CN114031844B - Halogen-free flame-retardant master batch for continuous long glass fiber reinforced polypropylene and preparation method thereof - Google Patents
Halogen-free flame-retardant master batch for continuous long glass fiber reinforced polypropylene and preparation method thereof Download PDFInfo
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Abstract
The halogen-free flame-retardant master batch for the continuous long glass fiber reinforced polypropylene comprises a polypropylene carrier, a halogen-free flame retardant, a hyperdispersant, a lubricant, a coupling agent and an antioxidant. The polypropylene carrier is a mixture of homo-polypropylene and co-polypropylene resin. The halogen-free flame retardant comprises a low-melting-point lubricating flame retardant auxiliary agent, and the low-melting-point lubricating flame retardant auxiliary agent is one or a mixture of more of phosphaphenanthrene derivatives or phosphazene derivatives with melting points lower than 170 ℃. The halogen-free flame-retardant master batch for the continuous long glass fiber reinforced polypropylene is extruded at the extrusion temperature of 170-210 ℃ and is prepared by granulating by a special long-strip granulator for LFTPP under the action of the pulling force of a tractor. The halogen-free flame-retardant master batch can improve the processing fluidity of the continuous long glass fiber reinforced polypropylene material and the uniform dispersion of powder, so that a product manufactured by the continuous long glass fiber reinforced polypropylene material has better uniformity. The invention also provides a preparation method of the halogen-free flame-retardant master batch.
Description
Technical Field
The invention relates to the technical field of flame retardant modification of engineering plastics, in particular to a halogen-free flame retardant master batch for continuous long glass fiber reinforced polypropylene and a preparation method thereof.
Background
Polypropylene (PP), which is one of five general plastics, is a semi-crystalline thermoplastic plastic with good mechanical properties and molding processability, and has high cost performance, and has been widely used in the fields of home appliances and automobiles. However, PP also has the defects of low strength, modulus, hardness, low-temperature impact strength, large molding shrinkage, easy aging, flammability and the like, and in practical production and application, it is often required to carry out toughening, filling, flame retardance and other modifications to meet the high performance requirements of products.
Long glass fiber reinforced polypropylene (Long Glass Fiber Reinforced polypropylene, LGFPP for short) is one of new varieties that are attracting attention. The LGFPP material retains longer fiber length (more than 3.1 mm) in the forming process, forms a fiber skeleton structure, has more excellent rigidity, impact strength, creep resistance and dimensional stability, and has wide application in the fields of automobiles, electronic appliances, aerospace and the like. However, LGFPP materials also suffer from disadvantages such as being more flammable, having a significant "wick effect" after ignition, making flame retarding of the material more difficult. At present, the addition of halogen flame retardants to LGFPP materials can improve the flame retardant properties of the materials, but has secondary environmental hazards. Therefore, developing and applying high-performance halogen-free flame retardants becomes an effective way to solve the flammability problem of LGFPP.
The halogen-free flame retardant developed for LGFPP materials needs to meet the following requirements: 1) The flame retardant has higher flame retardant property, improves the 'candle core effect', reduces the addition amount of the flame retardant and reduces the influence on the mechanical property of the material; 2) The thermal stability is higher, the processing temperature of the LGFPP material at 240-260 ℃ can be met, and the flame retardant is prevented from foaming degradation; 3) The flame retardant powder has good fluidity and dispersibility in the material, reduces the influence on the flow property of the material, is easy to process and mold, has no floating fiber and does not influence the appearance. In the existing halogen-free flame retardant system, a flame retardant product compounded by taking piperazine pyrophosphate as a core component has been applied to LGFPP materials by virtue of excellent performance. However, in the prior art, the dispersibility of the piperazine pyrophosphate compound powder flame retardant in the LGFPP material is poor, the influence on the mechanical property and the processing property of the material is large, and how to realize the balance of flame retardance, processing and mechanical property is a technical problem to be solved at present. Patent CN 107722450a discloses the use of piperazine pyrophosphate flame retardant in LFT-D materials, but the formulated flame retardant must be surface treated before use to be well dispersed in the material, on the one hand increasing the manufacturing cost, while the silane or silicone oil treatment used affects the flame retardant efficiency. Patent CN 108752732a discloses the flame retardant application of halogen-free flame retardant in long glass fiber modified homo-polypropylene, but is limited to use in homo-polypropylene materials with high melt index, limiting its application in co-polypropylene with slightly lower melt index flowability. Patent CN 110079009A discloses a piperazine pyrophosphate flame-retardant polypropylene material with ultrahigh fluidity, but the addition amount of a flame retardant is only 24-35%, and the melt index of polypropylene is required to be more than or equal to 120g/10min (230 ℃ and 2.16 Kg), so that the application of the piperazine pyrophosphate flame-retardant polypropylene material in an LGFPP material is limited.
