CN108976661A - A kind of flame-proof polyvinyl chloride penetration pipe and preparation method that graphene is modified - Google Patents
A kind of flame-proof polyvinyl chloride penetration pipe and preparation method that graphene is modified Download PDFInfo
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Abstract
The present invention relates to a kind of modified flame-proof polyvinyl chloride penetration pipe of graphene and preparation methods, belong to pvc pipe technical field.The technical problem to be solved by the present invention is to provide a kind of modified flame-proof polyvinyl chloride penetration pipe of graphene and preparation methods, this method passes through the dispersed graphite alkene in barium sulfate precursor component, the composite flame-proof synergist of preparation load graphene is precipitated using reaction, isolation and flame retardant synergism are played in barium sulfate load, both generation was reunited between being avoided that graphene, the significant increase flame retardant effect of penetration pipe again, additive amount is lower compared with single fire retardant simultaneously, it reduces costs, while avoiding influencing the buckle resistance energy of penetration pipe.This method is easy to operate, and cost is relatively low.The flame-proof PVC penetration pipe prepared by the method for the invention, good flame retardation effect, the mechanical properties such as tensile strength are higher, are outstanding flame-proof PVC threading tube materials.
Description
Technical field
The present invention relates to a kind of modified flame-proof polyvinyl chloride penetration pipe of graphene and preparation methods, belong to pvc pipe technology
Field.
Background technique
Penetration pipe full name " insulating electrical casing pipe for building " is a kind of tubing for being used to wear electric wire in electrical engineering field,
It is chiefly used in indoor normal environment and in high temperature, more dirt, the place for having vibration and fire-prone.It can also make in moist place
With.Existing spool has pvc pipe or a modified PVC pipe mostly, and basic demand is anticorrosion, fire-retardant, should also have certain resistance to compression
With bend resistance ability.Especially in certain special application fields, spool used also requirement must have the property such as antistatic, high flame retardant
Can, comprehensive performance requires high.
Raw materials used polyvinyl chloride (PVC) belongs to self-extinguishing in PVC penetration pipe, but PVC can be released greatly in burning
The black smoke and toxic gas of amount.Such as HCl, CO, a small amount of phosgene, benzene, naphthalene aromatic compound.A large amount of personnel are caused in fire
It is choked to death and is died due to smog, this is subject to certain restrictions the application range of PVC.Meanwhile it being added and increasing in PVC pipe process
The auxiliary agents such as modeling agent, lubricant can also reduce the flame retardant property and smoke suppressing of material.So carrying out smoke-inhibiting flame retardant to PVC pipe
Modified research is increasingly taken seriously.Therefore, it develops and is seemed very necessary suitable for the flame-retardant smoke inhibition technology of PV penetration pipe.
Application No. is 201610750178.7 patents of invention to disclose a kind of fire-resistant smoke-inhibiting PVC pipe and its production method,
The fire-resistant smoke-inhibiting PVC pipe includes the raw material of following parts by weight: where 80-100 parts of Corvic, nanometer anhydrous slufuric acid
It is 20-30 parts of calcium, 5-10 parts of anti-flaming smoke-inhibiting agent, 2-6 parts of compound stabilizer, 1-3 parts of modifying agent, 0.5-2.0 parts of PE wax, silane coupled
0.5-2 parts of agent, 0.2-0.5 parts of composite antioxidant.The invention raw material is simple and easy to get, low in cost, and toughness is high, and elongation is big,
Low temperature resistant good toughness, and black smoke and toxic gas that pvc pipe is discharged in burning can greatly be reduced, substantially reduce fire
The casualties as caused by smog asphyxia in accident.
Application No. is the patents of invention of 201510377254.X to disclose a kind of flame-proof PVC tubing and preparation method thereof, should
PVC pipe is by following mass parts at being grouped as: 45-55 parts of polyvinyl chloride resin, 35-45 parts of precipitated calcium carbonate, silane coupling agent 0.5-1
Part, 1-5 parts of stabilizer, 0.5-1.5 parts of paraffin, 1-3 parts of stearic acid, 0.5-1.5 parts of titanium dioxide, 1-2 parts of aluminium hydroxide, carbon black
0.5-1 parts, mentioned component is sequentially placed into mixing drum according to the ratio and is stirred 3min, is successively heated, is co-extrusion, cold
But, traction, excision forming, finally obtain finished product.PVC pipe surface hardness of the invention and tensile strength are high, and ageing resistance
Good, normal service life was up to 50 years or more, acid and alkali-resistance fine corrosion resistance, was suitable for industrial wastewater discharge and conveying, and
Fire retardant property is excellent.
