CN107033454A - A kind of method of nano antimony tin oxide/calcining basic magnesium chloride/nanometer zinc aluminate composite flame-proof MODIFIED PP/PS alloys - Google Patents
A kind of method of nano antimony tin oxide/calcining basic magnesium chloride/nanometer zinc aluminate composite flame-proof MODIFIED PP/PS alloys Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
The invention discloses a kind of method of nano antimony tin oxide/calcining basic magnesium chloride/nanometer zinc aluminate composite flame-proof MODIFIED PP/PS alloys, first nano antimony tin oxide/calcining basic magnesium chloride composite is made using collosol and gel calcination method in the present invention, then nano antimony tin oxide/fire-retardant MODIFIED PP of calcining basic magnesium chloride composite is made using situ aggregation method；Then nano antimony tin oxide/nanometer zinc aluminate composite is made using sol-gal process, then the fire-retardant modified PS of nano antimony tin oxide/nanometer zinc aluminate composite is made using situ aggregation method；The fire-retardant modified PS of nano antimony tin oxide/fire-retardant MODIFIED PP of calcining basic magnesium chloride composite and nano antimony tin oxide/nanometer zinc aluminate composite is finally subjected to melt blending PP/PS alloys are made, by nano antimony tin oxide, calcining basic magnesium chloride, nanometer zinc aluminate compounding cooperative effect so that PP/PS alloys have excellent fire resistance and physical and mechanical properties concurrently.
Description
Technical field
The present invention relates to a kind of nano antimony tin oxide/calcining basic magnesium chloride/nanometer zinc aluminate composite flame-proof MODIFIED PP/PS
The method of alloy, belongs to polymeric material field.
Background technology
Polypropylene（PP）It is a kind of one of important high polymer material, yield is big, cheap, with good processability
Energy and mechanical property.But PP is present that hardness is relatively low, impact resistance is poor, easy aging, big shaping yield rate the shortcomings of, the day of one's doom
PP further development and application are made.Use polystyrene（PS）The intensity and rigidity for improving PP obtain the pass of many researchers
Note, PS can improve the tensile strength and bending strength of PP/PS blend alloys.PP/PS alloys have PS and PP common feature, its
Rigidity and impact property are higher than PP.Due to the particular/special requirement of application field, its fire resistance is increasingly subject to the concern of people, nearly ten
Nian Lai, the exploitation of fire-retardant PP/PS alloys has turned into a focus of each major company's research in the world today.
Wang Guancai, Lu Zhongyuan, the small equality people of Hu are at it《The Research Progress of Inorganic Flame Retardant applied in the plastic》In one text
Elaborate a few class inorganic combustion inhibitors currently used for plastics：（1）Hydroxide：Hydroxide flame retardant mainly has aluminium hydroxide
(ATH), magnesium hydroxide (MH), layered double-hydroxide (LDHS) etc.；（2）Inorganic phosphorous compound：Inorganic phosphorus flame retardant is main
There are red phosphorus, phosphate and APP etc.,；（3）Antimony oxide；（4）Borate：Borate series of products have ammonium metaborate, inclined boron
Sour sodium, barium metaborate, ammonium pentaborate, Firebrake ZB etc.；（5）Molybdenum compound：Such as molybdenum trioxide, ammonium molybdate, zinc molybdate and calcium molybdate
Deng；（6）Nano layered silicate.Increasingly increase with the demand of the inorganic combustion inhibitor in plastics, its fire resistance is wanted
Also more and more higher is sought, the compounding cooperative effect of various inorganic combustion inhibitors is to improve flame retarding efficiency, as inorganic combustion inhibitor in recent years
One of developing direction.But yet there are no nano antimony tin oxide, calcining basic magnesium chloride, nanometer zinc aluminate compound use and use
In flame-retardant modified PP/PS alloys.
Therefore, first nano antimony tin oxide/calcining basic magnesium chloride composite wood is made using collosol and gel-calcination method in the present invention
Material, then nano antimony tin oxide/fire-retardant MODIFIED PP of calcining basic magnesium chloride composite is made using situ aggregation method；Then use
Nano antimony tin oxide/nanometer zinc aluminate composite is made in sol-gel process, then nano tin dioxide is made using situ aggregation method
The fire-retardant modified PS of antimony/nanometer zinc aluminate composite；It is finally that nano antimony tin oxide/calcining basic magnesium chloride composite is fire-retardant
MODIFIED PP and the fire-retardant modified PS of nano antimony tin oxide/nanometer zinc aluminate composite carry out melt blending and PP/PS alloys are made, and lead to
Cross nano antimony tin oxide, calcining basic magnesium chloride, the compounding cooperative effect of nanometer zinc aluminate, give full play to nano antimony tin oxide,
Calcine basic magnesium chloride, the performance advantage of nanometer zinc aluminate so that PP/PS alloys have excellent fire resistance and physical mechanical concurrently
Performance.
