3 part of anti-dripping agent: 0.2-0.5 parts of lubricant: 0.5-1 part; the invention also discloses a preparation method thereof, which comprises the steps of weighing and mixing the raw materials except the whiskers according to a formula, carrying out melt extrusion granulation by using a double-screw extruder, and adding the whiskers through a side feeding port with a weightless scale in the extrusion process. The polypropylene material prepared by the invention can pass a UL94-5VA2.0 mm-grade flame retardant test, and the product is basically free from warping and has high cost performance.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material and a preparation method thereof.
Background
Polypropylene (PP) is widely used in many fields such as injection molding, film and fiber production as one of five general-purpose resins. However, PP itself is flammable as a plastic, and flame retardant property can be obtained only by flame retardant modification, and a method of adding a flame retardant is usually adopted for the flame retardant modification of PP.
The flame retardants currently used in PP are classified into halogenated flame retardants and halogen-free flame retardants according to the presence or absence of halogen. With the gradual enhancement of environmental protection consciousness of people, toxic substances and dense smoke generated during the combustion of the halogen flame retardant PP have been paid attention by people, and the halogen-free environment-friendly flame retardant used for replacing the halogen flame retardant has been the direction of research of people for a long time and has obtained a plurality of research achievements and successful cases.
In the prior art, the UL94 flame retardant test standard is the most widely used plastic flammability test standard, and with the progress of flame retardant modification technology, the UL94 vertical burning test level cannot meet the increasingly strict requirements of people on polypropylene products, especially in the household appliance industry, and various manufacturers with UL94-5VA levels increasingly serve as the flame retardant standard of products. Chinese patent CN102936371B discloses a halogen-free flame-retardant reinforced polypropylene composite material, which uses a halogen-free phosphorus-nitrogen flame retardant and alkali-free glass fiber as a reinforcing filler, and the prepared polypropylene material can pass UL94-5VA level test. Japanese patent JP6375655B2 discloses a fiber-reinforced polypropylene flame-retardant resin composition, and a polypropylene material prepared by using polypropylene having long chain branches, with glass fibers and carbon fibers as fillers, can also pass the UL94-5VA rating test. The glass fiber used in the two methods is used as a supporting and connecting material to ensure that the UL94-5VA bulk sample cannot be burnt through in the test process, and most manufacturers in the market adopt the method at present. However, the use of glass fibers as fillers significantly reduces the flowability of PP, making molding difficult and sometimes causing fiber floating, which affects the appearance of the product. Meanwhile, the irregular orientation of the glass fiber in the polypropylene matrix can cause the warping of the product, and the assembly and the use of the polypropylene product are seriously affected. In addition, during the processing of the glass fiber reinforced polypropylene, the generation of a large amount of shear heat due to the presence of the glass fiber can cause the decomposition of the phosphorus-nitrogen flame retardant, thereby causing serious obstruction to the processing process.
Therefore, a novel low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material and a preparation method thereof are provided.
Disclosure of Invention
Aiming at the problems, the invention provides a low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material and a preparation method thereof, wherein whiskers growing in a micron-sized single crystal form are used as reinforcing filler, high-impact polypropylene with a long-chain branch structure is matched, an ethylene-octene elastomer is used as a melt strength regulator, an ammonium polyphosphate-based flame-retardant master batch is used as flame-retardant filler, the prepared material can pass an UL942.0mm5VA flame-retardant test, and a molded product is basically non-warped and high in cost performance.
In order to achieve the technical purpose, the invention provides the following technical scheme:
a low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material is prepared from the following components in parts by mass:
polypropylene resin: 45-55 parts of a solvent;
ammonium polyphosphate based flame retardant masterbatch: 40-45 parts of a solvent;
whisker: 0.5-5 parts;
ethylene-octene elastomer: 5-10 parts;
main antioxidant: 0.1-0.2 parts;
auxiliary antioxidant: 0.2-0.3 part;
anti-dripping agent: 0.2 to 0.5 portion.
Lubricant: 0.5-1 part.