In view of the above problems, development of a high-concentration master batch product of piperazine pyrophosphate flame retardant used for LGFPP materials is an effective solution, but related technologies have not been reported yet.
Disclosure of Invention
In view of the above, the present invention provides a halogen-free flame retardant masterbatch for continuous long glass fiber reinforced polypropylene and a preparation method thereof, so as to meet the above-mentioned needs.
The halogen-free flame-retardant master batch for the continuous long glass fiber reinforced polypropylene consists of a polypropylene carrier, a halogen-free flame retardant, a hyperdispersant, a lubricant, a coupling agent and an antioxidant. The polypropylene carrier is a mixture of homo-polypropylene and co-polypropylene resin, and the mass percentage content of the polypropylene carrier is 15% -48%. The halogen-free flame retardant accounts for 50-80% by mass. The mass percentage content of the hyper-dispersant is 0.8-1.8%. The mass percentage content of the lubricant is 0.2-0.5%. The mass percentage content of the coupling agent is 0.8-1.5%. The antioxidant accounts for 0.2 to 1.0 percent of the total mass of the water-soluble polymer. The melt index of the homo-polypropylene at 230 ℃ and under 10Kg pressure is more than or equal to 25g/10min, and the melt index of the co-polypropylene at 230 ℃ and under 10Kg pressure is more than or equal to 15g/10min. The halogen-free flame retardant comprises a low-melting-point lubricating flame retardant auxiliary agent, and the low-melting-point lubricating flame retardant auxiliary agent is one or a mixture of more of phosphaphenanthrene derivatives or phosphazene derivatives with melting points lower than 170 ℃. The halogen-free flame-retardant master batch for the continuous long glass fiber reinforced polypropylene is extruded at the extrusion temperature of 170-210 ℃ and is prepared by granulating by a special long-strip granulator for LFTPP under the action of the pulling force of a tractor.
Further, the effective concentration of the halogen-free flame retardant in the halogen-free flame retardant master batch is 50% -80%, the length of the master batch is 6-14 mm, and the melt index of the halogen-free flame retardant master batch at 230 ℃ and under 10Kg pressure is more than or equal to 30g/10min.
Further, in the polypropylene carrier, the mass percentage of the homo-polypropylene is 20% -40%, the mass percentage of the copolymerization polypropylene is 60% -80%, and the impact strength of the copolymerization polypropylene is more than or equal to 20kJ/m 2 。
Further, the halogen-free flame retardant further comprises piperazine pyrophosphate, ammonium polyphosphate or melamine and derivatives thereof, and metal oxide, wherein the mass percentage of the piperazine pyrophosphate is 40% -75%, the mass percentage of the ammonium polyphosphate or melamine and derivatives thereof is 20% -50%, the mass percentage of the metal oxide is 2% -10%, and the mass percentage of the low-melting-point lubricating flame retardant auxiliary is 2% -10%.
Further, the piperazine pyrophosphate is prepared by high-temperature dehydration polymerization of piperazine and phosphoric acid; the ammonium polyphosphate is I I ammonium polyphosphate with the polymerization degree more than 1000, the melamine and the derivative thereof are one or a mixture of more than one of melamine, melamine phosphate, melamine pyrophosphate, melamine polyphosphate and melamine cyanurate, and the metal oxide is one or a mixture of more than one of zinc oxide, zinc borate, silicon dioxide, titanium dioxide, aluminum hypophosphite and zinc stannate.
Further, the hyper-dispersant is one or a mixture of a plurality of polyether hyper-dispersants, carboxyl-terminated polyester hyper-dispersants and carboxyl-terminated or hydroxyl-terminated polyacrylate hyper-dispersants.
Further, the lubricant is one or a mixture of a plurality of polyhydroxy compounds, stearate, ethylene Bis Stearamide (EBS), ji Qu tetraol stearate (PETS), modified EBS (EBC) and silicone powder.
Further, the coupling agent is one of a silane coupling agent, a rare earth coupling agent, a maleic anhydride graft, a titanate coupling agent and an aluminate coupling agent.
Further, the antioxidant is a hindered phenol main antioxidant 1010 or 1076, and is compounded with a phosphite ester auxiliary antioxidant 168 according to the mass ratio of 1 (1-2).