The content of the invention
It is an object of the invention to provide a kind of compound resistance of nano antimony tin oxide/calcining basic magnesium chloride/nanometer zinc aluminate
Fire MODIFIED PP/PS alloys method, the present invention by nano antimony tin oxide, calcining basic magnesium chloride, nanometer zinc aluminate compounding
Cooperative effect, gives full play to nano antimony tin oxide, calcining basic magnesium chloride, the performance advantage of nanometer zinc aluminate so that PP/PS is closed
Gold has excellent fire resistance and physical and mechanical properties concurrently.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of method of nano antimony tin oxide/calcining basic magnesium chloride/nanometer zinc aluminate composite flame-proof MODIFIED PP/PS alloys, bag
Include following steps：
（1）The preparation of nano antimony tin oxide/fire-retardant MODIFIED PP of calcining basic magnesium chloride composite：
The aqueous solution that mass concentration is 50-60% is made in the bischofite stirring that adds water by 1a., then is added magnesia under agitation, is made
Obtain MgO2、MgCl2Mol ratio control in 1-3:1, ultrasonic disperse 1-3h, then water-bath is to 70-80 DEG C, stirring reaction 2-4h, close
Envelope stands 6-8 days, filters, and washing dry, pulverize the particle for particle diameter≤30 μm, produce basic magnesium chloride；
1b. according to the amount of material ratio 2-3:1 mixes metallic tin powder, antimony oxide, according still further to liquid Lemon acid and metal
The amount ratio of material is 2-4:1 adds liquid Lemon acid, and magnetic agitation 20-30min is subsequently placed in ice-water bath, is then added dropwise
10mol/L salpeter solutions, until forming stable transparent solution, then are added dropwise acetonitrile into clear solution, treat that solution is changed into from transparent
During milky colloidal sol shape, stop that acetonitrile is added dropwise, then add equivalent to alkali formula chlorine made from colloidal sol quality 15-20% step 1a
Change magnesium, magnetic agitation 3-4h when colloidal sol is converted into gel, stops stirring, stands 24-48h, 10000-15000r/min centrifugations
20-30min is separated, upper solution is discarded, absolute ethyl alcohol, supersound washing, after so circulating 3-5 times, by gel in 90- is added
110 DEG C of drying, grinding crosses 600-800 mesh sieves, the powder after sieving then is warming up into 300-350 DEG C with 3-5 DEG C/min, forged
2-4h is burnt, then 520-580 DEG C is warming up to 2-4 DEG C/min, 3-5h is incubated, produces nano antimony tin oxide/calcining basic magnesium chloride
Composite；
1c. weighs 1 according to mass ratio:12-14:0.15-0.25 weighs magnesium acetate, titanium tetrachloride and ethyl benzoate；Then will
It is put into through the 100-110 DEG C of magnesium acetate being dried overnight in reactor, dehydration 1-3h is vacuumized at 95-105 DEG C, four are then added
Titanium chloride and ethyl benzoate, the stirring reaction 1.5-2.5h at 45-55 DEG C, product are washed three times after filtering out with toluene, and room temperature is true
Sky is drained, and obtains catalyst, and whole process ensures anhydrous and oxygen-free in reactor；
After 1d. replaces reactor 3-4 times through propylene pump drainage, temperature control is at 50-60 DEG C, under magnetic stirring according to volume ratio
1:0.2-0.5:0.1-0.3 sequentially adds toluene, triethyl aluminum and dimethoxydiphenylsilane, leads to after propylene to dissolving saturation
The catalyst of the nano antimony tin oxide/calcining basic magnesium chloride composite and 4-8% equivalent to solution quality 10-15% is added,
Stirring reaction 5-7h, then uses acidic ethanol terminating reaction, and product ethanol washes clean is filtered, 70-80 DEG C of vacuum drying,
Produce required fire-retardant PP；
（2）The fire-retardant modified PS of nano antimony tin oxide/nanometer zinc aluminate composite preparation：
2a. is according to mol ratio 2-3:1 mixes metallic tin powder, antimony oxide, according still further to liquid Lemon acid and metal molar ratio
For 2-4:1 adds liquid Lemon acid, and magnetic agitation 20-30min is subsequently placed in ice-water bath, 10mol/L nitric acid is then added dropwise molten
Liquid, until forming stable transparent solution, then is added dropwise acetonitrile into clear solution, treats that solution is changed into milky colloidal sol shape from transparent
When, stop that acetonitrile is added dropwise, magnetic agitation 3-4h when colloidal sol is converted into gel, stops stirring, stands 24-48h, centrifuges,
Upper solution is discarded, absolute ethyl alcohol is added, ultrasound mashing washing, so circulation 3-5 times produce gel A；
2b. is 1 by zinc-aluminium mol ratio:Zinc nitrate hexahydrate, Aluminium chloride hexahydrate are well mixed by 1-2, then add equivalent to
In the water of 10-15 times of mixture quality, after magnetic agitation to zinc salt and aluminium salt are completely dissolved, according still further to liquid Lemon acid and sun from
Sub- mol ratio is 1-2:1 adds liquid Lemon acid, and magnetic agitation is allowed to fully be complexed with two metal ion species, then according to third
Acrylamide is 8-10 with cation mole ratio:1 adds acrylamide, and magnetic agitation is uniform, waits after solution clarification, according to liquid
Methylene-bisacrylamide is 1 with acrylamide mol ratio:4-6 adds crosslinking agent methylene-bisacrylamide, and magnetic agitation is equal
It is even, when for well mixed, clarification solution, 25% ammonia spirit is added dropwise and adjusts solution PH to 2-4, heating water bath to 80-90
DEG C, magnetic agitation reaction 5-10min, clear solution is that can be changed into white gels body, produces gel B；
2c. mixes gel A with gel B, and magnetic agitation is uniform, then in 100-120 DEG C of dry 24-36h, and 500- is crossed in grinding
600 mesh sieves, are then warming up to 330-370 DEG C with 4-7 DEG C/min by the powder after sieving, calcine 2-3h, then with 3-6 DEG C/min liters
Temperature is incubated 3-4h to 600-650 DEG C, then is warming up to 840-890 DEG C with 2-4 DEG C/min, is incubated 1-2h, produces nano tin dioxide
Antimony/nanometer zinc aluminate composite；
2d. is according to mass ratio 1:0.1-0.2 mixes styrene with nano antimony tin oxide/nanometer zinc aluminate composite, ultrasound
Scattered 10-15min, then adds water of 4-6 times equivalent to styrene quality, after stirring heating water bath to 75-85 DEG C,
Add the lauryl sodium sulfate equivalent to styrene quality 2-3% and 0.3-0.7% ammonium persulfate, constant temperature stirring reaction 3-
5h, then uses 10%Al2(SO4)3The aqueous solution is demulsified to obtain white depositions, washing, suction filtration 3-4 time, and is dried in vacuo in 60-70 DEG C
To constant weight, required fire-retardant PS is produced；
（3）The preparation of fire-retardant PP/PS alloys：
According to mass ratio 6-9:1-3 is by nano antimony tin oxide/fire-retardant MODIFIED PP of calcining basic magnesium chloride composite and nano oxygen
Change tin antimony/fire-retardant modified PS of nanometer zinc aluminate composite to be added in high-speed mixer, in 3000-4000r/min rotating speed
Lower stirring mixing 5-10min, adds the compatilizer SBS resins equivalent to mixture quality 4-8%, in 2000-3000r/min
Rotating speed under stirring mixing 10-15min, be then added in double screw extruder and carry out melt blending, extruding pelletization produces institute
The fire-retardant PP/PS alloys needed.
