CN107619604A - Special powder calcium zinc stabilizers of environment friendly medical level PVC and preparation method thereof - Google Patents
Special powder calcium zinc stabilizers of environment friendly medical level PVC and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the special powder calcium zinc stabilizers of environment friendly medical level PVC, by weight, its preparing raw material includes：The calcium stearate of 100 parts by weight, the zinc stearate of 10~40 parts by weight, the nano titanium oxide of 5~10 parts by weight, the nano silicon of 5~10 parts by weight, the glycerin monostearate of 5~10 parts by weight, the carbon nano-tube modification polyphosphazene polyethersulfone block copolymer of 5~10 parts by weight, the β positive octadecanol esters of (hydroxy phenyl of 3,5 di-t-butyl 4) propionic acid of 1~5 parts by weight and the ultra-violet absorber UV 531 of 1~5 parts by weight.The special powder calcium zinc stabilizer good weatherabilities of environment friendly medical level PVC of the present invention, it is not easy to change, can both improve the life-span of PVC medical materials, its mechanical strength can be greatly improved again, also with it is heat-resisting good and environmentally friendly the characteristics of.
Description
Technical field
The invention belongs to chemical stabilizer technical field, more particularly it relates to which a kind of environment friendly medical level PVC is special
With powder calcium zinc stabilizer and preparation method thereof.
Background technology
With the development of medical industry, the demand of medical grade PVC (PVC) constantly increases.In the prior art, make
During standby PVC medical materials, it usually needs add stabilizer to improve performance.Generally, it is typically compound using nontoxic calcium zinc
Stabilizer, it is universally acknowledged nontoxic, environment-benign heat stabilizer, and has the advantages that cheap, lubricity is good.But
It is calcium-zinc composite stabilizing agent in the market, on the one hand, weatherability is bad, easily discoloration；On the other hand, content is added
Compared with the intensity that Gao Shihui significantly reduces PVC material.Therefore, it is necessary to developing one kind both has good heat resistance and weatherability, again
The environment-friendly calcium-zinc compound stabilizer of the intensity of PVC material will not be reduced.
The content of the invention
Therefore, one aspect of the present invention provides the special powder calcium zinc stabilizers of environment friendly medical level PVC, by weight
Meter, its preparing raw material include：
The calcium stearate of 100 parts by weight, the zinc stearate of 10~40 parts by weight, the nano titanium oxide of 5~10 parts by weight, 5~
The nano silicon of 10 parts by weight, the glycerin monostearate of 5~10 parts by weight, the carbon nano-tube modification of 5~10 parts by weight
β-positive octadecanol of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid of polyphosphazene-polyethersulfone block copolymer, 1~5 parts by weight
The ultraviolet absorbent UV-531 of ester and 1~5 parts by weight.
In a preferred approach, the described special powder calcium zinc stabilizers of environment friendly medical level PVC, by weight
Meter, its preparing raw material include：
The calcium stearate of 100 parts by weight, the zinc stearate of 20~30 parts by weight, the nano titanium oxide of 6~9 parts by weight, 6~9
The nano silicon of parts by weight, the glycerin monostearate of 6~9 parts by weight, the poly- phosphorus of the carbon nano-tube modification of 6~8 parts by weight
Nitrile-polyethersulfone block copolymer, 2~4 parts by weight β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid with
And 2~4 parts by weight ultraviolet absorbent UV-531.
In more preferably scheme, the described special powder calcium zinc stabilizers of environment friendly medical level PVC, by weight
Part meter, its preparing raw material include：
The calcium stearate of 100 parts by weight, the zinc stearate of 25 parts by weight, the nano titanium oxide of 8 parts by weight, 8 parts by weight are received
Carbon nano-tube modification polyphosphazene-polyethersulfone block copolymerization of rice silica, the glycerin monostearate of 8 parts by weight, 7 parts by weight
The ultraviolet of thing, β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid of 3 parts by weight and 3 parts by weight is inhaled
Receive agent UV-531.
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, the average grain diameter of the nano silicon is 50-500 nanometers；Preferably 150 nanometers.
In a preferred approach, the average grain diameter of the nano titanium oxide is 100-300 nanometers；Preferably 200 nanometers.
In a preferred approach, the described special powder calcium zinc stabilizers of environment friendly medical level PVC, by weight, it is made
Standby raw material also includes：The sulfonated phosphazene modified manometer silicon dioxide of 5-10 parts by weight.
In a preferred approach, the preparation method of the sulfonated phosphazene modified manometer silicon 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
150 nanometers of 0.5 gram of 3 grams of nano silicon, 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 and obtain within 48 hours sulfonated phosphazene modification
Nano silicon.