The preparation method of the halogen-free flame-retardant master batch for the continuous long glass fiber reinforced polypropylene comprises the following steps:
providing a raw material for preparing the halogen-free flame retardant master batch for the continuous long glass fiber reinforced polypropylene, wherein the raw material for preparing the halogen-free flame retardant master batch for the continuous long glass fiber reinforced polypropylene comprises a polypropylene carrier, a halogen-free flame retardant, a hyperdispersant, a lubricant, a coupling agent and an antioxidant, wherein the polypropylene carrier is a mixture of homo-polypropylene and co-polypropylene resin, the mass percent of the polypropylene carrier is 15-48%, the mass percent of the halogen-free flame retardant is 50-80%, the mass percent of the hyperdispersant is 0.8-1.8%, the mass percent of the lubricant is 0.2-0.5%, the mass percent of the coupling agent is 0.8-1.5%, the mass percent of the antioxidant is 0.2-1.0%, the melt index of the homo-polypropylene at 230 ℃ and under 10Kg pressure is more than or equal to 25g/10min, the melt index of the co-polypropylene at 230 ℃ and under 10Kg pressure is more than or equal to 15g/10min, and the flame retardant auxiliary agent comprises flame retardant auxiliary agents with a melting point lower than 170 ℃ and lower than one or more flame retardant derivative of phosphazene derivatives;
the raw material components in the halogen-free flame retardant are added into a high-speed mixer according to the corresponding mass percentages, premixed for 5 to 10 minutes, and discharged to obtain the uniformly mixed halogen-free flame retardant;
the polypropylene carrier, the hyperdispersant, the lubricant, the coupling agent and the antioxidant raw materials are added into a high-speed mixer according to corresponding mass percentages, and are premixed for 3 to 5 minutes;
adding halogen-free flame retardant in corresponding mass percent, mixing for 5-10 min, and discharging to obtain premixed particles;
adding the premixed particles into a double-screw extruder, extruding at 170-210 ℃ and at the rotating speed of 200-350 r/min, pulling by an air-cooled drag chain, and granulating by a special long-strip granulator for LFTPP under the action of the pulling force of a tractor, thereby obtaining the continuous long glass fiber reinforced polypropylene halogen-free flame-retardant master batch with the length of 6-14 mm.
Compared with the prior art, the halogen-free flame-retardant master batch is applied to continuous long glass fiber reinforced polypropylene materials, and the polypropylene materials consistent with the glass fiber reinforced polypropylene application matrix are selected as carrier resins on the premise that the mechanical properties of the materials are not affected. The polypropylene carrier resin is a mixture of homo-polypropylene and co-polypropylene, wherein the melt index of the homo-polypropylene is more than or equal to 25g/10min (230 ℃ C., 10 Kg), and the melt index of the co-polypropylene is more than or equal to 15g/10min (230 ℃ C., 10 Kg). Through the mixed use of the two polypropylene resins, the advantages of the mechanical property of the copolymerized polypropylene and the high fluidity of the homo-polymerized polypropylene are combined, the balance of the toughness and the fluidity of the carrier resin is realized, the melt index of the halogen-free flame retardant master batch is more than or equal to 30g/10min (230 ℃ and 10 Kg), the filling quantity of the halogen-free flame retardant and the compatibility of the master batch and the material are fully improved, the mechanical property of the flame retardant product is not reduced, and the high-melting finger can fully infiltrate the long glass fiber to prevent floating fiber. Meanwhile, as the phosphaphenanthrene (DOPO) derivative or the phosphazene derivative is used as a lubricating flame-retardant auxiliary agent, the melting point of the phosphaphenanthrene (DOPO) derivative or the phosphazene derivative is lower than 170 ℃, the phosphazene derivative can be melted into a liquid state in the extrusion processing process of the polypropylene carrier flame-retardant master batch, on one hand, the effect of a lubricant can be achieved, the consumption of the lubricant is reduced, the auxiliary agent has excellent flame retardance, and the flame retardant efficiency of a flame retardant system can be improved; on the other hand, the phosphaphenanthrene (DOPO) derivative or the phosphazene derivative can increase the melt index of the shearing blending system, further improve the processing fluidity of the continuous long glass fiber reinforced polypropylene material and the uniform dispersion of the powder, and ensure that the product manufactured by the continuous long glass fiber reinforced polypropylene material has better uniformity.
Detailed Description
Specific embodiments of the present invention are described in further detail below. It should be understood that the description herein of the embodiments of the invention is not intended to limit the scope of the invention.
