CN110194865A - A kind of plastic matrix and preparation method of road guard purification vehicle exhaust - Google Patents
A kind of plastic matrix and preparation method of road guard purification vehicle exhaust Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K2201/001—Conductive additives
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention belongs to the technical fields of plastic matrix, provide the plastic matrix and preparation method of a kind of road guard purification vehicle exhaust.Nanometer porous graphite phase carbon nitride is made using rich nitrogen raw material in this method, then graphene aerogel/titanium dioxide/graphite phase carbon nitride solid powder is made as raw material with butyl titanate, graphene aerogel, nitric acid/dehydrated alcohol mixed solution, sodium borohydride, dehydrated alcohol, with linear low density polyethylene, polypropylene, polyvinyl chloride, auxiliary agent mixing extruding pelletization after coupling agent treatment, the road guard plastic matrix of purification vehicle exhaust is made.It is compared with the traditional method, the plastic matrix of preparation of the invention, not only absorption property is good, but also has good photocatalytic activity and visible light utilization efficiency, and the road guard prepared using the masterbatch is very significant to the catharsis of vehicle exhaust.
Description
Technical field
The invention belongs to the technical fields of plastic matrix, provide a kind of plastic master of road guard purification vehicle exhaust
Material and preparation method.
Background technique
With the fast high speed development of China's economy, our people's living standard is continuously improved, and the car ownership in China is fast
Speed increases, and social automobile now has become the indispensable vehicles, but while the increase of automobile quantity, vehicle exhaust row
It is also increasingly severe to put pollution on the environment.The main component of vehicle exhaust has CO, NOx、SO2Deng serious harm people
Health and environmental quality.According to statistics, the CO in Chinese big city 60%, 50% NOx, 30% hydrocarbon be by vapour
Caused by vehicle emission.2 kinds of forms are controlled outside interior control organic to the main control means of automobile exhaust pollution at present and machine,
Wherein external purification mainly reduces CO, NO in the method for photocatalytic degradationxRow content.
Nano-photocatalyst material is with its good photocatalytic activity, chemical stability and recyclable property, by conduct
Purify the new material of air.It is at present generally that catalysis material titanium dioxide is applied to drip with the addition manner for coating or mixing
In green ground surface material, the environment protection asphalt pavement for the vehicle exhaust that can degrade is formed.But pavement of road loss is big, is sprayed
Photochemical catalyst easily fall off with abrasion, cannot longer degradation of contaminant, service life it is shorter.Therefore, research has photocatalysis
Other road equipments of cleaning of off-gas, such as road guard are paid close attention to by people.
In photocatalytic semiconductor material, graphite phase carbon nitride (g-C3N4) a kind of be typically made of nonmetalloid
Polymer semiconductor, raw material needed for preparing is cheap and easily-available, and has preferable physics and chemical stability.Meanwhile graphite
Phase carbon nitride forbidden bandwidth is 2.7eV, has preferable absorption in visible region, it is wide that these features become a kind of application prospect
Wealthy novel photocatalysis material.However, research discovery graphite phase carbon nitride photo-generate electron-hole recombination rate is high, lead to its photocatalysis
Activity reduces, and adsorbs deficiency, influences purification efficiency, limits it and be widely applied.
It has been achieved in terms of purifying vehicle exhaust technology, especially light catalytic purifying vehicle exhaust both at home and abroad at present certain
Effect.Wherein Pang Laixue et al. has invented a kind of asphalt material with photocatalytic degradation exhaust emission function and its preparation
Method (Chinese invention patent application number 201610428106.0), the invention constituent content are matrix pitch by weight percentage
60 ~ 80%, titaniferous and rare earth blast-furnace cinder 20 ~ 40%；The invention is to utilize containing after the addition heat treatment in matrix pitch
TiO2、Fe2O3, ZnO and V2O5Blast-furnace cinder be made, the TiO in the asphalt material2、Fe2O3, ZnO and V2O5Under sunlight
Photocatalysis occurs, realizes the purpose of carbon monoxide, nitrogen oxides in catalysis oxidation tail gas etc., plays degrading tail gas row
Put the function of object Cleaning Air.In addition, Li Di et al. has invented the function composite resin coated and its system of a kind of cleaning of off-gas
Preparation Method (Chinese invention patent application number 201610768858.1) is layered composite structure, is respectively arranged with height from bottom to top
Concentration photocatalysis resin layer and photochemical catalyst rubble load layer.Resin material and former road surface adhesive property are strong, are not easy peeling peeling,
The durability of photocatalysis coating is improved, while providing adherency bearing function for metalling；Attached work is wrapped up in using photochemical catalyst rubble in advance
Skill makes optic catalytic composite material be carried on rubble surface, comes into full contact with tail gas, improves tail gas degradation effect.
