CN108250565B - High-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for coil framework and preparation method thereof - Google Patents
High-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for coil framework and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for a coil framework and a preparation method thereof. The polypropylene composite material consists of 40-60% of flame-retardant master batch and the balance of glass fiber master batch by mass percent. Also discloses a preparation method of the polypropylene composite material. The hyperbranched polymer is added, so that the fluidity of the polypropylene composite material is obviously improved, the spiral flow length is improved, the molding time is shortened, and the processing efficiency is improved. In addition, the bending performance and the processing efficiency of the composite material are obviously improved by adding the alpha nucleating agent with the characteristic of isotropic shrinkage. By introducing active nano zinc oxide and adopting double-stage side feeding, the flame retardant effect of the composite material reaches V0 under the thickness of 0.8 mm. Finally, the POE-g-MAH with high fluidity and the co-polypropylene with high fluidity and high rigidity can play a synergistic role in the bending resistance of the coil skeleton.
Description
Technical Field
The invention relates to a high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for a coil framework and a preparation method thereof.
Background
Coil skeleton in the market, small device, such as electronic transformer, relay, solenoid valve etc. mainly use engineering plastics such as fire-retardant PA, fire-retardant PBT and PPO, however these materials all have the problem with high costs. Meanwhile, nylon materials even have a problem of easy water absorption.
Polypropylene is a substitute material favored by the industry because of its low cost, non-hygroscopic property, and good electrical properties and high-frequency insulation. CN 101875738A discloses a flame-retardant glass fiber reinforced polypropylene composite material used in the field, however, the traditional bromine-antimony flame-retardant system used in the invention does not meet the non-halogenation development trend in the field at present. The flame retardant grade of the halogen-free flame retardant polypropylene special material disclosed by CN103756152A is only V2 grade, and cannot meet the application occasions with higher flame retardant grade requirements.
From the viewpoint of processing, the high fluidity not only means lower production energy consumption and higher production efficiency, but also can avoid the occurrence of wire breakage caused by the poor surfaces of burrs, floating fibers and the like of materials (particularly when the materials contain glass fibers) during injection molding when the coil skeleton is wound. And further, the production cost of enterprises can be reduced, and the competitiveness of products is improved.
The two independent coil frameworks are used in the conventional U-shaped iron core motor, so that when the winding of the coil frameworks is finished and the encapsulation is carried out, due to the fact that the injection molding pressure is high, part of winding on the frameworks is occasionally extruded into a gap between two flanges which are not connected, and the phenomenon that the product is exposed is caused, and further the product is scrapped. In order to reduce the above undesirable situations, CN203674838U discloses a foldable dual-electromagnetic coil bobbin, which well solves the coil exposure phenomenon during encapsulation. This means that the coil skeleton material not only needs to meet the related physical requirements in the industry, but also needs to have good bending resistance at the joint of the two skeletons when the coil skeleton material is injection molded into the skeleton material. Unfortunately, no report on the halogen-free flame-retardant polypropylene composite material with high fluidity and bending resistance for coil frame exists at present.
Disclosure of Invention
The invention aims to provide a high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for a coil framework and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for a coil framework is composed of 40-60% of flame-retardant master batches by mass and the balance of glass fiber master batches;
the flame-retardant master batch comprises the following raw materials in parts by mass:
the glass fiber master batch is prepared from the following raw materials in parts by mass:
the length of the flame-retardant master batch is 3-4 mm.
The length of the glass fiber master batch is 3 mm-4 mm.
The melt index of the polypropylene copolymer at 230 ℃ and 2.16kg is more than or equal to 90g/10 min.
The flexural modulus of the polypropylene copolymer is more than or equal to 1600 MPa.
The melt index of the homopolymerized polypropylene at 230 ℃ and 2.16kg is more than or equal to 100g/10 min.
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 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 nitrogen-phosphorus compound flame retardant is subjected to surface treatment by a silane coupling agent or melamine formaldehyde resin and consists of the following raw materials in parts by mass: 30-50 parts of organic or inorganic hypophosphite coated by silane, 35-50 parts of halogen-free organic phosphate or derivatives thereof coated by melamine formaldehyde resin, and 15-40 parts of melamine cyanurate.
