CN108250573A - A kind of halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance and preparation method thereof - Google Patents
A kind of halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance and preparation method thereof Download PDFInfo
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- CN108250573A CN108250573A CN201711462497.9A CN201711462497A CN108250573A CN 108250573 A CN108250573 A CN 108250573A CN 201711462497 A CN201711462497 A CN 201711462497A CN 108250573 A CN108250573 A CN 108250573A
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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
- C08L23/12—Polypropene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
Halogen-free environment-friendly flame-proof polypropylene material the invention discloses a kind of heat oxygen aging resistance and preparation method thereof, the halogen-free environment-friendly flame-proof polypropylene material are made of the raw material of following mass parts：Acrylic resin：50~60 parts；One-piece type fire retardant：20~25 parts；Synergistic fire retardant：3~10 parts；Inorganic filler：5~15 parts；Compatilizer：3~5 parts；Primary antioxidant：0.1~0.2 part；Auxiliary antioxidant：0.2~0.3 part；Coupling agent：0.1~1.5 part；Lubricant：0.1~1 part；Anti-dripping agent：0.1~0.5 part.The halogen-free environment-friendly flame-proof polypropylene material preparation method for material of the heat oxygen aging resistance of the present invention is simple, is in batches sufficiently mixed each material uniformly.The halogen-free environment-friendly flame-proof polypropylene material tie rod of the heat oxygen aging resistance of the present invention crosses neatly, there is excellent flame retardant property, resistance to immersion performance and heatproof air aging performance is precipitated, and processing performance is excellent, preparation process is simple, can carry out large-scale industrial production.
Description
Technical field
Halogen-free environment-friendly flame-proof polypropylene material the present invention relates to a kind of heat oxygen aging resistance and preparation method thereof, belongs to fire-retardant
Technical field of composite materials.
Background technology
Polypropylene (PP) belongs to one of five big general-purpose plastics, is a kind of semicrystalline thermoplastic, possesses good
Mechanical property and processing performance, and cost-effective, have to compare and are widely applied in many fields.Moreover, with polymerization system
With the fast development of catalyst system and catalyzing, polyacrylic kind is continuously increased, and application range constantly extends, and is estimated following one section very long
In time, domestic and international polyacrylic demand will still stablize rising.However, PP is in itself as a kind of plastics and most of modelings
For material equally there are inflammable defect, itself oxygen index (OI) is only 17%~18%.PP calorific values during burning are very big, and companion
With molten drop, easily as flame transmission source, it is therefore desirable to PP be carried out flame-retardant modified.
At present, what common fire-retardant PP was mostly used has halogen fire retardant, and technology is extremely ripe.Such as CN
102690465A discloses a kind of polypropylene flame redardant compounded using decabromodiphenylethane and antimony oxide as flame-retardant system；
CN 102964682A disclose a kind of flame-retardant polypropylene compounded using eight bromo ether and synergistic flame retardant containing antimony as flame-retardant system
Alkene.A large amount of black smog and poisonous gas can be given out during halogen PP product burns, serious threat the health of the mankind, while
Escape, rescue when fire occurs cause no small obstruction.Therefore, the PP materials containing halogen-free flame retardants just come into being.
Most widely used halogen-free flame retardants is the expansion type flame retardant based on ammonium polyphosphate (APP) in halogen-free flameproof PP, addition
The PP products of the expansion type flame retardant have many advantages, such as low cigarette, halogen-free environmental in burning.However, APP is water-soluble larger in itself,
Facile hydrolysis, the ammonium ion in ammonium polyphosphate can be converted into ammonia in lasting thermal histories and overflow system, and in high temperature process
Easily degradation in the process, these can all cause the flame retarding efficiency of the fire retardant based on APP to be remarkably decreased or even lose fire-retardant
Performance.
Invention content
The purpose of the present invention is to provide a kind of halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance and its preparation sides
Method.
The technical solution used in the present invention is：
A kind of halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance, is made of the raw material of following mass parts：
Acrylic resin：50~60 parts；
One-piece type fire retardant：20~25 parts；
Synergistic fire retardant：3~10 parts；
Inorganic filler：5~15 parts；
Compatilizer：3~5 parts；
Primary antioxidant：0.1~0.2 part；
Auxiliary antioxidant：0.2~0.3 part；
Coupling agent：0.1~1.5 part；
Lubricant：0.1~1 part；
Anti-dripping agent：0.1~0.5 part.
The acrylic resin is at least one in homopolypropylene, block copolymerization polypropylene, atactic copolymerized polypropene
Kind, melt index be 1~50g/10min, 230 DEG C/2.16kg.
The structural formula of the one-piece type fire retardant is：Wherein,
1≤a≤10000,1≤b≤200,1≤c≤10000, M are one kind in ethanol amine, piperidines, morpholine.
The synergistic fire retardant wraps up at least one in phosphate, melamine polyphosphate, melamine for melamine
Kind.
The inorganic filler is the talcum powder of 1000~2500 mesh, the barium sulfate of 1000~2000 mesh, 1000~1500
At least one of purpose wollastonite.
The compatilizer is polypropylene grafted maleic anhydride, the carboxylic polypropylene graft copolymer of side chain, side chain contain
At least one of polypropylene graft copolymer of epoxy group.
The coupling agent is at least one of silane coupling agent, titante coupling agent.