Application No. is 201610638445.1 patent of invention disclose a kind of heat-resistant fireproof anti-aging PVC tubing and its
Preparation method, the heat-resistant fireproof anti-aging PVC tubing, the component including following mass fraction: 70~90 parts of PVC resin powders,
20~50 parts of fillers, 1~3 part of heat stabilizer, 0.5~1 part of ACR resin, 2~4 parts of CPE, 0.3~0.5 part of lubricant, 0.2
~0.5 part of carbon black, 0.5~1 part of aluminium hydroxide, 1~4 part of fire retardant and 0.1~0.2 part of age resister, preparation method include mixed
Conjunction, extrusion, sizing, cooling and cutting.Heat-resistant fireproof anti-aging PVC tubing described in the invention, passes through matching for each component
The PVC pipe heat resistance with higher and anti-flammability for closing preparation, still maintain in the Xenon lamp weather resistance test of long period
There is biggish tensile strength.
As it can be seen that currently, production flame-proof PVC Guan Jun is the method using additional fire retardant, and common fire retardant is halogen
Fire retardant (contains chlorine or brominated flame-retardant, such as tetrabromobisphenol A, deca-BDE, Brominated Polystyrene, pentabromotoluene and hexabromo ring
Dodecane etc.).As outer additive flame retardant, such material using generally existing environmental pollution the problem of, and material after being applicable in
The defects of expecting that flame retardant property is not high and tearing toughness is poor.And if this based flame retardant of single use, flame retardant effect is undesirable, adds
Dosage is big, not only increases production cost, and affects the mechanical property of spool.
Summary of the invention
For current single fire retardant effect is undesirable and additive amount leads to greatly the defect of bend resistance reduced performance,
The present invention proposes a kind of flame-proof polyvinyl chloride penetration pipe and preparation method that graphene is modified.
First technical problem that the present invention solves is to provide a kind of flame-proof polyvinyl chloride penetration pipe of graphene modification
Preparation method.
The preparation method of the modified flame-proof polyvinyl chloride penetration pipe of graphene of the present invention, includes the following steps:
A, baryta water and graphene aqueous dispersions are mixed, under agitation, excessive zinc sulfate is then added
Aqueous solution continues to be stirred to react 60~200min, is separated by solid-liquid separation, and 130 DEG C of heating 30min obtain graphene composite flame-proof synergistic
Agent；Wherein, the concentration of baryta water is 5~10wt%, and in graphene aqueous dispersions, the weight percent of graphene is 7
~15%, the concentration of zinc sulfate solution is 5~10wt%；The volume ratio of baryta water and graphene aqueous dispersions is 1
~3:1；
B, silane coupling agent is added to the water, constant temperature stirs at 60~90 DEG C, magnesium hydroxide is added after mixing, by stirring rate
Control stirs 60~120min, then dries, be ground into fine powder in 500~1000rpm, the magnesium hydroxide being surface-treated；
Silane coupling agent, water, magnesium hydroxide mass ratio be 1:5:30.
C, by the magnesium hydroxide of the surface treatment of the graphene composite flame-proof synergist of a step and b step in 60~90 DEG C
Mixing, then with PVC, heat stabilizer, filler and mix lubricant, melt blending, extrusion molding, cooling and shaping obtain graphene
Modified flame-proof polyvinyl chloride penetration pipe, wherein by weight, at 10~20 parts of graphene composite flame-proof synergist, surface
2~8 parts of 10~30 parts of 5~8 parts of 60~80 parts of 5~10 parts of magnesium hydroxide, PVC, heat stabilizer, filler, the lubricant of reason.
The method of the present invention precipitates preparation cladding stone using reaction by the dispersed graphite alkene in barium sulfate precursor component
The composite flame-proof synergist of black alkene, barium sulfate clad play isolation and flame retardant synergism, have both been avoided that between graphene and have generated
Reunite, and the significant increase flame retardant effect of penetration pipe, while additive amount is lower compared with single fire retardant, reduce costs,
Avoid influencing the buckle resistance energy of penetration pipe simultaneously.