The hyperbranched polymer is multi-stage branched polyester.
The alpha nucleating agent is a Milliken nucleating agent.
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 continuous glass fiber or short glass fiber subjected to surface treatment by a silane coupling 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 high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for the coil framework comprises the following steps:
1) preparing a flame-retardant master batch: weighing the raw materials according to the composition of the flame-retardant master batch, firstly mixing the polypropylene copolymer, the POE-g-MAH, the hyperbranched polymer, the active nano zinc oxide, the antioxidant and the lubricant, adding the mixture into a main feeding port of a double-screw extruder, adding the nitrogen-phosphorus compound flame retardant from a side feeding port, and extruding and granulating to obtain the flame-retardant master batch;
2) preparing glass fiber master batch: weighing raw materials according to the composition of the glass fiber master batch, mixing homo-polypropylene, PP-g-MAH, an alpha nucleating agent, a hyperbranched polymer, an antioxidant and a lubricant, sending the mixture to a double-screw extruder, adding glass fiber at a natural exhaust port or a side feed port of the double-screw extruder, and performing extrusion granulation to obtain the glass fiber master batch;
3) preparing a polypropylene composite material: and mixing the flame-retardant master batches and the glass fiber master batches, and performing injection molding to obtain the high-fluidity bending-resistant halogen-free expansion-resistant flame-retardant glass fiber reinforced polypropylene composite material for the coil framework.
The invention has the beneficial effects that:
the hyperbranched polymer is added, so that the fluidity of the polypropylene composite material is obviously improved, the spiral flow length is improved from 1200mm to 1500mm before adding, the molding time is shortened by 3 seconds, and the processing efficiency is improved by 16.7%. In addition, by adding the alpha nucleating agent with the characteristic of isotropic shrinkage, the bending performance and the processing efficiency of the composite material are obviously superior to those of the composite material without adding or adding a common alpha nucleating agent. By introducing active nano zinc oxide and adopting double-stage side feeding, the flame retardant effect of the composite material reaches V0 under the thickness of 0.8 mm. Finally, the POE-g-MAH with high fluidity and the co-polypropylene with high fluidity and high rigidity can play a synergistic role in the bending resistance of the coil skeleton.
Specifically, the phosphorus-nitrogen compounded halogen-free intumescent flame retardant meeting the current environmental protection development trend, the high-fluidity polypropylene resin, the surface-treated flame retardant and the auxiliary agent for increasing dispersion and improving compatibility are adopted to prepare the flame-retardant master batch through double-screw granulation with super length-diameter ratio. Then, high-fluidity polypropylene is used as base resin, and a compatilizer, a dispersant and a nucleating agent with a size stabilizing effect are matched to prepare the glass fiber master batch. And finally, uniformly mixing the two materials in proportion, and directly performing injection molding to obtain the high-fluidity halogen-free intumescent flame retardant glass fiber reinforced polypropylene composite material for the coil framework. Compared with the prior art, the invention has the following advantages:
1. the preparation method comprises the steps of taking the copolymerized polypropylene with ultrahigh fluidity and high rigidity as a carrier of the flame retardant, carrying out melt blending extrusion in a double-screw extruder with double-stage side feeding and an ultra length-diameter ratio (56:1), and adding the hyperbranched polymer for assisting dispersion so as to improve the dispersion effect of the flame retardant;
2. high-fluidity PP-g-MAH is added into the homo-polypropylene with ultrahigh fluidity to assist the hyperbranched polymer, so that the infiltration degree of the glass fiber surface and the compatibility of the glass fiber surface and a polypropylene matrix are improved;
3. the glass fiber and the compound 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 compound flame retardant and the resin;
4. the alpha nucleating agent with isotropic shrinkage is added into the formula, so that the size instability caused by a master batch mixing method is reduced.
Detailed Description
A high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for a coil framework is composed of 40-60% of flame-retardant master batches by mass and the balance of glass fiber master batches;
the flame-retardant master batch comprises the following raw materials in parts by mass:
the glass fiber master batch is prepared from the following raw materials in parts by mass:
preferably, the length of the flame-retardant master batch is 3 mm-4 mm.