Wherein the whisker is at least one of aluminum borate whisker, magnesium sulfate whisker and calcium sulfate whisker. When the aluminum borate whisker is used, the aluminum borate whisker is white acicular, the length is 20-60 mu m, the diameter is 0.5-3 mu m, and the length-diameter ratio is 15: 1-20: 1; preferably, the magnesium sulfate whisker is fibrous, has the length of 15-60 mu m, the diameter of 0.5-1.5 mu m and the length-diameter ratio of 15: 1-20: 1; preferably, the calcium sulfate whisker is fibrous, has the length of 10-90 mu m, the diameter of 1-10 mu m and the length-diameter ratio of 15: 1-20: 1;
the polypropylene resin is high-melt-strength polypropylene with a long branched chain structure, and the higher the melt strength of the polypropylene, the less prone to tearing when a UL94-5VA block sample test is carried out.
The ammonium polyphosphate based flame-retardant master batch is filled with a flame retardant which is prepared from an acid source, a gas source and a carbon source according to the mass ratio (5-6): (0.5-1): (1-1.5). Wherein, the ammonium polyphosphate is an acid source, the melamine is an air source, and the triazine derivative is a carbon source.
The ammonium polyphosphate based flame-retardant master batch takes polypropylene as a carrier, and the effective content is 75-80%.
The ethylene-octene elastomer is an elastomer with excellent fluidity, and has a melt index: 4-10 g/10 min. The addition of the elastomer can play a role in adjusting the body melt strength, and is beneficial to the test of UL94-5VA bulk samples.
The main antioxidant is hindered phenol antioxidant 3, 5-di-tert-butyl-4-hydroxyphenyl propionic acid n-octadecyl ester which has obvious synergistic effect with hindered amine light stabilizer.
The auxiliary antioxidant is phosphate antioxidant tris [2, 4-di-tert-butylphenyl ] phosphite ester which has a synergistic effect with the main antioxidant 1073.
The anti-dripping agent is a pure powder type anti-dripping agent.
The lubricant is N, N' -ethylene bis stearamide EB-FF.
The preparation method of the low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material comprises the following steps:
the method comprises the following steps: mixing polypropylene resin, ammonium polyphosphate flame-retardant master batch, lubricant EB-FF, main antioxidant 1010, auxiliary antioxidant 168 and anti-dripping agent according to a formula proportion, stirring for 3-5 minutes by using a high-speed mixer at the rotating speed of 1000-1500 revolutions per minute, and putting the uniformly stirred material into a double-screw main feed;
step two: the whiskers were fed into a twin-screw extruder from a side feed equipped with a loss-in-weight scale.
Step three: and (3) starting the double-screw extruder, adjusting the temperature and the rotating speed of the double screws, adjusting the feeding speeds of the main feeding and the side feeding, starting vacuum, and extruding and granulating to obtain the low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material.
According to the preparation method of the low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material, a twin-screw extruder is a parallel twin-screw extruder with the ratio of 44: 1-50: 1, the temperature of the extruder is set to be 170-195 ℃, the head is 175-180 ℃, the rotating speed is 250-400 r/min, and the vacuum degree is-0.05-0.9 MPa.
The side feeding system is equipped with a weightlessness scale, and the feeding precision is +/-0.5%.
The material is subjected to mechanical test, and a sample strip meeting the standard is prepared and subjected to tensile property test by referring to an ASTM D638 plastic tensile property test method. And preparing a sample bar meeting the standard and testing the bending property by referring to the standard ASTM D790 which does not strengthen and strengthens the bending property of the plastic and the electric insulating material. And preparing a sample strip meeting the standard and testing the impact property by referring to a standard ASTM D256 plastic impact property testing method. Density measurements were made with reference to standard astm d792 plastic density and relative density test methods. The melt index is measured by reference to the test method of measuring the flow rate of thermoplastics melt with extruded plastics according to standard astm d 1238.