The preparation method of the halogen-free environment-friendly flame-proof polypropylene material of above-mentioned heat oxygen aging resistance, includes the following steps：
1) acrylic resin, compatilizer, primary antioxidant, auxiliary antioxidant, lubricant and anti-dripping agent are added in mixed at a high speed
Conjunction machine is uniformly mixed, then material is transferred to the main drawing-in device of double screw extruder；
2) one-piece type fire retardant, synergistic fire retardant and inorganic filler are added in into high-speed mixer, are uniformly mixed, then by material
It is transferred to the side drawing-in device of double screw extruder；
3) coupling agent is fitted into the liquid charging device that double screw extruder adds fine mouth；
4) start double screw extruder, adjust twin-screw temperature and screw speed, vacuumize, regulate main feeding dress
It puts, the charging rate of side drawing-in device and liquid charging device, squeezes out, cross water cooling, then cool down through air blower through sink, cut
Grain, obtains the halogen-free environment-friendly flame-proof polypropylene granules of heat oxygen aging resistance.
Liquid charging device described in step 3) is heat preserving type Weightlessness balance liquid charging device, and charging precision is ± 0.5%.
The double screw extruder is parallel equidirectional two-screw extruder, and screw slenderness ratio is (40~75)：1, screw rod
Rotating speed is 300~600r/min, and vacuum degree is -0.07~-1.1MPa, and each area's temperature is：One 170~180 DEG C of area, two-four areas
180~185 DEG C, 185~190 DEG C of five-six area, 190~195 DEG C of seven-nine area, 180~185 DEG C of ten-ten one area, head 160~
180℃。
The beneficial effects of the invention are as follows：The halogen-free environment-friendly flame-proof polypropylene material tie rod of the heat oxygen aging resistance of the present invention crosses water
There is excellent flame retardant property, resistance to immersion performance and heatproof air aging performance is precipitated, and processing performance is excellent, prepare for not neatly
It is simple for process, large-scale industrial production can be carried out.
1) the one-piece type fire retardant that the present invention uses has stable chemical constitution, water-soluble small, and collection acid source, carbon source are gentle
Source is integrated, and is different from conventional expanded fire retardant acid source, carbon source and the separated state of air source, proportions when avoiding processing
It floats, ensure that the stability in use of fire retardant；
2) synergistic fire retardant that the present invention uses can be heated in one-piece type fire retardant and the ammonium ion in system is overflowed
In the case of leading to flame retardant property decline, play and supply the fire-retardant effect of air source, synergistic；
3) present invention coordinates side feeding using Weightlessness balance liquid charging device, makes fire retardant, inorganic filler and coupling agent etc.
Disperse in whole system more uniformly, the overall performance of material is obviously improved.
Specific embodiment
A kind of halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance, is made of the raw material of following mass parts：
Acrylic resin：50~60 parts；
One-piece type fire retardant：20~25 parts；
Synergistic fire retardant：3~10 parts；
Inorganic filler：5~15 parts；
Compatilizer：3~5 parts；
Primary antioxidant：0.1~0.2 part；
Auxiliary antioxidant：0.2~0.3 part；
Coupling agent：0.1~1.5 part；
Lubricant：0.1~1 part；
Anti-dripping agent：0.1~0.5 part.
Preferably, the acrylic resin is homopolypropylene, in block copolymerization polypropylene, atactic copolymerized polypropene
At least one, melt index be 1~50g/10min, 230 DEG C/2.16kg.
Preferably, the structural formula of the one-piece type fire retardant is：
Wherein, 1≤a≤10000,1≤b≤200,1≤c≤10000, M are one kind in ethanol amine, piperidines, morpholine.
Preferably, the synergistic fire retardant is wrapped up for melamine in phosphate, melamine polyphosphate, melamine
It is at least one.
Preferably, the inorganic filler is the talcum powder of 1000~2500 mesh, the barium sulfate of 1000~2000 mesh, 1000
At least one of wollastonite of~1500 mesh.
Preferably, the compatilizer for polypropylene grafted maleic anhydride, the carboxylic polypropylene graft copolymer of side chain,
At least one of the polypropylene graft copolymer of side chain containing epoxy group, they can enhance the phase between PP and polarity powder
Capacitive.
Preferably, the primary antioxidant is Hinered phenols antioxidant, and Hinered phenols antioxidant can terminate the uncle in PP
Carbon radicals.
It is further preferred that the primary antioxidant is antioxidant 1010.
Preferably, the auxiliary antioxidant is phosphite ester kind antioxidant, and phosphite ester kind antioxidant can decompose
Oxide prevents the generation of tertiary carbon free radical in PP, has apparent synergistic effect with the cooperation of Hinered phenols primary antioxidant.
It is further preferred that the auxiliary antioxidant is irgasfos 168.
Preferably, the coupling agent is at least one of silane coupling agent, titante coupling agent.
Preferably, the lubricant be N, N'- ethylenebisstearamides (EB-FF), polyethylene wax, stearic acid, oxygen
Change at least one of polyethylene wax, they may be inserted into inside PP resins, reduce the interaction between molecular resin, play interior
The effect of lubrication can also can be reduced by resin melt internal migration to surface between resin particle product, melt and equipment
Outer lubrication is played the role of in phase mutual friction.
Preferably, the anti-dripping agent is pure powder type anti-drip agents.
