CN114015187A - Halogen-free flame-retardant polypropylene material for automotive interior and preparation method thereof - Google Patents
Halogen-free flame-retardant polypropylene material for automotive interior and preparation method thereof Download PDFInfo
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- CN114015187A CN114015187A CN202111406504.XA CN202111406504A CN114015187A CN 114015187 A CN114015187 A CN 114015187A CN 202111406504 A CN202111406504 A CN 202111406504A CN 114015187 A CN114015187 A CN 114015187A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a halogen-free flame-retardant polypropylene material for automotive interiors, which comprises the following raw materials in parts by weight: 40-70 parts of polypropylene, 10-20 parts of coated ammonium polyphosphate, 5-10 parts of piperazine pyrophosphate, 5-10 parts of a synergistic flame retardant, 0.5-2 parts of a compatilizer, 0-10 parts of an inorganic filler, 10-20 parts of a toughening agent, 0.2-1 part of a deodorant and 0.3-1.5 parts of a stabilizer, wherein the coated ammonium polyphosphate is prepared by performing surface coating modification on high-polymeric ammonium polyphosphate by using melamine formaldehyde and epoxy resin. The polypropylene material disclosed by the invention not only meets the flame retardant property, but also has the characteristics of excellent rigidity and toughness balance, precipitation resistance and low odor, and is suitable for application in automotive industry interior trim, especially in passenger car interior trim.
Description
Technical Field
The invention relates to the technical field of modification of high polymer materials, in particular to a halogen-free flame-retardant polypropylene material for automotive interior and a preparation method thereof.
Background
With the improvement of the awareness of safety and environmental protection of people, particularly the frequent occurrence of passenger car fire injury accidents in recent years, the society has attracted high attention to the combustion safety performance of passenger car materials. The latest national standard GB38262-2019 is to be officially implemented in 7-1.7 in 2020, and the new national standard puts forward more strict requirements on horizontal combustion, vertical combustion, oxygen index and smoke density. In addition, the requirement of people on the quality of air in the automobile is higher and higher, and the main automobile manufacturers at home and abroad make clear requirements on the smell of the interior decoration materials.
The polypropylene has good processing performance, physical, mechanical and chemical properties, and is light in weight and low in cost, so that the polypropylene can be widely applied to automotive interior parts. However, polypropylene is easy to burn in case of fire and can not meet the requirements of interior materials of passenger cars, so that the polypropylene needs to be modified for flame retardance, the currently produced flame-retardant polypropylene is generally a flame retardant polypropylene-polypropylene composite, and although the material has a good flame-retardant effect, the material has the defects of poor smell, poor toughness, precipitation of a flame retardant and the like, and cannot be well applied. The patent CN101475717B uses organic bromine as a flame retardant and uses a flame-retardant synergist antimony trioxide in a matching way, so that the flame-retardant aspect can meet the requirements of the passenger car, but the bromine flame retardant has pungent smell and high smoke density during combustion, and cannot meet the requirements of the passenger car on the aspects of smell and smoke density. The patent CN103756135B selects specific low-odor nitrogen-phosphorus halogen-free flame retardant and metal hydroxide as smoke suppressor, and adds odor adsorbent and TVOC remover to realize the effects of mechanical property, flame retardance and low smoke density. Patent CN103087399B adopts phosphorus-nitrogen expansion type flame retardant and elastomer to mix and granulate to prepare master batch, and then to blend with inorganic filler, to solve the problems of processing and material strength.
In the prior art, although the polypropylene has good flame retardant effect, the problems of low toughness, flame retardant precipitation and poor smell cannot be solved at the same time. Therefore, it is of great practical significance to develop polypropylene materials which not only have good flame retardant effect, but also have excellent rigidity and toughness balance, precipitation resistance and low odor.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a halogen-free flame-retardant polypropylene material for automotive interior and a preparation method thereof.
The invention provides a halogen-free flame-retardant polypropylene material for automotive interiors, which comprises the following raw materials in parts by weight: 40-70 parts of polypropylene, 10-20 parts of coated ammonium polyphosphate, 5-10 parts of piperazine pyrophosphate, 5-10 parts of a synergistic flame retardant, 0.5-2 parts of a coupling agent, 0-10 parts of an inorganic filler, 10-20 parts of a toughening agent, 0.2-1 part of a deodorant and 0.3-1.5 parts of a stabilizer;
the coated ammonium polyphosphate is prepared by performing surface coating modification on high polymeric ammonium polyphosphate by using melamine formaldehyde and epoxy resin.