Wherein, a step mainly prepares graphene composite flame-proof synergist, prepares baryta water and graphite respectively
Alkene aqueous dispersions, then by the two, continuing magnetic force is stirred in dynamic mixer, and excessive zinc sulfate solution, hydrogen-oxygen is added
Change barium and react generation barium sulfate precipitate with excess sulfuric acid zinc, forms the clad to graphene, obtain the compound of doped graphene
Fire retarding synergist.
Wherein, the excessive zinc sulfate solution refers to that the molal quantity of the sulfate ion in zinc sulfate solution is big
Barium ions molal quantity in barium hydroxide, i.e. sulfate ion are excessive.
The concentration of baryta water, graphene aqueous dispersions and zinc sulfate solution assists graphene composite flame-proof
The performance of effect agent is affected.Preferably, in a step, the concentration of the baryta water is 7wt%, graphene water dispersion
In liquid, the weight percent of graphene is 12%, and the concentration of zinc sulfate solution is 8wt%.In this way, the compound resistance of obtained graphene
It is best to fire synergist performance.
The volume ratio of baryta water and graphene aqueous dispersions will will affect the load performance of barium sulfate, preferably
, in a step, the volume ratio of baryta water and graphene aqueous dispersions is 2:1.
Preferably, in a step, it is stirred to react 120min.
B step is mainly to prepare the process of the magnesium hydroxide of surface treatment, using silane coupling agent to magnesium hydroxide surface
It is handled.
Magnesium hydroxide (Mg (OH) 2) have thermal stability it is good, it is non-volatile, be not precipitated, do not generate toxic gas, do not corrode plus
The advantages that construction equipment, obvious, cheap smoke elimination effect.But its surface has hydrophilic and oleophobic property, in most of hydrocarbon polymers
Bad dispersibility in (such as polyethylene, polypropylene, polystyrene, polyvinyl chloride), flame retarding efficiency is low, additive amount is big, is reaching
The processing performance and physical and mechanical property of material are often seriously damaged while flame-retardancy requirements.Therefore, it is necessary to magnesium hydroxide
Do surface modification treatment.The present invention mainly uses silane coupling agent to be modified processing to 2 surface Mg (OH).
The molecular structural formula of silane coupling agent is general are as follows: Y-R-Si (OR) 3 (mono- organic functional base of Y, mono- silane of SiOR in formula
Oxygroup).Siloxy has reactivity to inorganic matter, and organic functional base has reactivity or compatibility to organic matter.Therefore, when
Silane coupling agent between organic interface, can form organic matrix-silane coupling agent-inorganic matrix binder course between inorganic.
Silane coupling agent commonly used in the art is suitable for the present invention.Preferably, the silane coupling agent has A151 (ethylene
Ethyl triethoxy silicane alkane), A171 (vinyltrimethoxysilane) or .A172 (vinyl three (beta-methoxy ethyoxyl) silane).
Preferably, in b step, stirring rate control stirs 100min in 800rpm.
In the method for the present invention, a step and b step do not have time sequencing, it can and a step is first carried out, b step is being carried out,
B step can also be first carried out, then carries out a step, can also be carried out simultaneously with a step and b step.
Step c is to prepare the process of the modified flame-proof polyvinyl chloride penetration pipe product of graphene, by graphene composite flame-proof
The flame retardant of magnesium hydroxide of synergist and coupling agent surface treatment carries out that heat is dark to close, then with PVC, heat stabilizer, filler, lubrication
The mixing such as agent obtains the excellent PVC of flame retardant effect through screw extruder melt blending, extrusion molding, last cooling and shaping and threads
Pipe.
In step c, most important influence factor is the proportion between each raw material, and inventor is the study found that work as graphene
10~20 parts by weight of composite flame-proof synergist, 5~10 parts by weight of magnesium hydroxide of surface treatment, 60~80 parts by weight of PVC, heat
When 5~8 parts by weight of stabilizer, 10~30 parts by weight of filler, 2~8 parts by weight of lubricant, the flame-proof PVC penetration pipe that obtains at this time
Flame retardant property and mechanical property it is preferable, therefore, the method for the present invention limits the proportion of each raw material within the above range.As
Preferred embodiment, in step c, by weight, 18 parts of graphene composite flame-proof synergist, surface treatment 7 parts of magnesium hydroxide,
70 parts of PVC, 6 parts of heat stabilizer, 15 parts of filler, 4 parts of lubricant.In this way, the performance of obtained flame-proof PVC penetration pipe is best.
