CN107226993A - A kind of high-performance ABS/ maize straw composites and preparation method thereof - Google Patents
A kind of high-performance ABS/ maize straw composites and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high-performance ABS/ maize straw composites, by weight, its preparing raw material includes：100 parts of ABS resin, 8 15 parts of lignin, 5 10 parts of nano oxidized caesium, 5 10 parts of montmorillonite, polyphosphazene/0.5 1 parts of 5 12 parts of corn stalk powder of polyethersulfone block copolymer cladding, 5 10 parts of ABS g MAH, 5 10 parts of compatilizer and antioxidant.Gained high-performance ABS/ maize straw composites of the invention have good mechanical strength, fire resistance and cost is relatively low, overcome prior art defect, there is good market prospects.
Description
Technical field
The invention belongs to technical field of composite materials, more particularly it relates to a kind of high-performance ABS/ maize straws
Composite and preparation method thereof.
Background technology
Acrylonitrile-butadiene-styrene copolymer (ABS) resin is a kind of universal engineering thermoplastic modeling of superior performance
Material, with higher impact strength, excellent electrical insulating property, good processing characteristics and chemical stability, it is easy to molded,
Product is widely used in the fields such as household electrical appliance, construction material, auto industry rich in gloss and higher toughness.Due to resistance
Fire performance requirement high, such as flameproof case, switch require that the fire resistance of material reaches UL-94V-0 grades, and ABS resin is in itself
Fire resistance can not meet demand, most common method is to add the composite flame-proof body of halogenated flame retardant and antimony oxide
System, but substantial amounts of cigarette and pernicious gas can be discharged during its burning, environment and human body can be damaged.As people are to rings of material
The continuous improvement of guaranteed request, inorganic combustion inhibitor or phosphorus system, nitrogenated flame retardant obtain certain use, but inorganic combustion inhibitor has resistance
Fuel efficiency rate is low, the problem of addition is big, and phosphorus flame retardant flame retarding efficiency is high, and addition is few, but it plastifies material, influences material
Mechanical property, it is limited to a certain extent and uses scope.In addition in order to reduce cost, it is by compound with straw
Good method, but this usually can further reduce fire resistance and mechanical strength again, it is difficult to it is applied.Therefore, it is necessary to
Technological improvement is carried out, the high-performance ABS/ maize straw composites that fire resistance is good, mechanical strength is high are obtained.
The content of the invention
Therefore, a kind of high-performance ABS/ maize straw composites of offer of the present invention, by weight, its preparing raw material
Including：100 parts of ABS resin, 8-15 parts of lignin, nano oxidized caesium 5-10 parts, 5-10 parts of montmorillonite, polyphosphazene/polyether sulfone it is embedding
0.5-1 parts of 5-12 parts of corn stalk powder of section copolymer cladding, 5-10 parts of ABS-g-MAH, 5-10 parts of compatilizer and antioxidant.
Preferably, described high-performance ABS/ maize straw composites, by weight, its preparing raw material includes：ABS
100 parts of resin, 9-12 parts of lignin, nano oxidized caesium 7-9 parts, 7-9 parts of montmorillonite, polyphosphazene/polyethersulfone block copolymer bag
Cover 0.7-0.9 parts of 7-10 parts of corn stalk powder, 6-9 parts of ABS-g-MAH, 5-10 parts of compatilizer and antioxidant.
It is highly preferred that described high-performance ABS/ maize straw composites, by weight, its preparing raw material includes：
100 parts of ABS resin, 10 parts of lignin, 8 parts of nano oxidized caesium, 8 parts of montmorillonite, polyphosphazene/polyethersulfone block copolymer cladding are beautiful
0.8 part of 8 parts of powder of straw of rice, 7 parts of ABS-g-MAH, 8 parts of compatilizer and antioxidant.