The flame retardant test of the invention refers to the UL94 plastic material flammability performance standard to carry out flame retardant performance test, the sample plate and the sample strip are prepared according to the UL94-5VA standard, the strip sample has the length and the width: 125 plus or minus 5mm 13.0 plus or minus 0.5 mm; bulk sample, length x width: 150 plus or minus 5mm, 2.0 plus or minus 0.05mm in thickness, 965ml/min in methane flow and 125 plus or minus 25mm water column in back pressure.
1) Strip sample test method: the burning is started from the sample angle point, the inner flame is ensured to contact the sample, the burner is inclined by 20 degrees, the burning is carried out for 5 +/-0.5 seconds, and the burning is stopped after 5 times of action. The flame extension, after flame time and whether the cotton was dripping were observed. If particles drop and the sample shrinks or stretches during the combustion process, the burner is adjusted correspondingly to ensure that the inner flame contacts the sample.
2) Test methods for bulk samples: the sample is horizontally held, the flame acts on the center of the bottom surface of the sample, the burner is inclined by 20 +/-5 degrees, and the inner flame contacts the sample. After 5 + 0.5 seconds of action, the combustion was removed and held for 5 + 0.5 seconds, and stopped after 5 actions, and when all afterflame and afterflame had stopped, the sample was observed and recorded as if it had burned through.
The invention has the following beneficial effects:
1) the material provided by the invention has a scientific formula, and the whiskers growing in a micron-sized single crystal form are used as reinforcing filling, and glass fibers are not used as a supporting and connecting material, so that the product warping caused by the irregular orientation of the glass fibers in a polypropylene matrix is avoided;
2) the material provided by the invention adopts polypropylene with a long-chain branch structure, and the higher melt strength is favorable for the melt sag of a UL94-5VA strip sample during testing and the top end tear of a block sample during testing;
3) the invention adopts the ethylene-octene elastomer as the melt strength regulator, which not only can improve the toughness of the material, but also is beneficial to the test of UL94-5VA massive samples.
4) The polypropylene material prepared by the invention can pass a UL94-5VA2.0 mm-grade flame retardant test, and the product is basically free from warping and has high cost performance.
5) The preparation method provided by the invention has the advantages of compact process and easy industrialization.
Drawings
FIG. 1 is a schematic diagram showing a sample state of a product after the material prepared in example 1 is baked at 105 ℃ for 4 h;
FIG. 2 is a schematic diagram showing the sample state of the material prepared in example 2 after being baked at 105 ℃ for 4 h;
FIG. 3 is a schematic diagram showing the sample state of the material prepared in example 3 after baking at 105 ℃ for 4 hours;
FIG. 4 is a schematic representation of the prototype state of the material prepared in comparative example 1 of the present invention after baking at 105 ℃ for 4 hours;
FIG. 5 is a schematic diagram showing the sample state of the material prepared in comparative example 2 of the present invention after baking at 105 ℃ for 4 hours.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention is described in detail below with reference to the accompanying figures 1-5 and the specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way.
Referring to the attached drawings 1-5, the low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material provided by the invention is prepared from the following components in parts by mass:
polypropylene resin: 45-55 parts of a solvent;
ammonium polyphosphate based flame retardant masterbatch: 40-45 parts of a solvent;
whisker: 0.5-5 parts;
ethylene-octene elastomer: 5-10 parts;
main antioxidant: 0.1-0.2 part;
auxiliary antioxidant: 0.2-0.3 part;
anti-dripping agent: 0.2 to 0.5 portion.
Lubricant: 0.5-1 part.
Wherein the whisker is at least one of aluminum borate whisker, magnesium sulfate whisker and calcium sulfate whisker. When the aluminum borate whisker is used, the aluminum borate whisker is white acicular, the length is 20-60 mu m, the diameter is 0.5-3 mu m, and the length-diameter ratio is 15: 1-20: 1; preferably, the magnesium sulfate whisker is fibrous, has the length of 15-60 mu m, the diameter of 0.5-1.5 mu m and the length-diameter ratio of 15: 1-20: 1; preferably, the calcium sulfate whisker is fibrous, has the length of 10-90 mu m, the diameter of 1-10 mu m and the length-diameter ratio of 15: 1-20: 1;
the polypropylene resin is high-melt-strength polypropylene with a long branched chain structure, and the higher the melt strength of the polypropylene, the less prone to tearing when a UL94-5VA block sample test is carried out.