The invention provides a halogen-free flame retardant master batch for continuous long glass fiber reinforced polypropylene, which consists of a polypropylene carrier, a halogen-free flame retardant, a hyperdispersant, a lubricant, a coupling agent and an antioxidant. The polypropylene carrier is a mixture of homo-polypropylene and co-polypropylene resin. As is well known, the preparation of the flame-retardant master batch needs to screen corresponding carrier resin, a lubricating system and a dispersing system according to the application scene and the mechanism characteristics of the flame retardant, and meanwhile, the matching among the resin, the flame retardant and the auxiliary agent is comprehensively considered, so that the influence of various auxiliary agents on the flame retardant performance of the flame-retardant system is reduced. The flowability, fillability and compatibility of the carrier resin with the target product are important factors influencing the selection of the flame retardant master batch carrier, the flame retardant and various auxiliary agents can be carried, the uniform dispersion of the master batch in the product is ensured, the mechanical properties of the processing and the product cannot be influenced, and therefore, the selection of each component is important. Therefore, the polypropylene carrier is selected on the premise of not affecting the mechanical properties of the material. The polypropylene carrier is a mixture of homo-polypropylene and co-polypropylene resin. The homo-polypropylene is also called isotactic polypropylene in the prior art, is polymerized by a single propylene monomer, does not contain ethylene monomer in a molecular chain, and has high regularity of the molecular chain. The disadvantage of homo-polypropylene is the relatively poor impact resistance, i.e.relatively brittle, poor toughness and dimensional stabilityPoor, easy aging, poor long-term heat resistance stability, but the advantages are also obvious, namely good strength and good fluidity. The melt index of the homo-polypropylene is more than or equal to 25g/10min (230 ℃ C., 10 Kg). The polypropylene copolymer is also the prior art, and is obtained by copolymerizing propylene monomer and a small amount of ethylene (1% -4%) monomer under the actions of heating, pressurizing and catalysts, wherein the ethylene monomer is randomly and randomly distributed in long chains of propylene. The polypropylene copolymer has the characteristics of good comprehensive performance, high strength, high rigidity, good heat resistance, good dimensional stability, excellent low-temperature toughness (good flexibility), good transparency and good glossiness. The melt index of the polypropylene copolymer is more than or equal to 15g/10min (230 ℃ C., 10 Kg), and the impact strength is more than or equal to 20kJ/m 2 . In the polypropylene carrier, the mass percentage of the homo-polypropylene is 20% -40%, and the mass percentage of the copolymerization polypropylene is 60% -80%. Through the mixed use of the two polypropylene resins, the advantages of mechanical properties of the copolymerized polypropylene and high fluidity of the homopolymerized polypropylene are combined, the balance of toughness and fluidity of the carrier resin is realized, and the melt index of the halogen-free flame retardant master batch is more than or equal to 30g/10min at 230 ℃ and under 10Kg pressure, so that the filling quantity of the halogen-free flame retardant and the compatibility of the master batch and materials are improved, the mechanical properties of a flame retardant product are not reduced, and meanwhile, the high-melting finger can fully infiltrate long glass fibers to prevent floating fibers.
The halogen-free flame retardant consists of piperazine pyrophosphate, ammonium polyphosphate or melamine and derivatives thereof, metal oxide and a low-melting-point lubricating flame retardant auxiliary agent. The mass percentage of the piperazine pyrophosphate is 40-75%, the mass percentage of the ammonium polyphosphate or melamine and its derivative is 20-50%, the mass percentage of the metal oxide is 2-10%, and the mass percentage of the low-melting-point lubricating flame retardant auxiliary is 2-10%. The piperazine pyrophosphate is prepared by high-temperature dehydration polymerization of piperazine and phosphoric acid. The ammonium polyphosphate is I I ammonium polyphosphate with the polymerization degree more than 1000. The ammonium polyphosphate may be untreated or surface-treated ammonium polyphosphate. The melamine and the derivative thereof can be one or a mixture of a plurality of melamine, melamine phosphate, melamine pyrophosphate, melamine polyphosphate and melamine cyanurate. The metal oxide can be one or a mixture of several of zinc oxide, zinc borate, silicon dioxide, titanium dioxide, aluminum hypophosphite and zinc stannate. The above-mentioned materials are themselves prior art and will not be described in detail here. By adding the halogen-free flame retardant, the flame retardant property of the halogen-free flame retardant master batch can be ensured. The low-melting-point lubricating flame retardant auxiliary is one or a mixture of more than one of phosphaphenanthrene derivatives or phosphazene derivatives with melting points lower than 170 ℃. Because the lubricant is added into the master batch to improve the compatibility of the materials, the use of the lubricant can affect the flame retardant property of the flame retardant and reduce the flame retardant efficiency. In the halogen-free flame retardant formula, phosphaphenanthrene (DOPO) derivatives or phosphazene derivatives with the melting point lower than 170 ℃ are used as lubricating flame retardant auxiliary agents, so that on one hand, partial lubricants can be replaced, the using amount of the lubricants is reduced, and meanwhile, the flame retardant auxiliary agents have certain flame retardance, and the flame retardant efficiency of a flame retardant system can be improved; on the other hand, the melting point of the flame retardant auxiliary is lower than 170 ℃, and the flame retardant auxiliary can be melted into a liquid state in the extrusion processing process of the polypropylene carrier flame retardant master batch, so that the melt index of a shearing blending system is increased, and the processing fluidity and the uniform dispersion of powder are improved. The halogen-free flame retardant accounts for 50-80% by mass.