Preferably, the preparation method of the coated ammonium polyphosphate comprises the following steps: adding 50g of APP into 200mL of absolute ethyl alcohol, ultrasonically dispersing for 0.5h, uniformly dispersing, adjusting the pH to be approximately equal to 6 by using 15% hydrochloric acid, slowly heating to 85 ℃, adding a proper amount of melamine-formaldehyde prepolymer, keeping the temperature at 85 ℃, continuously stirring for 2h, adding the same amount of epoxy resin, adding a curing agent, reacting for 0.5h, and curing the epoxy resin (EP) to prepare the EP-MF-APP coated with the melamine-formaldehyde resin (MF) and the epoxy resin in a double-layer manner.
Preferably, the high polymeric ammonium polyphosphate has a crystallinity n > 1000.
Preferably, the P content of the piperazine pyrophosphate is 20-25 wt%, and the polymerization degree is more than 20.
Preferably, the synergistic flame retardant is one or a mixture of melamine salt, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine cyanurate, melam polyphosphate, melem polyphosphate, cyanuramide polyphosphate, melamine condensation products; the coupling agent is one or a mixture of more of silane coupling agent, titanate coupling agent and aluminate coupling agent; the odor removing agent is one or a mixture of more of chelating type reactive organic salt and microporous silicate.
Preferably, the polypropylene is one or a mixture of block copolymerization polypropylene and homopolymerization polypropylene, and the melt flow rate of the polypropylene under the condition of 230 ℃/2.16KG is 1-100 g/10 min; the toughening agent is one or a mixture of more of ethylene-butene copolymer and ethylene-octene copolymer, and the density of the toughening agent is 0.88-0.90 g/cm3The melt flow rate is 0.5-30 g/10min under the condition of 190 ℃/2.16 KG.
Preferably, the stabilizer is one or a mixture of more of hindered phenol antioxidant, phosphite antioxidant and hindered amine light stabilizer; the inorganic filler is one or a mixture of more of wollastonite, sepiolite, talcum powder, mica and kaolin, and the particle size of the inorganic filler is 1-10 mu m.
The preparation method of the halogen-free flame-retardant polypropylene material for the automotive interior comprises the following steps:
s1, mixing the coated ammonium polyphosphate, the piperazine pyrophosphate and the synergistic flame retardant, heating to 100-120 ℃, adding the coupling agent, and uniformly mixing at a high speed to obtain the modified composite flame retardant;
s2, uniformly mixing the polypropylene, the modified composite flame retardant, the inorganic filler, the toughening agent, the deodorant and the stabilizer at a high speed to obtain a premix;
and S3, adding the premix into a double-screw extruder, and carrying out melting, extrusion, cooling and granulation to obtain the premix.
Preferably, in the step S3, the screw rotation speed of the double-screw extruder is 100-300 r/min, the length-diameter ratio of the screw is (40-44): 1, the temperature is 190-210 ℃, and the vacuum degree is-0.08-0.09 MPa; in the step S2, the high-speed mixing time is 5-15 min; in the step S1, the high-speed mixing condition is 100-150 rpm for 20-30 min.
According to the invention, the coated ammonium polyphosphate is adopted, and melamine, silane and melamine formaldehyde are introduced into the surface reaction coating, so that the ammonium polyphosphate keeps extremely low water solubility, and the problems of easy water absorption and easy precipitation of the ammonium polyphosphate are solved; meanwhile, the surface modification is carried out on the flame retardant through the coupling agent, so that the interfacial tension between the flame retardant and the polypropylene material is greatly reduced, the compatibility between the flame retardant and the high polymer material is increased, and the mechanical property of the composite material is improved; on the other hand, substances which are not easy to volatilize and have low odor are generated by the reaction of the microporous silicon structure or the active group of the odor removing agent and volatile organic compounds, so that TVOC and other small molecular substances generated in raw materials and processing processes can be effectively reduced, the odor is improved, and the VOC volatilization is reduced. Therefore, the polypropylene material disclosed by the invention can meet the flame retardant property, has the characteristics of excellent rigidity and toughness balance, precipitation resistance and low odor, and can be suitable for interior decoration of a passenger car.