Ultrasonic power described in step 1a is 200-400W.
Glass putty particle diameter described in step 1b is 15-20 μm；Described ultrasonic power is 150-250W.
Ultrasonic power described in step 2a is 250-350W.
Ultrasonic power described in step 2d is 350-450W.
Step（3）Described in double screw extruder processing temperature be 220-240 DEG C, screw speed 70-80r/min.
Beneficial effects of the present invention：
First nano antimony tin oxide/calcining basic magnesium chloride composite is made using collosol and gel-calcination method in the present invention, then uses
Nano antimony tin oxide/fire-retardant MODIFIED PP of calcining basic magnesium chloride composite is made in situ aggregation method；Then sol-gel is used
Legal system obtains nano antimony tin oxide/nanometer zinc aluminate composite, then nano antimony tin oxide/nano aluminum is made using situ aggregation method
The sour fire-retardant modified PS of zinc composite；Finally by nano antimony tin oxide/fire-retardant MODIFIED PP of calcining basic magnesium chloride composite and
The fire-retardant modified PS of nano antimony tin oxide/nanometer zinc aluminate composite carries out melt blending and PP/PS alloys is made, and passes through nano oxygen
Change tin antimony, calcining basic magnesium chloride, the compounding cooperative effect of nanometer zinc aluminate, give full play to nano antimony tin oxide, calcining basic formula
The performance advantage of magnesium chloride, nanometer zinc aluminate so that PP/PS alloys have excellent fire resistance and physical and mechanical properties concurrently.
Embodiment
Embodiment 1
A kind of method of nano antimony tin oxide/calcining basic magnesium chloride/nanometer zinc aluminate composite flame-proof MODIFIED PP/PS alloys, bag
Include following steps：
（1）The preparation of nano antimony tin oxide/fire-retardant MODIFIED PP of calcining basic magnesium chloride composite：
The aqueous solution that mass concentration is 50% is made in the bischofite stirring that adds water by 1a., then adds magnesia under agitation so that
MgO2、MgCl2Mol ratio control 1:1, ultrasonic disperse 1h, then water-bath is to 70 DEG C, stirring reaction 4h, sealing and standing 6 days,
Filtering, washing, dry, pulverize the particle for particle diameter≤30 μm, produces basic magnesium chloride；
1b. according to the amount of material ratio 2:1 mixes metallic tin powder, antimony oxide, according still further to liquid Lemon acid and metal object
The amount ratio of matter is 2:1 adds liquid Lemon acid, and magnetic agitation 25min is subsequently placed in ice-water bath, and 10mol/L nitre is then added dropwise
Acid solution, until forming stable transparent solution, then is added dropwise acetonitrile into clear solution, treats that solution is changed into milky colloidal sol from transparent
During shape, stop that acetonitrile is added dropwise, then add equivalent to basic magnesium chloride, magnetic agitation made from the step 1a of colloidal sol quality 15%
3h, when colloidal sol is converted into gel, stops stirring, stands 24h, and 10000r/min centrifuges 30min, discards upper solution,
Absolute ethyl alcohol is added, supersound washing after so circulating 3 times, by gel in 90 DEG C of drying, is ground, crosses 600 mesh sieves, then will
Powder after sieving is warming up to 300 DEG C with 3 DEG C/min, calcines 2h, then is warming up to 520 DEG C with 2 DEG C/min, is incubated 3h, produces and receive
Rice tin-antiomony oxide/calcining basic magnesium chloride composite；
1c. weighs 1 according to mass ratio:12:0.15 weighs magnesium acetate, titanium tetrachloride and ethyl benzoate；Then will be dry through 100 DEG C
Dry magnesium acetate overnight is put into reactor, and dehydration 3h is vacuumized at 95 DEG C, titanium tetrachloride and ethyl benzoate is then added,
The stirring reaction 2.5h at 45 DEG C, product is washed three times after filtering out with toluene, and room temperature in vacuo is drained, and obtains catalyst, and whole process is protected
Demonstrate,prove anhydrous and oxygen-free in reactor；
After 1d. replaces reactor 3 times through propylene pump drainage, temperature control is at 50 DEG C, under magnetic stirring according to volume ratio 1:
0.2:0.1 sequentially adds toluene, triethyl aluminum and dimethoxydiphenylsilane, logical propylene to dissolve added after saturation equivalent to
The nano antimony tin oxide of solution quality 10%/calcining basic magnesium chloride composite and 4% catalyst, stirring reaction 5h, then
Acidic ethanol terminating reaction is used, product ethanol washes clean, filtering, 70 DEG C of vacuum drying produce required fire-retardant PP；
（2）The fire-retardant modified PS of nano antimony tin oxide/nanometer zinc aluminate composite preparation：
2a. is according to mol ratio 2:1 mixes metallic tin powder, antimony oxide, is with metal molar ratio according still further to liquid Lemon acid
2:1 adds liquid Lemon acid, and magnetic agitation 20min is subsequently placed in ice-water bath, and 10mol/L salpeter solutions are then added dropwise, until
Form stable transparent solution, then be added dropwise into clear solution acetonitrile, whne solution from it is transparent be changed into milky colloidal sol shape when, stop drop
Plus acetonitrile, magnetic agitation 3h, when colloidal sol is converted into gel, stop stirring, stand 24h, centrifuge, discard upper solution,
Absolute ethyl alcohol is added, ultrasound mashing washing, so circulation 3 times produce gel A；
2b. is 1 by zinc-aluminium mol ratio:1 is well mixed zinc nitrate hexahydrate, Aluminium chloride hexahydrate, then adds equivalent to mixed
In the water that 10 times of compound quality, after magnetic agitation to zinc salt and aluminium salt are completely dissolved, rubbed according still further to liquid Lemon acid with cation
You are than being 1:1 adds liquid Lemon acid, and magnetic agitation is allowed to fully be complexed with two metal ion species, then according to acrylamide
It is 8 with cation mole ratio:1 adds acrylamide, and magnetic agitation is uniform, waits after solution clarification, according to liquid di-2-ethylhexylphosphine oxide third
Acrylamide is 1 with acrylamide mol ratio:4 add crosslinking agent methylene-bisacrylamide, and magnetic agitation is uniform, treat as mixing
During even, clarification solution, 25% ammonia spirit is added dropwise and adjusts solution PH to 2, heating water bath to 80 DEG C, magnetic agitation reaction
10min, clear solution is that can be changed into white gels body, produces gel B；
2c. mixes gel A with gel B, and magnetic agitation is uniform, then in 100 DEG C of dry 36h, and grinding crosses 500 mesh sieves, then
Powder after sieving is warming up to 330 DEG C with 4 DEG C/min, 2h is calcined, then 600 DEG C are warming up to 3 DEG C/min, 3h is incubated, then with 2
DEG C/min is warming up to 840 DEG C, 1h is incubated, nano antimony tin oxide/nanometer zinc aluminate composite is produced；
2d. is according to mass ratio 1:0.1 mixes styrene with nano antimony tin oxide/nanometer zinc aluminate composite, ultrasonic disperse
10min, then adds water of 4 times equivalent to styrene quality, after stirring heating water bath to 75 DEG C, add equivalent to
The lauryl sodium sulfate of styrene quality 2% and 0.3% ammonium persulfate, constant temperature stirring reaction 5h, then use 10%Al2(SO4)3
The aqueous solution is demulsified to obtain white depositions, washing, suction filtration 3 times, and is dried under vacuum to constant weight in 60-70 DEG C, fire-retardant needed for producing
PS；
（3）The preparation of fire-retardant PP/PS alloys：
According to mass ratio 6:1 by nano antimony tin oxide/fire-retardant MODIFIED PP of calcining basic magnesium chloride composite and nano tin dioxide
The fire-retardant modified PS of antimony/nanometer zinc aluminate composite is added in high-speed mixer, and mixing is stirred under 3000r/min rotating speed
10min, adds the compatilizer SBS resins equivalent to mixture quality 4%, and mixing is stirred under 2000r/min rotating speed
15min, is then added in double screw extruder and carries out melt blending, extruding pelletization, produces required fire-retardant PP/PS alloys.
Ultrasonic power described in step 1a is 400W.
Glass putty particle diameter described in step 1b is 15 μm；Described ultrasonic power is 250W.
Ultrasonic power described in step 2a is 350W.
Ultrasonic power described in step 2d is 450W.
Step（3）Described in double screw extruder processing temperature be 220 DEG C, screw speed 70r/min.