The ammonium polyphosphate based flame-retardant master batch is filled with a flame retardant which is prepared from an acid source, a gas source and a carbon source according to the mass ratio (5-6): (0.5-1): (1-1.5). Wherein, the ammonium polyphosphate is an acid source, the melamine is an air source, and the triazine derivative is a carbon source.
The ammonium polyphosphate based flame-retardant master batch takes polypropylene as a carrier, and the effective content is 75-80%.
The ethylene-octene elastomer is an elastomer with excellent fluidity, and has a melt index: 4-10 g/10 min. The addition of the elastomer can play a role in adjusting the body melt strength, and is beneficial to the test of UL94-5VA bulk samples.
The main antioxidant is hindered phenol antioxidant 3, 5-di-tert-butyl-4-hydroxyphenyl propionic acid n-octadecyl ester which has obvious synergistic effect with hindered amine light stabilizer.
The auxiliary antioxidant is phosphate antioxidant tris [2, 4-di-tert-butylphenyl ] phosphite ester which has a synergistic effect with the main antioxidant 1073.
The anti-dripping agent is a pure powder type anti-dripping agent.
The lubricant is preferably N, N' -ethylene bis stearamide EB-FF.
The preparation method of the low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material comprises the following steps:
the method comprises the following steps: mixing polypropylene resin, ammonium polyphosphate flame-retardant master batch, lubricant EB-FF, main antioxidant 1010, auxiliary antioxidant 168 and anti-dripping agent according to a formula proportion, stirring for 3-5 minutes by using a high-speed mixer at the rotating speed of 1000-1500 revolutions per minute, and putting the uniformly stirred material into a double-screw main feed;
step two: the whiskers were fed into a twin-screw extruder from a side feed equipped with a loss-in-weight scale.
Step three: and (3) starting the double-screw extruder, adjusting the temperature and the rotating speed of the double screws, adjusting the feeding speeds of the main feeding and the side feeding, starting vacuum, and extruding and granulating to obtain the low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material.
According to the preparation method of the low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material, a twin-screw extruder is a parallel twin-screw extruder with the ratio of 44: 1-50: 1, the temperature of the extruder is set to be 170-195 ℃, the head is 175-180 ℃, the rotating speed is 250-400 r/min, and the vacuum degree is-0.05-0.9 MPa.
The side feeding system is equipped with a weightlessness scale, and the feeding precision is +/-0.5%.
The material is subjected to mechanical test, and a sample strip meeting the standard is prepared and subjected to tensile property test by referring to an ASTM D638 plastic tensile property test method. With reference to the standard ASTM D790 for not reinforcing and reinforcing the bendability of plastics and electrically insulating materials, standard-compliant specimens were prepared and subjected to bending property tests. And preparing a sample strip meeting the standard and testing the impact property by referring to a standard ASTM D256 plastic impact property testing method. Density measurements were made with reference to standard astm d792 plastic density and relative density test methods. The melt index is measured by reference to the test method of measuring the flow rate of thermoplastics melt with extruded plastics according to standard astm d 1238.
The flame retardant test of the invention refers to the UL94 plastic material flammability performance standard to carry out flame retardant performance test, the sample plate and the sample strip are prepared according to the UL94-5VA standard, the strip sample has the length and width: 125 plus or minus 5mm 13.0 plus or minus 0.5 mm; bulk sample, length by width: 150 plus or minus 5mm, 2.0 plus or minus 0.05mm in thickness, 965ml/min in methane flow and 125 plus or minus 25mm water column in back pressure.