Another aspect of the present invention provides the preparation method of the special powder calcium zinc stabilizers of environment friendly medical level PVC, including：
Described recipe ingredient is added in homogenizer, 5min-10min is stirred under the conditions of 60-90 DEG C, stir speed (S.S.) is
1200-1500r/min, obtained after cooling.
In a preferred approach, the preparation method of the described special powder calcium zinc stabilizers of environment friendly medical level PVC, at 70 DEG C
Under the conditions of stir 8min, stir speed (S.S.) 1300r/min.
Compared with prior art, beneficial effects of the present invention are：
1st, by the addition of carbon nano-tube modification polyphosphazene-polyethersulfone block copolymer, the intensity, resistance to of material can be greatly improved
Hot and toughness.
2nd, by the addition of sulfonated phosphazene modified manometer silicon dioxide, the intensity of material and tough can further be improved
Property.
Embodiment
Raw material:
Nano silicon（150 nanometers of average grain diameter）, nano titanium oxide（200 nanometers of average grain diameter）, silane coupler KH-
550th, KH-560 is purchased from Aladdin reagent.CNT is multi-walled carbon nanotube, and average 10 microns of pipe range, average caliber 50 is received
Rice, heap density 0.09g/cm3Scheme purchased from Shenzhen spirit.Purchased from graphene oxide purchased from permanent ball science and technology.Other raw materials are purchased from traditional Chinese medicines
Group.
Embodiment 1
Successively by the calcium stearate of 100 parts by weight, the zinc stearate of 10 parts by weight, the nano titanium oxide of 5 parts by weight, 5 weight
Nano silicon, the glycerin monostearate, the carbon nano-tube modification polyphosphazene-polyether sulfone of 5 parts by weight of 5 parts by weight of part are embedding
Section copolymer, β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid of 1 parts by weight and the purple of 1 parts by weight
Ultraviolet absorbers UV-531 is added in homogenizer, stirs 8min under the conditions of 70 DEG C, stir speed (S.S.) 1300r/min, cold
But calcium-zinc composite stabilizing agent is obtained afterwards；
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
Successively by the calcium stearate of 100 parts by weight, the zinc stearate of 40 parts by weight, the nano titanium oxide of 10 parts by weight, 10 weights
Measure the nano silicon of part, the glycerin monostearate of 10 parts by weight, carbon nano-tube modification polyphosphazene-polyethers of 10 parts by weight
Sulfone block copolymer, β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid of 5 parts by weight and 5 parts by weight
Ultraviolet absorbent UV-531 add homogenizer in, 8min, stir speed (S.S.) 1300r/ are stirred under the conditions of 70 DEG C
Min, calcium-zinc composite stabilizing agent is obtained after cooling；
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
Successively by the calcium stearate of 100 parts by weight, the zinc stearate of 25 parts by weight, the nano titanium oxide of 8 parts by weight, 8 weight
Nano silicon, the glycerin monostearate, the carbon nano-tube modification polyphosphazene-polyether sulfone of 7 parts by weight of 8 parts by weight of part are embedding
Section copolymer, β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid of 3 parts by weight and the purple of 3 parts by weight
Ultraviolet absorbers UV-531 is added in homogenizer, stirs 8min under the conditions of 70 DEG C, stir speed (S.S.) 1300r/min, cold
But calcium-zinc composite stabilizing agent is obtained afterwards；
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
Successively by the calcium stearate of 100 parts by weight, the zinc stearate of 25 parts by weight, the nano titanium oxide of 8 parts by weight, 8 weight
Nano silicon, the glycerin monostearate, the carbon nano-tube modification polyphosphazene-polyether sulfone of 7 parts by weight of 8 parts by weight of part are embedding
Section copolymer, β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, the ultraviolet of 3 parts by weight of 3 parts by weight
Absorbent UV-531 and the sulfonated phosphazene modified manometer silicon dioxide of 8 parts by weight are added in homogenizer, in 70 DEG C of bars
8min is stirred under part, stir speed (S.S.) 1300r/min, calcium-zinc composite stabilizing agent is obtained after cooling；
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 manometer silicon 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
150 nanometers of 0.5 gram of 3 grams of nano silicon, 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 and obtain within 48 hours sulfonated phosphazene modification
Nano silicon.