The mass percentage content of the hyper-dispersant is 0.8-1.8%. The hyper-dispersant is one or a mixture of a plurality of polyether hyper-dispersant, carboxyl-terminated polyester hyper-dispersant and carboxyl-terminated polyacrylate hyper-dispersant. The hyperdispersant is a strong-polarity polyether hyperdispersant, or a series of intermediate-polarity polyester hyperdispersant with carbamate groups or chain segments uniformly distributed on molecular chains or grafted side chains, or a mixture of one or more intermediate-polarity grafted acrylic hyperdispersants with free carboxylic acid and sulfonic acid hydrophilic groups, wherein tertiary amine and a cyclic structure are used as anchoring groups. Because the halogen-free flame retardant comprises piperazine pyrophosphate, the piperazine pyrophosphate has certain polarity and is easy to absorb water and agglomerate. The hyperdispersant used also needs to have a certain polarity according to similar compatibility principles. The hyperdispersant replaces hydrophilic and lipophilic groups of traditional dispersants such as surfactants and the like with anchoring groups and solvated chains, and is tightly adsorbed on the surfaces of powder flame retardant particles through interaction such as ionic bonds, hydrogen bonds, covalent bonds, van der Waals forces and the like, so that agglomeration among particles is inhibited, the particle size of the flame retardant powder is reduced, bridging does not occur in the blanking process, and the dispersibility in resin and the smoothness of the product surface are improved. The dispersing effect of the hyperdispersant on the flame retardant in the formula is close to the effect of surface treatment on the flame retardant, the effect can be achieved through a formula mixing process, the process of surface treatment on the flame retardant is not needed to be increased, the manufacturing cost is reduced, and the efficiency is improved.
The lubricant can be one or more of polyhydroxy compound, stearate, ethylene Bis Stearamide (EBS), ji Qu tetraol stearate (PETS), modified EBS (EBC) and silicone powder. The above-mentioned various substances are all the prior art, and the characteristics, advantages and disadvantages, preparation methods and the like thereof are not described in detail herein. The mass percentage content of the lubricant is 0.2-0.5%. The function of the lubricant itself is known in the art and will not be described in detail here.
The coupling agent can be one of a silane coupling agent, a rare earth coupling agent, a maleic anhydride graft, a titanate coupling agent and an aluminate coupling agent. The materials selected for the coupling agent are all known in the art and will not be described in detail herein. The mass percentage content of the coupling agent is 0.8-1.5%. The function of the coupling agent itself is also known in the art and will not be described in detail here.
The antioxidant can be hindered phenol primary antioxidant 1010 or 1076 and phosphite ester secondary antioxidant 168 according to the mass ratio of 1 (1-2). The antioxidant accounts for 0.2 to 1.0 percent of the total mass of the water-soluble polymer. The function of the antioxidant itself is also known in the art and will not be described in detail here.
The invention also provides a preparation method of the halogen-free flame-retardant master batch for the continuous long glass fiber reinforced polypropylene, which comprises the following steps:
STEP101, providing a raw material for preparing the halogen-free flame-retardant master batch for the continuous long glass fiber reinforced polypropylene, wherein the raw material for preparing the halogen-free flame-retardant master batch for the continuous long glass fiber reinforced polypropylene consists of a polypropylene carrier, a halogen-free flame retardant, a hyperdispersant, a lubricant, a coupling agent and an antioxidant;
STEP102, namely feeding the raw material components in the halogen-free flame retardant into a high-speed mixer according to the corresponding mass percentages, premixing for 5-10 min, and discharging to obtain the uniformly mixed halogen-free flame retardant;
STEP103, namely feeding the polypropylene carrier, the hyperdispersant, the lubricant, the coupling agent and the antioxidant raw materials into a high-speed mixer according to corresponding mass percentages, and premixing for 3-5 min;
STEP104, namely adding the halogen-free flame retardant with corresponding mass percent, mixing for 5-10 min, and discharging to obtain premixed particles;
STEP105, adding the premixed particles into a double screw extruder, extruding at 170-210 ℃ and rotating at 200-350 r/min, pulling the particles by an air-cooled drag chain, and granulating the particles by a special long-strip granulator for LFTPP under the action of the pulling force of a tractor, thereby obtaining the continuous long glass fiber reinforced polypropylene halogen-free flame-retardant master batch with the length of 6-14 mm.