In a preferred approach, the preparation method of the polyphosphazene/polyethersulfone block copolymer cladding corn stalk powder is：
（1）In 250 milliliters of round-bottomed flasks, by 0.42 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.2 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 5 h in 180 milliliters of acetonitriles, after reaction terminates,
Solvent is centrifuged off, washed product is distinguished 3 times with deionized water and acetone, 24 h is finally dried in vacuo at 50 DEG C and obtain white
Color polyphosphazene powder；
（2）Under nitrogen protection, 1.23g is added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
Above-mentioned steps（1）Gained white polyphosphazene powder, 4.256g diallyls bisphenol S, 3.810g 4,4 '-difluorodiphenyl sulfone, 20ml
Sulfolane, 2.277g potassium carbonate, 15ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
170 DEG C are risen to, is reacted 8 hours, is discharged in water, obtain bar shaped polymer, obtained bar shaped polymer is smashed to pieces with bruisher,
Again with after distilled water boiling washing 6 times, it is placed on 40 DEG C of drying in vacuum drying oven and obtains within 48 hours polyphosphazene/polyethersulfone block copolymerization
Thing；
（3）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（2）Gained polyphosphazene/polyethersulfone block copolymer
10g, corn stalk powder 25g, dimethyl sulfoxide (DMSO) 150ml, acetic acid 0.5 ml, KH-550 2g and KH-560 5g, system temperature
50 DEG C are risen to, is reacted 6 hours, is discharged in water, obtain fluffy solid, the fluffy solid is washed with deionized 3 times, finally
24 h are dried in vacuo at 50 DEG C and obtain the polyphosphazene/polyethersulfone block copolymer cladding corn stalk powder.
In a preferred approach, described high-performance ABS/ maize straw composites, by weight, its preparing raw material is also
Including：Hydride modified sulfonated phosphazene 5-10 parts.
In more preferably scheme, described high-performance ABS/ maize straw composites, by weight, its preparing raw material
Also include：Hydride modified 8 parts of sulfonated phosphazene.
In a preferred approach, the preparation method for stating hydride modified sulfonated phosphazene is：
In 250 milliliters of round-bottomed flasks, by 0.4 gram of hexachlorocyclotriph,sphazene and 0.91 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 150 milliliters of acetonitriles, 1.1 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 h, after reaction terminates, centrifugation
Solvent is removed, washed product is distinguished 3 times with deionized water and acetone, 24 h are finally dried in vacuo at 40 DEG C and obtain white poly-
Phosphonitrile powder；
0.5 gram of above-mentioned white polyphosphazene powder is added in 50 milliliters of three-neck flasks, the dense of 10 milliliters of mass fractions 98% is added
Sulfuric acid, is placed in 60 DEG C of water-baths, and 10h is reacted under mechanical stirring, after reaction terminates, product is slowly poured into cold water, and
It is stirred continuously, is centrifuged off unreacted sulfuric acid, product is then washed with deionized 5 times, is finally dried in vacuo at 50 DEG C
48 h are to obtain sulfonated phosphazene powder；
1 gram of above-mentioned sulfonated phosphazene powder, 0.3 gram of silane coupler KH-560 and 10 are added in 50 milliliters of three-neck flasks
Milliliter dimethyl sulfoxide (DMSO), heats up after 50 DEG C of reaction 4h, is down to room temperature and slowly pours into product in cold water, and is stirred continuously, so
After product is washed with deionized 5 times, being finally dried in vacuo 48 h at 50 DEG C obtains hydride modified sulfonated phosphazene.
In a preferred approach, described high-performance ABS/ maize straw composites, by weight, its preparing raw material is also
Including：1-10 parts of 2- chloro- 4,5- dihydros -1H- imidazole sulfonic acids salt, 1-5 parts of 2-mercaptobenzimidazole -5- sodium sulfonate dihydrates.
Invention further provides a kind of preparation method of high-performance ABS/ maize straw composites, including following step
Suddenly：
Described raw material is first mixed into 10-50min in super mixer, mixed raw material is then added into twin-screw extrusion
In machine, it is 200-230 DEG C to control extrusion temperature, and after melting extrusion, cooling granulation obtains high-performance ABS/ maize straw composite woods
Material.
The present invention has been still further provided in described high-performance ABS/ maize straws composite in household electrical appliances, building, automobile
Industry and the application of medical field.
The present invention advantageous effects be：
Intensity and fire resistance that corn stalk powder improves material are coated by polyphosphazene/polyethersulfone block copolymer, pass through silicon
Alkane modification sulfonated phosphazene, the chloro- 4,5- dihydros -1H- imidazole sulfonic acids salt of 2- and the water of 2-mercaptobenzimidazole -5- sodium sulfonates two
Compound further improves crosslink density, anti-flammability and the intensity of material.
