CN107501793A - Environment-friendly type stalk modified polyvinyl chloride awning film and preparation method thereof - Google Patents
Environment-friendly type stalk modified polyvinyl chloride awning film and preparation method thereof Download PDFInfo
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01G13/00—Protecting plants
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Abstract
The invention discloses environment-friendly type stalk modified polyvinyl chloride awning film, it is characterised in that its preparing raw material includes：100 parts of Corvic, 1 10 parts of nano titanium oxide, 20 50 parts of corn stalk powder, single 28 parts of glyceryl linolenate, 0 20 parts of 0.2 1 parts of polyoxyethylene sorbitol acid anhydride monoleate, 0.5 1.5 parts of antioxidant 1010 and carbon nano-tube modification polyphosphazene polyethersulfone block copolymer 1.The environment-friendly type stalk modified polyvinyl chloride awning film good weatherability of the present invention, not easy to change, mechanical strength is good, also with the characteristics of degradable, environmentally friendly.
Description
Technical field
The invention belongs to greenhouse technical field of membrane, more particularly it relates to a kind of environment-friendly type stalk modified polyvinyl chloride
Alkene awning film and preparation method thereof.
Background technology
As the development of agricultural, greenhouse quantity are more and more.Awning film generally used now has a PVC film and PE films, PE films by
In itself crystallization it is larger cause the transparency it is poor.PVC film uses traditional films factory formula and technique more, but PVC is not degradable,
Therefore not environmentally.Its degradation capability can be greatly improved by adding stalk, but often reduces intensity, causes durability
Difference, this problems demand solve.
The content of the invention
Therefore, one aspect of the present invention provides environment-friendly type stalk modified polyvinyl chloride awning film, calculate by weight, its
Preparing raw material includes：
100 parts of Corvic, nano titanium oxide 1-10 parts, corn stalk powder 20-50 parts, single glyceryl linolenate 2-8
Part, polyoxyethylene sorbitol acid anhydride monoleate 0.2-1 parts, antioxidant 1010 0.5-1.5 parts and the poly- phosphorus of carbon nano-tube modification
Nitrile-polyethersulfone block copolymer 1 0-20 parts.
In a preferred approach, described environment-friendly type stalk modified polyvinyl chloride awning film, is calculated by weight, and it prepares former
Material includes：
100 parts of Corvic, nano titanium oxide 2-6 parts, corn stalk powder 30-40 parts, single glyceryl linolenate 3-7
Part, polyoxyethylene sorbitol acid anhydride monoleate 0.3-0.8 parts, antioxidant 1010 1-1.3 parts and the poly- phosphorus of carbon nano-tube modification
Nitrile-polyethersulfone block copolymer 1 2-18 parts.
In more preferably scheme, described environment-friendly type stalk modified polyvinyl chloride awning film, calculate by weight, it is prepared
Raw material includes：
100 parts of Corvic, 5 parts of nano titanium oxide, 35 parts of corn stalk powder, single 5 parts of glyceryl linolenate, polyoxygenated
0.5 part of ethene sorbitan mono-oleic acid ester, 1.2 parts of antioxidant 1010 and carbon nano-tube modification polyphosphazene-polyethersulfone block are common
15 parts of polymers.
In a preferred approach, the average grain diameter of the nano titanium oxide is 50-500 nanometers.
In a preferred approach, the corn stalk powder is 200-1000 mesh.