The preparation method of the halogen-free environment-friendly flame-proof polypropylene material of above-mentioned heat oxygen aging resistance, includes the following steps：
1) acrylic resin, compatilizer, primary antioxidant, auxiliary antioxidant, lubricant and anti-dripping agent are added in mixed at a high speed
Conjunction machine is uniformly mixed, then material is transferred to the main drawing-in device of double screw extruder；
2) one-piece type fire retardant, synergistic fire retardant and inorganic filler are added in into high-speed mixer, are uniformly mixed, then by material
It is transferred to the side drawing-in device of double screw extruder；
3) coupling agent is fitted into the liquid charging device that double screw extruder adds fine mouth；
4) start double screw extruder, adjust twin-screw temperature and screw speed, vacuumize, regulate main feeding dress
It puts, the charging rate of side drawing-in device and liquid charging device, squeezes out, cross water cooling, then cool down through air blower through sink, cut
Grain, obtains the halogen-free environment-friendly flame-proof polypropylene granules of heat oxygen aging resistance.
Preferably, the liquid charging device described in step 3) is heat preserving type Weightlessness balance liquid charging device, and charging precision is
± 0.5%.
Preferably, the double screw extruder is parallel equidirectional two-screw extruder, and screw slenderness ratio is (40~75)：
1, screw speed is 300~600r/min, and vacuum degree is -0.07~-1.1MPa, and each area's temperature is：One 170~180 DEG C of area,
Two-four 180~185 DEG C of areas, 185~190 DEG C of five-six area, 190~195 DEG C of seven-nine area, 180~185 DEG C of ten-ten one area, machine
First 160~180 DEG C.
The present invention is made further explanation and description with reference to specific embodiment.
Embodiment 1：
A kind of halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance, is made of the raw material of following mass parts：
Homopolypropylene (trade mark H110MA, India's letter is sincere, melt index 10.1g/10min, 230 DEG C/2.16kg)：50
Part；
One-piece type fire retardant (AMP, Qingyuan Presafer Phosphor Chemical Company Limited)：25 parts；
Melamine package ammonium polyphosphate (APP262, Qingyuan Presafer Phosphor Chemical Company Limited)：3 parts；
Talcum powder (2000 mesh, pure and fresh courser)：15 parts；
Grafted maleic anhydride compatilizer (trade mark KT-1, Qingdao Lv Wei Chemical Co., Ltd.s)：5 parts；
Antioxidant 1010 (Shandong San Feng Chemical Co., Ltd.s)：0.1 part；
Irgasfos 168 (Shandong San Feng Chemical Co., Ltd.s)：0.2 part；
Titanate coupling agent (trade mark NT201, monarch please)：1 part；
N,N' ethylene bis stearmide (Japanese Kao)：0.4 part；
Pure powder type anti-dripping agent (trade mark M532, Daikin)：0.3 part.
The preparation method of the halogen-free environment-friendly flame-proof polypropylene material of above-mentioned heat oxygen aging resistance is as follows：
1) by homopolypropylene, grafted maleic anhydride compatilizer, antioxidant 1010, irgasfos 168, N, N'- ethylidene
Bis-stearamides and pure powder type anti-dripping agent add in high-speed mixer, and adjustment blender rotating speed to 1200r/min stirs 3min,
Material is transferred to the main drawing-in device of double screw extruder again；
2) one-piece type fire retardant, melamine package ammonium polyphosphate and talcum powder are added in into high-speed mixer, adjustment blender turns
Speed stirs 5min, then material is transferred to the side drawing-in device of double screw extruder to 1800r/min；
3) titanate coupling agent loading double screw extruder is added to the liquid charging device (model of fine mouth：LF-DL-50, Zheng
State Bart's Melt Pump Co., Ltd) in；
4) start double screw extruder (Nanjing section Asia, screw diameter 36mm, screw slenderness ratio 48:1) double spiral shells, are adjusted
Bar extrusion built-in temperature is 170~195 DEG C, rotating speed 300r/min, vacuum degree are -0.8MPa, regulates main drawing-in device, side
The charging rate of drawing-in device and liquid charging device squeezes out, water cooling is crossed, then through air blower through 25 ± 5 DEG C of sink of water temperature
Cooling, pelletizing obtain the halogen-free environment-friendly flame-proof polypropylene granules of heat oxygen aging resistance；
5) the halogen-free environment-friendly flame-proof polypropylene granules of heat oxygen aging resistance are placed at 85 DEG C and dry 3h, then be transferred to horizontal injection press
(model：HS-1200, extra large stone molding machine), setting injection temperature is 180~195 DEG C, is molded into standard batten, 23 DEG C, 50% humidity
Under conditions of place 48h, then be tested for the property.
Embodiment 2：
A kind of halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance, is made of the raw material of following mass parts：
Homopolypropylene (trade mark H110MA, India's letter is sincere, melt index 10.1g/10min, 230 DEG C/2.16kg)：55
Part；
One-piece type fire retardant (AMP, Qingyuan Presafer Phosphor Chemical Company Limited)：25 parts；
Melamine package ammonium polyphosphate (APP262, Qingyuan Presafer Phosphor Chemical Company Limited)：3 parts；
Talcum powder (2000 mesh, pure and fresh courser)：10 parts；
Grafted maleic anhydride compatilizer (trade mark KT-1, Qingdao Lv Wei Chemical Co., Ltd.s)：5 parts；
Antioxidant 1010 (Shandong San Feng Chemical Co., Ltd.s)：0.1 part；
Irgasfos 168 (Shandong San Feng Chemical Co., Ltd.s)：0.2 part；
Titanate coupling agent (trade mark NT201, monarch please)：1 part；
N,N' ethylene bis stearmide (Japanese Kao)：0.4 part；
Pure powder type anti-dripping agent (trade mark M532, Daikin)：0.3 part.