Heat stabilizer is one of important class in plastic processing additives, in order to make up PVC homopolymer to the maximum extent and be total to
The major defect of polymers needs to eliminate the unstable position for causing to start dehydrochlorination with stabilizer；Or as the clear of hydrogen chloride
Except agent；Or it is just reacted when free radical generates；Or as antioxidant；Or change polyene structure to prevent color change, divide
Subchain fracture and crosslinking.Heat stabilizer commonly used in the art is suitable for the present invention, it is preferred that the heat stabilizer is stablized for tin
Agent.The tin stabilizer contains 1 or 2 carbon-tin key, remaining valence link is oxygen or sulphur-tin anion bond saturation tetravalent tin
Object is closed, is the most effective stabilizer of PVC, is the production that organotin oxides or organic tin chloride are reacted with acid appropriate or ester
Object.
Filler is also referred to as filler, incremental agent.Plastic filler is to reduce the institute in the plastic such as cost or improvement performance
The inert substance of addition.The type that filler is added can be selected according to the performance of required plastics, it is preferred that the filler is
One of oxide such as silica, calcium carbonate, talcum powder, mica powder.
The high polymers such as PVC of the present invention usual viscosity with higher after melting, in process, the height of melting is poly-
For object when through runners such as narrow slit, cast gates, polymer melt must will generate friction with processing equipment surface, some frictions are right
The processing of polymer be it is very unfavorable, these frictions reduce fluidity of molten, while serious friction can be such that film surface becomes
Must be coarse, lack gloss or flow liner occurs.It is glued for this reason, it may be necessary to which lubricant is added with improving lubricity, reduction friction, reducing interface
Attached performance.Preferably, the lubricant is stearic acid, butyl stearate, oleamide or ethylene bis stearamide
Preferably, in step c, by the hydrogen-oxygen of the surface treatment of the graphene composite flame-proof synergist of a step and b step
Change magnesium to mix in 80 DEG C.
Preferably, in step c, using double screw extruder melt blending, extrusion molding.
Second technical problem that the present invention solves is to provide a kind of flame-proof polyvinyl chloride penetration pipe that graphene is modified.
The modified flame-proof polyvinyl chloride penetration pipe of graphene of the present invention, by the modified flame-proof polyvinyl chloride of above-mentioned graphene
The preparation method of penetration pipe is prepared.The flame-proof PVC penetration pipe, fire-retardant anti-smoke performance is good, and mechanical property is also preferable.
Compared with prior art, the invention has the following beneficial effects:
The method of the present invention is precipitated by the dispersed graphite alkene in barium sulfate precursor component using reaction, and is heated at 130 DEG C,
Obtain the composite flame-proof synergist of the graphene loaded by barium sulfate, zinc oxide, by the formation of barium sulfate and zinc oxide, from
Son will be graphene-supported during gradually forming precipitating, be not only avoided that between graphene and generated reunion, but also significant increase threading
The flame retardant effect of pipe, while additive amount is lower compared with single fire retardant, reduces costs, while avoiding influencing the anti-of penetration pipe
Bending performance.This method is easy to operate, and cost is relatively low.
The flame-proof PVC penetration pipe prepared by the method for the invention, good flame retardation effect, the mechanical properties such as tensile strength are higher,
It is outstanding flame-proof PVC threading tube material.
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 modified flame-proof polyvinyl chloride penetration pipe of graphene is prepared with the following method:
A, baryta water and graphene aqueous dispersions are mixed, under agitation, excessive zinc sulfate is then added
Aqueous solution continues to be stirred to react 60min, is separated by solid-liquid separation, heats 30min under the conditions of 130 DEG C, makes to form barium sulfate drying, and
So that zinc hydroxide precipitation is converted into zinc oxide, obtains graphene composite flame-proof synergist by loading graphene；Wherein, hydroxide
The concentration of barium aqueous solution is 5wt%, and in graphene aqueous dispersions, the weight percent of graphene is 7%, zinc sulfate solution it is dense
Degree is 5wt%；The volume ratio of baryta water and graphene aqueous dispersions is 1:1.
