CN108250566B - Low-warpage halogen-free intumescent flame-retardant long glass fiber reinforced polypropylene composite material and preparation method thereof - Google Patents
Low-warpage halogen-free intumescent flame-retardant long glass fiber reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-warpage halogen-free intumescent flame-retardant long glass fiber reinforced polypropylene composite material and a preparation method thereof. The polypropylene composite material consists of 40-80% of halogen-free flame-retardant master batch and the balance of long glass fiber master batch by mass percent. Simultaneously, the preparation method of the low-warpage halogen-free intumescent flame-retardant long glass fiber reinforced polypropylene composite material is also disclosed. The polypropylene composite material effectively avoids the defects that the flame retardant is easy to agglomerate and the flame retardant performance is reduced when other resin is used as the carrier by adopting a proper flame retardant carrier and a relatively good processing technology; meanwhile, the flame retardant effect is further improved by adding the active nano zinc oxide, and the level of 0.8mmV0 is reached; finally, the warpage of the composite material is obviously improved by adding the alpha nucleating agent with the characteristic of isotropic shrinkage and the filler with the length-to-length ratio lower than that of the glass fiber.
Description
Technical Field
The invention relates to a low-warpage halogen-free intumescent flame-retardant long glass fiber reinforced polypropylene composite material and a preparation method thereof.
Background
The polypropylene is used as a plastic variety with light weight, no toxicity, acid and alkali resistance and relatively low price, and is widely applied to the fields of building, traffic, agriculture and industry. However, polypropylene has an oxygen index of only 17.4%, and is a flammable material. In addition, polypropylene has relatively low mechanical properties, and unless reinforced by fibers, it is difficult to meet some occasions with high requirements on mechanical strength. Therefore, it is necessary to impart flame retardant properties and improve mechanical strength by modification means.
The halogen-free intumescent flame retardant (N-P system) compounded by taking ammonium polyphosphate (APP) as a main raw material has high flame-retardant carbon forming effect, less smoke and low toxicity during combustion, does not generate harmful gas or generate molten drop phenomenon, and accords with the development trend of halogen-free environmental protection, thereby becoming a research hotspot of the academic community and being widely accepted by the industry. However, commercial APP is sensitive to shearing and processing temperatures due to its structural characteristics, and is easily degraded, especially in the presence of glass fibers. In order to effectively exert the advantage of the glass fiber in improving the mechanical property and simultaneously avoid the degradation of an N-P system caused by shear heat, some technicians respectively prepare master batches from the glass fiber and the master batches, and then directly mix the master batches for injection molding, so that a satisfactory effect is obtained.
Although CN1810862A relates to an N-P halogen-free intumescent flame retardant system, the description is very vague, and no relevant implementation example is given. The flame-retardant master batch of CN101418100A has relatively poor flame-retardant effect because the base material of the flame-retardant master batch is HDPE (PE has poor carbon forming property relative to PP, and HDPE is one of the three types of PE which has the most difficult carbon forming property), and the process is relatively complex because the mode of banburying and single screw is adopted. Although the halogen-free flame-retardant long glass fiber reinforced polypropylene composite material described in CN102516667A meets the requirements of the D451333 standard, the thickness of 1.6mm is difficult to reach the V0 level under the UL 94 standard, and in addition, because polypropylene is selected as a carrier of the flame retardant, the processing temperature is relatively high, and the decomposition of the flame retardant and the agglomeration of the flame retardant in the processing process are difficult to avoid. The three published documents do not provide detailed control and explanation for the problems of dimensional instability and relatively easy warping of products caused by the direct injection molding method of mixing the glass fiber master batch and the flame retardant master batch.
Disclosure of Invention
The invention aims to overcome the defects that an N-P master batch is easy to degrade, low in processing efficiency, easy to agglomerate and difficult to disperse in the processing process, and simultaneously solves the problems of size instability and warping caused by a master batch mixing injection molding method, so that the low-warping halogen-free intumescent flame-retardant long glass fiber reinforced polypropylene composite material and the preparation method thereof are provided.
