CN110144109A - A kind of weather-proof high CTI halogen-free flameproof PPO/HIPS composite material and preparation method - Google Patents
A kind of weather-proof high CTI halogen-free flameproof PPO/HIPS composite material and preparation method Download PDFInfo
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- CN110144109A CN110144109A CN201910466484.1A CN201910466484A CN110144109A CN 110144109 A CN110144109 A CN 110144109A CN 201910466484 A CN201910466484 A CN 201910466484A CN 110144109 A CN110144109 A CN 110144109A
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a kind of weather-proof high CTI halogen-free flameproof PPO/HIPS composite material and preparation methods, the composition of the composite material are as follows: PPO100 parts, HIPS10-20 parts by weight, toughener 5-25 parts by weight, photomask agent 2-8 parts by weight, 5-15 parts of heat-resistant agent, 0.5-2 parts of light stabilizer, 5 parts of fire retardant 10-25 parts by weight, auxiliary flame retardant 1-5 parts by weight, antioxidant 0.1-1 parts by weight and lubricant 0.1-1 weight；It is preferred that are as follows: PPO100 parts, HIPS15-20 parts by weight, toughener 10-20 parts by weight, photomask agent 4-6 parts by weight, 5-10 parts of heat-resistant agent, 0.5-1 parts of light stabilizer, fire retardant 15-20 parts by weight, auxiliary flame retardant 2-3 parts by weight, antioxidant 0.1-0.5 parts by weight and lubricant 0.1-0.5 parts by weight；The melt index of the PPO is 10-15g/10min, the relative density of the HIPS is 1.05, the number-average molecular weight of the HIPS is 6-15 ten thousand, the anti-flammability of PPO/HIPS, and Halogen are not only improved, it is environmentally protective, it can be widely applied to the preparation such as electronic apparatus components shell, tensile strength reaches 45MPa or more, and bending strength can achieve 60MPa or more, and notch impact strength can achieve 9.5-11.0KJ/m2.
Description
Technical field
The present invention relates to a kind of PPO/HIPS technical field of composite materials, specific field is a kind of weather-proof high CTI Halogen resistance
Fire PPO/HIPS composite material and preparation method.
Background technique
Polyphenylene oxide (PPO) is one of five large-engineering plastics, has rigidity greatly, and heat-resist, intensity is high, excellent electrical properties etc.
Advantage.Common product be it is composite modified with HIPS, this modified material have relative density it is small, linear expansion coefficient is low, electricity
The advantages that performance is good, hydrolysis, is widely used in office equipment, electronic apparatus, and auto parts and components etc. are particularly applied to electronic
The production of automobile or battery of electric bicycle shell.Battery case requires anti-flammability, prevents from catching fire and generating fire, use
Bromide fire retardant prepares high CTI flame-retardant PPO/HIPS composite, can be used for Low-voltage Electronic electric appliance and breaker of plastic casing and
The preparation of the products such as battery case.
Concern with people to environmental protection is reduced or in the world to the requirement of bittern-free flame-proof material without using halogen fire-retardant
Agent will necessarily become the trend of industry.The present invention uses halogen-free flame retardants compositional flame-retardant PPO/HIPS, while using light shield
Agent, the synergistics such as heat-resistant agent prepare weather-proof, high CTI halogen-free flameproof PPO/HIPS composite material.Widen PPO/HIPS's significantly
Green application.It is widely used in the preparation of electrical automobile or battery of electric bicycle shell, has broad application prospects.The present invention
It is weather-proof, high CTI halogen-free flameproof PPO/HIPS composite material and preparation method thereof, compound process and process are simple, easy to process
Preparation.
Summary of the invention
The purpose of the present invention is to provide a kind of weather-proof high CTI halogen-free flameproof PPO/HIPS composite material and its preparation sides
Method, to solve the problems mentioned in the above background technology.