In the above steps, the equipment used, such as a mixer, is known in the art and will not be described herein. In STEP105, the conventional granulator used in masterbatch processing generally has a granule cutting length of about 3mm to 4mm, whereas LFTPP particles have a length of 6mm to 15mm, and the two particles have a relatively large difference in length, which easily causes delamination of the particles during mixing or processing and blanking, and affects uniformity. In the invention, the special long-strip granulator for LFTPP is selected in the preparation process of the continuous long glass fiber reinforced polypropylene halogen-free flame retardant master batch, so that the length of the flame retardant master batch is kept between 6mm and 14mm, and the long-strip granulator is matched with LFTPP particles, thereby effectively avoiding layering problems in the mixing or processing blanking process and improving the performance uniformity.
Compared with the prior art, the halogen-free flame-retardant master batch for continuous long glass fiber reinforced polypropylene and the preparation method thereof have the following advantages:
(1) The mixture of homo-and co-polypropylene is used as a master batch carrier resin, so that the compatibility with a continuous long glass fiber reinforced polypropylene matrix is improved, the balance of fluidity and toughness of the carrier is realized, the dispersion uniformity of the master batch is improved due to high fluidity, and the influence of high toughness on the mechanical properties of the material is reduced.
(2) The phosphorus-nitrogen halogen-free flame retardant is used in the master batch, the high-efficiency environment-friendly flame retardant is efficient and environment-friendly, each component meets the processing temperature resistance requirement of the continuous long glass fiber polypropylene material, and the fluidity and the dispersibility of the flame retardant powder in the master batch are improved through the molten liquid phase transition of the low-melting-point lubricating flame retardant auxiliary agent in the processing, meanwhile, the using amount of the lubricant is reduced, and the flame retardant efficiency is improved.
(3) The hyper-dispersant is used for effectively inhibiting agglomeration of the flame retardant powder, improving the dispersibility of the high-concentration flame retardant powder in the master batch, and being matched with a small amount of coupling agent, the hyper-dispersant can achieve the effect of surface treatment of the flame retardant, but obviously reduces the treatment cost and improves the processing efficiency.
(4) The LFTPP long-strip granulator is arranged in the masterbatch extrusion processing, the length of the masterbatch is optimized to be 6-14 mm, the layering problem of too short masterbatch in the mixing or processing blanking process is avoided, and the performance uniformity is improved.
The prepared halogen-free flame-retardant master batch for the high-fluidity continuous long glass fiber reinforced polypropylene can be directly used for flame retardance of continuous long glass fiber reinforced polypropylene materials, has good compatibility with the materials, is uniformly dispersed in the materials, can reach UL 94V-0 grade by adding 25% -40% of master batch into LGFPP materials, has little influence on the mechanical properties of the materials, and meanwhile, has good appearance of flame-retardant products and no appearance.
In the following embodiments or examples, unless otherwise specified, the raw material components used are commercial products purchased from the market by those skilled in the art or products prepared by a known method.
The sample test items and criteria are as follows:
1) Melt index (M I): measured according to GB/T3682.1 standard.
2) Vertical combustion progression: tested according to GB/T2408 standard.
3) Tensile strength: tested according to GB/T1040.2 standard.
4) Impact strength: tested according to GB/T1843 standard.
Examples 1-6 and comparative examples 1-4 according to the mass ratios of the components in table 1, according to the preparation method of halogen-free flame retardant master batches for continuous long glass fiber reinforced polypropylene in STEP 101-STEP 105, the master batches are pelletized by using an LFTPP special long-strip pelletizer, the length of the master batches is 6 mm-14 mm, and the melt index data of the corresponding halogen-free flame retardant master batches are shown in table 2.
Comparative example 5 according to the mass ratio of each component in table 1, according to the preparation method of halogen-free flame retardant master batch for continuous long glass fiber reinforced polypropylene in STEP101 to STEP105, the master batch is cut into particles by using a conventional granulator, the length of the master batch is 3mm to 4mm, and the melt index data of the corresponding halogen-free flame retardant master batch are shown in table 2.
TABLE 1 halogen-free flame retardant masterbatch formulations of examples 1-6 and comparative examples 1-5
TABLE 2 halogen-free flame retardant masterbatch Properties of examples 1-6 and comparative examples 1-5
The halogen-free flame retardant master batches obtained in examples 1 to 6 and comparative examples 1 to 5 were added to continuous long glass fiber reinforced polypropylene materials, and when the addition amount of the master batch was 35%, corresponding flame retardant continuous long glass fiber reinforced polypropylene test bars were prepared by mixing and injection molding, and the properties are shown in Table 3.