B, silane coupling agent is added to the water, constant temperature stirs at 60 DEG C, magnesium hydroxide is added after mixing, by stirring rate
Control stirs 120min, then dries, be ground into fine powder in 500rpm, the magnesium hydroxide being surface-treated；The silane is even
Connection agent is vinyltriethoxysilane.Silane coupling agent, water, magnesium hydroxide mass ratio be 1:5:30.
C, the graphene composite flame-proof synergist of a step is mixed with the magnesium hydroxide of the surface treatment of b step in 60 DEG C,
Again with PVC, heat stabilizer, filler and mix lubricant, using double screw extruder melt blending, extrusion molding, cooling and shaping,
Obtain the modified flame-proof polyvinyl chloride penetration pipe of graphene, wherein by weight, 10 parts of graphene composite flame-proof synergist,
8 parts of 10 parts of 5 parts of 60 parts of 5 parts of magnesium hydroxide, PVC, heat stabilizer, filler, the lubricant of surface treatment；The heat stabilizer is
Tin stabilizer；The filler is that material is silica；The lubricant is stearic acid.
Embodiment 2
The modified flame-proof polyvinyl chloride penetration pipe of graphene is prepared with the following method:
A, baryta water and graphene aqueous dispersions are mixed, under agitation, excessive zinc sulfate is then added
Aqueous solution continues to be stirred to react 200min, is separated by solid-liquid separation, heats 30min under the conditions of 130 DEG C, makes to form barium sulfate drying, and
So that zinc hydroxide precipitation is converted into zinc oxide, obtains graphene composite flame-proof synergist by loading graphene；Wherein, hydroxide
The concentration of barium aqueous solution is 10wt%, and in graphene aqueous dispersions, the weight percent of graphene is 15%, zinc sulfate solution
Concentration is 10wt%；The volume ratio of baryta water and graphene aqueous dispersions is 3:1.
B, silane coupling agent is added to the water, constant temperature stirs at 90 DEG C, magnesium hydroxide is added after mixing, by stirring rate
Control stirs 60min, then dries, be ground into fine powder in 1000rpm, the magnesium hydroxide being surface-treated；The silane is even
Connection agent is vinyltrimethoxysilane.Silane coupling agent, water, magnesium hydroxide mass ratio be 1:5:30.
C, the graphene composite flame-proof synergist of a step is mixed with the magnesium hydroxide of the surface treatment of b step in 90 DEG C,
Again with PVC, heat stabilizer, filler and mix lubricant, using double screw extruder melt blending, extrusion molding, cooling and shaping,
Obtain the modified flame-proof polyvinyl chloride penetration pipe of graphene, wherein by weight, 20 parts of graphene composite flame-proof synergist,
2 parts of 30 parts of 8 parts of 80 parts of 10 parts of magnesium hydroxide, PVC, heat stabilizer, filler, the lubricant of surface treatment；The heat stabilizer is
Tin stabilizer；The filler is that material is calcium carbonate；The lubricant is butyl stearate.
Embodiment 3
The modified flame-proof polyvinyl chloride penetration pipe of graphene is prepared with the following method:
A, baryta water and graphene aqueous dispersions are mixed, under agitation, excessive zinc sulfate is then added
Aqueous solution continues to be stirred to react 100min, is separated by solid-liquid separation, heats 30min under the conditions of 130 DEG C, makes to form barium sulfate drying, and
So that zinc hydroxide precipitation is converted into zinc oxide, obtains graphene composite flame-proof synergist by loading graphene；Wherein, hydroxide
The concentration of barium aqueous solution is 6wt%, and in graphene aqueous dispersions, the weight percent of graphene is 8%, zinc sulfate solution it is dense
Degree is 6wt%；The volume ratio of baryta water and graphene aqueous dispersions is 2:1.
B, silane coupling agent is added to the water, constant temperature stirs at 70 DEG C, magnesium hydroxide is added after mixing, by stirring rate
Control stirs 80min, then dries, be ground into fine powder in 600rpm, the magnesium hydroxide being surface-treated；The silane is even
Connection agent is vinyl three (beta-methoxy ethyoxyl) silane.Silane coupling agent, water, magnesium hydroxide mass ratio be 1:5:30.