The invention has the following beneficial effects:
(1) according to the invention, the coated ammonium polyphosphate and the synergistic flame retardant are compounded, so that the flame retardant can meet the flame retardant performance and solve the problems of easy water absorption and easy precipitation of the flame retardant.
(2) According to the invention, the surface of the flame retardant is modified by the coupling agent, so that the compatibility of the flame retardant and a high polymer material is increased, and the toughness of the composite material is improved by combining the toughness of the elastomer.
(3) By adding the deodorant, the microporous silicon structure or active groups of the deodorant react with volatile organic matters to generate substances with low volatility and low odor in the material processing process, so that the aims of low odor and low VOC can be achieved.
(4) The polypropylene has the advantages of good flame retardance, precipitation resistance, balanced mechanical properties, low odor and low TVOC, and is suitable for interior decoration of passenger cars.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
In the following examples and comparative examples, polypropylene was a block copolymerized propylene having a melt flow rate of 60g/10min and a designation BX 3900; the P content of the piperazine pyrophosphate is 20-25 wt%, and the polymerization degree is more than 20; the synergistic flame retardant is melamine polyphosphate; the coupling agent is silane coupling agent KH550, and the manufacturer is Nanjing volleyball chemical research institute; the degassing agent is a mixture of microporous aluminum silicate and organic matter, model CW-58, Changzhou new policy of manufacturers; the inorganic filler is needle-shaped wollastonite with the length-diameter ratio (7-10) of 1 and the particle size of 1-10 mu m; the toughening agent is ethylene-butylene copolymer with the trade mark LC565, and the manufacturer is LG company; the stabilizer consists of a main antioxidant, an auxiliary antioxidant and a light stabilizer according to the mass ratio of 2:1:1, wherein the model of the main antioxidant is Ciba IRGANOX1010, the model of the auxiliary oxidant is Ciba IRGAFOS168, and the model of the light stabilizer is Cyanote UV-3808PP 5.
Example 1
The halogen-free flame-retardant polypropylene material for the automotive interior comprises the following raw materials in parts by weight: 55 parts of polypropylene, 12.5 parts of coated ammonium polyphosphate, 6.25 parts of piperazine pyrophosphate, 6.25 parts of synergistic flame retardant, 0.5 part of coupling agent, 5 parts of inorganic filler, 15 parts of toughening agent, 0.5 part of odor removing agent and 0.6 part of stabilizer;
the preparation method of the coated ammonium polyphosphate comprises the following steps: adding 50g of APP into 200mL of absolute ethyl alcohol, ultrasonically dispersing for 0.5h, uniformly dispersing, adjusting the pH to be approximately equal to 6 by using 15% hydrochloric acid, slowly heating to 85 ℃, adding a proper amount of melamine-formaldehyde prepolymer, keeping the temperature at 85 ℃, continuously stirring for 2h, adding the same amount of epoxy resin, adding a curing agent, reacting for 0.5h, and curing the epoxy resin (EP) to prepare the EP-MF-APP coated by the melamine-formaldehyde resin (MF) and the epoxy resin in a double-layer manner; the crystallinity n of the high polymeric ammonium polyphosphate is more than 1000.
The preparation method of the halogen-free flame-retardant polypropylene material for the automotive interior comprises the following steps:
s1, mixing the coated ammonium polyphosphate, the piperazine pyrophosphate and the synergistic flame retardant, heating to 110 ℃, adding the coupling agent, and mixing at a high speed of 120rpm for 25min to obtain the modified composite flame retardant;
s2, mixing the polypropylene, the modified composite flame retardant, the inorganic filler, the toughening agent, the deodorant and the stabilizer at a high speed for 10min to obtain a premix;
s3, adding the premix into a double-screw extruder, and carrying out melting, extrusion, cooling and granulation to obtain the premix, wherein the rotating speed of a screw of the double-screw extruder is 200r/min, the length-diameter ratio of the screw is 42:1, the temperature is 190-210 ℃, and the vacuum degree is-0.085 MPa.