Comparative example 1
Successively by the calcium stearate of 100 parts by weight, the zinc stearate of 25 parts by weight, the nano titanium oxide of 8 parts by weight, 8 weight
Nano silicon, the glycerin monostearate, β-(the 3,5- di-tert-butyl-hydroxy phenyls) of 3 parts by weight of 8 parts by weight of part
The positive octadecanol ester of propionic acid and the ultraviolet absorbent UV-531 of 3 parts by weight are added in homogenizer, under the conditions of 70 DEG C
8min is stirred, stir speed (S.S.) is 1300r/min, and calcium-zinc composite stabilizing agent is obtained after cooling.
Comparative example 2
Successively by the calcium stearate of 100 parts by weight, the zinc stearate of 25 parts by weight, the nano titanium oxide of 8 parts by weight, 8 weight
Nano silicon, glycerin monostearate, the polyphosphazene-polyethersulfone block copolymer, 3 weights of 7 parts by weight of 8 parts by weight of part
Measure the β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid of part and the ultra-violet absorber UV- of 3 parts by weight
531 are added in homogenizer, and 8min, stir speed (S.S.) 1300r/min are stirred under the conditions of 70 DEG C, calcium zinc is obtained after cooling and is answered
Close stabilizer；
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.
Comparative example 3
Successively by the calcium stearate of 100 parts by weight, the zinc stearate of 25 parts by weight, the nano titanium oxide of 8 parts by weight, 8 weight
The nano silicon of part, the glycerin monostearate of 8 parts by weight, the polyphosphazene of 7 parts by weight, β-(uncles of 3,5- bis- of 3 parts by weight
Butyl -4- hydroxy phenyls) ultraviolet absorbent UV-531s of the positive octadecanol ester of propionic acid and 3 parts by weight adds homogenizer
In, 8min is stirred under the conditions of 70 DEG C, stir speed (S.S.) 1300r/min, calcium-zinc composite stabilizing agent is obtained after cooling；
The preparation method of the polyphosphazene is：
In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 190 milliliters of acetonitriles, 1.5 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours, after reaction terminates,
Solvent is centrifuged off, washed product is distinguished 5 times with deionized water and acetone, is finally dried in vacuo 25 hours and obtains at 50 DEG C
White polyphosphazene powder.
Comparative example 4
Successively by the calcium stearate of 100 parts by weight, the zinc stearate of 25 parts by weight, the nano titanium oxide of 8 parts by weight, 8 weight
Nano silicon, the glycerin monostearate, the carbon nano-tube modification polyphosphazene-polyether sulfone of 7 parts by weight of 8 parts by weight of part are embedding
Section copolymer, β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, the ultraviolet of 3 parts by weight of 3 parts by weight
Absorbent UV-531 and the polyphosphazene modified manometer silicon dioxide of 8 parts by weight are added in homogenizer, under the conditions of 70 DEG C
8min is stirred, stir speed (S.S.) 1300r/min, calcium-zinc composite stabilizing agent is obtained after cooling；
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 manometer silicon 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 150 are added in 50 milliliters of three-neck flasks
0.5 gram of 3 grams of nano silicon, 0.2 gram of silane resin acceptor kh-550 and the silane coupler KH-560 of nanometer and 10
Milliliter dimethyl sulfoxide (DMSO), 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
Silica.
Test condition
1st, weatherability is tested：Embodiment 1-4 and comparative example 1-4 calcium-zinc composite stabilizing agent are irradiated into 50h under ultraviolet light, it is ultraviolet
The model UVA-340 types of light lamp, ultraviolet tube number are 2, and each ultraviolet tube is 40w, and it is steady to test above-mentioned Ca Zn composite
Determine the aberration of agent.
2nd, prepare PVC board using embodiment 1-4 and comparative example 1-4 calcium-zinc composite stabilizing agent and test the sheet material
Intensity, specific method are：
A, by weight, by 20 parts of powdered whiting, embodiment 1-4 and the comparative example of 100 parts of SG-7 types polyvinyl chloride resin, 800 mesh
4 parts of 10 parts of any one calcium-zinc composite stabilizing agent and PVC processing aids (ACR401) are put into high-speed mixer and mixed in 1-4
When reaching 100 DEG C to temperature of charge, 2 parts of AC foaming agents are added；Continue to mix to temperature of charge reach 120 DEG C when, material is arranged
Enter in low speed mixer, continue to mix to temperature of charge reach 60 DEG C when discharge it is standby；
B, by the material input high temperature conical double screw extruder obtained by step A, extrusion process is into tabular fused materials；
C, the fused materials for obtaining step B, through stock mould cooling and shaping into sheet material；
D, the sheet material for obtaining step C, 1 × 2m is cut into through double-cut saw2Sheet material；So as to obtain PVC board.