As it can be seen that in the prior art when carrying out purification vehicle exhaust using photocatalysis technology, there are photocatalytic activities, absorption
Insufficient, the disadvantages of efficiency is undesirable, in addition, the graphite phase carbon nitride as novel photocatalysis material, there are photo-generate electron-holes
The problem of recombination rate is high, leads to the reduction of its photocatalytic activity, and adsorbs deficiency, influence purification efficiency.
Summary of the invention
In response to this, it is proposed that a kind of road guard use purifies the plastic matrix and preparation method of vehicle exhaust,
Utilization rate with good photocatalytic activity and visible light, the significant increase efficiency of photocatalysis degradation organic contaminant, gained
The road guard of masterbatch preparation is significant to the clean-up effect of vehicle exhaust.
To achieve the above object, specific technical solution of the present invention is as follows:
A kind of road guard preparation method of the plastic matrix of purification vehicle exhaust, is made nanometer porous using rich nitrogen raw material
Graphite phase carbon nitride, then with butyl titanate, graphene aerogel, nitric acid/dehydrated alcohol mixed solution, sodium borohydride, nothing
Water-ethanol as raw material be made graphene aerogel/titanium dioxide/graphite phase carbon nitride solid powder, after coupling agent treatment with
Road guard purification vehicle exhaust is made in linear low density polyethylene, polypropylene, polyvinyl chloride, auxiliary agent mixing extruding pelletization
Plastic matrix, specific step is as follows for preparation:
(1) rich nitrogen raw material is mixed with template nanometer calcium carbonate, 30 ~ 40min is ground with the revolving speed of 200 ~ 300r/min, then
It moves into tube furnace, 300 ~ 600 DEG C of 1 ~ 4h of insulation reaction is heated in the environment of being passed through argon gas, then continue to grind by product
40 ~ 60min, after wash, dry, nanometer porous graphite phase carbon nitride is made；
(2) porous graphite phase carbon nitride made from step (1), butyl titanate are added to absolute ethanol, with 500 ~ 600r/
The revolving speed of min stirs 30 ~ 40min strongly, obtains solution A；Then by graphene aerogel immerse solution A in, and be added nitric acid/
Dehydrated alcohol mixed solution continues stirring with the revolving speed of 300 ~ 400r/min until forming colloidal sol；Then slowly add in colloidal sol
Enter sodium borohydride, continue stirring until forming gel, by gel at 45 ~ 50 DEG C dry 6 ~ 7h, with turning for 150 ~ 200r/min
Grinding product, is then transferred in the vacuum tube furnace under atmosphere of inert gases, with 10 ~ 15 DEG C/min's by speed 30 ~ 50min of grinding
Speed is warming up to 500 ~ 550 DEG C, 3 ~ 4h of isothermal holding, after be cooled to room temperature, be first washed with distilled water 3 ~ 5 times, then use nothing
Water-ethanol washs 2 ~ 4 times, and graphene aerogel/titanium dioxide/graphite phase carbon nitride solid powder is made in drying；
(3) foot is added in graphene aerogel/titanium dioxide/graphite phase carbon nitride solid powder made from step (2) and coupling agent
Measure distilled water in, stir process, after filtering, drying, then with mix dry after linear low density polyethylene, poly- third
Alkene, Corvic raw material and auxiliary agent addition high-speed mixer and mixing are uniform, then put into extruder, at 180 ~ 200 DEG C
Temperature range extruding pelletization, be made road guard with purification vehicle exhaust plastic matrix.
Step (1) selects simple thermal polycondensation method to prepare nanometer porous graphite phase carbon nitride, polymerization process must compared with
It is carried out under high-temperature, but reaction temperature is unsuitable excessively high, because carbonitride can be decomposed into ammonia and C at 700 DEG C or morexNyHz, therefore
Select reaction temperature for 300 ~ 600 DEG C；In addition, in terms of the selection of raw material, using the rich nitrogen raw material of cyano-containing as presoma, to receive
Rice calcium carbonate is template, and nano-porous structure can be better achieved.Preferably, the rich nitrogen raw material is single cyano amine, dicyan
At least one of base amine, melamine, cyanuric trichloride, template are nanometer calcium carbonate；The washing process is first to use matter
Salt acid elution 2 ~ 4 times that concentration is 10 ~ 15% are measured, then are washed with distilled water 2 ~ 4 times；The parts by weight of each raw material are that rich nitrogen is former
Expect 96 ~ 98 parts by weight, 2 ~ 4 parts by weight of template.