In a preferred approach, the preparation method of the carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）Under nitrogen protection, 1.23 are added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
Gram above-mentioned steps（1）Gained white polyphosphazene powder, 4.250 grams of diallyl bisphenol Ss, 3.811 grams of 4,4 '-difluorodiphenyl sulfones,
30 milliliters of sulfolane, 2.6 grams of potassium carbonate, 20 milliliters of toluene, 140 DEG C of backflows, band water raise temperature, steam toluene after 4 hours,
System temperature rises to 165 DEG C, reacts 20 hours, discharges in water, obtain bar shaped polymer, by obtained bar shaped polymer with smashing
Broken machine is smashed to pieces, then obtains polyphosphazene-polyethers within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Sulfone block copolymer；
（3）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（2）Gained polyphosphazene-polyethersulfone block copolymer 10
Gram, 1 gram of graphene oxide, 2.5 grams of CNT, 150 milliliters of dimethyl sulfoxide (DMSO), 1 milliliter of acetic acid, silane resin acceptor kh-550 2
Gram and 5 grams of silane coupler KH-560, system temperature rise to 50 DEG C, react 6 hours, discharge in water, obtain cotton-shaped production
Thing, the fluffy solid is washed respectively 3 times, be finally dried in vacuo at 50 DEG C described in obtaining within 24 hours with deionized water and ethanol
Carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer.
In a preferred approach, described environment-friendly type stalk modified polyvinyl chloride awning film, its preparing raw material also include：1-10
The sulfonated phosphazene modified nano-titanium dioxide of parts by weight.
In a preferred approach, the preparation method of the sulfonated phosphazene modified nano-titanium dioxide is：
In 250 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.92 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 200 milliliters of acetonitriles, 1.3 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 hours, after reaction terminates, from
The heart removes solvent, distinguishes washed product 5 times with deionized water and acetone, is finally dried in vacuo 18 hours at 50 DEG C and obtains white
Polyphosphazene powder；
0.6 gram of above-mentioned white polyphosphazene powder is added in 100 milliliters of three-neck flasks, adds 10 milliliters of mass fractions 98%
The concentrated sulfuric acid, it is placed in 50 DEG C of water-baths, reacts 15 hours under mechanical stirring, after reaction terminates, product is slowly poured into cold water
In, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, finally the vacuum at 50 DEG C
Dry 48 hours and obtain sulfonated phosphazene powder；
0.7 gram of above-mentioned sulfonated phosphazene powder, 0.07 gram of epoxy resin E51, average grain diameter are added in 50 milliliters of three-neck flasks
For 0.5 gram of 150 nanometers of 3 grams of nano titanium oxide, 0.2 gram of silane resin acceptor kh-550 and silane coupler KH-560 with
And 10 milliliters of dimethyl sulfoxide (DMSO)s, heat up 120 DEG C after reacting 2 hours, be down to room temperature and slowly pour into product in cold water, and constantly
Stirring, is then washed with deionized product 5 times, and it is to obtain sulfonated phosphazene to change that 48 hours are finally dried in vacuo at 50 DEG C
Property nano titanium oxide.
The present invention also provides the preparation method of environment-friendly type stalk modified polyvinyl chloride awning film, including：
（1）The raw material is mixed in mixer, during 100 ~ 130 DEG C of mixing temperature, when temperature of charge is cooled to 38 ~ 42 DEG C
Discharging；
（2）The material of above-mentioned discharging is used into individual layer calendering technology, rolling temperature is 160 DEG C ~ 200 DEG C, obtains awning film.
In a preferred approach, the mixing temperature is 120 DEG C, and the rolling temperature is 180 DEG C.
Compared with prior art, beneficial effects of the present invention are：
1st, by the addition of stalk, the degradability and cost of material can be greatly improved.
2nd, by the addition of carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer, the strong of material can be greatly improved
Degree, weatherability.
3rd, by the addition of sulfonated phosphazene modified nano-titanium dioxide, the intensity of material and weather-proof can further be improved
Property.
Embodiment
Raw material:
Polyvinyl chloride（PVC）Purchased from safe in Xinjiang, model SG-5.Nano titanium oxide（150 nanometers of average grain diameter）, corn stalk
Stalk powder（800 mesh）, silane resin acceptor kh-550, silane coupler KH-560 be purchased from Aladdin reagent.CNT is more wall carbon
Nanotube, average 10 microns of pipe range, average 50 nanometers of caliber, heap density 0.09g/cm3Scheme purchased from Shenzhen spirit.Graphene oxide is purchased
From permanent ball science and technology.Other raw materials are purchased from Chinese medicines group.