Example 2
The halogen-free flame-retardant polypropylene material for the automotive interior comprises the following raw materials in parts by weight: 52 parts of polypropylene, 14 parts of coated ammonium polyphosphate, 7 parts of piperazine pyrophosphate, 7 parts of a synergistic flame retardant, 0.8 part of a coupling agent, 5 parts of an inorganic filler, 15 parts of a toughening agent, 0.5 part of a deodorant and 0.3 part of a stabilizer;
the preparation method of the coated ammonium polyphosphate comprises the following steps: adding 50g of APP into 200mL of absolute ethyl alcohol, ultrasonically dispersing for 0.5h, uniformly dispersing, adjusting the pH to be approximately equal to 6 by using 15% hydrochloric acid, slowly heating to 85 ℃, adding a proper amount of melamine-formaldehyde prepolymer, keeping the temperature at 85 ℃, continuously stirring for 2h, adding the same amount of epoxy resin, adding a curing agent, reacting for 0.5h, and curing the epoxy resin (EP) to prepare the EP-MF-APP coated by the melamine-formaldehyde resin (MF) and the epoxy resin in a double-layer manner; the crystallinity n of the high polymeric ammonium polyphosphate is more than 1000.
The preparation method of the halogen-free flame-retardant polypropylene material for the automotive interior comprises the following steps:
s1, mixing the coated ammonium polyphosphate, the piperazine pyrophosphate and the synergistic flame retardant, heating to 100 ℃, adding the coupling agent, and mixing at a high speed of 100rpm for 20min to obtain the modified composite flame retardant;
s2, mixing the polypropylene, the modified composite flame retardant, the inorganic filler, the toughening agent, the deodorant and the stabilizer at a high speed for 5min to obtain a premix;
s3, adding the premix into a double-screw extruder, and carrying out melting, extrusion, cooling and granulation to obtain the premix, wherein the rotating speed of a screw of the double-screw extruder is 100r/min, the length-diameter ratio of the screw is 40:1, the temperature is 190-210 ℃, and the vacuum degree is-0.08 MPa.
Example 3
The halogen-free flame-retardant polypropylene material for the automotive interior comprises the following raw materials in parts by weight: 50 parts of polypropylene, 15 parts of coated ammonium polyphosphate, 7.5 parts of piperazine pyrophosphate, 7.5 parts of synergistic flame retardant, 1.5 parts of coupling agent, 5 parts of inorganic filler, 15 parts of toughening agent, 0.5 part of odor removing agent and 0.6 part of stabilizer;
the preparation method of the coated ammonium polyphosphate comprises the following steps: adding 50g of APP into 200mL of absolute ethyl alcohol, ultrasonically dispersing for 0.5h, uniformly dispersing, adjusting the pH to be approximately equal to 6 by using 15% hydrochloric acid, slowly heating to 85 ℃, adding a proper amount of melamine-formaldehyde prepolymer, keeping the temperature at 85 ℃, continuously stirring for 2h, adding the same amount of epoxy resin, adding a curing agent, reacting for 0.5h, and curing the epoxy resin (EP) to prepare the EP-MF-APP coated by the melamine-formaldehyde resin (MF) and the epoxy resin in a double-layer manner; the crystallinity n of the high polymeric ammonium polyphosphate is more than 1000.
The preparation method of the halogen-free flame-retardant polypropylene material for the automotive interior comprises the following steps:
s1, mixing the coated ammonium polyphosphate, the piperazine pyrophosphate and the synergistic flame retardant, heating to 100 ℃, adding the coupling agent, and mixing at a high speed of 150rpm for 30min to obtain the modified composite flame retardant;
s2, mixing the polypropylene, the modified composite flame retardant, the inorganic filler, the toughening agent, the deodorant and the stabilizer at a high speed for 15min to obtain a premix;
s3, adding the premix into a double-screw extruder, and carrying out melting, extrusion, cooling and granulation to obtain the premix, wherein the rotating speed of a screw of the double-screw extruder is 300r/min, the length-diameter ratio of the screw is 44:1, the temperature is 190-210 ℃, and the vacuum degree is-0.09 MPa.