Embodiment
Raw material is as follows：ABS resin is the strange U.S. PA-727 in Taiwan.Compatilizer SEBS-g-MAH is shell Kraton G1901X.
Lignin is purchased from Shanghai cloud philosophy, model MN-1A.ABS-g-MAH（Maleic anhydride modified ABS, maleic anhydride grafting ratio 3%）、
Nano oxidized caesium average grain diameter is 50 nanometers, montmorillonite average grain diameter is 650 nanometers, silane resin acceptor kh-550, KH-560 are equal
Purchased from Sigma.Other reagents are purchased from Aladdin.
Embodiment 1
By weight, by 100 parts of ABS resin, 8 parts of lignin, 5 parts of nano oxidized caesium, 5 parts of montmorillonite, polyphosphazene/polyether sulfone
5 parts of corn stalk powder of block copolymer cladding, 5 parts of ABS-g-MAH, 5 parts of compatilizer SEBS-g-MAH and antioxidant 1010
0.5 part mixes 20 min in super mixer, and mixing rate is 1500 revs/min, and mixed raw material then is added into double spiral shells
In bar extruder, it is 215 DEG C to control extrusion temperature, after melting extrusion, cooling granulation, obtains high-performance ABS/ maize straws and is combined
Material；
The preparation method of the polyphosphazene/polyethersulfone block copolymer cladding corn stalk powder is：
（1）In 250 milliliters of round-bottomed flasks, by 0.42 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.2 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 5 h in 180 milliliters of acetonitriles, after reaction terminates,
Solvent is centrifuged off, washed product is distinguished 3 times with deionized water and acetone, 24 h is finally dried in vacuo at 50 DEG C and obtain white
Color polyphosphazene powder；
（2）Under nitrogen protection, 1.23g is added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
Above-mentioned steps（1）Gained white polyphosphazene powder, 4.256g diallyls bisphenol S, 3.810g 4,4 '-difluorodiphenyl sulfone, 20ml
Sulfolane, 2.277g potassium carbonate, 15ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
170 DEG C are risen to, is reacted 8 hours, is discharged in water, obtain bar shaped polymer, obtained bar shaped polymer is smashed to pieces with bruisher,
Again with after distilled water boiling washing 6 times, it is placed on 40 DEG C of drying in vacuum drying oven and obtains within 48 hours polyphosphazene/polyethersulfone block copolymerization
Thing；
（3）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（2）Gained polyphosphazene/polyethersulfone block copolymer
10g, corn stalk powder 25g, dimethyl sulfoxide (DMSO) 150ml, acetic acid 0.5 ml, KH-550 2g and KH-560 5g, system temperature
50 DEG C are risen to, is reacted 6 hours, is discharged in water, obtain fluffy solid, the fluffy solid is washed with deionized 3 times, finally
24 h are dried in vacuo at 50 DEG C and obtain the polyphosphazene/polyethersulfone block copolymer cladding corn stalk powder.