Embodiment 1
Calculate by weight, successively by 100 parts of Corvic, nano titanium oxide（150 nanometers of average grain diameter）It is 1 part, beautiful
20 parts of powder of straw of rice, single 2 parts of glyceryl linolenate, 0.2 part of polyoxyethylene sorbitol acid anhydride monoleate, antioxidant 1010 0.5
Part and carbon nano-tube modification polyphosphazene -0 part of polyethersulfone block copolymer 1 mixed in mixer, during 120 DEG C of mixing temperature,
Mixing rate is 1700r/min, is discharged when temperature of charge is cooled to 40 DEG C；
The material of above-mentioned discharging is used into individual layer calendering technology, rolling temperature is 180 DEG C, obtains awning film；
The preparation method of the carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）Under nitrogen protection, 1.23 are added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
Gram above-mentioned steps（1）Gained white polyphosphazene powder, 4.250 grams of diallyl bisphenol Ss, 3.811 grams of 4,4 '-difluorodiphenyl sulfones,
30 milliliters of sulfolane, 2.6 grams of potassium carbonate, 20 milliliters of toluene, 140 DEG C of backflows, band water raise temperature, steam toluene after 4 hours,
System temperature rises to 165 DEG C, reacts 20 hours, discharges in water, obtain bar shaped polymer, by obtained bar shaped polymer with smashing
Broken machine is smashed to pieces, then obtains polyphosphazene-polyethers within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Sulfone block copolymer；
（3）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（2）Gained polyphosphazene-polyethersulfone block copolymer 10
Gram, 1 gram of graphene oxide, 2.5 grams of CNT, 150 milliliters of dimethyl sulfoxide (DMSO), 1 milliliter of acetic acid, silane resin acceptor kh-550 2
Gram and 5 grams of silane coupler KH-560, system temperature rise to 50 DEG C, react 6 hours, discharge in water, obtain cotton-shaped production
Thing, the fluffy solid is washed respectively 3 times, be finally dried in vacuo at 50 DEG C described in obtaining within 24 hours with deionized water and ethanol
Carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer.
Embodiment 2
Calculate by weight, successively by 100 parts of Corvic, nano titanium oxide（150 nanometers of average grain diameter）It is 10 parts, beautiful
50 parts of powder of straw of rice, single 8 parts of glyceryl linolenate, 1 part of polyoxyethylene sorbitol acid anhydride monoleate, 1.5 parts of antioxidant 1010
And carbon nano-tube modification polyphosphazene -20 parts of polyethersulfone block copolymer mixes in mixer, during 120 DEG C of mixing temperature, mix
Conjunction speed is 1700r/min, is discharged when temperature of charge is cooled to 40 DEG C；
The material of above-mentioned discharging is used into individual layer calendering technology, rolling temperature is 180 DEG C, obtains awning film；
The preparation method of the carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）Under nitrogen protection, 1.23 are added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
Gram above-mentioned steps（1）Gained white polyphosphazene powder, 4.250 grams of diallyl bisphenol Ss, 3.811 grams of 4,4 '-difluorodiphenyl sulfones,
30 milliliters of sulfolane, 2.6 grams of potassium carbonate, 20 milliliters of toluene, 140 DEG C of backflows, band water raise temperature, steam toluene after 4 hours,
System temperature rises to 165 DEG C, reacts 20 hours, discharges in water, obtain bar shaped polymer, by obtained bar shaped polymer with smashing
Broken machine is smashed to pieces, then obtains polyphosphazene-polyethers within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Sulfone block copolymer；
（3）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（2）Gained polyphosphazene-polyethersulfone block copolymer 10
Gram, 1 gram of graphene oxide, 2.5 grams of CNT, 150 milliliters of dimethyl sulfoxide (DMSO), 1 milliliter of acetic acid, silane resin acceptor kh-550 2
Gram and 5 grams of silane coupler KH-560, system temperature rise to 50 DEG C, react 6 hours, discharge in water, obtain cotton-shaped production
Thing, the fluffy solid is washed respectively 3 times, be finally dried in vacuo at 50 DEG C described in obtaining within 24 hours with deionized water and ethanol
Carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer.