1) Strip sample test method: the burning is started from the sample angle point, the inner flame is ensured to contact the sample, the burner is inclined by 20 degrees, the burning is carried out for 5 +/-0.5 seconds, and the burning is stopped after 5 times of action. The flame extension, after flame time and whether the cotton was dripping were observed. If particles drop and the sample shrinks or stretches during the combustion process, the burner is adjusted correspondingly to ensure that the inner flame contacts the sample.
2) Test methods for bulk samples: the sample is horizontally held, the flame acts on the center of the bottom surface of the sample, the burner is inclined by 20 +/-5 degrees, and the inner flame contacts the sample. After 5 + 0.5 seconds of action, the combustion was removed and held for 5 + 0.5 seconds, and stopped after 5 actions, and when all afterflame and afterflame had stopped, the sample was observed and recorded as if it had burned through.
Example 1
The low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material provided by the embodiment of the invention is prepared from the following components in parts by weight: 50.5 parts of polypropylene (brand K9026, maurianite), 42.0 parts of ammonium polyphosphate flame-retardant master batch (brand 100MB75PP, Puseofur chemical Co., Ltd., Qingyuan), 5.0 parts of ethylene-octene elastomer (brand 8150, Dow USA), 1 part of aluminum borate whisker (brand NP-BW2, Shanghai Fangzhu composite new material science Co., Ltd.), 0.1 part of main antioxidant (brand 1076, basf), 0.2 part of auxiliary antioxidant (brand 168, basf), 0.5 part of lubricant ethylene bis stearamide (EB-FF, Japan flower King) and 0.2 part of pure powder type anti-dripping agent (brand M532, Japan gold). Specifically, the aluminum borate whisker is white needle-shaped, has the length of 20-60 mu m, the diameter of 0.5-3 mu m and the length-diameter ratio of 15: 1-20: 1.
The preparation method comprises the following steps:
the method comprises the following steps: mixing polypropylene resin, ammonium polyphosphate flame-retardant master batch 100MB75PP, main antioxidant 1076, auxiliary antioxidant 168, EB-FF and anti-dripping agent M532 according to a formula proportion, setting the rotating speed at 400 revolutions per minute, stirring and mixing for 3 minutes, and then adding into a main feed;
step two: putting the aluminum borate whisker into a side feed with a weightlessness scale;
step three: setting the temperature of an extruder to be 170-195 ℃, the rotating speed to be 200 rpm, the vacuum degree to be-0.8 MPa, cooling by a water tank with the water temperature of 25 +/-5 ℃, and granulating to obtain the low-warpage UL94-5 VA-level halogen-free flame-retardant polypropylene material;
step four: putting the particles into a forced air drier, setting the temperature to be 85 ℃, and drying for 3 hours; setting the injection molding temperature to be 180-195 ℃, performing injection molding to obtain a standard sample strip, standing at 23 ℃ and 50% humidity for 48 hours, and testing.
Example 2
The low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material and the preparation method thereof provided by the embodiment of the invention are basically the same as the embodiment 1, and the difference is that the low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material is prepared from the components in the weight parts listed in the table 1, and specifically adopts magnesium sulfate whiskers (brand NP-YW2, Shanghai Pingyun Turke composite New Material science and technology Co., Ltd.). The magnesium sulfate whisker is fibrous, has a length of 15-60 mu m, a diameter of 0.5-1.5 mu m and an aspect ratio of 15: 1-20: 1.
Example 3
The preparation method is the same as that of the embodiment 1, except that the calcium sulfate whisker (trade name NP-M02, Shanghai pelargonium composite new material science and technology Co., Ltd.) is adopted, the shape of the calcium sulfate whisker is fibrous, the length of the calcium sulfate whisker is 10-90 μ M, the diameter of the calcium sulfate whisker is 1-10 μ M, and the length-diameter ratio of the calcium sulfate whisker is 15: 1-20: 1.
Comparative example 1
The preparation method was the same as in example 1 except that no whiskers were used.