Embodiment 2
By weight, by 100 parts of ABS resin, 15 parts of lignin, 10 parts of nano oxidized caesium, 10 parts of montmorillonite, polyphosphazene/poly-
12 parts of corn stalk powder of ether sulfone block copolymer cladding, 10 parts of ABS-g-MAH, 10 parts of compatilizer SEBS-g-MAH and antioxidant
1010 1 parts mix 20 min in super mixer, and mixing rate is 1500 revs/min, then add mixed raw material double
In screw extruder, it is 215 DEG C to control extrusion temperature, after melting extrusion, cooling granulation, obtains high-performance ABS/ maize straws and answers
Condensation material；
The preparation method of the polyphosphazene/polyethersulfone block copolymer cladding corn stalk powder is：
（1）In 250 milliliters of round-bottomed flasks, by 0.42 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.2 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 5 h in 180 milliliters of acetonitriles, after reaction terminates,
Solvent is centrifuged off, washed product is distinguished 3 times with deionized water and acetone, 24 h is finally dried in vacuo at 50 DEG C and obtain white
Color polyphosphazene powder；
（2）Under nitrogen protection, 1.23g is added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
Above-mentioned steps（1）Gained white polyphosphazene powder, 4.256g diallyls bisphenol S, 3.810g 4,4 '-difluorodiphenyl sulfone, 20ml
Sulfolane, 2.277g potassium carbonate, 15ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
170 DEG C are risen to, is reacted 8 hours, is discharged in water, obtain bar shaped polymer, obtained bar shaped polymer is smashed to pieces with bruisher,
Again with after distilled water boiling washing 6 times, it is placed on 40 DEG C of drying in vacuum drying oven and obtains within 48 hours polyphosphazene/polyethersulfone block copolymerization
Thing；
（3）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（2）Gained polyphosphazene/polyethersulfone block copolymer
10g, corn stalk powder 25g, dimethyl sulfoxide (DMSO) 150ml, acetic acid 0.5 ml, KH-550 2g and KH-560 5g, system temperature
50 DEG C are risen to, is reacted 6 hours, is discharged in water, obtain fluffy solid, the fluffy solid is washed with deionized 3 times, finally
24 h are dried in vacuo at 50 DEG C and obtain the polyphosphazene/polyethersulfone block copolymer cladding corn stalk powder.
Embodiment 3
By weight, by 100 parts of ABS resin, 10 parts of lignin, 8 parts of nano oxidized caesium, 8 parts of montmorillonite, polyphosphazene/polyethers
8 parts of corn stalk powder of sulfone block copolymer cladding, 7 parts of ABS-g-MAH, 8 parts of compatilizer SEBS-g-MAH and antioxidant 1010
0.8 part mixes 20 min in super mixer, and mixing rate is 1500 revs/min, and mixed raw material then is added into double spiral shells
In bar extruder, it is 215 DEG C to control extrusion temperature, after melting extrusion, cooling granulation, obtains high-performance ABS/ maize straws and is combined
Material；
The preparation method of the polyphosphazene/polyethersulfone block copolymer cladding corn stalk powder is：
（1）In 250 milliliters of round-bottomed flasks, by 0.42 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.2 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 5 h in 180 milliliters of acetonitriles, after reaction terminates,
Solvent is centrifuged off, washed product is distinguished 3 times with deionized water and acetone, 24 h is finally dried in vacuo at 50 DEG C and obtain white
Color polyphosphazene powder；
（2）Under nitrogen protection, 1.23g is added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
Above-mentioned steps（1）Gained white polyphosphazene powder, 4.256g diallyls bisphenol S, 3.810g 4,4 '-difluorodiphenyl sulfone, 20ml
Sulfolane, 2.277g potassium carbonate, 15ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
170 DEG C are risen to, is reacted 8 hours, is discharged in water, obtain bar shaped polymer, obtained bar shaped polymer is smashed to pieces with bruisher,
Again with after distilled water boiling washing 6 times, it is placed on 40 DEG C of drying in vacuum drying oven and obtains within 48 hours polyphosphazene/polyethersulfone block copolymerization
Thing；
（3）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（2）Gained polyphosphazene/polyethersulfone block copolymer
10g, corn stalk powder 25g, dimethyl sulfoxide (DMSO) 150ml, acetic acid 0.5 ml, KH-550 2g and KH-560 5g, system temperature
50 DEG C are risen to, is reacted 6 hours, is discharged in water, obtain fluffy solid, the fluffy solid is washed with deionized 3 times, finally
24 h are dried in vacuo at 50 DEG C and obtain the polyphosphazene/polyethersulfone block copolymer cladding corn stalk powder.