The technical scheme adopted by the invention is as follows:
a low-warpage halogen-free expansion flame-retardant long glass fiber reinforced polypropylene composite material is composed of 40-80% of halogen-free flame-retardant master batch and the balance of long glass fiber master batch by mass percent;
the halogen-free flame-retardant master batch comprises the following raw materials in parts by mass:
the long glass fiber master batch is prepared from the following raw materials in parts by mass:
the length of the halogen-free flame-retardant master batch is 10 mm-12 mm.
The length of the long glass fiber master batch is 10 mm-12 mm.
The propylene-based elastomer is a Vitam elastomer, and the melt index of the Vitam elastomer is more than or equal to 40g/10min at 230 ℃ and 2.16 kg.
The melt index of PP-g-MAH at 230 ℃ and 2.16kg is more than or equal to 100g/10 min.
The grafting rate of the PP-g-MAH is 0.6 to 1.2 percent.
The melt index of the POE-g-MAH at 190 ℃ under 2.16kg is more than or equal to 10g/10 min.
The grafting rate of the POE-g-MAH is 0.6 to 1.2 percent.
The N-P compound flame retardant is an N-P compound flame retardant subjected to surface treatment by a silane coupling agent or melamine formaldehyde resin.
The polypropylene resin is at least one of homopolymerized polypropylene, impact-resistant copolymerized polypropylene and random copolymerized polypropylene resin.
The melt index of the polypropylene resin at 230 ℃ and 2.16kg is more than or equal to 100g/10 min.
The filler is at least one of wollastonite and silicon micropowder.
The mesh number of the filler is at least 1250 meshes.
The hyperbranched polymer is multi-stage branched polyester.
The mass content of ZnO in the active nano zinc oxide is more than or equal to 99.7 percent.
The glass fiber is alkali-free glass fiber which is subjected to surface treatment by a silane coupling agent.
The alpha nucleating agent is a Milliken nucleating agent.
The antioxidant is at least one of antioxidants 1010, 168, 1098, 1075, 1076, 330, 245 and 626.
The lubricant is at least one of polyethylene wax, ethylene bis stearamide, calcium stearate and zinc stearate.
The preparation method of the low-warpage halogen-free intumescent flame-retardant long glass fiber reinforced polypropylene composite material comprises the following steps:
1) preparing halogen-free flame-retardant master batch: weighing raw materials according to the composition of the halogen-free flame-retardant master batch, mixing a propylene-based elastomer, PP-g-MAH, a filler, a hyperbranched polymer, active nano zinc oxide, an antioxidant and a lubricant, adding the mixture into a main feeding port of a double-screw extruder, adding an N-P compound flame retardant from a side feeding port, and performing extrusion granulation to obtain the halogen-free flame-retardant master batch;
2) preparing long glass fiber master batch: weighing the raw materials according to the composition of the long glass fiber master batch, mixing the polypropylene resin, the POE-g-MAH, the alpha nucleating agent, the hyperbranched polymer, the antioxidant and the lubricant, plasticizing by a double-screw extruder, sending to a melt tank to be fused and blended with the glass fiber, drawing, discharging and dicing to obtain the long glass fiber master batch;
3) preparing a polypropylene composite material: and mixing the halogen-free flame-retardant master batch and the long glass fiber master batch, and performing injection molding to obtain the low-warpage halogen-free intumescent flame-retardant long glass fiber reinforced polypropylene composite material.
The invention has the beneficial effects that:
the polypropylene composite material effectively avoids the defects that the flame retardant is easy to agglomerate and the flame retardant performance is reduced when other resin is used as the carrier by adopting a proper flame retardant carrier and a relatively good processing technology; meanwhile, the flame retardant effect is further improved by adding the active nano zinc oxide, and the level of 0.8mmV0 is reached; finally, the warpage of the composite material is obviously improved by adding the alpha nucleating agent with the characteristic of isotropic shrinkage and the filler with the length-to-length ratio lower than that of the glass fiber.