Step (2) selection has many advantages, such as satisfactory electrical conductivity, photostability, bigger serface, high intensity and low-density
Graphene aerogel is as carrier, by the generation of nano-titanium dioxide by porous graphite phase carbon nitride fixed load in aeroge
Pore interior, graphene aerogel carrier serve as conductive channel, can efficiently separate photo-generated carrier and inhibit the compound of hole,
So that photocatalytic activity and efficiency get a promotion, while graphene aerogel absorption property is excellent, more conducively absorption organic contamination
Object；Further, its photocatalytic activity can be improved in nano-titanium dioxide and the close interfacial contact of porous graphite phase carbon nitride
With the utilization rate to visible light, and then the efficiency of significant increase photocatalysis degradation organic contaminant.Preferably, the nitric acid/nothing
In water-ethanol mixed solution, nitric acid, dehydrated alcohol volume ratio be 5 ~ 10:90 ~ 95；The mass concentration of the nitric acid be 10 ~
20%；The inert gas is one of helium, neon, argon gas, Krypton, xenon；The parts by weight of step (2) each raw material
For 15 ~ 18 parts by weight of porous graphite phase carbon nitride, 6 ~ 10 parts by weight of butyl titanate, 24 ~ 44 parts by weight of dehydrated alcohol, graphite
25 ~ 30 parts by weight of alkene aeroge, nitric acid/8 ~ 13 parts by weight of dehydrated alcohol mixed solution, 2 ~ 5 parts by weight of sodium borohydride.
Step (3) first with coupling agent to graphene aerogel/titanium dioxide/graphite phase carbon nitride solid powder at
Reason, coupling agent select silane coupling agent, and since siloxy has reactivity to inorganic matter, organic functional base has organic matter
Reactive or compatibility can erect " molecule between inorganic substances and the interface of organic substance by using silane coupling agent
Bridge " links together the material of two kinds of property great disparities, improves the performance of composite material and increases the effect of adhesive strength, no
The interface compatibility of solid powder and matrix resin only can be improved, can also enhance each adhesion strength inside complex solid powder.It is excellent
Choosing, the coupling agent is vinyltriethoxysilane, vinyltrimethoxysilane, vinyl three (beta-methoxy ethyoxyl)
One of silane, isobutyl triethoxy silane, auxiliary agent are antioxidant, ultraviolet absorber, impact modifying agent, mould inhibitor, increasing
Mould at least one of agent, fire retardant；Further, the antioxidant is at least one of 1010,1076,168 or DLTP；
The ultraviolet absorber is one of UV-12, UV-326, UV-327, UV-328, UV-329, UV-770；The shock resistance
Modifying agent is the mixture of transparent butadiene-styrene impact resin and elastomer, and the elastomer is one of SBS, SBR, the butylbenzene
Transparent anti-impact resin and elastomer weight ratio are (5~10): (5~10)；The mould inhibitor is inorganic salts copper sulphate；The increasing
Moulding agent is one of WE, WX or OP paraffin；The fire retardant is nitrogen phosphorus system compound, aluminium hydroxide, one in magnesium hydroxide
Kind is a variety of, and wherein nitrogen phosphorus system compound is made of acid source, gas source, carbon source according to mass ratio for 3:1:1, and acid source is phosphoric acid, five
Two phosphorus, phosphorus oxychloride or ammonium polyphosphate are aoxidized, gas source is melamine, and carbon source is pentaerythrite；
Wherein the parts by weight of each raw material are graphene aerogel/titanium dioxide/10 ~ 30 weight of graphite phase carbon nitride solid powder
Part, 1 ~ 2 parts by weight of coupling agent, 20 ~ 25 parts by weight of linear low density polyethylene, 12 ~ 47 parts by weight of polypropylene, polyvinyl chloride 20 ~
25 parts by weight, 2 ~ 6 parts by weight of auxiliary agent.
The present invention also provides a kind of road guard that above-mentioned preparation method is prepared plastics of purification vehicle exhaust
Masterbatch.The plastic matrix is that nanometer porous graphite phase carbon nitride is made using rich nitrogen raw material, then with butyl titanate, graphite
Graphene aerogel/dioxy is made as raw material in alkene aeroge, nitric acid/dehydrated alcohol mixed solution, sodium borohydride, dehydrated alcohol
Change titanium/graphite phase carbon nitride solid powder, after coupling agent treatment with linear low density polyethylene, polypropylene, polyvinyl chloride, help
Agent mixing extruding pelletization and be made.The product of gained masterbatch has good photocatalytic activity and visible light utilization efficiency.
The present invention provides a kind of road guard plastic matrixs and preparation method of purification vehicle exhaust, with the prior art
It compares, the feature and excellent effect protruded is:
1. plastic matrix prepared by the present invention, the road guard prepared using the masterbatch is very aobvious to the catharsis of vehicle exhaust
It writes.
2. preparation method of the invention, using graphene aerogel as carrier and nano-titanium dioxide and porous stone
Black phase carbon nitride is in close contact, and not only absorption property is good, but also has good photocatalytic activity and visible light utilization efficiency, for
Organic pollutant has excellent catharsis.