Embodiment 4
By weight, by 100 parts of ABS resin, 10 parts of lignin, 8 parts of nano oxidized caesium, 8 parts of montmorillonite, polyphosphazene/polyethers
8 parts of corn stalk powder of sulfone block copolymer cladding, 7 parts of ABS-g-MAH, 8 parts of compatilizer SEBS-g-MAH, antioxidant 1010
0.8 part and 8 parts of hydride modified sulfonated phosphazene mix 20 min in super mixer, and mixing rate is 1500 revs/min, so
Mixed raw material is added in double screw extruder afterwards, it is 215 DEG C to control extrusion temperature, after melting extrusion, cooling granulation,
Obtain high-performance ABS/ maize straw composites；
The preparation method of the polyphosphazene/polyethersulfone block copolymer cladding corn stalk powder is：
（1）In 250 milliliters of round-bottomed flasks, by 0.42 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.2 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 5 h in 180 milliliters of acetonitriles, after reaction terminates,
Solvent is centrifuged off, washed product is distinguished 3 times with deionized water and acetone, 24 h is finally dried in vacuo at 50 DEG C and obtain white
Color polyphosphazene powder；
（2）Under nitrogen protection, 1.23g is added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
Above-mentioned steps（1）Gained white polyphosphazene powder, 4.256g diallyls bisphenol S, 3.810g 4,4 '-difluorodiphenyl sulfone, 20ml
Sulfolane, 2.277g potassium carbonate, 15ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
170 DEG C are risen to, is reacted 8 hours, is discharged in water, obtain bar shaped polymer, obtained bar shaped polymer is smashed to pieces with bruisher,
Again with after distilled water boiling washing 6 times, it is placed on 40 DEG C of drying in vacuum drying oven and obtains within 48 hours polyphosphazene/polyethersulfone block copolymerization
Thing；
（3）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（2）Gained polyphosphazene/polyethersulfone block copolymer
10g, corn stalk powder 25g, dimethyl sulfoxide (DMSO) 150ml, acetic acid 0.5 ml, KH-550 2g and KH-560 5g, system temperature
50 DEG C are risen to, is reacted 6 hours, is discharged in water, obtain fluffy solid, the fluffy solid is washed with deionized 3 times, finally
24 h are dried in vacuo at 50 DEG C and obtain the polyphosphazene/polyethersulfone block copolymer cladding corn stalk powder；
The preparation method of the hydride modified sulfonated phosphazene is：
In 250 milliliters of round-bottomed flasks, by 0.4 gram of hexachlorocyclotriph,sphazene and 0.91 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 150 milliliters of acetonitriles, 1.1 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 h, after reaction terminates, centrifugation
Solvent is removed, washed product is distinguished 3 times with deionized water and acetone, 24 h are finally dried in vacuo at 40 DEG C and obtain white poly-
Phosphonitrile powder；
0.5 gram of above-mentioned white polyphosphazene powder is added in 50 milliliters of three-neck flasks, the dense of 10 milliliters of mass fractions 98% is added
Sulfuric acid, is placed in 60 DEG C of water-baths, and 10h is reacted under mechanical stirring, after reaction terminates, product is slowly poured into cold water, and
It is stirred continuously, is centrifuged off unreacted sulfuric acid, product is then washed with deionized 5 times, is finally dried in vacuo at 50 DEG C
48 h are to obtain sulfonated phosphazene powder；
1 gram of above-mentioned sulfonated phosphazene powder, 0.3 gram of silane coupler KH-560 and 10 are added in 50 milliliters of three-neck flasks
Milliliter dimethyl sulfoxide (DMSO), heats up after 50 DEG C of reaction 4h, is down to room temperature and slowly pours into product in cold water, and is stirred continuously, so
After product is washed with deionized 5 times, being finally dried in vacuo 48 h at 50 DEG C obtains hydride modified sulfonated phosphazene.