The preparation method of the halogen-free environment-friendly flame-proof polypropylene material of above-mentioned heat oxygen aging resistance is as follows：
1) by homopolypropylene, grafted maleic anhydride compatilizer, antioxidant 1010, irgasfos 168, N, N'- ethylidene
Bis-stearamides and pure powder type anti-dripping agent add in high-speed mixer, and adjustment blender rotating speed to 1200r/min stirs 3min,
Material is transferred to the main drawing-in device of double screw extruder again；
2) one-piece type fire retardant, melamine package ammonium polyphosphate and talcum powder are added in into high-speed mixer, adjustment blender turns
Speed stirs 5min, then material is transferred to the side drawing-in device of double screw extruder to 1800r/min；
3) titanate coupling agent loading double screw extruder is added to the liquid charging device (model of fine mouth：LF-DL-50, Zheng
State Bart's Melt Pump Co., Ltd) in；
4) start double screw extruder (Nanjing section Asia, screw diameter 36mm, screw slenderness ratio 48:1) double spiral shells, are adjusted
Bar extrusion built-in temperature is 170~195 DEG C, rotating speed 300r/min, vacuum degree are -0.8MPa, regulates main drawing-in device, side
The charging rate of drawing-in device and liquid charging device squeezes out, water cooling is crossed, then through air blower through 25 ± 5 DEG C of sink of water temperature
Cooling, pelletizing obtain the halogen-free environment-friendly flame-proof polypropylene granules of heat oxygen aging resistance；
5) the halogen-free environment-friendly flame-proof polypropylene granules of heat oxygen aging resistance are placed at 85 DEG C and dry 3h, then be transferred to horizontal injection press
(model：HS-1200, extra large stone molding machine), setting injection temperature is 180~195 DEG C, is molded into standard batten, 23 DEG C, 50% humidity
Under conditions of place 48h, then be tested for the property.
Embodiment 3：
A kind of halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance, is made of the raw material of following mass parts：
Homopolypropylene (trade mark H110MA, India's letter is sincere, melt index 10.1g/10min, 230 DEG C/2.16kg)：60
Part；
One-piece type fire retardant (AMP, Qingyuan Presafer Phosphor Chemical Company Limited)：25 parts；
Melamine package ammonium polyphosphate (APP262, Qingyuan Presafer Phosphor Chemical Company Limited)：3 parts；
Talcum powder (2000 mesh, pure and fresh courser)：5 parts；
Grafted maleic anhydride compatilizer (trade mark KT-1, Qingdao Lv Wei Chemical Co., Ltd.s)：5 parts；
Antioxidant 1010 (Shandong San Feng Chemical Co., Ltd.s)：0.1 part；
Irgasfos 168 (Shandong San Feng Chemical Co., Ltd.s)：0.2 part；
Titanate coupling agent (trade mark NT201, monarch please)：1 part；
N,N' ethylene bis stearmide (Japanese Kao)：0.4 part；
Pure powder type anti-dripping agent (trade mark M532, Daikin)：0.3 part.
The preparation method of the halogen-free environment-friendly flame-proof polypropylene material of above-mentioned heat oxygen aging resistance is as follows：
1) by homopolypropylene, grafted maleic anhydride compatilizer, antioxidant 1010, irgasfos 168, N, N'- ethylidene
Bis-stearamides and pure powder type anti-dripping agent add in high-speed mixer, and adjustment blender rotating speed to 1200r/min stirs 3min,
Material is transferred to the main drawing-in device of double screw extruder again；
2) one-piece type fire retardant, melamine package ammonium polyphosphate and talcum powder are added in into high-speed mixer, adjustment blender turns
Speed stirs 5min, then material is transferred to the side drawing-in device of double screw extruder to 1800r/min；
3) titanate coupling agent loading double screw extruder is added to the liquid charging device (model of fine mouth：LF-DL-50, Zheng
State Bart's Melt Pump Co., Ltd) in；
4) start double screw extruder (Nanjing section Asia, screw diameter 36mm, screw slenderness ratio 48:1) double spiral shells, are adjusted
Bar extrusion built-in temperature is 170~195 DEG C, rotating speed 300r/min, vacuum degree are -0.8MPa, regulates main drawing-in device, side
The charging rate of drawing-in device and liquid charging device squeezes out, water cooling is crossed, then through air blower through 25 ± 5 DEG C of sink of water temperature
Cooling, pelletizing obtain the halogen-free environment-friendly flame-proof polypropylene granules of heat oxygen aging resistance；
5) the halogen-free environment-friendly flame-proof polypropylene granules of heat oxygen aging resistance are placed at 85 DEG C and dry 3h, then be transferred to horizontal injection press
(model：HS-1200, extra large stone molding machine), setting injection temperature is 180~195 DEG C, is molded into standard batten, 23 DEG C, 50% humidity
Under conditions of place 48h, then be tested for the property.