Preferably, the length of the glass fiber master batch is 3 mm-4 mm.
Preferably, the polypropylene copolymer in the flame-retardant master batch is high-fluidity, high-rigidity and high-impact polypropylene copolymer, and the melt index of the polypropylene copolymer at 230 ℃ and 2.16kg is more than or equal to 90g/10 min; the flexural modulus of the polypropylene copolymer is more than or equal to 1600 MPa.
Preferably, the melt index of the homopolymerized polypropylene is more than or equal to 100g/10min at 230 ℃ and 2.16 kg.
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 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 nitrogen-phosphorus compound flame retardant is subjected to surface treatment by a silane coupling agent or melamine formaldehyde resin, and consists of the following raw materials in parts by mass: 30-50 parts of organic or inorganic hypophosphite coated by silane, 35-50 parts of halogen-free organic phosphate or derivatives thereof coated by melamine formaldehyde resin, and 15-40 parts of melamine cyanurate; the nitrogen-phosphorus compound flame retardant is self-prepared by the applicant of the invention, and the specific method can be seen in patent CN 103160025B.
Preferably, the hyperbranched polymer is a multi-stage branched polyester.
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 instability brought by glass fibers and improve the processing efficiency.
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 continuous glass fiber or a short glass fiber surface-treated with a silane coupling agent.
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 high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for the coil framework comprises the following steps:
1) preparing a flame-retardant master batch: weighing the raw materials according to the composition of the flame-retardant master batch, firstly mixing the polypropylene copolymer, the POE-g-MAH, the hyperbranched polymer, the active nano zinc oxide, the antioxidant and the lubricant, adding the mixture into a main feeding port of a double-screw extruder, adding the nitrogen-phosphorus compound flame retardant from a side feeding port, and extruding and granulating to obtain the flame-retardant master batch;
2) preparing glass fiber master batch: weighing raw materials according to the composition of the glass fiber master batch, mixing homo-polypropylene, PP-g-MAH, an alpha nucleating agent, a hyperbranched polymer, an antioxidant and a lubricant, sending the mixture to a double-screw extruder, adding glass fiber at a natural exhaust port or a side feed port of the double-screw extruder, and performing extrusion granulation to obtain the glass fiber master batch;
3) preparing a polypropylene composite material: and mixing the flame-retardant master batches and the glass fiber master batches, and performing injection molding to obtain the high-fluidity bending-resistant halogen-free expansion-resistant flame-retardant glass fiber reinforced polypropylene composite material for the coil framework.
Preferably, in the step 1), the processing temperature of the double-screw extruder is 160-180 ℃, 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 compound flame retardant is fed into a double-screw extruder with a double-stage side feeding port, 55-65 wt% of the compound flame retardant is firstly added from a first-stage feeding port, and then the rest compound flame retardant is added from a second-stage feeding port; further preferably, in the step 1), 60 wt% of the compound flame retardant is added from the first-stage feeding port, and then 40 wt% of the compound flame retardant is added from the second-stage feeding port.
Preferably, in the step 2), the homo-polypropylene, the PP-g-MAH and white oil accounting for 1 per mill of the mass of the homo-polypropylene 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.
Further, in the step 2), when the length-diameter ratio of the twin-screw extruder is 40:1, the natural gas vent is positioned at the 5 th section of the twin-screw extruder, and the side feeding port is positioned at the 6 th section of the twin-screw extruder.
Further, in the step 2), when the glass fiber is alkali-free continuous glass fiber subjected to surface treatment by the silane coupling agent, adding the continuous glass fiber from a natural gas outlet; when the glass fiber is alkali-free short glass fiber subjected to surface treatment by the silane coupling agent, the short glass fiber enters from a side feeding port.