Embodiment 5
By weight, by 100 parts of ABS resin, 10 parts of lignin, 8 parts of nano oxidized caesium, 8 parts of montmorillonite, polyphosphazene/polyethers
8 parts of corn stalk powder of sulfone block copolymer cladding, 7 parts of ABS-g-MAH, 8 parts of compatilizer SEBS-g-MAH, antioxidant 1010
0.8 part, 8 parts of hydride modified sulfonated phosphazene, 6 parts of the chloro- 4,5- dihydros -1H- imidazole sulfonic acids salt of 2- and 2- sulfydryl benzo miaows
3 parts of azoles -5- sodium sulfonates dihydrate mixes 20 min in super mixer, and mixing rate is 1500 revs/min, then will mixing
Raw material afterwards is added in double screw extruder, and it is 215 DEG C to control extrusion temperature, and after melting extrusion, cooling granulation obtains high-performance
ABS/ maize straw composites；
The preparation method of the polyphosphazene/polyethersulfone block copolymer cladding corn stalk powder is：
（1）In 250 milliliters of round-bottomed flasks, by 0.42 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.2 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 5 h in 180 milliliters of acetonitriles, after reaction terminates,
Solvent is centrifuged off, washed product is distinguished 3 times with deionized water and acetone, 24 h is finally dried in vacuo at 50 DEG C and obtain white
Color polyphosphazene powder；
（2）Under nitrogen protection, 1.23g is added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
Above-mentioned steps（1）Gained white polyphosphazene powder, 4.256g diallyls bisphenol S, 3.810g 4,4 '-difluorodiphenyl sulfone, 20ml
Sulfolane, 2.277g potassium carbonate, 15ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
170 DEG C are risen to, is reacted 8 hours, is discharged in water, obtain bar shaped polymer, obtained bar shaped polymer is smashed to pieces with bruisher,
Again with after distilled water boiling washing 6 times, it is placed on 40 DEG C of drying in vacuum drying oven and obtains within 48 hours polyphosphazene/polyethersulfone block copolymerization
Thing；
（3）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（2）Gained polyphosphazene/polyethersulfone block copolymer
10g, corn stalk powder 25g, dimethyl sulfoxide (DMSO) 150ml, acetic acid 0.5 ml, KH-550 2g and KH-560 5g, system temperature
50 DEG C are risen to, is reacted 6 hours, is discharged in water, obtain fluffy solid, the fluffy solid is washed with deionized 3 times, finally
24 h are dried in vacuo at 50 DEG C and obtain the polyphosphazene/polyethersulfone block copolymer cladding corn stalk powder；
The preparation method of the hydride modified sulfonated phosphazene is：
In 250 milliliters of round-bottomed flasks, by 0.4 gram of hexachlorocyclotriph,sphazene and 0.91 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 150 milliliters of acetonitriles, 1.1 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 h, after reaction terminates, centrifugation
Solvent is removed, washed product is distinguished 3 times with deionized water and acetone, 24 h are finally dried in vacuo at 40 DEG C and obtain white poly-
Phosphonitrile powder；
0.5 gram of above-mentioned white polyphosphazene powder is added in 50 milliliters of three-neck flasks, the dense of 10 milliliters of mass fractions 98% is added
Sulfuric acid, is placed in 60 DEG C of water-baths, and 10h is reacted under mechanical stirring, after reaction terminates, product is slowly poured into cold water, and
It is stirred continuously, is centrifuged off unreacted sulfuric acid, product is then washed with deionized 5 times, is finally dried in vacuo at 50 DEG C
48 h are to obtain sulfonated phosphazene powder；
1 gram of above-mentioned sulfonated phosphazene powder, 0.3 gram of silane coupler KH-560 and 10 are added in 50 milliliters of three-neck flasks
Milliliter dimethyl sulfoxide (DMSO), heats up after 50 DEG C of reaction 4h, is down to room temperature and slowly pours into product in cold water, and is stirred continuously, so
After product is washed with deionized 5 times, being finally dried in vacuo 48 h at 50 DEG C obtains hydride modified sulfonated phosphazene.