Embodiment 2
A kind of method of nano antimony tin oxide/calcining basic magnesium chloride/nanometer zinc aluminate composite flame-proof MODIFIED PP/PS alloys, bag
Include following steps：
（1）The preparation of nano antimony tin oxide/fire-retardant MODIFIED PP of calcining basic magnesium chloride composite：
The aqueous solution that mass concentration is 55% is made in the bischofite stirring that adds water by 1a., then adds magnesia under agitation so that
MgO2、MgCl2Mol ratio control 2:1, ultrasonic disperse 2h, then water-bath is to 75 DEG C, stirring reaction 3h, sealing and standing 7 days,
Filtering, washing, dry, pulverize the particle for particle diameter≤30 μm, produces basic magnesium chloride；
1b. according to the amount of material ratio 2.5:1 mixes metallic tin powder, antimony oxide, according still further to liquid Lemon acid and metal
The amount ratio of material is 3:1 adds liquid Lemon acid, and magnetic agitation 25min is subsequently placed in ice-water bath, 10mol/L is then added dropwise
Salpeter solution, until forming stable transparent solution, then is added dropwise acetonitrile into clear solution, and treating solution, to be changed into milky molten from transparent
When gluey, stop that acetonitrile is added dropwise, then add equivalent to basic magnesium chloride made from the step 1a of colloidal sol quality 18%, magnetic force is stirred
3.5h is mixed, when colloidal sol is converted into gel, stops stirring, 36h is stood, 12000r/min centrifuges 25min, discards upper strata molten
Liquid, adds absolute ethyl alcohol, and supersound washing after so circulating 4 times, by gel in 100 DEG C of drying, is ground, crosses 700 mesh sieves, so
The powder after sieving is warming up to 320 DEG C with 4 DEG C/min afterwards, 3h is calcined, then 550 DEG C are warming up to 3 DEG C/min, 4h is incubated, i.e.,
Obtain nano antimony tin oxide/calcining basic magnesium chloride composite；
1c. weighs 1 according to mass ratio:13:0.2 weighs magnesium acetate, titanium tetrachloride and ethyl benzoate；Then will be dry through 105 DEG C
Dry magnesium acetate overnight is put into reactor, and dehydration 2h is vacuumized at 100 DEG C, titanium tetrachloride and benzoic acid second is then added
Ester, the stirring reaction 2h at 50 DEG C, product is washed three times after filtering out with toluene, and room temperature in vacuo is drained, and obtains catalyst, and whole process is protected
Demonstrate,prove anhydrous and oxygen-free in reactor；
After 1d. replaces reactor 3 times through propylene pump drainage, temperature control is at 55 DEG C, under magnetic stirring according to volume ratio 1:
0.3:0.2 sequentially adds toluene, triethyl aluminum and dimethoxydiphenylsilane, logical propylene to dissolve added after saturation equivalent to
The nano antimony tin oxide of solution quality 12%/calcining basic magnesium chloride composite and 6% catalyst, stirring reaction 6h, then
Acidic ethanol terminating reaction is used, product ethanol washes clean, filtering, 75 DEG C of vacuum drying produce required fire-retardant PP；
（2）The fire-retardant modified PS of nano antimony tin oxide/nanometer zinc aluminate composite preparation：
2a. is according to mol ratio 2.5:1 mixes metallic tin powder, antimony oxide, according still further to liquid Lemon acid and metal molar ratio
For 3:1 adds liquid Lemon acid, and magnetic agitation 25min is subsequently placed in ice-water bath, 10mol/L salpeter solutions is then added dropwise, directly
To forming stable transparent solution, then be added dropwise into clear solution acetonitrile, whne solution from it is transparent be changed into milky colloidal sol shape when, stop
Acetonitrile is added dropwise, magnetic agitation 3.5h when colloidal sol is converted into gel, stops stirring, stands 36h, centrifuges, discard upper strata molten
Liquid, adds absolute ethyl alcohol, ultrasound mashing washing, so circulation 4 times produce gel A；
2b. is 1 by zinc-aluminium mol ratio:1.5 are well mixed zinc nitrate hexahydrate, Aluminium chloride hexahydrate, then add equivalent to
In the water that 12 times of mixture quality, after magnetic agitation to zinc salt and aluminium salt are completely dissolved, according still further to liquid Lemon acid and cation
Mol ratio is 1.5:1 adds liquid Lemon acid, and magnetic agitation is allowed to fully be complexed with two metal ion species, then according to propylene
Acid amides is 9 with cation mole ratio:1 adds acrylamide, and magnetic agitation is uniform, waits after solution clarification, according to liquid methylene
Bisacrylamide is 1 with acrylamide mol ratio:5 add crosslinking agent methylene-bisacrylamide, and magnetic agitation is uniform, waits to be mixed
During the solution that conjunction is uniform, clarify, 25% ammonia spirit is added dropwise and adjusts solution PH to 3, heating water bath is to 85 DEG C, and magnetic agitation is reacted
8min, clear solution is that can be changed into white gels body, produces gel B；
2c. gels A is mixed with gel B, and magnetic agitation is uniform, then in 110 DEG C of dry 30h, and 550 mesh sieves are crossed in grinding, then will
Powder after sieving is warming up to 350 DEG C with 5 DEG C/min, calcines 2.5h, then is warming up to 630 DEG C with 4 DEG C/min, is incubated 3.5h, then
860 DEG C are warming up to 3 DEG C/min, 1.5h is incubated, produces nano antimony tin oxide/nanometer zinc aluminate composite；
2d. is according to mass ratio 1:0.15 mixes styrene with nano antimony tin oxide/nanometer zinc aluminate composite, ultrasonic disperse
12min, then adds water of 5 times equivalent to styrene quality, after stirring heating water bath to 80 DEG C, add equivalent to
The lauryl sodium sulfate of styrene quality 2.5% and 0.5% ammonium persulfate, constant temperature stirring reaction 4h, then use 10%Al2
(SO4)3The aqueous solution is demulsified to obtain white depositions, washing, suction filtration 3 times, and is dried under vacuum to constant weight in 65 DEG C, produces required resistance
Fire PS；
（3）The preparation of fire-retardant PP/PS alloys：
According to mass ratio 7:2 by nano antimony tin oxide/fire-retardant MODIFIED PP of calcining basic magnesium chloride composite and nano tin dioxide
The fire-retardant modified PS of antimony/nanometer zinc aluminate composite is added in high-speed mixer, and mixing is stirred under 3500r/min rotating speed
8min, adds the compatilizer SBS resins equivalent to mixture quality 6%, and mixing is stirred under 2500r/min rotating speed
12min, is then added in double screw extruder and carries out melt blending, extruding pelletization, produces required fire-retardant PP/PS alloys.