Specifically, the present invention has the following advantages:
1. the propylene-based elastomer Widamei with ultrahigh fluidity and low processing temperature and which does not generate negative effect on the flame retardant effect of the N-P flame retardant is used as a carrier of the flame retardant, so that the stability of the flame retardant master batch in the processing process is ensured;
2. a double-screw extruder with double-step side feeding and an ultra-length-diameter ratio (56:1) is adopted, and the hyperbranched polymer is added for assisting dispersion so as to improve the dispersibility of the flame retardant and further avoid thermal decomposition in the processing process of the flame retardant;
3. adding POE-g-MAH with high fluidity into polypropylene with ultrahigh fluidity to assist hyperbranched polymer, and improving the infiltration degree of the glass fiber surface and the compatibility of the glass fiber surface and the polypropylene matrix;
4. the glass fiber and the N-P flame retardant which are key components in the formula are subjected to surface treatment so as to further reduce the interfacial tension and improve the compatibility between the glass fiber and the N-P flame retardant and the resin;
5. the filler with lower length-to-length ratio than glass fiber and the alpha nucleating agent with isotropic shrinkage are added into the formula, so that the warping and dimensional instability in the injection molding process are reduced.
Detailed Description
A low-warpage halogen-free expansion flame-retardant long glass fiber reinforced polypropylene composite material is composed of 40-80% of halogen-free flame-retardant master batch and the balance of long glass fiber master batch by mass percent;
the halogen-free flame-retardant master batch comprises the following raw materials in parts by mass:
the long glass fiber master batch is prepared from the following raw materials in parts by mass:
preferably, the length of the halogen-free flame-retardant master batch is 10 mm-12 mm.
Preferably, the length of the long glass fiber master batch is 10 mm-12 mm.
Preferably, the propylene-based elastomer is a Widamet elastomer produced by Exxonmobil and having a melt index of not less than 40g/10min at 230 ℃ under 2.16 kg.
Preferably, the melt index of PP-g-MAH is more than or equal to 100g/10min at 230 ℃ and 2.16 kg.
Preferably, the grafting ratio of the PP-g-MAH is 0.6-1.2%.
Preferably, the POE-g-MAH has a melt index of 10g/10min or more at 190 ℃ under 2.16 kg.
Preferably, the POE-g-MAH grafting rate is 0.6-1.2%.
Preferably, the N-P compound flame retardant is an N-P compound flame retardant subjected to surface treatment by a silane coupling agent or melamine formaldehyde resin; further, the N-P compound flame retardant is a commercial product, and the main component of the N-P compound flame retardant is a mixture which is composed of ammonium polyphosphate, pentaerythritol or triazine macromolecules as a carbon forming agent and the like; before use, in order to improve the compatibility and the dispersibility of the N-P compound flame retardant, a silane coupling agent or melamine formaldehyde resin is adopted to treat the surface of the N-P compound flame retardant.
Preferably, the polypropylene resin is at least one of homo-polypropylene, impact co-polypropylene and random co-polypropylene resin.
Preferably, the polypropylene resin has a melt index of 100g/10min or more at 230 ℃ and 2.16 kg.
Preferably, the filler is at least one of wollastonite and fine silica powder.
Preferably, the mesh size of the filler is at least 1250 mesh.
Preferably, the hyperbranched polymer is a multi-stage branched polyester.
Preferably, the mass content of ZnO in the active nano zinc oxide is more than or equal to 99.7 percent; the main function of adding the active nano zinc oxide is to improve the effect of the flame retardant.
Preferably, the glass fiber is an alkali-free glass fiber surface-treated with a silane coupling agent, and has a diameter of 5 to 20 μm.
Preferably, the alpha nucleating agent is a Milliken nucleating agent; compared with the common nucleating agent, the used Milliken nucleating agent has the characteristic of isotropic shrinkage, and the added Milliken nucleating agent aims to further reduce the size deformation brought by glass fibers.