3. plastic matrix produced by the present invention, by test, the plastic products of preparation are for NOxAverage degradation rate be
123×10-6~127×10-6/20min。
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
The mono- cyano amine of 97kg is mixed with 3kg nanometer calcium carbonate, 34min is ground with the revolving speed of 260r/min, then moves into tubular type
In furnace, 500 DEG C of insulation reaction 2h are heated in the environment of being passed through argon gas, then by product continue grind 48min, after first
It uses mass concentration for salt acid elution 3 times of 13%, then is washed with distilled water 3 times, dry, nanometer porous graphite-phase nitrogen is made
Change carbon；Then 17kg porous graphite phase carbon nitride, 8kg butyl titanate are added in 34g dehydrated alcohol, with 500 ~ 600r/min
Revolving speed stir 30 ~ 40min strongly, obtain solution A；Then 27kg graphene aerogel is immersed in solution A, and 11kg is added
Nitric acid/dehydrated alcohol mixed solution, in nitric acid/dehydrated alcohol mixed solution, nitric acid that mass concentration is 15%, dehydrated alcohol
Volume ratio is 7:93, continues stirring with the revolving speed of 360r/min until forming colloidal sol；Then 3kg boron is slowly added in colloidal sol
Sodium hydride, continues stirring until forming gel, by gel at 47 DEG C dry 6.5h, 38in is ground with the revolving speed of 170r/min,
Then grinding product is transferred in the vacuum tube furnace under helium atmosphere, rises to 520 DEG C with the speed of 12 DEG C/min, isothermal holding
3.5h, after be cooled to room temperature, be first washed with distilled water 4 times, then washed 3 times with dehydrated alcohol, dry, be made graphene gas
Gel/titanium dioxide/graphite phase carbon nitride solid powder；Then 18kg graphene aerogel/titanium dioxide/graphite-phase is nitrogenized
Carbon solid powder and 1kg vinyltriethoxysilane are added in enough distilled water, stir process, after filtering, drying, then
With mix drying after 23kg linear low density polyethylene, 32kg polypropylene, 23kg polyvinyl chloride, 3kg auxiliary agent, auxiliary agent is by antioxygen
Agent, ultraviolet absorber, impact modifying agent composition, the antioxidant are 1010；The ultraviolet absorber is UV-12；Described is anti-
Impact modifying agent is the mixture of transparent butadiene-styrene impact resin and elastomer, and the elastomer is one of SBS, SBR, described
Transparent butadiene-styrene impact resin and elastomer weight ratio are 8:6；It is uniform that high-speed mixer and mixing is added, then puts into extruder,
The road guard plastic matrix of purification vehicle exhaust is made in extruding pelletization at a temperature of 190 DEG C.
Test method:
15cm × 15cm × 0.5cm sample is made in plastic matrix produced by the present invention, is placed in 1m3Vehicle exhaust test
It is tested in the chamber of system, the UVA ultraviolet light of setting 30W, is passed through vehicle exhaust in reaction chamber, utilizes vehicle exhaust point
Analyzer tests NOxConcentration, every 20min test is primary, total reaction time 120min, polluted gas initial concentration C0, after reaction
Concentration is C1, reaction time t, to test and calculating average degradation rate: ω=(C0 -C1)/t.
The data obtained is as shown in table 1.
Embodiment 2
96kg dicyanamide is mixed with 4kg nanometer calcium carbonate, 38min is ground with the revolving speed of 220r/min, then moves into tubular type
In furnace, 400 DEG C of insulation reaction 3h are heated in the environment of being passed through argon gas, then by product continue grind 45min, after first
It uses mass concentration for salt acid elution 4 times of 12%, then is washed with distilled water 2 times, dry, nanometer porous graphite-phase nitrogen is made
Change carbon；Then 16kg porous graphite phase carbon nitride, 7kg butyl titanate are added in 38kg dehydrated alcohol, with 520r/min's
Revolving speed stirs 38min strongly, obtains solution A；Then by 27kg graphene aerogel immerse solution A in, and be added 9kg nitric acid/
Dehydrated alcohol mixed solution, in nitric acid/dehydrated alcohol mixed solution, the volume ratio of nitric acid, dehydrated alcohol that mass concentration is 10%
Example is 6:94, continues stirring with the revolving speed of 320r/min until forming colloidal sol；Then 3kg hydroboration is slowly added in colloidal sol
Sodium continues stirring until forming gel, and by gel, at 46 DEG C then dry 7h will with the revolving speed grinding 45min of 160r/min
Grinding product is transferred in the vacuum tube furnace under neon atmosphere, rises to 510 DEG C, isothermal holding 4h with the speed of 11 DEG C/min, knot
It is cooled to room temperature, is first washed with distilled water 3 times after beam, then washed 2 times with dehydrated alcohol, dried, graphene aerogel/bis- are made
Titanium oxide/graphite phase carbon nitride solid powder；Then by 15kg graphene aerogel/titanium dioxide/graphite phase carbon nitride solid