TABLE 3 Properties of flame retardant continuous Long glass fiber reinforced Polypropylene materials corresponding to examples 1-6 and comparative examples 1-5
From the formulation in table 1, the melt index of the corresponding master batch in table 2 and the flame retardant and mechanical property data applied to the flame retardant continuous long glass fiber reinforced polypropylene material in table 3, it can be seen that the halogen-free flame retardant master batch for continuous long glass fiber reinforced polypropylene obtained in examples 1-6 has higher melt index, which indicates that the master batch has better processing fluidity, good melt dispersibility in the continuous long glass fiber reinforced polypropylene material, the flame retardant continuous long glass fiber reinforced polypropylene material can reach the UL 94V-0 (1.6 mm) grade, good mechanical property retention, no floating fiber appears on the surface, and the flame retardant continuous long glass fiber reinforced polypropylene material with good comprehensive properties is obtained.
In example 1, the melt index of the flame retardant master batch was higher than that of the master batch using the homo-polypropylene alone in comparative example 1 and the co-polypropylene alone in comparative example 2, indicating that the processing fluidity of the master batch can be improved by using the polypropylene carrier in combination. In addition, when the flame-retardant master batch prepared by independently using the homo-polypropylene as the carrier in comparative example 1 is applied to the continuous long glass fiber reinforced polypropylene material, the impact performance of the flame-retardant continuous long glass fiber reinforced polypropylene material is obviously reduced, and slight fiber floating occurs. When the flame-retardant master batch prepared by independently using the copolymerized polypropylene as the carrier in comparative example 2 is applied to the continuous long glass fiber reinforced polypropylene material, the tensile strength of the flame-retardant continuous long glass fiber reinforced polypropylene material is reduced, the processing fluidity is seriously reduced, and the floating fiber is obvious.
Compared with the comparative example 3 and the example 1, the comparative example 3 uses more lubricant EBS without polyether hyperdispersant, and the dispersibility of the compound flame retardant powder is slightly bad, but the flame retardant grade is reduced to V-2, and the mechanical property is also reduced to a certain extent.
Compared with the comparative example 4 and the example 1, the comparative example 4 is free from adding the low-melting-point lubricating flame retardant auxiliary agent, the melt index of the flame retardant master batch is reduced by 71.4%, the melt dispersibility of the master batch in processing is poor, the performance of the flame retardant material is uneven, the flame retardant grade is reduced to V-2, a certain candlewick effect still exists, and the mechanical property is reduced.
In comparative example 5, the master batch is pelletized by a conventional pelletizer, and the length of the master batch is only 3 mm-4 mm, and when the master batch is mixed and extruded with continuous long glass fiber reinforced polypropylene particles, layering occurs, so that the flame-retardant continuous long glass fiber reinforced polypropylene material is nonuniform in performance, unstable in flame retardant performance, reduced in mechanical property and floating fiber.
From the data of the above examples and comparative examples of the halogen-free flame retardant master batch for continuous long glass fiber reinforced polypropylene in fluidity, flame retardant property and mechanical property, the invention is characterized in that the halogen-free flame retardant master batch for continuous long glass fiber reinforced polypropylene is mixed with polypropylene resin carrier, flame retardant component and formula, low melting point lubricating flame retardant auxiliary agent, hyper-dispersant and other components, which are essential for realizing the balance of fluidity and mechanical property of the master batch.
The above is only a preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalent substitutions or improvements within the spirit of the present invention are intended to be covered by the claims of the present invention.
Claims (7)
1. The halogen-free flame-retardant master batch for the continuous long glass fiber reinforced polypropylene is characterized in that: the halogen-free flame retardant master batch for the continuous long glass fiber reinforced polypropylene consists of a polypropylene carrier, a halogen-free flame retardant, a hyperdispersant, a lubricant, a coupling agent and an antioxidant, wherein the polypropylene carrier is a mixture of homo-polypropylene and co-polypropylene resin, the mass percentage of the polypropylene carrier is 15-48%, the trade mark of the homo-polypropylene is T300, the trade mark of the co-polypropylene resin is K8003, the mass percentage of the halogen-free flame retardant is 50-80%, the mass percentage of the hyperdispersant is 0.8-1.8%, the mass percentage of the lubricant is 0.2-0.5%, the mass percentage of the coupling agent is 0.8-1.5%, the mass percentage of the antioxidant is 0.2-1.0%, the weight percentage of the homo-polypropylene in the polypropylene carrier is 20-40%, the weight percentage of the co-polypropylene is 60-80%, the halogen-free flame retardant comprises a low-melting-point lubricating flame retardant auxiliary agent which is one or a mixture of more of phosphaphenanthrene derivatives or phosphazene derivatives with the melting point lower than 170 ℃, the halogen-free flame retardant further comprises piperazine pyrophosphate, ammonium polyphosphate or melamine and derivatives thereof, and metal oxide, the weight percentage of the piperazine pyrophosphate is 40-75%, the weight percentage of the ammonium polyphosphate or melamine and derivatives thereof is 20-50%, the weight percentage of the metal oxide is 2-10%, the weight percentage of the low-melting-point lubricating flame retardant auxiliary agent is 2-10%, and the super-dispersant is polyether super-dispersant, the continuous long glass fiber reinforced polypropylene halogen-free flame-retardant master batch is extruded at the extrusion temperature of 170-210 ℃ and is prepared by granulating by a special long-strip granulator for LFTPP under the action of the pulling force of a tractor, wherein the length of the prepared master batch is 6-14 mm.