To achieve the above object, the invention provides the following technical scheme: a kind of weather-proof high CTI halogen-free flameproof PPO/HIPS
Composite material, the composition of the composite material are as follows: PPO100 parts, HIPS10-20 parts by weight, toughener 5-25 parts by weight, optical screen
Agent 2-8 parts by weight are covered, 5-15 parts of heat-resistant agent, 0.5-2 parts of light stabilizer, fire retardant 10-25 parts by weight, auxiliary flame retardant 1-5 are heavy
Measure part, antioxidant 0.1-1 parts by weight and lubricant 0.1-1 parts by weight；
It is preferred that are as follows: PPO100 parts, HIPS15-20 parts by weight, toughener 10-20 parts by weight, photomask agent 4-6 parts by weight,
5-10 parts of heat-resistant agent, 0.5-1 parts of light stabilizer, fire retardant 15-20 parts by weight, auxiliary flame retardant 2-3 parts by weight, antioxidant 0.1-
0.5 parts by weight and lubricant 0.1-0.5 parts by weight；
The melt index of the PPO is 10-15g/10min, and the relative density of the HIPS is 1.05, the number of the HIPS
Average molecular weight be 6-15 ten thousand, the Izod notch impact strength be 10.5-12.5KJ/m2, preferably 10.0-12KJ/m2, it is described
The mixing that toughener is hydrogenated polystyrene-butadiene-styrene (SEBS) and polyolefin elastomer (POE) ratio is 1:1
Object, wherein styrene segment content is 30-40%, the hardness 60-70A of POE in SEBS.
Preferably, the photomask agent is rutile type nano titanic oxide, purity 98-99%, particle size 100-150
Nanometer.
Preferably, the heat-resistant agent is styrene-maleic anhydride copolymer, and melt index is 6-9g/10min (200
DEG C/5Kg), the content of maleic anhydride is 18%-22%.
Preferably, the light stabilizer is the mixture of UV327 and UV944, and the ratio of the two is 1:1.
Preferably, the fire retardant be triphenylphosphine oxide, 150-156 DEG C of fusing point, purity 98-99%.Auxiliary flame retardant
For melamine cyanurate, purity 96-99%.Preferably, the primary antioxidant is
Antioxidant 1010 or 1076, preferably antioxidant 1010；Auxiliary antioxidant is irgasfos 168；Major-minor antioxidant is by weight
Amount is matched than 2:1-3:1；The lubricant is selected from one of ethylene bis stearamide, TAF and PETS.
A kind of preparation method of weather-proof high CTI halogen-free flameproof PPO/HIPS composite material, the described method comprises the following steps:
(1) PPO is dried；
(2) dried PPO and HIPS and fire retardant, heat-resistant agent, toughener, antioxidant and lubricant etc. will be measured to mix
Uniformly；
(3) it is added twin-screw extrude by the main spout of double screw extruder, melting extrusion, extruded material is through cold
But, to get weather-proof, high CTI, halogen-free flameproof PPO/HIPS composite material after air-dried, pelletizing, drying.
Preferably, in step (1), PPO drying is dried in vacuum drying oven, and temperature is 90-100 DEG C, dry
Time is 2-5h, preferably 3-4h；In step (2), incorporation time is mixing 10-15 minutes.
Preferably, the temperature setting range of double screw extruder is 220-250 DEG C, screw speed 300-400rpm, very
Reciprocal of duty cycle is -0.8--1.0Kgf/cm2；The temperature in each area of double screw extruder are as follows:
One Qu Wendu: 220-225 DEG C,
Two area's temperature: 225-230 DEG C,
Three Qu Wendu: 230-235 DEG C,
Four Qu Wendu: 235-240 DEG C,
Five Qu Wendu: 240-245 DEG C,
Six Qu Wendu: 245-250 DEG C,
Seven area's temperature: 250-245 DEG C.
Compared with prior art, the beneficial effects of the present invention are:
(1) provided by the present invention weather-proof, high CTI halogen-free flameproof PPO/HIPS composite material not only improves PPO/
The anti-flammability of HIPS, and Halogen, it is environmentally protective, it can be widely applied to the preparation such as electronic apparatus components shell.
(2) provided by the present invention weather-proof, high CTI halogen-free flameproof PPO/HIPS composite material, tensile strength reaches 45MPa
More than, bending strength can achieve 60MPa or more, and notch impact strength can achieve 9.5-11.0KJ/m2.
(3) provided by the present invention weather-proof, high CTI halogen-free flameproof PPO/HIPS composite material and preparation method thereof, compound process
It is simple with process, preparation easy to process.
Specific embodiment
Below in conjunction with embodiment, technical solution of the present invention is clearly and completely described, it is clear that described
Embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field
Those of ordinary skill's every other embodiment obtained without making creative work, belongs to protection of the present invention
Range.