Embodiment 3
Calculate by weight, successively by 100 parts of Corvic, nano titanium oxide（150 nanometers of average grain diameter）It is 5 parts, beautiful
35 parts of powder of straw of rice, single 5 parts of glyceryl linolenate, 0.5 part of polyoxyethylene sorbitol acid anhydride monoleate, antioxidant 1010 1.2
Part and carbon nano-tube modification polyphosphazene -5 parts of polyethersulfone block copolymer 1 mixed in mixer, during 120 DEG C of mixing temperature,
Mixing rate is 1700r/min, is discharged when temperature of charge is cooled to 40 DEG C；
The material of above-mentioned discharging is used into individual layer calendering technology, rolling temperature is 180 DEG C, obtains awning film；
The preparation method of the carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）Under nitrogen protection, 1.23 are added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
Gram above-mentioned steps（1）Gained white polyphosphazene powder, 4.250 grams of diallyl bisphenol Ss, 3.811 grams of 4,4 '-difluorodiphenyl sulfones,
30 milliliters of sulfolane, 2.6 grams of potassium carbonate, 20 milliliters of toluene, 140 DEG C of backflows, band water raise temperature, steam toluene after 4 hours,
System temperature rises to 165 DEG C, reacts 20 hours, discharges in water, obtain bar shaped polymer, by obtained bar shaped polymer with smashing
Broken machine is smashed to pieces, then obtains polyphosphazene-polyethers within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Sulfone block copolymer；
（3）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（2）Gained polyphosphazene-polyethersulfone block copolymer 10
Gram, 1 gram of graphene oxide, 2.5 grams of CNT, 150 milliliters of dimethyl sulfoxide (DMSO), 1 milliliter of acetic acid, silane resin acceptor kh-550 2
Gram and 5 grams of silane coupler KH-560, system temperature rise to 50 DEG C, react 6 hours, discharge in water, obtain cotton-shaped production
Thing, the fluffy solid is washed respectively 3 times, be finally dried in vacuo at 50 DEG C described in obtaining within 24 hours with deionized water and ethanol
Carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer.
Embodiment 4
Calculate by weight, successively by 100 parts of Corvic, nano titanium oxide（150 nanometers of average grain diameter）It is 5 parts, beautiful
35 parts of powder of straw of rice, single 5 parts of glyceryl linolenate, 0.5 part of polyoxyethylene sorbitol acid anhydride monoleate, antioxidant 1010 1.2
Part, 5 parts of carbon nano-tube modification polyphosphazene -5 parts of polyethersulfone block copolymer 1 and sulfonated phosphazene modified nano-titanium dioxide exist
Mix in mixer, during 120 DEG C of mixing temperature, mixing rate 1700r/min, discharged when temperature of charge is cooled to 40 DEG C；
The material of above-mentioned discharging is used into individual layer calendering technology, rolling temperature is 180 DEG C, obtains awning film；
The preparation method of the carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）Under nitrogen protection, 1.23 are added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
Gram above-mentioned steps（1）Gained white polyphosphazene powder, 4.250 grams of diallyl bisphenol Ss, 3.811 grams of 4,4 '-difluorodiphenyl sulfones,