Preferably, in the step 3), the injection molding temperature is 180-200 ℃; 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 high-fluidity, high-rigidity co-polypropylene used was BX3920 produced by SK and had MI of 100g/10min (230 ℃ C. 2.16 kg). The homopolypropylene used was H7900 manufactured by LG in Korea and had an MI of 200g/10min (230 ℃ C. and 2.16 kg). The antioxidant is prepared by compounding 1010 and 168 according to the proportion of 1: 2.
The spiral flow length and the injection molding temperature of the molding cycle test are 185 ℃, and the injection molding pressure is 30-45 Mpa.
The bending angle of the bending resistance evaluation test is 180 ℃, the bending times are 10 times, and the linking part is required to have no fracture and no crack.
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: 33 parts of BX3920, 5 parts of POE-g-MAH, 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 are stirred at a high speed and mixed uniformly, then added from a main feeding port, and then 60 parts of nitrogen-phosphorus compound flame retardant are added into an extruder from a side feeding port in two times, and finally particles with the length of about 3.5mm, namely flame retardant master batches with the flame retardant content of 60%, are obtained.
(2) Preparing the glass fiber master batch: firstly, uniformly stirring 44 parts of H7900, 5 parts of PP-g-MAH and 1% of white oil (the added aims are 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, and then regulating the length-diameter ratio to be 40:1, adding continuous glass fiber into a natural exhaust port (section 5) or adding short glass fiber into a side feeding port (section 6) after plasticizing the double-screw extruder, and finally obtaining the glass fiber master batch with the length of about 3.5mm and the glass fiber content of 50 percent.
(3) Preparing a composite material: and (3) uniformly mixing the master batches obtained in the first two steps according to a ratio of 1:1, and performing injection molding to obtain the high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for the coil framework in the embodiment 1.
Example 2:
(1) preparing the flame-retardant master batch: 33 parts of BX3920, 5 parts of POE-g-MAH, 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 are stirred at a high speed and mixed uniformly, then added from a main feeding port, and then 60 parts of nitrogen-phosphorus compound flame retardant are added into an extruder from a side feeding port in two times, and finally particles with the length of about 3.5mm, namely flame retardant master batches with the flame retardant content of 60%, are obtained.
(2) Preparing the glass fiber master batch: firstly, uniformly stirring 34 parts of H7900, 5 parts of PP-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, and then regulating the length-diameter ratio to be 40:1, adding continuous glass fiber into a natural exhaust port (section 5) or adding short glass fiber into a side feeding port (section 6) after plasticizing the double-screw extruder, and finally obtaining the glass fiber master batch with the length of about 3.5mm and the glass fiber content of 60 percent.
(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 high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for the coil framework in the embodiment 2.
Example 3:
(1) preparing the flame-retardant master batch: 27 parts of BX3920, 6 parts of POE-g-MAH, 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 are stirred at a high speed and mixed uniformly, then added from a main feeding port, and then 65 parts of nitrogen-phosphorus compound flame retardant are added into an extruder from a side feeding port in two times, and finally particles with the length of about 3.5mm, namely flame retardant master batches with the flame retardant content of 65%, are obtained.
(2) Preparing the glass fiber master batch: firstly, uniformly stirring 44 parts of H7900, 5 parts of PP-g-MAH and 1% of white oil (the added aims are 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, and then regulating the length-diameter ratio to be 40:1, adding continuous glass fiber from a natural exhaust port (section 5) or adding short glass fiber from a side feeding port (section 6) after plasticizing by using a double-screw extruder, and finally obtaining the glass fiber master batch with the length of about 3.5mm and the glass fiber content of 50 percent.
(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 high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for the coil framework in the embodiment 3.
Example 4:
(1) preparing the flame-retardant master batch: 27 parts of BX3920, 6 parts of POE-g-MAH, 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 are stirred at a high speed and mixed uniformly, then added from a main feeding port, and then 65 parts of nitrogen-phosphorus compound flame retardant are added into an extruder from a side feeding port in two times, and finally particles with the length of about 3.5mm, namely flame retardant master batches with the flame retardant content of 65%, are obtained.