Preferably, the antioxidant is at least one of antioxidants 1010, 168, 1098, 1075, 1076, 330, 245 and 626.
Preferably, the lubricant is at least one of polyethylene wax, ethylene bis stearamide, calcium stearate and zinc stearate.
The preparation method of the low-warpage halogen-free intumescent flame-retardant long glass fiber reinforced polypropylene composite material comprises the following steps:
1) preparing halogen-free flame-retardant master batch: weighing raw materials according to the composition of the halogen-free flame-retardant master batch, mixing a propylene-based elastomer, PP-g-MAH, a filler, a hyperbranched polymer, active nano zinc oxide, an antioxidant and a lubricant, adding the mixture into a main feeding port of a double-screw extruder, adding an N-P compound flame retardant from a side feeding port, and performing extrusion granulation to obtain the halogen-free flame-retardant master batch;
2) preparing long glass fiber master batch: weighing the raw materials according to the composition of the long glass fiber master batch, mixing the polypropylene resin, the POE-g-MAH, the alpha nucleating agent, the hyperbranched polymer, the antioxidant and the lubricant, plasticizing by a double-screw extruder, sending to a melt tank to be fused and blended with the glass fiber, drawing, discharging and dicing to obtain the long glass fiber master batch;
3) preparing a polypropylene composite material: and mixing the halogen-free flame-retardant master batch and the long glass fiber master batch, and performing injection molding to obtain the low-warpage halogen-free intumescent flame-retardant long glass fiber reinforced polypropylene composite material.
Preferably, in the step 1), the processing temperature of the double-screw extruder is 130-160 ℃, the rotating speed of a main machine is 200-400 rpm, and the vacuum degree is more than or equal to 0.08 MPa.
Further, in the step 1), the length-diameter ratio of the twin-screw extruder is 56:1, the twin-screw extruder is provided with 14 sections, the natural exhaust port is positioned at the 6 th section, and the vacuum exhaust port is positioned at the 13 th section; the twin screw extruder contains a two-stage side feed port, wherein the first stage feed port is located at stage 7 and the second stage feed port is located at stage 10.
Preferably, in the step 1), when the N-P compound flame retardant is fed into a double-screw extruder with a double-stage side feeding port, 55-65 wt% of the N-P compound flame retardant is fed into the first-stage feeding port, and the rest N-P compound flame retardant is fed into the second-stage feeding port; further preferably, in the step 1), 60 wt% of the N-P compound flame retardant is added from the first-stage feeding port, and then 40 wt% of the N-P compound flame retardant is added from the second-stage feeding port.
Preferably, in the step 2), the polypropylene resin, the POE-g-MAH and the white oil accounting for 1 per mill of the mass of the polypropylene resin are uniformly mixed, and then the mixture is mixed with the alpha nucleating agent, the hyperbranched polymer, the antioxidant and the lubricant; the purpose of adding the white oil is to adsorb the nucleating agent and the hyperbranched polymer.
Preferably, in the step 2), the length-diameter ratio of the double-screw extruder is (36-44) 1; further preferably, in step 2), the length-to-diameter ratio of the twin-screw extruder is 40: 1.
Preferably, in the step 2), the heating temperature of the melt tank is 250-300 ℃.
Preferably, in the step 3), the injection molding temperature is 190-205 ℃; the injection pressure is 30 MPa-50 MPa.
The present invention will be described in further detail with reference to specific examples. These examples are merely representative descriptions of the present invention, but the present invention is not limited thereto.
The propylene-based elastomer used is of the designation VistamaxxTM6502 and MI of 45g/10min (230 deg.C, 2.16 kg). The polypropylene used was a high-flow homopolypropylene H7900 produced by LG and having an MI of 200g/10min (2.16 kg at 230 ℃). The antioxidant is prepared by compounding 1010 and 168 according to the proportion of 1: 2. Other raw materials used in the following examples are those conventionally commercially available, unless otherwise specified. The test methods used are, unless otherwise specified, conventional or in accordance with relevant standard requirements.