2. The halogen-free flame retardant master batch for continuous long glass fiber reinforced polypropylene according to claim 1, wherein the effective concentration of the halogen-free flame retardant in the halogen-free flame retardant master batch is 50% -80%, and the melt index of the halogen-free flame retardant master batch at 230 ℃ and under 10Kg pressure is more than or equal to 30g/10min.
3. The halogen-free flame retardant masterbatch for continuous long glass fiber reinforced polypropylene according to claim 1, wherein piperazine pyrophosphate is prepared by high-temperature dehydration polymerization of piperazine and phosphoric acid; the ammonium polyphosphate is type II ammonium polyphosphate with the polymerization degree more than 1000, the melamine and the derivative thereof are one or a mixture of more than one of melamine, melamine phosphate, melamine pyrophosphate, melamine polyphosphate and melamine cyanurate, and the metal oxide is one or a mixture of more than one of zinc oxide, zinc borate, silicon dioxide, titanium dioxide, aluminum hypophosphite and zinc stannate.
4. The halogen-free flame retardant masterbatch for continuous long glass fiber reinforced polypropylene according to claim 1, wherein the lubricant is one or a mixture of several of polyhydroxy compounds, stearate, ethylene bis-stearamide, pentaerythritol stearate, modified EBS and silicone powder.
5. The halogen-free flame retardant master batch for continuous long glass fiber reinforced polypropylene according to claim 1, wherein the coupling agent is one of a silane coupling agent, a rare earth coupling agent, a maleic anhydride graft, a titanate coupling agent and an aluminate coupling agent.
6. The halogen-free flame retardant master batch for continuous long glass fiber reinforced polypropylene according to claim 1, wherein the antioxidant is a hindered phenol main antioxidant 1010 or 1076 and is compounded with a phosphite auxiliary antioxidant 168 according to the mass ratio of 1 (1-2).
7. A method for preparing the halogen-free flame retardant masterbatch for continuous long glass fiber reinforced polypropylene according to any one of claims 1 to 6, comprising the steps of:
providing a raw material for preparing the halogen-free flame retardant master batch for the continuous long glass fiber reinforced polypropylene, wherein the raw material for preparing the halogen-free flame retardant master batch for the continuous long glass fiber reinforced polypropylene comprises a polypropylene carrier, a halogen-free flame retardant, a hyperdispersant, a lubricant, a coupling agent and an antioxidant, wherein the polypropylene carrier is a mixture of homo-polypropylene and co-polypropylene resin, the mass percentage of the polypropylene carrier is 15-48%, the mass percentage of the halogen-free flame retardant is 50-80%, the mass percentage of the hyperdispersant is 0.8-1.8%, the mass percentage of the lubricant is 0.2-0.5%, the mass percentage of the coupling agent is 0.8-1.5%, the mass percentage of the antioxidant is 0.2-1.0%, and the halogen-free flame retardant comprises a low-melting-point lubricating flame retardant auxiliary agent which is one or a mixture of phosphaphenanthrene derivative or phosphazene derivative with a melting point lower than 170 ℃;
the raw material components in the halogen-free flame retardant are added into a high-speed mixer according to the corresponding mass percentages, premixed for 5 to 10 minutes, and discharged to obtain the uniformly mixed halogen-free flame retardant;
the polypropylene carrier, the hyperdispersant, the lubricant, the coupling agent and the antioxidant raw materials are added into a high-speed mixer according to corresponding mass percentages, and are premixed for 3 to 5 minutes;
adding halogen-free flame retardant in corresponding mass percent, mixing for 5-10 min, and discharging to obtain premixed particles;
adding the premixed particles into a double-screw extruder, extruding at 170-210 ℃ and at the rotating speed of 200-350 r/min, pulling by an air-cooled drag chain, and granulating by a special long-strip granulator for LFTPP under the action of the pulling force of a tractor, thereby obtaining the continuous long glass fiber reinforced polypropylene halogen-free flame-retardant master batch with the length of 6-14 mm.
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