30 milliliters of sulfolane, 2.6 grams of potassium carbonate, 20 milliliters of toluene, 140 DEG C of backflows, band water raise temperature, steam toluene after 4 hours,
System temperature rises to 165 DEG C, reacts 20 hours, discharges in water, obtain bar shaped polymer, by obtained bar shaped polymer with smashing
Broken machine is smashed to pieces, then obtains polyphosphazene-polyethers within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Sulfone block copolymer；
（3）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（2）Gained polyphosphazene-polyethersulfone block copolymer 10
Gram, 1 gram of graphene oxide, 2.5 grams of CNT, 150 milliliters of dimethyl sulfoxide (DMSO), 1 milliliter of acetic acid, silane resin acceptor kh-550 2
Gram and 5 grams of silane coupler KH-560, system temperature rise to 50 DEG C, react 6 hours, discharge in water, obtain cotton-shaped production
Thing, the fluffy solid is washed respectively 3 times, be finally dried in vacuo at 50 DEG C described in obtaining within 24 hours with deionized water and ethanol
Carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer；
The preparation method of the sulfonated phosphazene modified nano-titanium dioxide is：
In 250 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.92 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 200 milliliters of acetonitriles, 1.3 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 hours, after reaction terminates, from
The heart removes solvent, distinguishes washed product 5 times with deionized water and acetone, is finally dried in vacuo 18 hours at 50 DEG C and obtains white
Polyphosphazene powder；
0.6 gram of above-mentioned white polyphosphazene powder is added in 100 milliliters of three-neck flasks, adds 10 milliliters of mass fractions 98%
The concentrated sulfuric acid, it is placed in 50 DEG C of water-baths, reacts 15 hours under mechanical stirring, after reaction terminates, product is slowly poured into cold water
In, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, finally the vacuum at 50 DEG C
Dry 48 hours and obtain sulfonated phosphazene powder；
0.7 gram of above-mentioned sulfonated phosphazene powder, 0.07 gram of epoxy resin E51, average grain diameter are added in 50 milliliters of three-neck flasks
For 0.5 gram of 150 nanometers of 3 grams of nano titanium oxide, 0.2 gram of silane resin acceptor kh-550 and silane coupler KH-560 with
And 10 milliliters of dimethyl sulfoxide (DMSO)s, heat up 120 DEG C after reacting 2 hours, be down to room temperature and slowly pour into product in cold water, and constantly
Stirring, is then washed with deionized product 5 times, and it is to obtain sulfonated phosphazene to change that 48 hours are finally dried in vacuo at 50 DEG C
Property nano titanium oxide.
Comparative example 1
Calculate by weight, successively by 100 parts of Corvic, nano titanium oxide（150 nanometers of average grain diameter）It is 5 parts, beautiful
35 parts of powder of straw of rice, single 5 parts of glyceryl linolenate, 0.5 part of polyoxyethylene sorbitol acid anhydride monoleate, antioxidant 1010 1.2
Part mix in mixer, during 120 DEG C of mixing temperature, mixing rate 1700r/min, go out when temperature of charge is cooled to 40 DEG C
Material；
The material of above-mentioned discharging is used into individual layer calendering technology, rolling temperature is 180 DEG C, obtains awning film.