Test result see the table below
| Example | Stable aberration | Tensile strength | Elongation at break | MOR | Heat distortion temperature |
| Embodiment 1 | 0.02 | 72Mpa | 8.3% | 91 Mpa | 115℃ |
| Embodiment 2 | 0.02 | 67Mpa | 9.1% | 85 Mpa | 110℃ |
| Embodiment 3 | 0.01 | 85 Mpa | 8.3% | 98 Mpa | 123℃ |
| Embodiment 4 | 0 | 97 Mpa | 6.4% | 105 Mpa | 139℃ |
| Comparative example 1 | 0.73 | 28 Mpa | 3.7% | 35 Mpa | 79℃ |
| Comparative example 2 | 0.08 | 43 Mpa | 5.5% | 57 Mpa | 88℃ |
| Comparative example 3 | 0.22 | 35 Mpa | 6.2% | 47 Mpa | 82℃ |
| Comparative example 4 | 0.01 | 87 Mpa | 2.1% | 90 Mpa | 118℃ |
Claims (10)
1. the special powder calcium zinc stabilizers of environment friendly medical level PVC, it is characterised in that by weight, its preparing raw material includes：
The calcium stearate of 100 parts by weight, the zinc stearate of 10~40 parts by weight, the nano titanium oxide of 5~10 parts by weight, 5~
The nano silicon of 10 parts by weight, the glycerin monostearate of 5~10 parts by weight, the carbon nano-tube modification of 5~10 parts by weight
β-positive octadecanol of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid of polyphosphazene-polyethersulfone block copolymer, 1~5 parts by weight
The ultraviolet absorbent UV-531 of ester and 1~5 parts by weight.
2. the special powder calcium zinc stabilizers of environment friendly medical level PVC according to claim 1, its feature
It is, by weight, its preparing raw material includes：
The calcium stearate of 100 parts by weight, the zinc stearate of 20~30 parts by weight, the nano titanium oxide of 6~9 parts by weight, 6~9
The nano silicon of parts by weight, the glycerin monostearate of 6~9 parts by weight, the poly- phosphorus of the carbon nano-tube modification of 6~8 parts by weight
Nitrile-polyethersulfone block copolymer, 2~4 parts by weight β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid with
And 2~4 parts by weight ultraviolet absorbent UV-531.
3. the special powder calcium zinc stabilizers of environment friendly medical level PVC according to claim 2, its feature
It is, by weight, its preparing raw material includes：
The calcium stearate of 100 parts by weight, the zinc stearate of 25 parts by weight, the nano titanium oxide of 8 parts by weight, 8 parts by weight are received
Carbon nano-tube modification polyphosphazene-polyethersulfone block copolymerization of rice silica, the glycerin monostearate of 8 parts by weight, 7 parts by weight
The ultraviolet of thing, β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid of 3 parts by weight and 3 parts by weight is inhaled
Receive agent UV-531.
4. the special powder calcium zinc stabilizers of environment friendly medical level PVC according to claim any one of 1-3, its feature exist
In 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.
5. the special powder calcium zinc stabilizers of environment friendly medical level PVC according to claim any one of 1-3, its feature exist
In the average grain diameter of the nano silicon is 50-500 nanometers.
6. the special powder calcium zinc stabilizers of environment friendly medical level PVC according to claim any one of 1-3, its feature exist
In the average grain diameter of the nano titanium oxide is 100-300 nanometers.
7. the special powder calcium zinc stabilizers of environment friendly medical level PVC according to claim any one of 1-3, its feature exist
In by weight, its preparing raw material also includes：The sulfonated phosphazene modified manometer silicon dioxide of 5-10 parts by weight.
8. the special powder calcium zinc stabilizers of environment friendly medical level PVC according to claim 7, it is characterised in that the sulphur
Change polyphosphazene modified manometer silicon dioxide preparation method be：
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
150 nanometers of 0.5 gram of 3 grams of nano silicon, 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 and obtain within 48 hours sulfonated phosphazene modification
Nano silicon.
9. the preparation method of the special powder calcium zinc stabilizers of environment friendly medical level PVC, it is characterised in that including：
Recipe ingredient any one of claim 1-8 is added in homogenizer, stirred under the conditions of 60-90 DEG C
5min-10min, stir speed (S.S.) 1200-1500r/min, obtained after cooling.
10. the preparation method of the special powder calcium zinc stabilizers of environment friendly medical level PVC according to claim 9, its feature
It is, 8min, stir speed (S.S.) 1300r/min is stirred under the conditions of 70 DEG C.
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| CN110358215A (en) * | 2019-07-11 | 2019-10-22 | 临安市锦新塑料化工有限公司 | A kind of PVC weather-proof calcium zinc stabilizer and preparation method thereof |
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