Comparative example 2
The preparation method was the same as in example 1, except that alkali-free glass fiber (No. 438G, Mount Tai glass fiber) was used
Examples 1-3, comparative examples 1-2 formulations are as follows in Table 1:
table 1: the specific components and proportions of the various examples
The results of the flame retardant tests of examples 1 to 3 and comparative examples 1 to 2 are shown in the following tables 2 and 3:
table 2 shows the results of the flame retardant tests of the strip samples of examples 1 to 3 and comparative examples 1 to 2UL94-5 VA.
Remarking: NG: nogood, meaning no pass, the same below;
table 3 shows the results of the flame retardant tests of the block samples of examples 1 to 3 and comparative examples 1 to 2UL94-5 VA.
Examples 1-3, comparative examples 1-2 mechanical property comparison Table 4 below:
table 4 shows the mechanical properties of examples 1 to 3 and comparative examples 1 to 2.
As can be seen from the data in tables 2 and 3, the samples with the whiskers can be tested by strip samples and block samples with UL94-5VA2.0mm, while the samples without the whiskers can only be tested by strip samples with UL94-5VA2.0mm, because the flame strength of 5VA level is high, the heat cannot be completely isolated by only relying on the formed carbon of the ammonium polyphosphate flame retardant, the surface which is not in contact with the flame is molten due to the overhigh heat, the melt is torn due to the violent movement of PP molecular chains, and the existence of the whiskers plays a role in stabilizing the carbon layer and simultaneously plays a role in supporting and connecting in the matrix, thereby effectively avoiding the top end tearing. It can also be obtained from the experimental results that the products added with the glass fiber can pass the UL94-5VA2.0mm block sample test, but the strip sample test result is not ideal, which is caused by the wick effect of the glass fiber when the glass fiber is vertically burned. Meanwhile, the decomposition temperature of the ammonium polyphosphate flame retardant is low, and due to the existence of glass fibers, the flame retardant is decomposed due to excessive shear heat during processing, so that the flame retardant efficiency is influenced.
From the data in Table 4, it is clear that the mechanical properties of the samples with whiskers are lower in elongation at break and higher in notched impact strength than those of the samples without whiskers. The mechanical property of the sample added with the glass fiber is greatly improved, which is caused by the excellent reinforcing property of the glass fiber.
As can be seen from fig. 1, the whisker-added sample was almost warp-free after baking at 105 ℃ for 4h, while the glass fiber-added sample was relatively severe in warp due to irregular orientation of the glass fibers in the polypropylene matrix. And the existence of whiskers in the product is more isotropic, thus not causing the product to warp.
It should be noted that, in the above embodiments of the present invention, each component and specific ingredient are not listed, and within the scope of the present invention, the components can be specifically selected according to the needs, and all technical effects described in the present invention can be achieved.
In conclusion, the invention adopts the whiskers growing in the form of micron-sized single crystals as reinforcing filler, matches high-impact polypropylene with a long branched chain structure, assists ethylene-octene elastomer as a melt strength regulator, and uses ammonium polyphosphate-based flame-retardant master batch as flame-retardant filler to prepare the halogen-free environment-friendly polypropylene material which can pass a UL94-5VA2.0mm flame-retardant test, and a molded product is basically not warped and has high cost performance. The above embodiments are only some of the preferred embodiments, and are not intended to limit the embodiments of the present invention, and other variations and modifications may be made on the basis of the above examples. Variations or substitutions by one skilled in the art based on the technical solution of the present invention should be included in the protective scope of the present invention.
Claims (8)
1. A low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material is characterized in that: the composite material is prepared from the following components in parts by mass:
polypropylene resin: 45-55 parts of a solvent;
ammonium polyphosphate based flame retardant masterbatch: 40-45 parts of a solvent;
whisker: 0.5-5 parts;
ethylene-octene elastomer: 5-10 parts;
main antioxidant: 0.1-0.2 parts;
auxiliary antioxidant: 0.2 to 0.3 portion
Anti-dripping agent: 0.2-0.5 part;
lubricant: 0.5-1 part;
the crystal whisker is at least one of magnesium sulfate, calcium sulfate and calcium sulfate crystal whisker, the length-diameter ratio of the crystal whisker is (10-15): 1, the ammonium polyphosphate based flame-retardant master batch takes ammonium polyphosphate as an acid source, melamine as an air source, triazine derivatives as a carbon source and polypropylene as a carrier, and the ammonium polyphosphate based flame-retardant master batch is prepared by banburying and two-stage extrusion and water ring granulation.