Example 1:
(1) preparing the flame-retardant master batch: 35 parts of VistamaxxTM6502, 5 parts of PP-g-MAH, 8 parts of filler, 0.5 part of hyperbranched polymer, 0.5 part of active nano zinc oxide, 0.4 part of antioxidant and 0.6 part of lubricant, stirring at high speed, mixing uniformly, adding from a main feeding port, adding 50 parts of flame retardant into an extruder from a side feeding port in two times, and finally obtaining particles with the length of 10-12mm, namely flame retardant master batches with the flame retardant content of 50%.
(2) Preparing long glass fiber master batch: firstly, uniformly stirring 44 parts of polypropylene resin, 5 parts of P0E-g-MAH and 1% of white oil (the added purpose is to adsorb a nucleating agent and a hyperbranched polymer), then adding 0.1 part of alpha nucleating agent, 0.3 part of hyperbranched polymer, 0.3 part of antioxidant and 0.3 part of lubricant, uniformly stirring, plasticizing by a double-screw extruder with the length-diameter ratio of 40, then entering a melt tank, then infiltrating and drawing 50 parts of glass fiber from the melt tank, and pelletizing to obtain long glass fiber master batch with the length of 10-12mm and the glass fiber content of 50%.
(3) Preparing a composite material: and (3) uniformly mixing the master batches obtained in the first two steps according to the ratio of 1:1, and performing injection molding to obtain the low-warpage halogen-free intumescent flame retardant long glass fiber reinforced polypropylene composite material in the embodiment 1.
Example 2:
(1) preparing the flame-retardant master batch: 28 parts of VistamaxxTM6502, 5 parts of PP-g-MAH, 5 parts of filler, 0.5 part of hyperbranched polymer, 0.5 part of active nano zinc oxide, 0.4 part of antioxidant and 0.6 part of lubricant, stirring at high speed, mixing uniformly, adding from a main feeding port, then adding 60 parts of flame retardant into an extruder from a side feeding port in two times, and finally obtaining particles with the length of 10-12mm, namely flame retardant master batches with the flame retardant content of 60%.
(2) Preparing long glass fiber master batch: firstly, uniformly stirring 34 parts of polypropylene resin, 5 parts of P0E-g-MAH and 1% of white oil (the added purpose is to adsorb a nucleating agent and a hyperbranched polymer), then adding 0.1 part of alpha nucleating agent, 0.3 part of hyperbranched polymer, 0.3 part of antioxidant and 0.3 part of lubricant, uniformly stirring, plasticizing by a double-screw extruder with the length-diameter ratio of 40, then entering a melt tank, then infiltrating and drawing 60 parts of glass fiber from the melt tank, and pelletizing to obtain long glass fiber master batch with the length of 10-12mm and the glass fiber content of 60%.
(3) Preparing a composite material: and (3) uniformly mixing the master batches obtained in the first two steps according to the ratio of 1:1, and performing injection molding to obtain the low-warpage halogen-free intumescent flame retardant long glass fiber reinforced polypropylene composite material of the embodiment 2.
Example 3:
(1) preparing the flame-retardant master batch: 28 parts of VistamaxxTM6502, 5 parts of PP-g-MAH, 5 parts of filler, 0.5 part of hyperbranched polymer, 0.5 part of active nano zinc oxide, 0.4 part of antioxidant and 0.6 part of lubricant, stirring at high speed, mixing uniformly, adding from a main feeding port, then adding 60 parts of flame retardant into an extruder from a side feeding port in two times, and finally obtaining particles with the length of 10-12mm, namely flame retardant master batches with the flame retardant content of 60%.