Powder and 1kg vinyltrimethoxysilane are added in enough distilled water, stir process, after filtering, drying, then with mix
21kg linear low density polyethylene, 38kg polypropylene after drying, 22kg polyvinyl chloride, 3kg auxiliary agent, auxiliary agent is by mould inhibitor, increasing
Agent, fire retardant composition are moulded, the mould inhibitor is inorganic salts copper sulphate；The plasticizer is WE；The fire retardant is nitrogen phosphorus system
One of compound, aluminium hydroxide, magnesium hydroxide are a variety of, and wherein nitrogen phosphorus system compound is by acid source, gas source, carbon source according to matter
Amount is than being that 3:1:1 is constituted, and acid source is phosphoric acid, and gas source is melamine, and carbon source is pentaerythrite；It is equal that high-speed mixer and mixing is added
It is even, it then puts into extruder, in 185 DEG C of temperature extruding pelletization, the road guard plastic master of purification vehicle exhaust is made
Material.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Embodiment 3
98kg melamine is mixed with 2kg nanometer calcium carbonate, 32min is ground with the revolving speed of 280r/min, then moves into tubular type
In furnace, 500 DEG C of insulation reaction 2h are heated in the environment of being passed through argon gas, then by product continue grind 55min, after first
It uses mass concentration for salt acid elution 4 times of 14%, then is washed with distilled water 3 times, dry, nanometer porous graphite-phase nitrogen is made
Change carbon；Then 17kg porous graphite phase carbon nitride, 9kg butyl titanate are added in 31kg dehydrated alcohol, with 580r/min's
Revolving speed stirs 32min strongly, obtains solution A；Then by 28kg graphene aerogel immerse solution A in, and be added 11kg nitric acid/
Dehydrated alcohol mixed solution, in nitric acid/dehydrated alcohol mixed solution, the volume ratio of nitric acid, dehydrated alcohol that mass concentration is 20%
Example is 9:91, continues stirring with the revolving speed of 380r/min until forming colloidal sol；Then 4kg hydroboration is slowly added in colloidal sol
Sodium continues stirring until forming gel, and by gel, at 48 DEG C then dry 6h will with the revolving speed grinding 35min of 190r/min
Grinding product is transferred in the vacuum tube furnace under argon atmosphere, rises to 540 DEG C, isothermal holding 3h with the speed of 14 DEG C/min, knot
It is cooled to room temperature, is first washed with distilled water 5 times after beam, then washed 3 times with dehydrated alcohol, dried, graphene aerogel/bis- are made
Titanium oxide/graphite phase carbon nitride solid powder；Then by 25kg graphene aerogel/titanium dioxide/graphite phase carbon nitride solid
Powder and (beta-methoxy ethyoxyl) silane of 2kg vinyl three are added in enough distilled water, stir process, after filtering, drying, so
Afterwards with mix drying after 24kg linear low density polyethylene, 20kg polypropylene, 24kg polyvinyl chloride, 5kg auxiliary agent, auxiliary agent is by resisting
Oxygen agent, ultraviolet absorber, impact modifying agent, mould inhibitor composition, the antioxidant are DLTP；The ultraviolet absorber is UV-
326；The anti-impact modifier is the mixture of transparent butadiene-styrene impact resin and elastomer, and the elastomer is SBS, SBR
One of, the transparent butadiene-styrene impact resin and elastomer weight ratio are 5:10；The mould inhibitor is inorganic salts copper sulphate；
It is uniform that high-speed mixer and mixing is added, then puts into extruder, in 195 DEG C of temperature extruding pelletization, road guard is made with only
Change the plastic matrix of vehicle exhaust.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Embodiment 4
96kg cyanuric trichloride is mixed with 4kg nanometer calcium carbonate, 40min is ground with the revolving speed of 200r/min, then moves into tubular type
In furnace, 300 DEG C of insulation reaction 4h are heated in the environment of being passed through argon gas, then by product continue grind 40min, after first
It uses mass concentration for salt acid elution 2 times of 10%, then is washed with distilled water 2 times, dry, nanometer porous graphite-phase nitrogen is made
Change carbon；Then 15kg porous graphite phase carbon nitride, 6kg butyl titanate are added in 44kg dehydrated alcohol, with 500r/min's
Revolving speed stirs 40min strongly, obtains solution A；Then by 25kg graphene aerogel immerse solution A in, and be added 8kg nitric acid/
Dehydrated alcohol mixed solution, in nitric acid/dehydrated alcohol mixed solution, the volume ratio of nitric acid, dehydrated alcohol that mass concentration is 16%
Example is 5:95, continues stirring with the revolving speed of 300r/min until forming colloidal sol；Then 2kg hydroboration is slowly added in colloidal sol
Sodium continues stirring until forming gel, and by gel, at 45 DEG C then dry 7h will with the revolving speed grinding 50min of 150r/min