Comparative example 2
Calculate by weight, successively by 100 parts of Corvic, nano titanium oxide（150 nanometers of average grain diameter）It is 5 parts, beautiful
35 parts of powder of straw of rice, single 5 parts of glyceryl linolenate, 0.5 part of polyoxyethylene sorbitol acid anhydride monoleate, antioxidant 1010 1.2
5 parts of part, polyphosphazene -5 parts of polyethersulfone block copolymer 1 and sulfonated phosphazene modified nano-titanium dioxide mix in mixer
Close, during 120 DEG C of mixing temperature, mixing rate 1700r/min, discharged when temperature of charge is cooled to 40 DEG C；
The material of above-mentioned discharging is used into individual layer calendering technology, rolling temperature is 180 DEG C, obtains awning film；
The preparation method of the polyphosphazene-polyethersulfone block copolymer is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）Under nitrogen protection, 1.23 are added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
Gram above-mentioned steps（1）Gained white polyphosphazene powder, 4.250 grams of diallyl bisphenol Ss, 3.811 grams of 4,4 '-difluorodiphenyl sulfones,
30 milliliters of sulfolane, 2.6 grams of potassium carbonate, 20 milliliters of toluene, 140 DEG C of backflows, band water raise temperature, steam toluene after 4 hours,
System temperature rises to 165 DEG C, reacts 20 hours, discharges in water, obtain bar shaped polymer, by obtained bar shaped polymer with smashing
Broken machine is smashed to pieces, then obtains polyphosphazene-polyethers within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Sulfone block copolymer；
The preparation method of the sulfonated phosphazene modified nano-titanium dioxide is：
In 250 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.92 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 200 milliliters of acetonitriles, 1.3 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 hours, after reaction terminates, from
The heart removes solvent, distinguishes washed product 5 times with deionized water and acetone, is finally dried in vacuo 18 hours at 50 DEG C and obtains white
Polyphosphazene powder；
0.6 gram of above-mentioned white polyphosphazene powder is added in 100 milliliters of three-neck flasks, adds 10 milliliters of mass fractions 98%
The concentrated sulfuric acid, it is placed in 50 DEG C of water-baths, reacts 15 hours under mechanical stirring, after reaction terminates, product is slowly poured into cold water
In, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, finally the vacuum at 50 DEG C
Dry 48 hours and obtain sulfonated phosphazene powder；
0.7 gram of above-mentioned sulfonated phosphazene powder, 0.07 gram of epoxy resin E51, average grain diameter are added in 50 milliliters of three-neck flasks
For 0.5 gram of 150 nanometers of 3 grams of nano titanium oxide, 0.2 gram of silane resin acceptor kh-550 and silane coupler KH-560 with
And 10 milliliters of dimethyl sulfoxide (DMSO)s, heat up 120 DEG C after reacting 2 hours, be down to room temperature and slowly pour into product in cold water, and constantly
Stirring, is then washed with deionized product 5 times, and it is to obtain sulfonated phosphazene to change that 48 hours are finally dried in vacuo at 50 DEG C
Property nano titanium oxide.
Comparative example 3
Calculate by weight, successively by 100 parts of Corvic, nano titanium oxide（150 nanometers of average grain diameter）It is 5 parts, beautiful
35 parts of powder of straw of rice, single 5 parts of glyceryl linolenate, 0.5 part of polyoxyethylene sorbitol acid anhydride monoleate, antioxidant 1010 1.2
5 parts of part, carbon nano-tube modification polyphosphazene -5 parts of polyethersulfone block copolymer 1 and polyphosphazene modified nano-titanium dioxide are mixing
Mix in machine, during 120 DEG C of mixing temperature, mixing rate 1700r/min, discharged when temperature of charge is cooled to 40 DEG C；
The material of above-mentioned discharging is used into individual layer calendering technology, rolling temperature is 180 DEG C, obtains awning film；
The preparation method of the carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）Under nitrogen protection, 1.23 are added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