(2) Preparing long glass fiber master batch: firstly, uniformly stirring 44 parts of polypropylene resin, 5 parts of P0E-g-MAH and 1% of white oil (the added purpose is to adsorb a nucleating agent and a hyperbranched polymer), then adding 0.1 part of alpha nucleating agent, 0.3 part of hyperbranched polymer, 0.3 part of antioxidant and 0.3 part of lubricant, uniformly stirring, plasticizing by a double-screw extruder with the length-diameter ratio of 40, then entering a melt tank, then infiltrating and drawing 50 parts of glass fiber from the melt tank, and pelletizing to obtain long glass fiber master batch with the length of 10-12mm and the glass fiber content of 50%.
(3) Preparing a composite material: and (3) uniformly mixing the master batches obtained in the first two steps according to the ratio of 1:1, and performing injection molding to obtain the low-warpage halogen-free intumescent flame retardant long glass fiber reinforced polypropylene composite material in the embodiment 3.
Comparative example 1:
the only difference between the process and example 1 is that the carrier resin of the flame retardant masterbatch was replaced by HDPE SH4502(MI 45g/10min, 190 ℃ C. 2.16 kg).
Comparative example 2:
the only difference between the process and example 1 is that the carrier resin of the flame retardant masterbatch was replaced with LDPE MG70(MI 70g/10min, 190 ℃ 2.16 kg).
Comparative example 3:
the method is different from the embodiment 1 in that the carrier resin of the flame-retardant master batch is replaced by the high-fluidity polypropylene H7900 which is the same as the long glass fiber master batch, the processing temperature of the flame-retardant master batch is 165-180 ℃, and other processes are consistent.
Comparative example 4:
the only difference between the method and the method in example 1 is that no hyperbranched polymer is added to both master batches.
Comparative example 5:
the only difference between the method and the embodiment 3 is that the flame-retardant master batch is not added with the active nano zinc oxide.
Comparative example 6:
the only difference between the method and the embodiment 1 is that the common alpha nucleating agent (without isotropic shrinkage) is added into the long glass fiber master batch.
Comparative example 7:
the method is mainly different from the method in example 1 in that no filler is added into the flame-retardant master batch (the content of the flame retardant is 50%), and no alpha nucleating agent is added into the long glass fiber master batch (the content of the long glass fiber is 50%).
Comparative example 8:
the method is mainly different from the embodiment 1 in that the flame-retardant master batch (the content of the flame retardant is 50 percent) is fed by only one-order side, and other process parameters are consistent with those of the embodiment 1.
The main performance and warpage comparison results of the polypropylene materials of examples 1 to 3 and comparative examples 1 to 8 are shown in Table 1.
TABLE 1 comparison of the Properties of the Polypropylene materials of the examples and comparative examples
From a summary of the test data in table 1 it can be seen that: the preparation method has the advantages that a proper flame retardant carrier, namely Widamei, is adopted, has obvious advantages compared with PP and PE (embodiment 1 and comparative examples 1-3), and overcomes the defects that the PE has low carbon forming effect during flame retardance and PP processing temperature is higher so as to cause flame retardant decomposition. In addition, the dispersion effect of the flame retardant is better by adding the hyperbranched polymer and adopting two-stage side feeding compared with the traditional feeding or first-stage side feeding (example 1, comparative example 4 and comparative example 8). By introducing the active nano zinc oxide, the flame-retardant synergistic effect is obviously achieved (example 3 and comparative example 5). Finally, the warpage of the composite was significantly improved by the addition of an alpha nucleating agent with isotropic shrinkage characteristics and a filler with a lower length to length ratio than the glass fiber (example 1 and comparative examples 6 and 7).
Therefore, the low-warpage halogen-free intumescent flame retardant long glass fiber reinforced polypropylene composite material obtained by the invention not only effectively solves warpage caused by batch mixing and injection molding of traditional master batches, but also well solves the problems that the flame retardant efficiency of the flame retardant is reduced and the flame retardant is easy to agglomerate due to improper carrier or processing technology of the flame retardant.