C, the graphene composite flame-proof synergist of a step is mixed with the magnesium hydroxide of the surface treatment of b step in 70 DEG C,
Again with PVC, heat stabilizer, filler and mix lubricant, using double screw extruder melt blending, extrusion molding, cooling and shaping,
Obtain the modified flame-proof polyvinyl chloride penetration pipe of graphene, wherein by weight, 12 parts of graphene composite flame-proof synergist,
3 parts of 15 parts of 6 parts of 65 parts of 6 parts of magnesium hydroxide, PVC, heat stabilizer, filler, the lubricant of surface treatment；The heat stabilizer is
Tin stabilizer；The filler is that material is talcum powder；The lubricant is ethylene bis stearamide.
Embodiment 4
The modified flame-proof polyvinyl chloride penetration pipe of graphene is prepared with the following method:
A, baryta water and graphene aqueous dispersions are mixed, under agitation, excessive zinc sulfate is then added
Aqueous solution continues to be stirred to react 180min, is separated by solid-liquid separation, heats 30min under the conditions of 130 DEG C, makes to form barium sulfate drying, and
So that zinc hydroxide precipitation is converted into zinc oxide, obtains graphene composite flame-proof synergist by loading graphene；Wherein, hydroxide
The concentration of barium aqueous solution is 9wt%, and in graphene aqueous dispersions, the weight percent of graphene is 13%, zinc sulfate solution
Concentration is 9wt%；The volume ratio of baryta water and graphene aqueous dispersions is 2:1.
B, silane coupling agent is added to the water, constant temperature stirs at 85 DEG C, magnesium hydroxide is added after mixing, by stirring rate
Control stirs 110min, then dries, be ground into fine powder in 900rpm, the magnesium hydroxide being surface-treated；The silane is even
Connection agent is vinyltriethoxysilane.Silane coupling agent, water, magnesium hydroxide mass ratio be 1:5:30.
C, the graphene composite flame-proof synergist of a step is mixed with the magnesium hydroxide of the surface treatment of b step in 85 DEG C,
Again with PVC, heat stabilizer, filler and mix lubricant, using double screw extruder melt blending, extrusion molding, cooling and shaping,
Obtain the modified flame-proof polyvinyl chloride penetration pipe of graphene, wherein by weight, 18 parts of graphene composite flame-proof synergist,
7 parts of 22 parts of 7 parts of 75 parts of 6 parts of magnesium hydroxide, PVC, heat stabilizer, filler, the lubricant of surface treatment；The heat stabilizer is
Tin stabilizer；The filler is that material is calcium carbonate；The lubricant is oleamide.
Embodiment 5
The modified flame-proof polyvinyl chloride penetration pipe of graphene is prepared with the following method:
A, baryta water and graphene aqueous dispersions are mixed, under agitation, excessive zinc sulfate is then added
Aqueous solution continues to be stirred to react 150min, is separated by solid-liquid separation, heats 30min under the conditions of 130 DEG C, makes to form barium sulfate drying, and
So that zinc hydroxide precipitation is converted into zinc oxide, obtains graphene composite flame-proof synergist by loading graphene；Wherein, hydroxide
The concentration of barium aqueous solution is 7wt%, and in graphene aqueous dispersions, the weight percent of graphene is 11%, zinc sulfate solution
Concentration is 9wt%；The volume ratio of baryta water and graphene aqueous dispersions is 2:1.
B, silane coupling agent is added to the water, constant temperature stirs at 85 DEG C, magnesium hydroxide is added after mixing, by stirring rate
Control stirs 100min, then dries, be ground into fine powder in 800rpm, the magnesium hydroxide being surface-treated；The silane is even
Connection agent is vinyltriethoxysilane.Silane coupling agent, water, magnesium hydroxide mass ratio be 1:5:30.
C, the graphene composite flame-proof synergist of a step is mixed with the magnesium hydroxide of the surface treatment of b step in 80 DEG C,
Again with PVC, heat stabilizer, filler and mix lubricant, using double screw extruder melt blending, extrusion molding, cooling and shaping,
Obtain the modified flame-proof polyvinyl chloride penetration pipe of graphene, wherein by weight, 15 parts of graphene composite flame-proof synergist,
4 parts of 18 parts of 6 parts of 80 parts of 5 parts of magnesium hydroxide, PVC, heat stabilizer, filler, the lubricant of surface treatment；The heat stabilizer is
Tin stabilizer；The filler is that material is dolomite；The lubricant is stearic acid.