(2) Preparing the glass fiber master batch: firstly, uniformly stirring 34 parts of H7900, 5 parts of PP-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, and then regulating the length-diameter ratio to be 40:1, adding continuous glass fiber into a natural exhaust port (section 5) or adding short glass fiber into a side feeding port (section 6) after plasticizing the double-screw extruder, and finally obtaining the glass fiber master batch with the length of about 3.5mm and the glass fiber content of 60 percent.
(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 high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for the coil framework in the embodiment 4.
Comparative example 1:
the method is different from the method in the embodiment 1 in that the flame-retardant master batch and the glass fiber master batch do not use hyperbranched polymer.
Comparative example 2:
the only difference between the method and the embodiment 1 is that the common alpha nucleating agent is used in the glass master batch.
Comparative example 3:
the only difference between the method and the method of example 1 is that no alpha nucleating agent is used in the glass master batch.
Comparative example 4:
the only difference between the method and the embodiment 1 is that the flame-retardant master batch is not added with the active nano zinc oxide.
Comparative example 5:
the method is mainly different from the embodiment 1 in that the flame-retardant master batch (the content of the flame retardant is 60 percent) is fed by only one-order side, and other process parameters are consistent with those of the embodiment 1.
Comparative example 6:
the only difference between the method and example 1 is that the polypropylene used in the flame retardant masterbatch is the same as that used in the fiberglass masterbatch (H7900).
Comparative example 7:
the only difference between the method and the method of example 1 is that the MI of the POE-g-MAH used in the flame-retardant master batch (the content of the flame retardant is 60%) is 3.0g/10min (2.16 kg at 190 ℃).
The main performance comparison results of the polypropylene materials of examples 1 to 4 and comparative examples 1 to 7 are shown in Table 1.
TABLE 1 comparison of the Properties of the Polypropylene materials of the examples and comparative examples
As can be seen from the test results in table 1, all examples met the requirements. After the hyperbranched polymer (example 1 and comparative example 1) is added, the fluidity of the composite material is obviously improved, the spiral flow length is improved from 1200mm to 1500mm before the hyperbranched polymer is added, the molding time is shortened by 3 seconds, and the processing efficiency is improved by 16.7%. In addition, by adding the alpha nucleating agent with the characteristic of isotropic shrinkage, the bending performance and the processing efficiency of the composite material are obviously superior to those of the composite material without adding or adding a common alpha nucleating agent. By introducing active nano zinc oxide (example 1 and comparative example 4) and adopting double-stage side feeding (example 1 and comparative example 5), the flame retardant effect of the composite material reaches V0 under the condition that the thickness is 0.8 mm. Finally, in the case where the kind of resin (comparative example 6) or MI of the compatibilizer (comparative example 7) was improperly used, the bending property at the link of the bobbin was directly affected, resulting in failure, and the high-fluidity, high-rigidity copolymerized polypropylene and the high-fluidity POE-g-MAH exerted a synergistic effect. Therefore, the coil skeleton obtained by the formula has the characteristics of high fluidity and bending resistance.
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 (7)
1. The utility model provides a fine reinforced polypropylene composite of fire-retardant glass of high fluidity is able to bear or endure to buckle and is had no halogen expansion which is used for coil skeleton which characterized in that: the flame-retardant glass fiber master batch consists of 40-60% of flame-retardant master batch and the balance of glass fiber master batch by mass percentage;
the flame-retardant master batch comprises the following raw materials in parts by mass:
the glass fiber master batch is prepared from the following raw materials in parts by mass:
the melt index of the polypropylene copolymer at 230 ℃ under 2.16kg is more than or equal to 90g/10min, and the flexural modulus of the polypropylene copolymer is more than or equal to 1600 MPa; the melt index of the homopolymerized polypropylene at 230 ℃ and 2.16kg is more than or equal to 100g/10 min;
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 POE-g-MAH is 0.6-1.2%; 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 PP-g-MAH is 0.6-1.2%;
the alpha nucleating agent is a Milliken nucleating agent;
the preparation method of the flame-retardant master batch comprises the following steps: mixing the polypropylene copolymer, the POE-g-MAH, the hyperbranched polymer, the active nano zinc oxide, the antioxidant and the lubricant, adding the mixture into a main feeding port of a double-screw extruder, adding the nitrogen-phosphorus compound flame retardant from a side feeding port, and extruding and granulating to obtain 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 nitrogen-phosphorus compound flame retardant is fed into a double-screw extruder with a double-order side feeding port, 55-65 wt% of the nitrogen-phosphorus compound flame retardant is firstly added from a first-order feeding port, and then the rest of the nitrogen-phosphorus compound flame retardant is added from a second-order feeding port.