Comparative example 1
By weight, by 100 parts of ABS resin, 10 parts of lignin, 8 parts of nano oxidized caesium, 8 parts of montmorillonite, corn stalk powder 8
Part, 7 parts of ABS-g-MAH, 8 parts of compatilizer SEBS-g-MAH, 0.8 part of antioxidant 1010,8 parts of hydride modified sulfonated phosphazene,
3 parts of 6 parts of the chloro- 4,5- dihydros -1H- imidazole sulfonic acids salt of 2- and 2-mercaptobenzimidazole -5- sodium sulfonates dihydrate are mixed in high speed
20 min are mixed in clutch, mixing rate is 1500 revs/min, is then added mixed raw material in double screw extruder, control
Extrusion temperature processed is 215 DEG C, and after melting extrusion, cooling granulation obtains high-performance ABS/ maize straw composites；
The preparation method of the hydride modified sulfonated phosphazene is：
In 250 milliliters of round-bottomed flasks, by 0.4 gram of hexachlorocyclotriph,sphazene and 0.91 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 150 milliliters of acetonitriles, 1.1 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 h, after reaction terminates, centrifugation
Solvent is removed, washed product is distinguished 3 times with deionized water and acetone, 24 h are finally dried in vacuo at 40 DEG C and obtain white poly-
Phosphonitrile powder；
0.5 gram of above-mentioned white polyphosphazene powder is added in 50 milliliters of three-neck flasks, the dense of 10 milliliters of mass fractions 98% is added
Sulfuric acid, is placed in 60 DEG C of water-baths, and 10h is reacted under mechanical stirring, after reaction terminates, product is slowly poured into cold water, and
It is stirred continuously, is centrifuged off unreacted sulfuric acid, product is then washed with deionized 5 times, is finally dried in vacuo at 50 DEG C
48 h are to obtain sulfonated phosphazene powder；
1 gram of above-mentioned sulfonated phosphazene powder, 0.3 gram of silane coupler KH-560 and 10 are added in 50 milliliters of three-neck flasks
Milliliter dimethyl sulfoxide (DMSO), heats up after 50 DEG C of reaction 4h, is down to room temperature and slowly pours into product in cold water, and is stirred continuously, so
After product is washed with deionized 5 times, being finally dried in vacuo 48 h at 50 DEG C obtains hydride modified sulfonated phosphazene.
Comparative example 2
By weight, by 100 parts of ABS resin, 10 parts of lignin, 8 parts of nano oxidized caesium, 8 parts of montmorillonite, corn stalk powder 8
Part, 7 parts of ABS-g-MAH, 8 parts of compatilizer SEBS-g-MAH, 0.8 part of antioxidant 1010, the chloro- 4,5- dihydros -1H- imidazoles of 2-
3 parts of 6 parts of sulfonate and 2-mercaptobenzimidazole -5- sodium sulfonates dihydrate mix 20 min in super mixer, mixing
Speed is 1500 revs/min, then adds mixed raw material in double screw extruder, and it is 215 DEG C to control extrusion temperature, through molten
Melt after extrusion, cooling granulation, obtain high-performance ABS/ maize straw composites.
Test result is shown in Table 1.
Table 1
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and that described in above-described embodiment and specification is the present invention
Principle, various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention, these change and
Improvement is both fallen within the range of claimed invention.The protection domain of application claims by appended claims and its
Equivalent is defined.
Claims (10)
1. a kind of high-performance ABS/ maize straw composites, it is characterised in that by weight, its preparing raw material includes：ABS
100 parts of resin, 8-15 parts of lignin, nano oxidized caesium 5-10 parts, 5-10 parts of montmorillonite, polyphosphazene/polyethersulfone block copolymer
Coat 0.5-1 parts of 5-12 parts of corn stalk powder, 5-10 parts of ABS-g-MAH, 5-10 parts of compatilizer and antioxidant.
2. high-performance ABS/ maize straw composites according to claim 1, it is characterised in that by weight, its
Preparing raw material includes：100 parts of ABS resin, 9-12 parts of lignin, nano oxidized caesium 7-9 parts, 7-9 parts of montmorillonite, polyphosphazene/poly-
7-10 parts of corn stalk powder of ether sulfone block copolymer cladding, 6-9 parts of ABS-g-MAH, 5-10 parts of compatilizer and antioxidant 0.7-
0.9 part.
3. high-performance ABS/ maize straw composites according to claim 2, it is characterised in that by weight, its
Preparing raw material includes：100 parts of ABS resin, 10 parts of lignin, 8 parts of nano oxidized caesium, 8 parts of montmorillonite, polyphosphazene/polyether sulfone are embedding
0.8 part of 8 parts of corn stalk powder of section copolymer cladding, 7 parts of ABS-g-MAH, 8 parts of compatilizer and antioxidant.