Embodiment 6
The modified flame-proof polyvinyl chloride penetration pipe of graphene is prepared with the following method:
A, baryta water and graphene aqueous dispersions are mixed, under agitation, excessive zinc sulfate is then added
Aqueous solution continues to be stirred to react 120min, is separated by solid-liquid separation, heats 30min under the conditions of 130 DEG C, makes to form barium sulfate drying, and
So that zinc hydroxide precipitation is converted into zinc oxide, obtains graphene composite flame-proof synergist by loading graphene；Wherein, hydroxide
The concentration of barium aqueous solution is 7wt%, and in graphene aqueous dispersions, the weight percent of graphene is 12%, zinc sulfate solution
Concentration is 8wt%；The volume ratio of baryta water and graphene aqueous dispersions is 2:1.
B, silane coupling agent is added to the water, constant temperature stirs at 80 DEG C, magnesium hydroxide is added after mixing, by stirring rate
Control stirs 100min, then dries, be ground into fine powder in 800rpm, the magnesium hydroxide being surface-treated；The silane is even
Connection agent is vinyltriethoxysilane.Silane coupling agent, water, magnesium hydroxide mass ratio be 1:5:30.
C, by the magnesium hydroxide of the surface treatment of the graphene composite flame-proof synergist of a step and b step in 60~90 DEG C
Mixing, then with PVC, heat stabilizer, filler and mix lubricant, using double screw extruder melt blending, extrusion molding, cooling
Sizing obtains the modified flame-proof polyvinyl chloride penetration pipe of graphene, wherein by weight, graphene composite flame-proof synergist
18 parts, 7 parts of the magnesium hydroxide of surface treatment, 70 parts of PVC, 6 parts of heat stabilizer, 15 parts of filler, 4 parts of lubricant；The thermostabilization
Agent is tin stabilizer；The filler is that material is silica；The lubricant is stearic acid.
Comparative example 1
The modified flame-proof polyvinyl chloride penetration pipe of graphene is prepared with the following method:
A, silane coupling agent is added to the water, constant temperature stirs at 60~90 DEG C, magnesium hydroxide is added after mixing, by stirring rate
Control stirs 100min, then dries, be ground into fine powder in 800rpm, the magnesium hydroxide being surface-treated；The silane is even
Connection agent is vinyltriethoxysilane.Silane coupling agent, water, magnesium hydroxide mass ratio be 1:5:30.
B, graphene is mixed with the magnesium hydroxide of the surface treatment of a step in 80 DEG C, then with PVC, heat stabilizer, filler
And mix lubricant obtains the fire-retardant of graphene modification using double screw extruder melt blending, extrusion molding, cooling and shaping
Polyvinyl chloride penetration pipe, wherein by weight, 18 parts of graphene composite flame-proof synergist, the magnesium hydroxide 7 being surface-treated
Part, 70 parts of PVC, 6 parts of heat stabilizer, 15 parts of filler, 4 parts of lubricant；The heat stabilizer is tin stabilizer；The filler is
Material is silica；The lubricant is stearic acid.
Detect the flame retardant property and mechanical property of Examples 1 to 6 and the resulting flame-proof PVC penetration pipe of comparative example 1, system
The standby tubing with a thickness of 3mm at same specification, the result is shown in tables 1.Wherein, fire-retardant rank test is referring to UL94 standard, smoke density
Test is referring to GB/T 8323.2-2008.
Table 1
Claims (10)
1. a kind of preparation method of the modified flame-proof polyvinyl chloride penetration pipe of graphene, which comprises the steps of:
A, baryta water and graphene aqueous dispersions are mixed, under agitation, excessive zinc sulfate is then added
Aqueous solution continues to be stirred to react 60~200min, is separated by solid-liquid separation, and 130 DEG C of heating 30min obtain graphene composite flame-proof synergistic
Agent；Wherein, the concentration of baryta water is 5~10wt%, and in graphene aqueous dispersions, the weight percent of graphene is 7
~15%, the concentration of zinc sulfate solution is 5~10wt%；The volume ratio of baryta water and graphene aqueous dispersions is 1
~3:1；
B, silane coupling agent is added to the water, constant temperature stirs at 60~90 DEG C, magnesium hydroxide is added after mixing, by stirring rate
Control stirs 60~120min, then dries, be ground into fine powder in 500~1000rpm, the magnesium hydroxide being surface-treated；
Silane coupling agent, water, magnesium hydroxide mass ratio be 1:5:30；
C, the graphene composite flame-proof synergist of a step is mixed with the magnesium hydroxide of the surface treatment of b step in 60~90 DEG C,
Again with PVC, heat stabilizer, filler and mix lubricant, melt blending, extrusion molding, cooling and shaping obtain what graphene was modified
Flame-proof polyvinyl chloride penetration pipe, wherein by weight, 10~20 parts of graphene composite flame-proof synergist, the hydrogen being surface-treated
5~10 parts of magnesia, 60~80 parts of PVC, 5~8 parts of heat stabilizer, 10~30 parts of filler, 2~8 parts of lubricant.