Example 4
The halogen-free flame-retardant polypropylene material for the automotive interior comprises the following raw materials in parts by weight: 70 parts of polypropylene, 20 parts of coated ammonium polyphosphate, 5 parts of piperazine pyrophosphate, 0.5 part of coupling agent, 5 parts of toughening agent, 0.2 part of odor removing agent and 1.5 parts of stabilizing agent;
the preparation method of the coated ammonium polyphosphate comprises the following steps: adding 50g of APP into 200mL of absolute ethyl alcohol, ultrasonically dispersing for 0.5h, uniformly dispersing, adjusting the pH to be approximately equal to 6 by using 15% hydrochloric acid, slowly heating to 85 ℃, adding a proper amount of melamine-formaldehyde prepolymer, keeping the temperature at 85 ℃, continuously stirring for 2h, adding the same amount of epoxy resin, adding a curing agent, reacting for 0.5h, and curing the epoxy resin (EP) to prepare the EP-MF-APP coated by the melamine-formaldehyde resin (MF) and the epoxy resin in a double-layer manner; the crystallinity n of the high polymeric ammonium polyphosphate is more than 1000.
The preparation method of the halogen-free flame-retardant polypropylene material for the automotive interior comprises the following steps:
s1, mixing the coated ammonium polyphosphate, the piperazine pyrophosphate and the synergistic flame retardant, heating to 100 ℃, adding the coupling agent, and mixing at a high speed of 100rpm for 20min to obtain the modified composite flame retardant;
s2, mixing the polypropylene, the modified composite flame retardant, the inorganic filler, the toughening agent, the deodorant and the stabilizer at a high speed for 5min to obtain a premix;
s3, adding the premix into a double-screw extruder, and carrying out melting, extrusion, cooling and granulation to obtain the premix, wherein the rotating speed of a screw of the double-screw extruder is 100r/min, the length-diameter ratio of the screw is 40:1, the temperature is 190-210 ℃, and the vacuum degree is-0.08 MPa.
Example 5
The halogen-free flame-retardant polypropylene material for the automotive interior comprises the following raw materials in parts by weight: 40 parts of polypropylene, 10 parts of coated ammonium polyphosphate, 10 parts of piperazine pyrophosphate, 10 parts of a synergistic flame retardant, 2 parts of a coupling agent, 10 parts of an inorganic filler, 20 parts of a toughening agent, 1 part of a deodorant and 0.6 part of a stabilizer;
the preparation method of the coated ammonium polyphosphate comprises the following steps: adding 50g of APP into 200mL of absolute ethyl alcohol, ultrasonically dispersing for 0.5h, uniformly dispersing, adjusting the pH to be approximately equal to 6 by using 15% hydrochloric acid, slowly heating to 85 ℃, adding a proper amount of melamine-formaldehyde prepolymer, keeping the temperature at 85 ℃, continuously stirring for 2h, adding the same amount of epoxy resin, adding a curing agent, reacting for 0.5h, and curing the epoxy resin (EP) to prepare the EP-MF-APP coated by the melamine-formaldehyde resin (MF) and the epoxy resin in a double-layer manner; the crystallinity n of the high polymeric ammonium polyphosphate is more than 1000.
The preparation method of the halogen-free flame-retardant polypropylene material for the automotive interior comprises the following steps:
s1, mixing the coated ammonium polyphosphate, the piperazine pyrophosphate and the synergistic flame retardant, heating to 100 ℃, adding the coupling agent, and mixing at a high speed of 100rpm for 20min to obtain the modified composite flame retardant;
s2, mixing the polypropylene, the modified composite flame retardant, the inorganic filler, the toughening agent, the deodorant and the stabilizer at a high speed for 5min to obtain a premix;
s3, adding the premix into a double-screw extruder, and carrying out melting, extrusion, cooling and granulation to obtain the premix, wherein the rotating speed of a screw of the double-screw extruder is 100r/min, the length-diameter ratio of the screw is 40:1, the temperature is 190-210 ℃, and the vacuum degree is-0.08 MPa.