Embodiment 4：
A kind of halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance, is made of the raw material of following mass parts：
Homopolypropylene (trade mark H110MA, India's letter is sincere, melt index 10.1g/10min, 230 DEG C/2.16kg)：55
Part；
One-piece type fire retardant (AMP, Qingyuan Presafer Phosphor Chemical Company Limited)：23 parts；
Melamine polyphosphate (MPP200, Qingyuan Presafer Phosphor Chemical Company Limited)：5 parts；
Talcum powder (2000 mesh, pure and fresh courser)：10 parts；
Grafted maleic anhydride compatilizer (trade mark KT-1, Qingdao Lv Wei Chemical Co., Ltd.s)：5 parts；
Antioxidant 1010 (Shandong San Feng Chemical Co., Ltd.s)：0.1 part；
Irgasfos 168 (Shandong San Feng Chemical Co., Ltd.s)：0.2 part；
Titanate coupling agent (trade mark NT201, monarch please)：1 part；
N,N' ethylene bis stearmide (Japanese Kao)：0.4 part；
Pure powder type anti-dripping agent (trade mark M532, Daikin)：0.3 part.
The preparation method of the halogen-free environment-friendly flame-proof polypropylene material of above-mentioned heat oxygen aging resistance is as follows：
1) by homopolypropylene, grafted maleic anhydride compatilizer, antioxidant 1010, irgasfos 168, N, N'- ethylidene
Bis-stearamides and pure powder type anti-dripping agent add in high-speed mixer, and adjustment blender rotating speed to 1200r/min stirs 3min,
Material is transferred to the main drawing-in device of double screw extruder again；
2) one-piece type fire retardant, melamine package ammonium polyphosphate and talcum powder are added in into high-speed mixer, adjustment blender turns
Speed stirs 5min, then material is transferred to the side drawing-in device of double screw extruder to 1800r/min；
3) titanate coupling agent loading double screw extruder is added to the liquid charging device (model of fine mouth：LF-DL-50, Zheng
State Bart's Melt Pump Co., Ltd) in；
4) start double screw extruder (Nanjing section Asia, screw diameter 36mm, screw slenderness ratio 48:1) double spiral shells, are adjusted
Bar extrusion built-in temperature is 170~195 DEG C, rotating speed 300r/min, vacuum degree are -0.8MPa, regulates main drawing-in device, side
The charging rate of drawing-in device and liquid charging device squeezes out, water cooling is crossed, then through air blower through 25 ± 5 DEG C of sink of water temperature
Cooling, pelletizing obtain the halogen-free environment-friendly flame-proof polypropylene granules of heat oxygen aging resistance；
5) the halogen-free environment-friendly flame-proof polypropylene granules of heat oxygen aging resistance are placed at 85 DEG C and dry 3h, then be transferred to horizontal injection press
(model：HS-1200, extra large stone molding machine), setting injection temperature is 180~195 DEG C, is molded into standard batten, 23 DEG C, 50% humidity
Under conditions of place 48h, then be tested for the property.
Embodiment 5：
A kind of halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance, is made of the raw material of following mass parts：
Homopolypropylene (trade mark H110MA, India's letter is sincere, melt index 10.1g/10min, 230 DEG C/2.16kg)：55
Part；
One-piece type fire retardant (AMP, Qingyuan Presafer Phosphor Chemical Company Limited)：20 parts；
Melamine (trade mark H101, Sichuan fine chemistry industry)：8 parts；
Talcum powder (2000 mesh, pure and fresh courser)：10 parts；
Grafted maleic anhydride compatilizer (trade mark KT-1, Qingdao Lv Wei Chemical Co., Ltd.s)：5 parts；
Antioxidant 1010 (Shandong San Feng Chemical Co., Ltd.s)：0.1 part；
Irgasfos 168 (Shandong San Feng Chemical Co., Ltd.s)：0.2 part；
Titanate coupling agent (trade mark NT201, monarch please)：1 part；
N,N' ethylene bis stearmide (Japanese Kao)：0.5 part；
Pure powder type anti-dripping agent (trade mark M532, Daikin)：0.3 part.
The preparation method of the halogen-free environment-friendly flame-proof polypropylene material of above-mentioned heat oxygen aging resistance is as follows：
1) by homopolypropylene, grafted maleic anhydride compatilizer, antioxidant 1010, irgasfos 168, N, N'- ethylidene
Bis-stearamides and pure powder type anti-dripping agent add in high-speed mixer, and adjustment blender rotating speed to 1200r/min stirs 3min,
Material is transferred to the main drawing-in device of double screw extruder again；
2) one-piece type fire retardant, melamine package ammonium polyphosphate and talcum powder are added in into high-speed mixer, adjustment blender turns
Speed stirs 5min, then material is transferred to the side drawing-in device of double screw extruder to 1800r/min；
3) titanate coupling agent loading double screw extruder is added to the liquid charging device (model of fine mouth：LF-DL-50, Zheng
State Bart's Melt Pump Co., Ltd) in；
4) start double screw extruder (Nanjing section Asia, screw diameter 36mm, screw slenderness ratio 48:1) double spiral shells, are adjusted
Bar extrusion built-in temperature is 170~195 DEG C, rotating speed 300r/min, vacuum degree are -0.8MPa, regulates main drawing-in device, side
The charging rate of drawing-in device and liquid charging device squeezes out, water cooling is crossed, then through air blower through 25 ± 5 DEG C of sink of water temperature
Cooling, pelletizing obtain the halogen-free environment-friendly flame-proof polypropylene granules of heat oxygen aging resistance；
5) the halogen-free environment-friendly flame-proof polypropylene granules of heat oxygen aging resistance are placed at 85 DEG C and dry 3h, then be transferred to horizontal injection press
(model：HS-1200, extra large stone molding machine), setting injection temperature is 180~195 DEG C, is molded into standard batten, 23 DEG C, 50% humidity
Under conditions of place 48h, then be tested for the property.