2. the preparation method of the modified flame-proof polyvinyl chloride penetration pipe of graphene according to claim 1, it is characterised in that:
In a step, the concentration of the baryta water is 7wt%, and in graphene aqueous dispersions, the weight percent of graphene is
12%, the concentration of zinc sulfate solution is 8wt%.
3. the preparation method of the modified flame-proof polyvinyl chloride penetration pipe of graphene according to claim 1, it is characterised in that:
In a step, the volume ratio of baryta water and graphene aqueous dispersions is 2:1.
4. the preparation method of the modified flame-proof polyvinyl chloride penetration pipe of graphene according to claim 1, it is characterised in that:
In a step, it is stirred to react 120min.
5. the preparation method of the modified flame-proof polyvinyl chloride penetration pipe of graphene according to claim 1, it is characterised in that:
In b step, the silane coupling agent is vinyltriethoxysilane, vinyltrimethoxysilane or the (β-first of vinyl three
Oxygen ethyoxyl) silane.
6. the preparation method of the modified flame-proof polyvinyl chloride penetration pipe of graphene according to claim 1, it is characterised in that:
In b step, stirring rate control stirs 100min in 800rpm.
7. the preparation method of the modified flame-proof polyvinyl chloride penetration pipe of graphene according to claim 1, it is characterised in that:
In step c, in step c, by weight, 18 parts of graphene composite flame-proof synergist, surface treatment 7 parts of magnesium hydroxide,
70 parts of PVC, 6 parts of heat stabilizer, 15 parts of filler, 4 parts of lubricant.
8. the preparation method of the modified flame-proof polyvinyl chloride penetration pipe of graphene according to claim 1, it is characterised in that:
In step c, the heat stabilizer is tin heat stabilizer；The filler is that material is silica, talcum powder, calcium carbonate, mica powder
One of；The lubricant is stearic acid, butyl stearate, oleamide or ethylene bis stearamide.
9. the preparation method of the modified flame-proof polyvinyl chloride penetration pipe of graphene according to claim 1, it is characterised in that:
In step c, using double screw extruder melt blending, extrusion molding.
10. a kind of modified flame-proof polyvinyl chloride penetration pipe of graphene, it is characterised in that: as described in any one of claim 1~9
The preparation method of the modified flame-proof polyvinyl chloride penetration pipe of graphene be prepared.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110845936A (en) * | 2019-11-18 | 2020-02-28 | 成都新柯力化工科技有限公司 | Corrosion-resistant coating for buried plastic pipe and preparation method thereof |
| CN115449165A (en) * | 2022-09-01 | 2022-12-09 | 安徽嘉阳新材料科技有限公司 | Environment-friendly flame-retardant polyvinyl chloride/graphene composite decorative film for rail transit |
-
2018
- 2018-06-29 CN CN201810699094.4A patent/CN108976661A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110845936A (en) * | 2019-11-18 | 2020-02-28 | 成都新柯力化工科技有限公司 | Corrosion-resistant coating for buried plastic pipe and preparation method thereof |
| CN110845936B (en) * | 2019-11-18 | 2021-12-03 | 李燕玲 | Corrosion-resistant coating for buried plastic pipe and preparation method thereof |
| CN115449165A (en) * | 2022-09-01 | 2022-12-09 | 安徽嘉阳新材料科技有限公司 | Environment-friendly flame-retardant polyvinyl chloride/graphene composite decorative film for rail transit |
| CN115449165B (en) * | 2022-09-01 | 2023-07-28 | 安徽嘉阳新材料科技有限公司 | Environment-friendly flame-retardant polyvinyl chloride/graphene composite decorative film for rail transit |
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