Comparative example 1
Comparative example 1 is a control of example 2, specifically:
52 parts of polypropylene, 14 parts of ammonium polyphosphate, 7 parts of piperazine pyrophosphate, 7 parts of a synergistic flame retardant, 0.8 part of a coupling agent, 5 parts of an inorganic filler, 15 parts of a toughening agent, 0.5 part of a deodorant and 0.3 part of a stabilizer;
the preparation method of the polypropylene material comprises the following steps:
s1, mixing ammonium polyphosphate, piperazine pyrophosphate and a synergistic flame retardant, heating to 100 ℃, adding a coupling agent, and mixing at a high speed of 100rpm for 20min to obtain a modified composite flame retardant;
s2, mixing the polypropylene, the modified composite flame retardant, the inorganic filler, the toughening agent, the deodorant and the stabilizer at a high speed for 5min to obtain a premix;
s3, adding the premix into a double-screw extruder, and carrying out melting, extrusion, cooling and granulation to obtain the premix, wherein the rotating speed of a screw of the double-screw extruder is 100r/min, the length-diameter ratio of the screw is 40:1, the temperature is 190-210 ℃, and the vacuum degree is-0.08 MPa.
Comparative example 2
Comparative example 2 is a control of example 3, specifically:
the polypropylene material comprises the following raw materials in parts by weight: 50 parts of polypropylene, 15 parts of coated ammonium polyphosphate, 7.5 parts of piperazine pyrophosphate, 1.5 parts of coupling agent, 5 parts of inorganic filler, 15 parts of toughening agent, 0.5 part of odor removing agent and 0.6 part of stabilizing agent;
the preparation method of the coated ammonium polyphosphate comprises the following steps: adding 50g of APP into 200mL of absolute ethyl alcohol, ultrasonically dispersing for 0.5h, uniformly dispersing, adjusting the pH to be approximately equal to 6 by using 15% hydrochloric acid, slowly heating to 85 ℃, adding a proper amount of melamine-formaldehyde prepolymer, keeping the temperature at 85 ℃, continuously stirring for 2h, adding the same amount of epoxy resin, adding a curing agent, reacting for 0.5h, and curing the epoxy resin (EP) to prepare the EP-MF-APP coated by the melamine-formaldehyde resin (MF) and the epoxy resin in a double-layer manner; the crystallinity n of the high polymeric ammonium polyphosphate is more than 1000.
The preparation method of the polypropylene material comprises the following steps:
s1, mixing the coated ammonium polyphosphate and the piperazine pyrophosphate, heating to 100 ℃, adding the coupling agent, and mixing at a high speed of 150rpm for 30min to obtain the modified composite flame retardant;
s2, mixing the polypropylene, the modified composite flame retardant, the inorganic filler, the toughening agent, the deodorant and the stabilizer at a high speed for 15min to obtain a premix;
s3, adding the premix into a double-screw extruder, and carrying out melting, extrusion, cooling and granulation to obtain the premix, wherein the rotating speed of a screw of the double-screw extruder is 300r/min, the length-diameter ratio of the screw is 44:1, the temperature is 190-210 ℃, and the vacuum degree is-0.09 MPa.
Comparative example 3
Comparative example 3 is a control of example 3, specifically:
the polypropylene material comprises the following raw materials in parts by weight: 50 parts of polypropylene, 15 parts of coated ammonium polyphosphate, 7.5 parts of piperazine pyrophosphate, 7.5 parts of synergistic flame retardant, 5 parts of inorganic filler, 15 parts of toughening agent, 0.5 part of odor removing agent and 0.6 part of stabilizer;
the preparation method of the coated ammonium polyphosphate comprises the following steps: adding 50g of APP into 200mL of absolute ethyl alcohol, ultrasonically dispersing for 0.5h, uniformly dispersing, adjusting the pH to be approximately equal to 6 by using 15% hydrochloric acid, slowly heating to 85 ℃, adding a proper amount of melamine-formaldehyde prepolymer, keeping the temperature at 85 ℃, continuously stirring for 2h, adding the same amount of epoxy resin, adding a curing agent, reacting for 0.5h, and curing the epoxy resin (EP) to prepare the EP-MF-APP coated by the melamine-formaldehyde resin (MF) and the epoxy resin in a double-layer manner; the crystallinity n of the high polymeric ammonium polyphosphate is more than 1000.