Grinding product is transferred in the vacuum tube furnace under Krypton atmosphere, rises to 550 DEG C, isothermal holding 3h with the speed of 10 DEG C/min, knot
It is cooled to room temperature, is first washed with distilled water 3 times after beam, then washed 2 times with dehydrated alcohol, dried, graphene aerogel/bis- are made
Titanium oxide/graphite phase carbon nitride solid powder；Then by 10kg graphene aerogel/titanium dioxide/graphite phase carbon nitride solid
Powder and 1kg isobutyl triethoxy silane are added in enough distilled water, stir process, after filtering, drying, then with mix
20kg linear low density polyethylene, 47kg polypropylene after drying, 20kg polyvinyl chloride, 2kg auxiliary agent, auxiliary agent is by antioxidant, purple
Outer absorbent composition, the antioxidant are 168；The ultraviolet absorber is UV-328；It is uniform that high-speed mixer and mixing is added, then
It puts into extruder, in 180 DEG C of temperature extruding pelletization, the road guard plastic matrix of purification vehicle exhaust is made.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Embodiment 5
The mono- cyano amine of 98kg is mixed with 2kg nanometer calcium carbonate, 30min is ground with the revolving speed of 300r/min, then moves into tubular type
In furnace, 600 DEG C of insulation reaction 1h are heated in the environment of being passed through argon gas, then by product continue grind 40min, after first
It uses mass concentration for salt acid elution 4 times of 15%, then is washed with distilled water 4 times, dry, nanometer porous graphite-phase nitrogen is made
Change carbon；Then 18kg porous graphite phase carbon nitride, 10kg butyl titanate are added in 24kg dehydrated alcohol, with 600r/min's
Revolving speed stirs 30min strongly, obtains solution A；Then by 30kg graphene aerogel immerse solution A in, and be added 13kg nitric acid/
Dehydrated alcohol mixed solution, in nitric acid/dehydrated alcohol mixed solution, the volume ratio of nitric acid, dehydrated alcohol that mass concentration is 18%
Example is 10:90, continues stirring with the revolving speed of 400r/min until forming colloidal sol；Then 5kg hydroboration is slowly added in colloidal sol
Sodium continues stirring until forming gel, and by gel, at 50 DEG C then dry 6h will with the revolving speed grinding 30min of 200r/min
Grinding product is transferred in the vacuum tube furnace under xenon atmosphere, rises to 550 DEG C, isothermal holding 3h with the speed of 15 DEG C/min, knot
It is cooled to room temperature, is first washed with distilled water 5 times after beam, then washed 4 times with dehydrated alcohol, dried, graphene aerogel/bis- are made
Titanium oxide/graphite phase carbon nitride solid powder；Then by 30kg graphene aerogel/titanium dioxide/graphite phase carbon nitride solid
Powder and 2kg vinyltriethoxysilane are added in enough distilled water, stir process, after filtering, drying, then with mix
25kg linear low density polyethylene, 12kg polypropylene after drying, 25kg polyvinyl chloride, 6kg auxiliary agent, auxiliary agent is by antioxidant, purple
Outer absorbent, impact modifying agent, mould inhibitor, plasticizer, fire retardant composition, the antioxidant are 1076；The ultraviolet absorber
For UV-328；The anti-impact modifier is the mixture of transparent butadiene-styrene impact resin and elastomer, and the elastomer is
One of SBS, SBR, the transparent butadiene-styrene impact resin and elastomer weight ratio are 8:5；The mould inhibitor is inorganic salts
Copper sulphate；The plasticizer is OP paraffin；The fire retardant is nitrogen phosphorus system compound, and wherein nitrogen phosphorus system compound is by acid source, gas
Source, carbon source are 3:1:1 composition according to mass ratio, and acid source is ammonium polyphosphate, and gas source is melamine, and carbon source is pentaerythrite；Add
It is uniform to enter high-speed mixer and mixing, then puts into extruder, in 200 DEG C of temperature extruding pelletization, road guard purification is made
The plastic matrix of vehicle exhaust.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Embodiment 6
97kg melamine is mixed with 3kg nanometer calcium carbonate, 35min is ground with the revolving speed of 250r/min, then moves into tubular type
In furnace, 450 DEG C of insulation reaction 2h are heated in the environment of being passed through argon gas, then by product continue grind 50min, after first
It uses mass concentration for salt acid elution 3 times of 12%, then is washed with distilled water 3 times, dry, nanometer porous graphite-phase nitrogen is made
Change carbon；Then 16kg porous graphite phase carbon nitride, 8kg butyl titanate are added in 35kg dehydrated alcohol, with 550r/min's
Revolving speed stirs 35min strongly, obtains solution A；Then by 28kg graphene aerogel immerse solution A in, and be added 10kg nitric acid/
Dehydrated alcohol mixed solution, in nitric acid/dehydrated alcohol mixed solution, the volume ratio of nitric acid, dehydrated alcohol that mass concentration is 12%