The above detailed description of the present invention is only a preferred embodiment of the present invention, and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (8)
1. The low-warpage halogen-free expansion flame-retardant long glass fiber reinforced polypropylene composite material is characterized in that: the flame-retardant glass fiber master batch is composed of 40-80% of halogen-free flame-retardant master batch and the balance of long glass fiber master batch by mass percent;
the halogen-free flame-retardant master batch comprises the following raw materials in parts by mass:
20-35 parts of a propylene-based elastomer;
4-6 parts of PP-g-MAH;
40-65 parts of an N-P compound flame retardant;
4-8 parts of a filler;
0.3-0.5 part of hyperbranched polymer;
0.3-0.5 part of active nano zinc oxide;
0.3-0.5 part of antioxidant;
0.4-0.6 part of a lubricant;
the long glass fiber master batch is prepared from the following raw materials in parts by mass:
30-50 parts of polypropylene resin;
5-8 parts of POE-g-MAH;
45-60 parts of glass fiber;
0.03-0.1 part of alpha nucleating agent;
0.1-0.5 part of hyperbranched polymer;
0.2-0.5 part of antioxidant;
0.2-0.5 part of a lubricant;
the propylene-based elastomer is a Vitamet elastomer, and the melt index of the Vitamet elastomer is more than or equal to 40g/10min at 230 ℃ under 2.16 kg; the melt index of PP-g-MAH at 230 ℃ and 2.16kg is more than or equal to 100g/10 min; the grafting rate of the PP-g-MAH is 0.6-1.2%; the melt index of the POE-g-MAH at 190 ℃ under 2.16kg is more than or equal to 10g/10 min; the grafting rate of the POE-g-MAH is 0.6-1.2%;
the alpha nucleating agent is a Milliken nucleating agent;
the preparation method of the halogen-free flame-retardant master batch comprises the following steps: mixing a propylene-based elastomer, PP-g-MAH, a filler, a hyperbranched polymer, active nano zinc oxide, an antioxidant and a lubricant, adding the mixture into a main feeding port of a double-screw extruder, adding an N-P compound flame retardant from a side feeding port, and performing extrusion granulation to obtain halogen-free flame-retardant master batches;
the double-screw extruder is provided with 14 sections and comprises a double-stage side feeding port, wherein the first-stage feeding port is positioned at the 7 th section, and the second-stage feeding port is positioned at the 10 th section; when the N-P compound flame retardant is fed into a double-screw extruder with a double-stage side feeding port, 55-65 wt% of the N-P compound flame retardant is fed into the first-stage feeding port, and the rest N-P compound flame retardant is fed into the second-stage feeding port.
2. The low-warpage halogen-free expansion flame-retardant long glass fiber reinforced polypropylene composite material according to claim 1, wherein: the length of the halogen-free flame-retardant master batch is 10 mm-12 mm; the length of the long glass fiber master batch is 10 mm-12 mm.
3. The low-warpage halogen-free expansion flame-retardant long glass fiber reinforced polypropylene composite material according to claim 1, wherein: the N-P compound flame retardant is an N-P compound flame retardant subjected to surface treatment by a silane coupling agent or melamine formaldehyde resin.
4. The low-warpage halogen-free expansion flame-retardant long glass fiber reinforced polypropylene composite material according to claim 1, wherein: the polypropylene resin is at least one of homopolymerized polypropylene, impact-resistant copolymerized polypropylene and random copolymerized polypropylene resin; the melt index of the polypropylene resin at 230 ℃ and 2.16kg is more than or equal to 100g/10 min.
5. The low-warpage halogen-free expansion flame-retardant long glass fiber reinforced polypropylene composite material according to claim 1, wherein: the filler is at least one of wollastonite and silicon micropowder; the mesh number of the filler is at least 1250 meshes.
6. The low-warpage halogen-free expansion flame-retardant long glass fiber reinforced polypropylene composite material according to claim 1, wherein: the hyperbranched polymer is multi-stage branched polyester; the mass content of ZnO in the active nano zinc oxide is more than or equal to 99.7 percent; the glass fiber is alkali-free glass fiber which is subjected to surface treatment by a silane coupling agent.