The preparation method of the polypropylene material comprises the following steps:
s1, mixing the coated ammonium polyphosphate, the piperazine pyrophosphate and the synergistic flame retardant, heating to 100 ℃, and mixing at a high speed of 150rpm for 30min to obtain a modified composite flame retardant;
s2, mixing the polypropylene, the modified composite flame retardant, the inorganic filler, the toughening agent, the deodorant and the stabilizer at a high speed for 15min to obtain a premix;
s3, adding the premix into a double-screw extruder, and carrying out melting, extrusion, cooling and granulation to obtain the premix, wherein the rotating speed of a screw of the double-screw extruder is 300r/min, the length-diameter ratio of the screw is 44:1, the temperature is 190-210 ℃, and the vacuum degree is-0.09 MPa.
Comparative example 4
Comparative example 4 is a control of example 5, specifically:
the polypropylene material comprises the following raw materials in parts by weight: 40 parts of polypropylene, 10 parts of coated ammonium polyphosphate, 10 parts of piperazine pyrophosphate, 10 parts of a synergistic flame retardant, 2 parts of a coupling agent, 10 parts of an inorganic filler, 20 parts of a toughening agent and 0.6 part of a stabilizer;
the preparation method of the coated ammonium polyphosphate comprises the following steps: adding 50g of APP into 200mL of absolute ethyl alcohol, ultrasonically dispersing for 0.5h, uniformly dispersing, adjusting the pH to be approximately equal to 6 by using 15% hydrochloric acid, slowly heating to 85 ℃, adding a proper amount of melamine-formaldehyde prepolymer, keeping the temperature at 85 ℃, continuously stirring for 2h, adding the same amount of epoxy resin, adding a curing agent, reacting for 0.5h, and curing the epoxy resin (EP) to prepare the EP-MF-APP coated by the melamine-formaldehyde resin (MF) and the epoxy resin in a double-layer manner; the crystallinity n of the high polymeric ammonium polyphosphate is more than 1000.
The preparation method of the polypropylene material comprises the following steps:
s1, mixing the coated ammonium polyphosphate, the piperazine pyrophosphate and the synergistic flame retardant, heating to 100 ℃, adding the coupling agent, and mixing at a high speed of 100rpm for 20min to obtain the modified composite flame retardant;
s2, mixing the polypropylene, the modified composite flame retardant, the inorganic filler, the toughening agent and the stabilizer at a high speed for 5min to obtain a premix;
s3, adding the premix into a double-screw extruder, and carrying out melting, extrusion, cooling and granulation to obtain the premix, wherein the rotating speed of a screw of the double-screw extruder is 100r/min, the length-diameter ratio of the screw is 40:1, the temperature is 190-210 ℃, and the vacuum degree is-0.08 MPa.
The polypropylene materials prepared in examples 1-5 and comparative examples 1-4 are dried in a forced air oven at 90-100 ℃ for 2-3 hours, and then the dried particles are subjected to injection molding on an injection molding machine to prepare a sample, and a performance test is performed. The bending performance test is carried out according to ISO 178 standard, the size of a test sample is 80 multiplied by 10 multiplied by 4mm, the span is 64mm, and the bending speed is 2 mm/min; the impact performance test of the simply supported beam is carried out according to the ISO 179-1 standard, the size of a sample is 80 multiplied by 10 multiplied by 4mm, and the depth of a notch is one third of the thickness of the sample; the flame retardance is tested according to GB/T32086 and vertical combustion is carried out; odor rating was tested according to VDA270 standard; the resistance to precipitation was measured by storing the sample in a hot and humid cabinet at 85 deg.C/85% humidity for 168 hours and evaluating the appearance. The test results are shown in table 1:
TABLE 1 results of performance test of examples and comparative examples
Experimental data show that through selection of the flame retardant and the coupling agent, the coated ammonium polyphosphate can obviously improve the precipitation resistance of the flame retardant material, the flame retardance of the material can be met by compounding the coated ammonium polyphosphate and the synergistic flame retardant, the notch impact strength of the coupling agent on the material after the surface of the flame retardant is modified is obviously improved, the rigidity and toughness balance of the mechanical property can be realized, meanwhile, substances which are difficult to volatilize and have low odor are generated by combining the reaction of a smell removing agent on small molecules generated in a material system and a processing process, and various technical index requirements of interior materials of a passenger car can be met.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. The halogen-free flame-retardant polypropylene material for the automotive interior is characterized by comprising the following raw materials in parts by weight: 40-70 parts of polypropylene, 10-20 parts of coated ammonium polyphosphate, 5-10 parts of piperazine pyrophosphate, 5-10 parts of a synergistic flame retardant, 0.5-2 parts of a coupling agent, 0-10 parts of an inorganic filler, 10-20 parts of a toughening agent, 0.2-1 part of a deodorant and 0.3-1.5 parts of a stabilizer;
the coated ammonium polyphosphate is prepared by performing surface coating modification on high polymeric ammonium polyphosphate by using melamine formaldehyde and epoxy resin.