Gram above-mentioned steps（1）Gained white polyphosphazene powder, 4.250 grams of diallyl bisphenol Ss, 3.811 grams of 4,4 '-difluorodiphenyl sulfones,
30 milliliters of sulfolane, 2.6 grams of potassium carbonate, 20 milliliters of toluene, 140 DEG C of backflows, band water raise temperature, steam toluene after 4 hours,
System temperature rises to 165 DEG C, reacts 20 hours, discharges in water, obtain bar shaped polymer, by obtained bar shaped polymer with smashing
Broken machine is smashed to pieces, then obtains polyphosphazene-polyethers within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Sulfone block copolymer；
（3）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（2）Gained polyphosphazene-polyethersulfone block copolymer 10
Gram, 1 gram of graphene oxide, 2.5 grams of CNT, 150 milliliters of dimethyl sulfoxide (DMSO), 1 milliliter of acetic acid, silane resin acceptor kh-550 2
Gram and 5 grams of silane coupler KH-560, system temperature rise to 50 DEG C, react 6 hours, discharge in water, obtain cotton-shaped production
Thing, the fluffy solid is washed respectively 3 times, be finally dried in vacuo at 50 DEG C described in obtaining within 24 hours with deionized water and ethanol
Carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer；
The preparation method of the polyphosphazene modified nano-titanium dioxide is：
In 250 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.92 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 200 milliliters of acetonitriles, 1.3 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 hours, after reaction terminates, from
The heart removes solvent, distinguishes washed product 5 times with deionized water and acetone, is finally dried in vacuo 18 hours at 50 DEG C and obtains white
Polyphosphazene powder；
0.7 gram of above-mentioned polyphosphazene powder, 0.07 gram of epoxy resin E51, average grain diameter are added in 50 milliliters of three-neck flasks is
150 nanometers of 0.5 gram of 3 grams of nano titanium oxide, 0.2 gram of silane resin acceptor kh-550 and silane coupler KH-560 and
10 milliliters of dimethyl sulfoxide (DMSO)s, heat up 120 DEG C after reacting 2 hours, be down to room temperature and slowly pour into product in cold water, and constantly stir
Mix, product is then washed with deionized 5 times, be finally dried in vacuo at 50 DEG C 48 hours and obtain polyphosphazene modified Nano
Titanium dioxide.
Test result is shown in Table 1.
Table 1
Claims (10)
1. environment-friendly type stalk modified polyvinyl chloride awning film, it is characterised in that calculate by weight, its preparing raw material includes：
100 parts of Corvic, nano titanium oxide 1-10 parts, corn stalk powder 20-50 parts, single glyceryl linolenate 2-8
Part, polyoxyethylene sorbitol acid anhydride monoleate 0.2-1 parts, antioxidant 1010 0.5-1.5 parts and the poly- phosphorus of carbon nano-tube modification
Nitrile-polyethersulfone block copolymer 1 0-20 parts.
2. environment-friendly type stalk modified polyvinyl chloride awning film according to claim 1, it is characterised in that by weight
Calculate, its preparing raw material includes：
100 parts of Corvic, nano titanium oxide 2-6 parts, corn stalk powder 30-40 parts, single glyceryl linolenate 3-7
Part, polyoxyethylene sorbitol acid anhydride monoleate 0.3-0.8 parts, antioxidant 1010 1-1.3 parts and the poly- phosphorus of carbon nano-tube modification
Nitrile-polyethersulfone block copolymer 1 2-18 parts.
3. environment-friendly type stalk modified polyvinyl chloride awning film according to claim 2, it is characterised in that by weight
Calculate, its preparing raw material includes：
100 parts of Corvic, 5 parts of nano titanium oxide, 35 parts of corn stalk powder, single 5 parts of glyceryl linolenate, polyoxygenated
0.5 part of ethene sorbitan mono-oleic acid ester, 1.2 parts of antioxidant 1010 and carbon nano-tube modification polyphosphazene-polyethersulfone block are common
15 parts of polymers.
4. the environment-friendly type stalk modified polyvinyl chloride awning film according to claim any one of 1-3, it is characterised in that described
The average grain diameter of nano titanium oxide is 50-500 nanometers.
5. the environment-friendly type stalk modified polyvinyl chloride awning film according to claim any one of 1-3, it is characterised in that described
Corn stalk powder is 200-1000 mesh.