7. The low-warpage halogen-free expansion flame-retardant long glass fiber reinforced polypropylene composite material according to claim 1, wherein: the antioxidant is at least one of antioxidants 1010, 168, 1098, 1076, 330, 245 and 626; the lubricant is at least one of polyethylene wax, ethylene bis stearamide, calcium stearate and zinc stearate.
8. The preparation method of the low-warpage halogen-free intumescent flame retardant long glass fiber reinforced polypropylene composite material as claimed in any one of claims 1 to 7, is characterized in that: the method comprises the following steps:
1) preparing halogen-free flame-retardant master batch: weighing raw materials according to the composition of the halogen-free flame-retardant master batch of claim 1, mixing a propenyl elastomer, PP-g-MAH, a filler, a hyperbranched polymer, active nano zinc oxide, an antioxidant and a lubricant, adding the mixture into a main feeding port of a double-screw extruder, adding an N-P compound flame retardant from a side feeding port, and performing extrusion granulation to obtain the halogen-free flame-retardant master batch;
2) preparing long glass fiber master batch: weighing the raw materials according to the composition of the long glass fiber master batch of claim 1, mixing the polypropylene resin, the POE-g-MAH, the alpha nucleating agent, the hyperbranched polymer, the antioxidant and the lubricant, plasticizing by a double-screw extruder, delivering to a melt tank to be melted and blended with the glass fiber, drawing, discharging and dicing to obtain the long glass fiber master batch;
3) preparing a polypropylene composite material: and mixing the halogen-free flame-retardant master batch and the long glass fiber master batch, and performing injection molding to obtain the low-warpage halogen-free intumescent flame-retardant long glass fiber reinforced polypropylene composite material.
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| CN110760126A (en) * | 2018-07-27 | 2020-02-07 | 中国石油化工股份有限公司 | Heat-resistant impact-resistant polypropylene composition and preparation method thereof |
| CN109971071B (en) * | 2019-04-02 | 2021-05-11 | 金旸（厦门）新材料科技有限公司 | Polypropylene composite material for water purifier filter bottle shell, preparation method and application |
| CN110079009B (en) * | 2019-04-03 | 2021-08-17 | 广东聚石化学股份有限公司 | Halogen-free flame-retardant polypropylene composite material with ultrahigh fluidity and preparation method thereof |
| CN111138755A (en) * | 2019-12-25 | 2020-05-12 | 江苏金发科技新材料有限公司 | Low-density low-dielectric polypropylene composite material and preparation method thereof |
| CN112063092B (en) * | 2020-09-18 | 2021-09-14 | 湖南大学 | High-toughness long glass fiber reinforced random copolymerization polypropylene composite material and preparation method thereof |
| CN112175336A (en) * | 2020-09-23 | 2021-01-05 | 句容市百事特复合材料有限公司 | Halogen-free flame-retardant long glass fiber PP composite material and preparation method thereof |
| CN112778599B (en) * | 2020-12-24 | 2023-02-21 | 武汉金发科技有限公司 | Flame-retardant reinforced polyolefin composite material applied to dung leaking plate |
| CN114015164A (en) * | 2021-11-25 | 2022-02-08 | 安庆会通新材料有限公司 | Flame-retardant polypropylene material and preparation method thereof |
| CN114181457A (en) * | 2021-12-14 | 2022-03-15 | 安庆会通新材料有限公司 | Halogen-free flame-retardant master batch, preparation method thereof and reinforced polypropylene composite material |
| CN114854133B (en) * | 2022-04-26 | 2024-04-09 | 会通新材料股份有限公司 | Halogen-free flame-retardant long glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN116199976A (en) * | 2022-10-19 | 2023-06-02 | 青岛海纳新材料有限公司 | Halogen-free flame-retardant glass fiber reinforced polypropylene composite material for 5G |
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