2. The low warpage UL94-5VA grade halogen-free flame retardant polypropylene material of claim 1, wherein: the ammonium polyphosphate based flame-retardant master batch is filled with a flame retardant which is prepared from an acid source, a gas source and a carbon source according to the mass ratio (5-6): (0.5-1): (1-1.5), wherein ammonium polyphosphate is used as an acid source, melamine is used as an air source, and triazine derivatives are used as a carbon source.
3. The low warpage UL94-5VA grade halogen-free flame retardant polypropylene material of claim 1, wherein: the polypropylene resin is high-melt-strength polypropylene containing a long branched chain structure.
4. The low warpage UL94-5VA grade halogen-free flame retardant polypropylene material of claim 1, wherein: the ethylene-octene elastomer is an elastomer with excellent fluidity, and has a melt index: 4-10 g/10 min.
5. The low warpage UL94-5VA grade halogen-free flame retardant polypropylene material of claim 1, wherein: the main antioxidant is hindered phenol antioxidant 3, 5-di-tert-butyl-4-hydroxyphenyl propionic acid n-octadecyl ester which has obvious synergistic effect with hindered amine light stabilizer.
6. The low warpage UL94-5VA grade halogen-free flame retardant polypropylene material of claim 1, wherein: the auxiliary antioxidant is phosphate antioxidant tris [2, 4-di-tert-butylphenyl ] phosphite with synergistic effect with the main antioxidant 1073.
7. The low warpage UL94-5VA grade halogen-free flame retardant polypropylene material of claim 1, wherein: the anti-dripping agent is a pure powder type anti-dripping agent, and the lubricant is N, N' -ethylene bis stearamide EB-FF.
8. The preparation method of the low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material according to any one of claims 1 to 7, characterized by comprising the following steps:
the method comprises the following steps: firstly, mixing polypropylene resin, ammonium polyphosphate flame-retardant master batch, a lubricant EB-FF, a main antioxidant 1010, an auxiliary antioxidant 168 and an anti-dripping agent according to a formula proportion, stirring for 3-5 minutes by using a high-speed mixer at the rotating speed of 1000-1500 revolutions per minute, and putting the uniformly stirred materials into a double-screw main feed;
step two: feeding the whiskers into a double-screw extruder from a side feed with a weightless scale;
step three: and (3) starting the double-screw extruder, adjusting the temperature and the rotating speed of the double screws, adjusting the feeding speeds of the main feeding and the side feeding, starting vacuum, and extruding and granulating to obtain the low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material.
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| CN109337210A (en) * | 2018-10-17 | 2019-02-15 | 安庆市泽烨新材料技术推广服务有限公司 | Fire-retardant low warp glass fiber reinforced polypropylene compound material and preparation method thereof |
| CN110467777A (en) * | 2019-08-29 | 2019-11-19 | 会通新材料(上海)有限公司 | A kind of low linear expansion coefficient halogen-free anti-flaming polypropylene material and preparation method thereof |
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| CN108250572A (en) * | 2017-12-28 | 2018-07-06 | 清远市普塞呋磷化学有限公司 | One kind can cross the UL94-5VA high fire-retardances halogen-free environment-friendly flame-proof of resistance to light-heat aging polypropylene material and preparation method thereof |
| CN109337210A (en) * | 2018-10-17 | 2019-02-15 | 安庆市泽烨新材料技术推广服务有限公司 | Fire-retardant low warp glass fiber reinforced polypropylene compound material and preparation method thereof |
| CN110467777A (en) * | 2019-08-29 | 2019-11-19 | 会通新材料(上海)有限公司 | A kind of low linear expansion coefficient halogen-free anti-flaming polypropylene material and preparation method thereof |
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