Comparative example 1：
A kind of common halogen-free environment-friendly flame-proof polypropylene material, is made of the raw material of following mass parts：
Homopolypropylene (trade mark H110MA, India's letter is sincere, melt index 10.1g/10min, 230 DEG C/2.16kg)：50
Part；
Ammonium polyphosphate：25 parts；
Melamine package ammonium polyphosphate (APP262, Qingyuan Presafer Phosphor Chemical Company Limited)：3 parts；
Talcum powder (2000 mesh, pure and fresh courser)：15 parts；
Grafted maleic anhydride compatilizer (trade mark KT-1, Qingdao Lv Wei Chemical Co., Ltd.s)：5 parts；
Antioxidant 1010 (Shandong San Feng Chemical Co., Ltd.s)：0.1 part；
Irgasfos 168 (Shandong San Feng Chemical Co., Ltd.s)：0.2 part；
Titanate coupling agent (trade mark NT201, monarch please)：1 part；
N,N' ethylene bis stearmide (Japanese Kao)：0.4 part；
Pure powder type anti-dripping agent (trade mark M532, Daikin)：0.3 part.
The preparation method of above-mentioned common halogen-free environment-friendly flame-proof polypropylene material is as follows：
1) by homopolypropylene, grafted maleic anhydride compatilizer, antioxidant 1010, irgasfos 168, N, N'- ethylidene
Bis-stearamides and pure powder type anti-dripping agent add in high-speed mixer, and adjustment blender rotating speed to 1200r/min stirs 3min,
Material is transferred to the main drawing-in device of double screw extruder again；
2) ammonium polyphosphate, melamine package ammonium polyphosphate and talcum powder are added in into high-speed mixer, adjustment blender rotating speed is extremely
1800r/min stirs 5min, then material is transferred to the side drawing-in device of double screw extruder；
3) titanate coupling agent loading double screw extruder is added to the liquid charging device (model of fine mouth：LF-DL-50, Zheng
State Bart's Melt Pump Co., Ltd) in；
4) start double screw extruder (Nanjing section Asia, screw diameter 36mm, screw slenderness ratio 48:1) double spiral shells, are adjusted
Bar extrusion built-in temperature is 170~195 DEG C, rotating speed 300r/min, vacuum degree are -0.8MPa, regulates main drawing-in device, side
The charging rate of drawing-in device and liquid charging device squeezes out, water cooling is crossed, then through air blower through 25 ± 5 DEG C of sink of water temperature
Cooling, pelletizing obtain common halogen-free environment-friendly flame-proof polypropylene granules；
5) common halogen-free environment-friendly flame-proof polypropylene granules are placed at 85 DEG C and dry 3h, then be transferred to horizontal injection press (model：
HS-1200, extra large stone molding machine), setting injection temperature is 180~195 DEG C, is molded into standard batten, 23 DEG C, the condition of 50% humidity
Lower placement 48h, then be tested for the property.
Comparative example 2：
A kind of common halogen-free environment-friendly flame-proof polypropylene material, is made of the raw material of following mass parts：
Homopolypropylene (trade mark H110MA, India's letter is sincere, melt index 10.1g/10min, 230 DEG C/2.16kg)：50
Part；
One-piece type fire retardant (AMP, Qingyuan Presafer Phosphor Chemical Company Limited)：25 parts；
Melamine package ammonium polyphosphate (APP262, Qingyuan Presafer Phosphor Chemical Company Limited)：3 parts；
Talcum powder (2000 mesh, pure and fresh courser)：15 parts；
Grafted maleic anhydride compatilizer (trade mark KT-1, Qingdao Lv Wei Chemical Co., Ltd.s)：5 parts；
Antioxidant 1010 (Shandong San Feng Chemical Co., Ltd.s)：0.1 part；
Irgasfos 168 (Shandong San Feng Chemical Co., Ltd.s)：0.2 part；
Titanate coupling agent (trade mark NT201, monarch please)：1 part；
N,N' ethylene bis stearmide (Japanese Kao)：0.4 part；
Pure powder type anti-dripping agent (trade mark M532, Daikin)：0.3 part.
The preparation method of above-mentioned common halogen-free environment-friendly flame-proof polypropylene material is as follows：
1) by homopolypropylene, grafted maleic anhydride compatilizer, antioxidant 1010, irgasfos 168, N, N'- ethylidene
Bis-stearamides, pure powder type anti-dripping agent and titanate coupling agent add in high-speed mixer, adjustment blender rotating speed to 1200r/
Min stirs 3min, then material is transferred to double screw extruder；
2) one-piece type fire retardant, melamine package ammonium polyphosphate and talcum powder are added in into high-speed mixer, adjustment blender turns
Speed stirs 5min, then material is transferred to double screw extruder to 1800r/min；
3) start double screw extruder (Nanjing section Asia, screw diameter 36mm, screw slenderness ratio 48:1) double spiral shells, are adjusted
Bar squeezes out that built-in temperature is 170~195 DEG C, rotating speed 300r/min, vacuum degree are -0.8MPa, squeezes out, through 25 ± 5 DEG C of water temperature
Sink cross water cooling, then cooled down through air blower, pelletizing, obtain common halogen-free environment-friendly flame-proof polypropylene granules；
4) common halogen-free environment-friendly flame-proof polypropylene granules are placed at 85 DEG C and dry 3h, then be transferred to horizontal injection press (model：
HS-1200, extra large stone molding machine), setting injection temperature is 180~195 DEG C, is molded into standard batten, 23 DEG C, the condition of 50% humidity
Lower placement 48h, then be tested for the property.