Example is 8:92, continues stirring with the revolving speed of 350r/min until forming colloidal sol；Then 4kg hydroboration is slowly added in colloidal sol
Sodium, continues stirring until forming gel, by gel at 48 DEG C dry 6.5h, 40min is ground with the revolving speed of 180r/min, then
Grinding product is transferred in the vacuum tube furnace under helium atmosphere, rises to 520 DEG C with the speed of 12 DEG C/min, isothermal holding
3.5h, after be cooled to room temperature, be first washed with distilled water 4 times, then washed 3 times with dehydrated alcohol, dry, be made graphene gas
Gel/titanium dioxide/graphite phase carbon nitride solid powder；Then 20kg graphene aerogel/titanium dioxide/graphite-phase is nitrogenized
Carbon solid powder and 1kg vinyltrimethoxysilane are added in enough distilled water, stir process, after filtering, drying, then
With mix drying after 22kg linear low density polyethylene, 30kg polypropylene, 23kg polyvinyl chloride, 4kg auxiliary agent, auxiliary agent is by antioxygen
Agent, ultraviolet absorber, impact modifying agent, mould inhibitor, plasticizer, fire retardant composition, the antioxidant are DLTP；The ultraviolet suction
Receipts agent is UV-770；The anti-impact modifier is the mixture of transparent butadiene-styrene impact resin and elastomer, the elastomer
For one of SBS, SBR, the transparent butadiene-styrene impact resin and elastomer weight ratio are 10:8；The mould inhibitor is inorganic
Salt copper sulphate；The plasticizer is WX paraffin；The fire retardant is magnesium hydroxide；It is uniform that high-speed mixer and mixing is added, then throws
Enter in extruder, in 190 DEG C of temperature extruding pelletization, the road guard plastic matrix of purification vehicle exhaust is made.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Comparative example 1
In plastic matrix preparation process, it is not added with graphene aerogel, other preparation conditions and embodiment 6 are consistent.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Table 1:
Claims (10)
1. a kind of road guard preparation method of the plastic matrix of purification vehicle exhaust, which is characterized in that utilize rich nitrogen raw material
Nanometer porous graphite phase carbon nitride is made, is then mixed with butyl titanate, graphene aerogel, nitric acid/dehydrated alcohol molten
Graphene aerogel/titanium dioxide/graphite phase carbon nitride solid powder, warp is made as raw material in liquid, sodium borohydride, dehydrated alcohol
With linear low density polyethylene, polypropylene, polyvinyl chloride, auxiliary agent mixing extruding pelletization after coupling agent treatment, road guard is made
With the plastic matrix of purification vehicle exhaust, specific step is as follows for preparation:
(1) rich nitrogen raw material is mixed with template nanometer calcium carbonate, 30 ~ 40min is ground with the revolving speed of 200 ~ 300r/min, then
It moves into tube furnace, 300 ~ 600 DEG C of 1 ~ 4h of insulation reaction is heated in the environment of being passed through argon gas, then continue to grind by product
40 ~ 60min, after wash, dry, nanometer porous graphite phase carbon nitride is made；
(2) porous graphite phase carbon nitride made from step (1), butyl titanate are added to absolute ethanol, with 500 ~ 600r/
The revolving speed of min stirs 30 ~ 40min strongly, obtains solution A；Then by graphene aerogel immerse solution A in, and be added nitric acid/
Dehydrated alcohol mixed solution continues stirring with the revolving speed of 300 ~ 400r/min until forming colloidal sol；Then slowly add in colloidal sol
Enter sodium borohydride, continue stirring until forming gel, by gel at 45 ~ 50 DEG C dry 6 ~ 7h, with turning for 150 ~ 200r/min
Grinding product, is then transferred in the vacuum tube furnace under atmosphere of inert gases, with 10 ~ 15 DEG C/min's by speed 30 ~ 50min of grinding
Speed is warming up to 500 ~ 550 DEG C, 3 ~ 4h of isothermal holding, after be cooled to room temperature, be first washed with distilled water 3 ~ 5 times, then use nothing
Water-ethanol washs 2 ~ 4 times, and graphene aerogel/titanium dioxide/graphite phase carbon nitride solid powder is made in drying；
(3) foot is added in graphene aerogel/titanium dioxide/graphite phase carbon nitride solid powder made from step (2) and coupling agent
Measure distilled water in, stir process, after filtering, drying, then with mix dry after linear low density polyethylene, poly- third
Alkene, Corvic raw material and auxiliary agent addition high-speed mixer and mixing are uniform, then put into extruder, at 180 ~ 200 DEG C
Temperature range extruding pelletization, be made road guard with purification vehicle exhaust plastic matrix.
2. preparation method of a kind of road guard with the plastic matrix of purification vehicle exhaust according to claim 1, feature
Be: step (1) the rich nitrogen raw material is at least one of single cyano amine, dicyanamide, melamine, cyanuric trichloride.