4. the high-performance ABS/ maize straw composites according to claim any one of 1-3, it is characterised in that described poly-
The preparation method of phosphonitrile/polyethersulfone block copolymer cladding corn stalk powder is：
（1）In 250 milliliters of round-bottomed flasks, by 0.42 gram of hexachlorocyclotriph,sphazene and 0.93 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.2 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 5 h in 180 milliliters of acetonitriles, after reaction terminates,
Solvent is centrifuged off, washed product is distinguished 3 times with deionized water and acetone, 24 h is finally dried in vacuo at 50 DEG C and obtain white
Color polyphosphazene powder；
（2）Under nitrogen protection, 1.23g is added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
Above-mentioned steps（1）Gained white polyphosphazene powder, 4.256g diallyls bisphenol S, 3.810g 4,4 '-difluorodiphenyl sulfone, 20ml
Sulfolane, 2.277g potassium carbonate, 15ml toluene, 140 DEG C of backflows, band water raise temperature, steam toluene, system temperature after 4 hours
170 DEG C are risen to, is reacted 8 hours, is discharged in water, obtain bar shaped polymer, obtained bar shaped polymer is smashed to pieces with bruisher,
Again with after distilled water boiling washing 6 times, it is placed on 40 DEG C of drying in vacuum drying oven and obtains within 48 hours polyphosphazene/polyethersulfone block copolymerization
Thing；
（3）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（2）Gained polyphosphazene/polyethersulfone block copolymer
10g, corn stalk powder 25g, dimethyl sulfoxide (DMSO) 150ml, acetic acid 0.5 ml, KH-550 2g and KH-560 5g, system temperature
50 DEG C are risen to, is reacted 6 hours, is discharged in water, obtain fluffy solid, the fluffy solid is washed with deionized 3 times, finally
24 h are dried in vacuo at 50 DEG C and obtain the polyphosphazene/polyethersulfone block copolymer cladding corn stalk powder.
5. high-performance ABS/ maize straw composites according to claim 1, it is characterised in that by weight, its
Preparing raw material also includes：Hydride modified sulfonated phosphazene 5-10 parts.
6. high-performance ABS/ maize straw composites according to claim 5, it is characterised in that by weight, its
Preparing raw material also includes：Hydride modified 8 parts of sulfonated phosphazene.
7. the high-performance ABS/ maize straw composites according to claim 5 or 6, it is characterised in that the silane is repaiied
Decorations sulfonated phosphazene preparation method be：
In 250 milliliters of round-bottomed flasks, by 0.4 gram of hexachlorocyclotriph,sphazene and 0.91 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 150 milliliters of acetonitriles, 1.1 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 h, after reaction terminates, centrifugation
Solvent is removed, washed product is distinguished 3 times with deionized water and acetone, 24 h are finally dried in vacuo at 40 DEG C and obtain white poly-
Phosphonitrile powder；
0.5 gram of above-mentioned white polyphosphazene powder is added in 50 milliliters of three-neck flasks, the dense of 10 milliliters of mass fractions 98% is added
Sulfuric acid, is placed in 60 DEG C of water-baths, and 10h is reacted under mechanical stirring, after reaction terminates, product is slowly poured into cold water, and
It is stirred continuously, is centrifuged off unreacted sulfuric acid, product is then washed with deionized 5 times, is finally dried in vacuo at 50 DEG C
48 h are to obtain sulfonated phosphazene powder；
1 gram of above-mentioned sulfonated phosphazene powder, 0.3 gram of silane coupler KH-560 and 10 are added in 50 milliliters of three-neck flasks
Milliliter dimethyl sulfoxide (DMSO), heats up after 50 DEG C of reaction 4h, is down to room temperature and slowly pours into product in cold water, and is stirred continuously, so
After product is washed with deionized 5 times, being finally dried in vacuo 48 h at 50 DEG C obtains hydride modified sulfonated phosphazene.
8. high-performance ABS/ maize straw composites according to claim 1, it is characterised in that by weight, its
Preparing raw material also includes：1-10 parts of 2- chloro- 4,5- dihydros -1H- imidazole sulfonic acids salt, the water of 2-mercaptobenzimidazole -5- sodium sulfonates two
1-5 parts of compound.
9. a kind of preparation method of high-performance ABS/ maize straw composites, comprises the following steps：
The raw material described in claim any one of 1-8 is first mixed into 10-50min in super mixer, then will be mixed
Raw material is added in double screw extruder, and it is 200-230 DEG C to control extrusion temperature, and after melting extrusion, cooling granulation obtains high-performance
ABS/ maize straw composites.
10. the high-performance ABS/ maize straws composite described in claim any one of 1-8 is in household electrical appliances, building, auto industry
And the application of medical field.
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