6. the environment-friendly type stalk modified polyvinyl chloride awning film according to claim any one of 1-3, it is characterised in that described
The preparation method of carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）Under nitrogen protection, 1.23 are added to being connected with the there-necked flask of mechanical agitation, air inlet pipe, water-taker and condenser pipe
Gram above-mentioned steps（1）Gained white polyphosphazene powder, 4.250 grams of diallyl bisphenol Ss, 3.811 grams of 4,4 '-difluorodiphenyl sulfones,
30 milliliters of sulfolane, 2.6 grams of potassium carbonate, 20 milliliters of toluene, 140 DEG C of backflows, band water raise temperature, steam toluene after 4 hours,
System temperature rises to 165 DEG C, reacts 20 hours, discharges in water, obtain bar shaped polymer, by obtained bar shaped polymer with smashing
Broken machine is smashed to pieces, then obtains polyphosphazene-polyethers within 24 hours with 50 DEG C of drying in vacuum drying oven after distilled water boiling washing 3 times, are placed on
Sulfone block copolymer；
（3）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（2）Gained polyphosphazene-polyethersulfone block copolymer 10
Gram, 1 gram of graphene oxide, 2.5 grams of CNT, 150 milliliters of dimethyl sulfoxide (DMSO), 1 milliliter of acetic acid, silane resin acceptor kh-550 2
Gram and 5 grams of silane coupler KH-560, system temperature rise to 50 DEG C, react 6 hours, discharge in water, obtain cotton-shaped production
Thing, the fluffy solid is washed respectively 3 times, be finally dried in vacuo at 50 DEG C described in obtaining within 24 hours with deionized water and ethanol
Carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer.
7. the environment-friendly type stalk modified polyvinyl chloride awning film according to claim any one of 1-3, it is characterised in that it is made
Standby raw material also includes：The sulfonated phosphazene modified nano-titanium dioxide of 1-10 parts by weight.
8. environment-friendly type stalk modified polyvinyl chloride awning film according to claim 7, it is characterised in that the poly- phosphorus of sulfonation
The preparation method of nitrile modified nano-titanium dioxide is：
In 250 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.92 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 200 milliliters of acetonitriles, 1.3 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 hours, after reaction terminates, from
The heart removes solvent, distinguishes washed product 5 times with deionized water and acetone, is finally dried in vacuo 18 hours at 50 DEG C and obtains white
Polyphosphazene powder；
0.6 gram of above-mentioned white polyphosphazene powder is added in 100 milliliters of three-neck flasks, adds 10 milliliters of mass fractions 98%
The concentrated sulfuric acid, it is placed in 50 DEG C of water-baths, reacts 15 hours under mechanical stirring, after reaction terminates, product is slowly poured into cold water
In, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, finally the vacuum at 50 DEG C
Dry 48 hours and obtain sulfonated phosphazene powder；
0.7 gram of above-mentioned sulfonated phosphazene powder, 0.07 gram of epoxy resin E51, average grain diameter are added in 50 milliliters of three-neck flasks
For 0.5 gram of 150 nanometers of 3 grams of nano titanium oxide, 0.2 gram of silane resin acceptor kh-550 and silane coupler KH-560 with
And 10 milliliters of dimethyl sulfoxide (DMSO)s, heat up 120 DEG C after reacting 2 hours, be down to room temperature and slowly pour into product in cold water, and constantly
Stirring, is then washed with deionized product 5 times, and it is to obtain sulfonated phosphazene to change that 48 hours are finally dried in vacuo at 50 DEG C
Property nano titanium oxide.
9. the preparation method of environment-friendly type stalk modified polyvinyl chloride awning film, it is characterised in that including：
（1）Raw material described in claim any one of 1-8 is mixed in mixer, during 100 ~ 130 DEG C of mixing temperature, treats material
Temperature discharges when being cooled to 38 ~ 42 DEG C；
（2）The material of above-mentioned discharging is used into individual layer calendering technology, rolling temperature is 160 DEG C ~ 200 DEG C, obtains awning film.
10. the preparation method of environment-friendly type stalk modified polyvinyl chloride awning film according to claim 9, it is characterised in that
The mixing temperature is 120 DEG C, and the rolling temperature is 180 DEG C.
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