3. preparation method of a kind of road guard with the plastic matrix of purification vehicle exhaust according to claim 1, feature
Be: step (1) described washing process is first to use mass concentration for salt acid elution 2 ~ 4 times of 10 ~ 15%, then washed with distillation
It washs 2 ~ 4 times.
4. preparation method of a kind of road guard with the plastic matrix of purification vehicle exhaust according to claim 1, feature
Be: the parts by weight of each raw material are in step (1), rich 96 ~ 98 parts by weight of nitrogen raw material, 2 ~ 4 parts by weight of template.
5. preparation method of a kind of road guard with the plastic matrix of purification vehicle exhaust according to claim 1, feature
Be: in step (2) nitric acid/dehydrated alcohol mixed solution, nitric acid, dehydrated alcohol volume ratio be 5 ~ 10;90~95；
The mass concentration of the nitric acid is 10 ~ 20%.
6. preparation method of a kind of road guard with the plastic matrix of purification vehicle exhaust according to claim 1, feature
Be: step (2) inert gas is one of helium, neon, argon gas, Krypton, xenon.
7. preparation method of a kind of road guard with the plastic matrix of purification vehicle exhaust according to claim 1, feature
Be: the parts by weight of each raw material are in step (2), 15 ~ 18 parts by weight of porous graphite phase carbon nitride, 6 ~ 10 weight of butyl titanate
Part, 24 ~ 44 parts by weight of dehydrated alcohol, 25 ~ 30 parts by weight of graphene aerogel, nitric acid/8 ~ 13 weight of dehydrated alcohol mixed solution
Part, 2 ~ 5 parts by weight of sodium borohydride.
8. preparation method of a kind of road guard with the plastic matrix of purification vehicle exhaust according to claim 1, feature
Be: step (3) coupling agent is vinyltriethoxysilane, vinyltrimethoxysilane, three (beta-methoxy of vinyl
Ethyoxyl) silane, one of isobutyl triethoxy silane, auxiliary agent is antioxidant, ultraviolet absorber, impact modifying agent, anti-
Mould dose, plasticizer, at least one of fire retardant；The antioxidant is at least one of 1010,1076,168 or DLTP；Institute
Stating ultraviolet absorber is one of UV-12, UV-326, UV-327, UV-328, UV-329, UV-770；The anti-impact clicks to change
Property agent be transparent butadiene-styrene impact resin and elastomer mixture, the elastomer is one of SBS, SBR, and the butylbenzene is saturating
Bright anti-impact resin and elastomer weight ratio are (5~10): (5~10)；The mould inhibitor is inorganic salts copper sulphate；The plasticising
Agent is one of WE, WX or OP paraffin；The fire retardant is one of nitrogen phosphorus system compound, aluminium hydroxide, magnesium hydroxide
Or it is a variety of, wherein nitrogen phosphorus system compound is made of acid source, gas source, carbon source according to mass ratio for 3:1:1, and acid source is phosphoric acid, five oxygen
Change two phosphorus, phosphorus oxychloride or ammonium polyphosphate, gas source is melamine, and carbon source is pentaerythrite.
9. preparation method of a kind of road guard with the plastic matrix of purification vehicle exhaust according to claim 1, feature
Be: the parts by weight of each raw material are in step (3), graphene aerogel/titanium dioxide/graphite phase carbon nitride solid powder 10 ~
30 parts by weight, 1 ~ 2 parts by weight of coupling agent, 20 ~ 25 parts by weight of linear low density polyethylene, 12 ~ 47 parts by weight of polypropylene, polychlorostyrene second
20 ~ 25 parts by weight of alkene, 2 ~ 6 parts by weight of auxiliary agent.
10. the plastic master for the road guard purification vehicle exhaust that any one of claim 1 ~ 9 preparation method is prepared
Material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511512A (en) * | 2019-09-29 | 2019-11-29 | 无锡市华美电缆有限公司 | A kind of fire-resistant cable material of Novel anti-ageing |
| CN114177928A (en) * | 2021-12-27 | 2022-03-15 | 吉林大学 | Composite photocatalyst Bi @ H-TiO with visible light response2/B-C3N4Preparation method and application thereof |
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2019
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511512A (en) * | 2019-09-29 | 2019-11-29 | 无锡市华美电缆有限公司 | A kind of fire-resistant cable material of Novel anti-ageing |
| CN114177928A (en) * | 2021-12-27 | 2022-03-15 | 吉林大学 | Composite photocatalyst Bi @ H-TiO with visible light response2/B-C3N4Preparation method and application thereof |
| CN114177928B (en) * | 2021-12-27 | 2023-10-03 | 吉林大学 | Composite photocatalyst Bi@H-TiO with visible light response 2 /B-C 3 N 4 Preparation method and application thereof |
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