Test case：
1) anti-flaming polypropylene material prepared to Examples 1 to 5 and comparative example 1~2 carries out flame retardant property test, test knot
Fruit is as follows：
The flame retardant property test result of the anti-flaming polypropylene material of 1 Examples 1 to 5 of table and comparative example 1~2
Note：Flame retardant test is carried out according to the flammable performance standard of UL94 plastic materials, and batten is prepared according to UL94 standards, thickness
Take 1.5 ± 0.2mm and 3.0 ± 0.1mm.
As shown in Table 1：Added with " one-piece type fire retardant (AMP)+synergistic fire retardant " and " ammonium polyphosphate+synergistic fire retardant "
The test sample that the anti-flaming polypropylene material of both flame-retardant systems makes does not occur when being tested according to UL94 standards
Molten drop drips, but the test sample that the anti-flaming polypropylene material added with " ammonium polyphosphate+synergistic fire retardant " flame-retardant system makes
It is longer to prolong the combustion time, and with the increase of talcum powder content, prolongs the combustion time and also has increased trend, the reason is as follows that：1) it is " one-piece type
In fire retardant (AMP)+synergistic fire retardant " flame-retardant system carbon source material and ammonium polyphosphate be by together with reaction bonded, will
It is added in polypropylene, and the ratio of acid source, carbon source and air source is all identical in the various pieces of polypropylene product, and is only had
Acid source, carbon source and air source are in a suitable ratio, and expansion type flame retardant can just reach best flame retardant effect, and " polyphosphoric acid
Ammonium+synergistic fire retardant " flame-retardant system is applied in polypropylene articles, disperses by batch mixing and screw rod shearing, polypropylene product
The ratio of the acid sources of various pieces, carbon source and air source is to float so that fire retardant efficiency is affected, and product is caused to prolong
Firing the time increases；2) inorganic fillers such as talcum powder can influence the compactness of expanding fire retardant carbon-coating, while influence char yield, and
" one-piece type fire retardant (AMP)+synergistic fire retardant " will be far better than " ammonium polyphosphate+cooperative flame retardant for the tolerance of talcum powder
Agent ".
2) anti-flaming polypropylene material prepared to Examples 1 to 5 and comparative example 1~2 carries out resistance to immersion and performance test is precipitated,
Test result is as follows：
The performance test results are precipitated in the resistance to immersion of the anti-flaming polypropylene material of 2 Examples 1 to 5 of table and comparative example 1~2
Note：Resistance to immersion is precipitated performance and the evaluation criteria for being used in the plastics in electric appliance is carried out according to UL746C.
The test method of weight-loss ratio is after immersion：The untreated batten prepared according to UL94 standards is weighed and remembered
Record quality is m1, will pass through according to the processed immersion battens of standard UL746C, taking-up is dried, (the 6h after batten restores room temperature
Interior completion) it is weighed and records quality as m2, weight-loss ratio is：
As shown in Table 2：Polypropylene flame redardant material added with " one-piece type fire retardant (AMP)+synergistic fire retardant " flame-retardant system
Expect the survey that the test sample made makes with the anti-flaming polypropylene material added with " ammonium polyphosphate+synergistic fire retardant " flame-retardant system
Test agent is compared, and it is more excellent that performance is precipitated in resistance to immersion.It is fire-retardant added with " one-piece type fire retardant (AMP)+synergistic fire retardant "
After the test sample that the anti-flaming polypropylene material of system makes carries out UL746C immersion tests, the batten weight-loss ratio of 1.5mm thickness
Less than 2%, and the batten weight-loss ratio of 3.0mm thickness is less than 1%, fire-retardant well below added with " ammonium polyphosphate+synergistic fire retardant "
The 9% and 6% of the test sample that the anti-flaming polypropylene material of system makes.Mainly due to the influence of compound molecular weight, one
As for, the high compound water soluble of molecular weight is smaller, and the molecular weight of one-piece type fire retardant (AMP) is compared to commercially available polyphosphoric acid
Ammonium is many higher.In addition, the triazine derivative introduced in one-piece type fire retardant (AMP) also has side for water-soluble reduction
It helps.
3) anti-flaming polypropylene material prepared to Examples 1 to 5 and comparative example 1~2 carries out heatproof air aging performance test,
Test result is as follows shown in table：
The heatproof air aging performance test result of the anti-flaming polypropylene material of 3 Examples 1 to 5 of table and comparative example 1~2
As shown in Table 3：Polypropylene flame redardant material added with " one-piece type fire retardant (AMP)+synergistic fire retardant " flame-retardant system
Expect the survey that the test sample made makes with the anti-flaming polypropylene material added with " ammonium polyphosphate+synergistic fire retardant " flame-retardant system
Test agent is compared, and heatproof air aging performance is more excellent.In general, the thermal decomposition of ammonium polyphosphate is mainly due to ammonium ion
Ammonia can be converted into after heated and overflows system, even if aging temperature does not reach its decomposition temperature, but with ageing time
Increase, the ammonium polyphosphate for also gradually having some low polymerization degrees decomposes.One-piece type fire retardant (AMP) will be although will be poly-
Ammonium phosphate and carbon source are combined together to form stable compound by chemical reaction, but still have can a part ammonium ion by
Hot spilling system, causes flame retardant effect to decline, and synergistic fire retardant can supply air source at this time, makes up ammonium ion and overflows and cause
Air source it is insufficient, while it is fire-retardant to play synergistic.