Embodiment 1, the present embodiment provides a kind of technical solutions: a kind of weather-proof high CTI halogen-free flameproof PPO/HIPS composite wood
Material, composition are as shown in table 1:
Table 1: unit (kg)
Wherein, the melt index of PPO is 10-15g/10min；HIPS relative density is 1.05, and number-average molecular weight is 100,000；
Izod notch impact strength is 10.8KJ/m2；Toughener is the mixture that SEBS and POE ratio is 1:1, wherein benzene second in SEBS
Alkene segment content is the hardness 65A of 30%, POE；Photomask agent is rutile type nano titanic oxide, purity 99%, partial size ruler
Very little 150 nanometers；Heat-resistant agent is styrene-maleic anhydride copolymer, and melt index is 9g/10min (200 DEG C/5Kg), Malaysia
Anhydride content is 18%；Light stabilizer is the mixture of UV327 and UV944, and the ratio of the two is 1:1；Fire retardant is triphenyl
Phosphine oxide, 154 DEG C of fusing point, purity 99%；Auxiliary flame retardant is melamine cyanurate, purity 99%；Primary antioxidant is anti-
Oxygen agent 1010, auxiliary antioxidant are irgasfos 168, and major-minor antioxidant is matched by weight 2:1；Lubricant is PETS.
Embodiment 2, the present embodiment provides a kind of technical solutions: a kind of weather-proof high CTI halogen-free flameproof PPO/HIPS composite wood
Material, composition are as shown in table 2:
Table 2: unit (kg)
Wherein, the melt index of PPO is 10-15g/10min；HIPS relative density is 1.05, and number-average molecular weight is 100,000；
Izod notch impact strength is 10.8KJ/m2；Toughener is the mixture that SEBS and POE ratio is 1:1, wherein benzene second in SEBS
Alkene segment content is the hardness 65A of 30%, POE；Photomask agent is rutile type nano titanic oxide, purity 99%, partial size ruler
Very little 150 nanometers；Heat-resistant agent is styrene-maleic anhydride copolymer, and melt index is 9g/10min (200 DEG C/5Kg), Malaysia
Anhydride content is 18%；Light stabilizer is the mixture of UV327 and UV944, and the ratio of the two is 1:1；Fire retardant is triphenyl
Phosphine oxide, 154 DEG C of fusing point, purity 99%；Auxiliary flame retardant is melamine cyanurate, purity 99%；Primary antioxidant is anti-
Oxygen agent 1010, auxiliary antioxidant are irgasfos 168, and major-minor antioxidant is matched by weight 2:1；Lubricant is PETS.
A kind of preparation method of weather-proof high CTI halogen-free flameproof PPO/HIPS composite material, which is characterized in that the method packet
Include following steps:
(1) PPO is dried；
(2) dried PPO and HIPS and fire retardant, heat-resistant agent, toughener, antioxidant and lubricant etc. will be measured to mix
Uniformly；
(3) it is added twin-screw extrude by the main spout of double screw extruder, melting extrusion, extruded material is through cold
But, to get weather-proof, high CTI, halogen-free flameproof PPO/HIPS composite material after air-dried, pelletizing, drying.
Specifically, PPO drying is dried in vacuum drying oven in step (1), temperature is 90-100 DEG C, is done
The dry time is 2-5h, preferably 3-4h；In step (2), incorporation time is mixing 10-15 minutes.
Specifically, the temperature setting range of double screw extruder is 220-250 DEG C, screw speed 300-400rpm,
Vacuum degree is -0.8--1.0Kgf/cm2；The temperature in each area of double screw extruder are as follows:
One Qu Wendu: 220-225 DEG C,
Two area's temperature: 225-230 DEG C,
Three Qu Wendu: 230-235 DEG C,
Four Qu Wendu: 235-240 DEG C,
Five Qu Wendu: 240-245 DEG C,
Six Qu Wendu: 245-250 DEG C,
Seven area's temperature: 250-245 DEG C.
What is be prepared is weather-proof, high CTI halogen-free flameproof PPO/HIPS composite property are as follows:
Mechanical performance index is tested according to corresponding ASTM standard, and anti-flammability is pressed according to UL94 standard testing, aging measurement
According to GB/T164222.2, carried out by light source of xenon lamp；The test of CTI is according to IEC950 standard testing；Halogen tests foundation
IEC61249-2-21。
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (9)
1. a kind of weather-proof high CTI halogen-free flameproof PPO/HIPS composite material, it is characterised in that: the composition of the composite material are as follows:
PPO100 parts, HIPS10-20 parts by weight, toughener 5-25 parts by weight, photomask agent 2-8 parts by weight, 5-15 parts of heat-resistant agent, light is steady
Determine 0.5-2 parts of agent, fire retardant 10-25 parts by weight, auxiliary flame retardant 1-5 parts by weight, antioxidant 0.1-1 parts by weight and lubricant
0.1-1 parts by weight；
It is preferred that are as follows: PPO100 parts, HIPS15-20 parts by weight, toughener 10-20 parts by weight, photomask agent 4-6 parts by weight are heat-resisting
5-10 parts of agent, 0.5-1 parts of light stabilizer, fire retardant 15-20 parts by weight, auxiliary flame retardant 2-3 parts by weight, antioxidant 0.1-0.5
Parts by weight and lubricant 0.1-0.5 parts by weight；
The melt index of the PPO is 10-15g/10min, and the relative density of the HIPS is 1.05, and the number of the HIPS is divided equally
Son amount is 6-15 ten thousand, and the Izod notch impact strength is 10.5-12.5KJ/m2, preferably 10.0-12KJ/m2, the toughener
The mixture for being 1:1 for hydrogenated polystyrene-butadiene-styrene (SEBS) and polyolefin elastomer (POE) ratio, wherein
Styrene segment content is 30-40%, the hardness 60-70A of POE in SEBS.