Ultrasonic power described in step 1a is 300W.
Glass putty particle diameter described in step 1b is 18 μm；Described ultrasonic power is 200W.
Ultrasonic power described in step 2a is 300W.
Ultrasonic power described in step 2d is 400W.
Step（3）Described in double screw extruder processing temperature be 230 DEG C, screw speed 75r/min.
Embodiment 3
A kind of method of nano antimony tin oxide/calcining basic magnesium chloride/nanometer zinc aluminate composite flame-proof MODIFIED PP/PS alloys, bag
Include following steps：
（1）The preparation of nano antimony tin oxide/fire-retardant MODIFIED PP of calcining basic magnesium chloride composite：
The aqueous solution that mass concentration is 60% is made in the bischofite stirring that adds water by 1a., then adds magnesia under agitation so that
MgO2, MgCl2 mol ratio are controlled 3:1, ultrasonic disperse 3h, then water-bath is to 80 DEG C, stirring reaction 2h, sealing and standing 8 days,
Filtering, washing, dry, pulverize the particle for particle diameter≤30 μm, produces basic magnesium chloride；
1b. according to the amount of material ratio 3:1 mixes metallic tin powder, antimony oxide, according still further to liquid Lemon acid and metal object
The amount ratio of matter is 4:1 adds liquid Lemon acid, and magnetic agitation 30min is subsequently placed in ice-water bath, and 10mol/L nitre is then added dropwise
Acid solution, until forming stable transparent solution, then is added dropwise acetonitrile into clear solution, treats that solution is changed into milky colloidal sol from transparent
During shape, stop that acetonitrile is added dropwise, then add equivalent to basic magnesium chloride, magnetic agitation made from the step 1a of colloidal sol quality 20%
4h, when colloidal sol is converted into gel, stops stirring, stands 48h, and 15000r/min centrifuges 20min, discards upper solution,
Absolute ethyl alcohol is added, supersound washing after so circulating 5 times, by gel in 110 DEG C of drying, is ground, crosses 800 mesh sieves, then will
Powder after sieving is warming up to 350 DEG C with 5 DEG C/min, calcines 4h, then is warming up to 580 DEG C with 4 DEG C/min, is incubated 5h, produces and receive
Rice tin-antiomony oxide/calcining basic magnesium chloride composite；
1c. weigh 1 according to mass ratio:14:0.25 weighs magnesium acetate, titanium tetrachloride and ethyl benzoate；Then will be dry through 110 DEG C
Dry magnesium acetate overnight is put into reactor, and dehydration 1h is vacuumized at 105 DEG C, titanium tetrachloride and benzoic acid second is then added
Ester, the stirring reaction 1.5h at 55 DEG C, product is washed three times after filtering out with toluene, and room temperature in vacuo is drained, and obtains catalyst, whole process
Ensure anhydrous and oxygen-free in reactor；
After 1d. replaces reactor 4 times through propylene pump drainage, temperature control is at 60 DEG C, under magnetic stirring according to volume ratio 1:
0.5:0.3 sequentially adds toluene, triethyl aluminum and dimethoxydiphenylsilane, logical propylene to dissolve added after saturation equivalent to
The nano antimony tin oxide of solution quality 15%/calcining basic magnesium chloride composite and 8% catalyst, stirring reaction 7h, then
Acidic ethanol terminating reaction is used, product ethanol washes clean, filtering, 80 DEG C of vacuum drying produce required fire-retardant PP；
（2）The fire-retardant modified PS of nano antimony tin oxide/nanometer zinc aluminate composite preparation：
2a. is according to mol ratio 3:1 mixes metallic tin powder, antimony oxide, is with metal molar ratio according still further to liquid Lemon acid
4:1 adds liquid Lemon acid, and magnetic agitation 30min is subsequently placed in ice-water bath, and 10mol/L salpeter solutions are then added dropwise, until
Form stable transparent solution, then be added dropwise into clear solution acetonitrile, whne solution from it is transparent be changed into milky colloidal sol shape when, stop drop
Plus acetonitrile, magnetic agitation 4h, when colloidal sol is converted into gel, stop stirring, stand 48h, centrifuge, discard upper solution,
Absolute ethyl alcohol is added, ultrasound mashing washing, so circulation 5 times produce gel A；
2b. is 1 by zinc-aluminium mol ratio:2 are well mixed zinc nitrate hexahydrate, Aluminium chloride hexahydrate, then add equivalent to mixed
In the water that 15 times of compound quality, after magnetic agitation to zinc salt and aluminium salt are completely dissolved, rubbed according still further to liquid Lemon acid with cation
You are than being 2:1 adds liquid Lemon acid, and magnetic agitation is allowed to fully be complexed with two metal ion species, then according to acrylamide
It is 10 with cation mole ratio:1 adds acrylamide, and magnetic agitation is uniform, waits after solution clarification, according to liquid di-2-ethylhexylphosphine oxide
Acrylamide is 1 with acrylamide mol ratio:6 add crosslinking agent methylene-bisacrylamide, and magnetic agitation is uniform, treat as mixing
Uniformly, during the solution of clarification, 25% ammonia spirit is added dropwise and adjusts solution PH to 4, heating water bath to 90 DEG C, magnetic agitation reaction