4) anti-flaming polypropylene material prepared to embodiment 1 and comparative example 2 carries out Mechanics Performance Testing, and test result is as follows
Shown in table：
The mechanical experimental results of the anti-flaming polypropylene material of 4 embodiment 1 of table and comparative example 2
As shown in Table 4：The anti-flaming polypropylene material of coupling agent preparation is added in and directly by coupling using liquid charging device
Agent is compared by anti-flaming polypropylene material prepared by the feeding of main feeding, and mechanical property is more excellent.This is mainly due to use
Liquid charging device can be obtained optimal dispersion, then be promoted fire retardant, talcum powder by adding in coupling agent between the feeding of main side
It preferably combines and disperses with PP, the mechanical property of end article gets a promotion.
In conclusion addition " one-piece type fire retardant (AMP)+synergistic fire retardant " and addition " ammonium polyphosphate+cooperative flame retardant
Agent " is compared, and the polypropylene flame redardant product being prepared possesses more excellent flame retardant property, performance and heat-resisting oxygen is precipitated in resistance to immersion
Ageing properties, and liquid charging device is used to feed liquid adjuvants, optimal dispersion performance can be obtained, and then obtain optimal
Mechanical property.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance, it is characterised in that：By the raw material group of following mass parts
Into：
Acrylic resin：50~60 parts；
One-piece type fire retardant：20~25 parts；
Synergistic fire retardant：3~10 parts；
Inorganic filler：5~15 parts；
Compatilizer：3~5 parts；
Primary antioxidant：0.1~0.2 part；
Auxiliary antioxidant：0.2~0.3 part；
Coupling agent：0.1~1.5 part；
Lubricant：0.1~1 part；
Anti-dripping agent：0.1~0.5 part.
2. the halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance according to claim 1, it is characterised in that：Described
Acrylic resin is homopolypropylene, block copolymerization polypropylene, at least one of atactic copolymerized polypropene, melt index 1
~50g/10min, 230 DEG C/2.16kg.
3. the halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance according to claim 1, it is characterised in that：Described
The structural formula of one-piece type fire retardant is：Wherein, 1≤a≤10000,1
≤ b≤200,1≤c≤10000, M are one kind in ethanol amine, piperidines, morpholine.
4. the halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance according to claim 1, it is characterised in that：Described
Synergistic fire retardant wraps up at least one of phosphate, melamine polyphosphate, melamine for melamine.
5. the halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance according to claim 1, it is characterised in that：Described
Inorganic filler is the talcum powder of 1000~2500 mesh, in the wollastonite of the barium sulfate of 1000~2000 mesh, 1000~1500 mesh
It is at least one.
6. the halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance according to claim 1, it is characterised in that：Described
Compatilizer is poly- third of polypropylene grafted maleic anhydride, the carboxylic polypropylene graft copolymer of side chain, side chain containing epoxy group
At least one of alkene graft copolymer.
7. the halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance according to claim 1, it is characterised in that：Described
Coupling agent is at least one of silane coupling agent, titante coupling agent.
8. the preparation side of the halogen-free environment-friendly flame-proof polypropylene material of the heat oxygen aging resistance in claim 1~7 described in any one
Method, it is characterised in that：Include the following steps：
1) acrylic resin, compatilizer, primary antioxidant, auxiliary antioxidant, lubricant and anti-dripping agent are added in into high-speed mixer,
It is uniformly mixed, then material is transferred to the main drawing-in device of double screw extruder；
2) one-piece type fire retardant, synergistic fire retardant and inorganic filler are added in into high-speed mixer, are uniformly mixed, then material is transferred to
The side drawing-in device of double screw extruder；
3) coupling agent is fitted into the liquid charging device that double screw extruder adds fine mouth；
4) start double screw extruder, adjust twin-screw temperature and screw speed, vacuumize, regulate main drawing-in device, side
The charging rate of drawing-in device and liquid charging device squeezes out, crosses water cooling, then cool down through air blower through sink, pelletizing obtains
The halogen-free environment-friendly flame-proof polypropylene granules of heat oxygen aging resistance.
9. preparation method according to claim 8, it is characterised in that：Liquid charging device described in step 3) is heat preserving type
Weightlessness balance liquid charging device, charging precision are ± 0.5%.
10. preparation method according to claim 8, it is characterised in that：The double screw extruder is parallel double in the same direction
Screw extruder, screw slenderness ratio are (40~75)：1, screw speed is 300~600r/min, vacuum degree for -0.07~-
1.1MPa, each area's temperature are：One 170~180 DEG C of area, 180~185 DEG C of two-four area, 185~190 DEG C of five-six area, seven-nine areas
190~195 DEG C, 180~185 DEG C of ten-ten one area, 160~180 DEG C of head.
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