2. The high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for the coil skeleton according to claim 1, is characterized in that: the length of the flame-retardant master batch is 3-4 mm; the length of the glass fiber master batch is 3 mm-4 mm.
3. The high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for the coil skeleton according to claim 1, is characterized in that: the nitrogen-phosphorus compound flame retardant consists of the following raw materials in parts by mass: 30-50 parts of organic or inorganic hypophosphite coated by silane, 35-50 parts of halogen-free organic phosphate or derivatives thereof coated by melamine formaldehyde resin and 15-40 parts of melamine cyanurate.
4. The high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for the coil skeleton according to claim 1, is characterized in that: the hyperbranched polymer is multi-stage branched polyester.
5. The high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for the coil skeleton according to claim 1, is characterized in that: 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 continuous glass fiber or short glass fiber subjected to surface treatment by a silane coupling agent.
6. The high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for the coil skeleton according to claim 1, is characterized in that: 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.
7. The preparation method of the high-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for the coil skeleton as claimed in any one of claims 1 to 6, is characterized by comprising the following steps: the method comprises the following steps:
1) preparing a flame-retardant master batch: weighing raw materials according to the composition of the flame-retardant master batch of claim 1, firstly mixing the polypropylene copolymer, the POE-g-MAH, the hyperbranched polymer, the active nano zinc oxide, the antioxidant and the lubricant, adding the mixture into a main feeding port of a double-screw extruder, adding the nitrogen-phosphorus compound flame retardant from a side feeding port, and performing extrusion granulation to obtain the flame-retardant master batch;
2) preparing glass fiber master batch: weighing raw materials according to the composition of the glass fiber master batch of claim 1, mixing homo-polypropylene, PP-g-MAH, alpha nucleating agent, hyperbranched polymer, antioxidant and lubricant, feeding the mixture to a double-screw extruder, adding glass fiber at a natural exhaust port or a side feed port of the double-screw extruder, and performing extrusion granulation to obtain the glass fiber master batch;
3) preparing a polypropylene composite material: and mixing the flame-retardant master batches and the glass fiber master batches, and performing injection molding to obtain the high-fluidity bending-resistant halogen-free expansion-resistant flame-retardant glass fiber reinforced polypropylene composite material for the coil framework.
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| 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 |
| CN113150443B (en) * | 2021-04-26 | 2022-05-27 | 浙江明江新材料科技股份有限公司 | Halogen-free flame-retardant polypropylene foaming composite material and preparation method thereof |
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| CN1810862A (en) * | 2006-02-23 | 2006-08-02 | 广州金发科技股份有限公司 | Continuous long fiber reinforced fire-retardant thermoplastic resin and its prepn |
| CN102585378A (en) * | 2012-03-17 | 2012-07-18 | 杭州金州高分子科技有限公司 | High heat resistant glass fiber enhanced halogen-free flame retardant polypropylene and preparation method thereof |
| CN105331078A (en) * | 2015-12-02 | 2016-02-17 | 威海晨源分子新材料有限公司 | Application of hyperbranched polyester to plastic processing |
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| CN1810862A (en) * | 2006-02-23 | 2006-08-02 | 广州金发科技股份有限公司 | Continuous long fiber reinforced fire-retardant thermoplastic resin and its prepn |
| CN102585378A (en) * | 2012-03-17 | 2012-07-18 | 杭州金州高分子科技有限公司 | High heat resistant glass fiber enhanced halogen-free flame retardant polypropylene and preparation method thereof |
| CN105331078A (en) * | 2015-12-02 | 2016-02-17 | 威海晨源分子新材料有限公司 | Application of hyperbranched polyester to plastic processing |
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