10min, clear solution is that can be changed into white gels body, produces gel B；
2c. mixes gel A with gel B, and magnetic agitation is uniform, then in 120 DEG C of dry 36h, and grinding crosses 600 mesh sieves, then
Powder after sieving is warming up to 370 DEG C with 7 DEG C/min, 3h is calcined, then 650 DEG C are warming up to 6 DEG C/min, 4h is incubated, then with 4
DEG C/min is warming up to 890 DEG C, 2h is incubated, nano antimony tin oxide/nanometer zinc aluminate composite is produced；
2d. is according to mass ratio 1:0.2 mixes styrene with nano antimony tin oxide/nanometer zinc aluminate composite, ultrasonic disperse
15min, then adds water of 6 times equivalent to styrene quality, after stirring heating water bath to 85 DEG C, add equivalent to
The lauryl sodium sulfate of styrene quality 3% and 0.7% ammonium persulfate, constant temperature stirring reaction 3h, then use 10%Al2(SO4)3
The aqueous solution is demulsified to obtain white depositions, washing, suction filtration 4 times, and is dried under vacuum to constant weight in 60-70 DEG C, fire-retardant needed for producing
PS；
（3）The preparation of fire-retardant PP/PS alloys：
According to mass ratio 9:3 by nano antimony tin oxide/fire-retardant MODIFIED PP of calcining basic magnesium chloride composite and nano tin dioxide
The fire-retardant modified PS of antimony/nanometer zinc aluminate composite is added in high-speed mixer, and mixing is stirred under 4000r/min rotating speed
5min, adds the compatilizer SBS resins equivalent to mixture quality 8%, and mixing is stirred under 3000r/min rotating speed
10min, is then added in double screw extruder and carries out melt blending, extruding pelletization, produces required fire-retardant PP/PS alloys.
Ultrasonic power described in step 1a is 200W.
Glass putty particle diameter described in step 1b is 20 μm；Described ultrasonic power is 150W.
Ultrasonic power described in step 2a is 250W.
Ultrasonic power described in step 2d is 350W.
Step（3）Described in double screw extruder processing temperature be 240 DEG C, screw speed 80r/min.
Claims (6)
1. a kind of method of nano antimony tin oxide/calcining basic magnesium chloride/nanometer zinc aluminate composite flame-proof MODIFIED PP/PS alloys,
It is characterised in that it includes following steps：
The preparation of nano antimony tin oxide/fire-retardant MODIFIED PP of calcining basic magnesium chloride composite：
The aqueous solution that mass concentration is 50-60% is made in the bischofite stirring that adds water by 1a., then is added magnesia under agitation, is made
Obtain MgO2、MgCl2Mol ratio control in 1-3:1, ultrasonic disperse 1-3h, then water-bath is to 70-80 DEG C, stirring reaction 2-4h, close
Envelope stands 6-8 days, filters, and washing dry, pulverize the particle for particle diameter≤30 μm, produce basic magnesium chloride；
1b. according to the amount of material ratio 2-3:1 mixes metallic tin powder, antimony oxide, according still further to liquid Lemon acid and metal
The amount ratio of material is 2-4:1 adds liquid Lemon acid, and magnetic agitation 20-30min is subsequently placed in ice-water bath, is then added dropwise
10mol/L salpeter solutions, until forming stable transparent solution, then are added dropwise acetonitrile into clear solution, treat that solution is changed into from transparent
During milky colloidal sol shape, stop that acetonitrile is added dropwise, then add equivalent to alkali formula chlorine made from colloidal sol quality 15-20% step 1a
Change magnesium, magnetic agitation 3-4h when colloidal sol is converted into gel, stops stirring, stands 24-48h, 10000-15000r/min centrifugations
20-30min is separated, upper solution is discarded, absolute ethyl alcohol, supersound washing, after so circulating 3-5 times, by gel in 90- is added
110 DEG C of drying, grinding crosses 600-800 mesh sieves, the powder after sieving then is warming up into 300-350 DEG C with 3-5 DEG C/min, forged
2-4h is burnt, then 520-580 DEG C is warming up to 2-4 DEG C/min, 3-5h is incubated, produces nano antimony tin oxide/calcining basic magnesium chloride
Composite；
1c. weighs 1 according to mass ratio:12-14:0.15-0.25 weighs magnesium acetate, titanium tetrachloride and ethyl benzoate；Then will
It is put into through the 100-110 DEG C of magnesium acetate being dried overnight in reactor, dehydration 1-3h is vacuumized at 95-105 DEG C, four are then added
Titanium chloride and ethyl benzoate, the stirring reaction 1.5-2.5h at 45-55 DEG C, product are washed three times after filtering out with toluene, and room temperature is true
Sky is drained, and obtains catalyst, and whole process ensures anhydrous and oxygen-free in reactor；
After 1d. replaces reactor 3-4 times through propylene pump drainage, temperature control is at 50-60 DEG C, under magnetic stirring according to volume ratio
1:0.2-0.5:0.1-0.3 sequentially adds toluene, triethyl aluminum and dimethoxydiphenylsilane, leads to after propylene to dissolving saturation
The catalyst of the nano antimony tin oxide/calcining basic magnesium chloride composite and 4-8% equivalent to solution quality 10-15% is added,
Stirring reaction 5-7h, then uses acidic ethanol terminating reaction, and product ethanol washes clean is filtered, 70-80 DEG C of vacuum drying,