2. The halogen-free flame-retardant polypropylene material for automotive interiors according to claim 1, wherein the preparation method of the coated ammonium polyphosphate comprises the following steps: adding 50g of APP into 200mL of absolute ethyl alcohol, ultrasonically dispersing for 0.5h, uniformly dispersing, adjusting the pH to be approximately equal to 6 by using 15% hydrochloric acid, slowly heating to 85 ℃, adding a proper amount of melamine-formaldehyde prepolymer, keeping the temperature at 85 ℃, continuously stirring for 2h, adding the same amount of epoxy resin, adding a curing agent, reacting for 0.5h, and curing the epoxy resin to prepare the EP-MF-APP coated with the melamine-formaldehyde resin and the epoxy resin in a double-layer manner.
3. The halogen-free flame-retardant polypropylene material for automotive interiors according to claim 1 or 2, wherein the high polymeric ammonium polyphosphate has a crystallinity n > 1000.
4. The halogen-free flame-retardant polypropylene material for automotive interiors according to claim 3, wherein the P content of piperazine pyrophosphate is 20-25 wt%, and the degree of polymerization is greater than 20.
5. The halogen-free flame-retardant polypropylene material for automotive interiors according to claim 4, wherein the synergistic flame retardant is a mixture of one or more of melamine salt, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine cyanurate, melam polyphosphate, melem polyphosphate, cyanuric polyphosphate, melamine condensation products; the coupling agent is one or a mixture of more of silane coupling agent, titanate coupling agent and aluminate coupling agent; the odor removing agent is one or a mixture of more of chelating type reactive organic salt and microporous silicate.
6. The halogen-free flame-retardant polypropylene material for automotive interiors according to claim 5, wherein the polypropylene is a mixture of one or more of block copolymer polypropylene and homo-polypropylene, and the melt flow rate of the polypropylene under 230 ℃/2.16KG is 1-100 g/10 min; the toughening agent is one or a mixture of more of ethylene-butene copolymer and ethylene-octene copolymer, and the density of the toughening agent is 0.88-0.90 g/cm3The melt flow rate is 0.5-30 g/10min under the condition of 190 ℃/2.16 KG.
7. The halogen-free flame-retardant polypropylene material for automotive interiors according to claim 6, wherein the stabilizer is one or a mixture of hindered phenol antioxidants, phosphite antioxidants and hindered amine light stabilizers; the inorganic filler is one or a mixture of more of wollastonite, sepiolite, talcum powder, mica and kaolin, and the particle size of the inorganic filler is 1-10 mu m.
8. The preparation method of the halogen-free flame-retardant polypropylene material for automotive interiors, which is characterized by comprising the following steps:
s1, mixing the coated ammonium polyphosphate, the piperazine pyrophosphate and the synergistic flame retardant, heating to 100-120 ℃, adding the coupling agent, and uniformly mixing at a high speed to obtain the modified composite flame retardant;
s2, uniformly mixing the polypropylene, the modified composite flame retardant, the inorganic filler, the toughening agent, the deodorant and the stabilizer at a high speed to obtain a premix;
and S3, adding the premix into a double-screw extruder, and carrying out melting, extrusion, cooling and granulation to obtain the premix.
9. The method for preparing the halogen-free flame retardant polypropylene material for automobile interiors according to claim 8, wherein in the step S3, the screw rotation speed of the twin-screw extruder is 100-300 r/min, the length-diameter ratio of the screw is (40-44): 1, the temperature is 190-210 ℃, and the vacuum degree is-0.08-0.09 MPa; in the step S2, the high-speed mixing time is 5-15 min; in the step S1, the high-speed mixing condition is 100-150 rpm for 20-30 min.
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