2. the weather-proof high CTI halogen-free flameproof PPO/HIPS composite material of one kind according to claim 1, it is characterised in that: institute
State photomask agent be rutile type nano titanic oxide, purity 98-99%, 100-150 nanometers of particle size.
3. the weather-proof high CTI halogen-free flameproof PPO/HIPS composite material of one kind according to claim 1, it is characterised in that: institute
Stating heat-resistant agent is styrene-maleic anhydride copolymer, and melt index is 6-9g/10min (200 DEG C/5Kg), maleic anhydride
Content is 18%-22%.
4. the weather-proof high CTI halogen-free flameproof PPO/HIPS composite material of one kind according to claim 1, it is characterised in that: institute
The mixture that light stabilizer is UV327 and UV944 is stated, the ratio of the two is 1:1.
5. the weather-proof high CTI halogen-free flameproof PPO/HIPS composite material of one kind according to claim 1, it is characterised in that: institute
State fire retardant be triphenylphosphine oxide, 150-156 DEG C of fusing point, purity 98-99%.Auxiliary flame retardant is melamine cyanurate
Salt, purity 96-99%.
6. the weather-proof high CTI halogen-free flameproof PPO/HIPS composite material of one kind according to claim 1, it is characterised in that: institute
Stating primary antioxidant is antioxidant 1010 or 1076, preferably antioxidant 1010；Auxiliary antioxidant is irgasfos 168；Major-minor antioxidant
It is matched by weight 2:1-3:1；The lubricant is selected from one of ethylene bis stearamide, TAF and PETS.
7. a kind of preparation method of weather-proof high CTI halogen-free flameproof PPO/HIPS composite material, which is characterized in that the method includes
Following steps:
(1) PPO is dried；
(2) will measure dried PPO and HIPS and fire retardant, heat-resistant agent, toughener, antioxidant and lubricant etc. mix it is equal
It is even；
(3) added twin-screw extrude by the main spout of double screw extruder, melting extrusion, extruded material through cooling,
To get weather-proof, high CTI, halogen-free flameproof PPO/HIPS composite material after air-dried, pelletizing, drying.
8. the preparation method of the weather-proof high CTI halogen-free flameproof PPO/HIPS composite material of one kind according to claim 7, special
Sign is: in step (1), PPO drying is dried in vacuum drying oven, and temperature is 90-100 DEG C, drying time 2-
5h, preferably 3-4h；In step (2), incorporation time is mixing 10-15 minutes.
9. the preparation method of the weather-proof high CTI halogen-free flameproof PPO/HIPS composite material of one kind according to claim 7, special
Sign is: the temperature setting range of double screw extruder be 220-250 DEG C, screw speed 300-400rpm, vacuum degree be-
0.8--1.0Kgf/cm2；The temperature in each area of double screw extruder are as follows:
One Qu Wendu: 220-225 DEG C,
Two area's temperature: 225-230 DEG C,
Three Qu Wendu: 230-235 DEG C,
Four Qu Wendu: 235-240 DEG C,
Five Qu Wendu: 240-245 DEG C,
Six Qu Wendu: 245-250 DEG C,
Seven area's temperature: 250-245 DEG C.
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Cited By (3)
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| CN111019319A (en) * | 2019-12-26 | 2020-04-17 | 南通大学 | PPE material for mobile phone charger shell and preparation method thereof |
| CN114213794A (en) * | 2021-11-30 | 2022-03-22 | 金发科技股份有限公司 | Heat-resistant size-stable styryl alloy composition and preparation method thereof |
| CN114907696A (en) * | 2022-07-01 | 2022-08-16 | 四川中物材料股份有限公司 | High CTI polyphenylene sulfide composite material and preparation method thereof |
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Application publication date: 20190820 |