Produce required fire-retardant PP；
（2）The fire-retardant modified PS of nano antimony tin oxide/nanometer zinc aluminate composite preparation：
2a. is according to mol ratio 2-3:1 mixes metallic tin powder, antimony oxide, according still further to liquid Lemon acid and metal molar ratio
For 2-4:1 adds liquid Lemon acid, and magnetic agitation 20-30min is subsequently placed in ice-water bath, 10mol/L nitric acid is then added dropwise molten
Liquid, until forming stable transparent solution, then is added dropwise acetonitrile into clear solution, treats that solution is changed into milky colloidal sol shape from transparent
When, stop that acetonitrile is added dropwise, magnetic agitation 3-4h when colloidal sol is converted into gel, stops stirring, stands 24-48h, centrifuges,
Upper solution is discarded, absolute ethyl alcohol is added, ultrasound mashing washing, so circulation 3-5 times produce gel A；
2b. is 1 by zinc-aluminium mol ratio:Zinc nitrate hexahydrate, Aluminium chloride hexahydrate are well mixed by 1-2, then add equivalent to
In the water of 10-15 times of mixture quality, after magnetic agitation to zinc salt and aluminium salt are completely dissolved, according still further to liquid Lemon acid and sun from
Sub- mol ratio is 1-2:1 adds liquid Lemon acid, and magnetic agitation is allowed to fully be complexed with two metal ion species, then according to third
Acrylamide is 8-10 with cation mole ratio:1 adds acrylamide, and magnetic agitation is uniform, waits after solution clarification, according to liquid
Methylene-bisacrylamide is 1 with acrylamide mol ratio:4-6 adds crosslinking agent methylene-bisacrylamide, and magnetic agitation is equal
It is even, when for well mixed, clarification solution, 25% ammonia spirit is added dropwise and adjusts solution PH to 2-4, heating water bath to 80-90
DEG C, magnetic agitation reaction 5-10min, clear solution is that can be changed into white gels body, produces gel B；
2c. mixes gel A with gel B, and magnetic agitation is uniform, then in 100-120 DEG C of dry 24-36h, and 500- is crossed in grinding
600 mesh sieves, are then warming up to 330-370 DEG C with 4-7 DEG C/min by the powder after sieving, calcine 2-3h, then with 3-6 DEG C/min liters
Temperature is incubated 3-4h to 600-650 DEG C, then is warming up to 840-890 DEG C with 2-4 DEG C/min, is incubated 1-2h, produces nano tin dioxide
Antimony/nanometer zinc aluminate composite；
2d. is according to mass ratio 1:0.1-0.2 mixes styrene with nano antimony tin oxide/nanometer zinc aluminate composite, ultrasound
Scattered 10-15min, then adds water of 4-6 times equivalent to styrene quality, after stirring heating water bath to 75-85 DEG C,
Add the lauryl sodium sulfate equivalent to styrene quality 2-3% and 0.3-0.7% ammonium persulfate, constant temperature stirring reaction 3-
5h, then uses 10%Al2(SO4)3The aqueous solution is demulsified to obtain white depositions, washing, suction filtration 3-4 time, and is dried in vacuo in 60-70 DEG C
To constant weight, required fire-retardant PS is produced；
The preparation of fire-retardant PP/PS alloys：
According to mass ratio 6-9:1-3 is by nano antimony tin oxide/fire-retardant MODIFIED PP of calcining basic magnesium chloride composite and nano oxygen
Change tin antimony/fire-retardant modified PS of nanometer zinc aluminate composite to be added in high-speed mixer, in 3000-4000r/min rotating speed
Lower stirring mixing 5-10min, adds the compatilizer SBS resins equivalent to mixture quality 4-8%, in 2000-3000r/min
Rotating speed under stirring mixing 10-15min, be then added in double screw extruder and carry out melt blending, extruding pelletization produces institute
The fire-retardant PP/PS alloys needed.
2. a kind of nano antimony tin oxide according to claim 1/calcining basic magnesium chloride/nanometer zinc aluminate composite flame-proof changes
Property PP/PS alloys method, it is characterised in that ultrasonic power described in step 1a is 200-400W.
3. a kind of nano antimony tin oxide according to claim 1/calcining basic magnesium chloride/nanometer zinc aluminate composite flame-proof changes
Property PP/PS alloys method, it is characterised in that glass putty particle diameter described in step 1b is 15-20 μm；Described ultrasonic power is
150-250W。
4. a kind of nano antimony tin oxide according to claim 1/calcining basic magnesium chloride/nanometer zinc aluminate composite flame-proof changes
Property PP/PS alloys method, it is characterised in that ultrasonic power described in step 2a is 250-350W.
5. a kind of nano antimony tin oxide according to claim 1/calcining basic magnesium chloride/nanometer zinc aluminate composite flame-proof changes
Property PP/PS alloys method, it is characterised in that ultrasonic power described in step 2d is 350-450W.
6. a kind of nano antimony tin oxide according to claim 1/calcining basic magnesium chloride/nanometer zinc aluminate composite flame-proof changes
The method of property PP/PS alloys, it is characterised in that step（3）Described in double screw extruder processing temperature be 220-240 DEG C,
Screw speed 70-80r/min.
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