CN110028740A - A kind of staged flame retardant plastics and preparation method thereof - Google Patents
A kind of staged flame retardant plastics and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of staged flame retardant plastics and preparation method thereof, it according to parts by weight include following components: 800~1200 parts of plastics, 30~120 parts of inorganic fire-retarded powder, 3~8 parts of zinc borate, 2~5 parts of silicon powder, 1~2 part of antismoke agent, 1~2 part of calcium carbonate, 0.3~1.2 part of macromolecule dispersing agent, 0.3~2 part of auxiliary agent；The preparation method comprising steps of inorganic fire-retarded powder preparation, the modification of fire proofing, the preparation of composite flame-proof material, the preparation of flame retardant plastics.Staged flame retardant plastics provided through the invention and preparation method thereof, obtained plastics can form different inflaming retarding shells at different temperatures, to have multistage flame retardant effect, form stepped fire-resisting protection to plastic basis material.
Description
Technical field
The present invention relates to macromolecule polymer material technical field, in particular to a kind of staged flame retardant plastics and its preparation
Method.
Background technique
With the fast development of high molecular material, electronics, electric appliance, machinery, automobile, ship, aerospace and chemical industry,
Plastic products are applied to the every field in people's lives and production more and more widely, while caused by the combustibility of plastics
Fire also brings huge Loss of Life and property.In the prior art, plastics are usually improved by addition fire retardant
Flame retardant property.Fire retardant is also known as incombustible agent, fire-proofing chemical or fireproof agent, is to confer to the functional material of combustible polymers flame retardancy
Material, the plastic products after fire retardant is processed effectively can prevent or terminate flame when being attacked by extraneous fire source
Propagation, to reach flame retardant effect.The use of fire retardant plays huge protective effect to the life and property safety of the mankind,
Therefore the development, production and popularization of fire-retardant for plastic and fire proofing are developed rapidly.
Existing fire retardant mainly includes two major classes, halogenated flame retardant and non-halogenated flame retardant, and wherein halogenated flame retardant is main
There are chlorinated paraffin, tetrabromobisphenol A, deca-BDE, is influenced due to the good flame retardation effect of halogenated flame retardant, on the performance of material
It is small, cost performance is high and is used widely, account for leading market status.But halogenated flame retardant due to deposit in environmental protection lack
It falls into, corrosive gas, noxious material and a large amount of harmful vapors can be discharged during fire-retardant, the developed countries such as America and Europe release one after another method
It advises to constrain the use of the based flame retardant, the dosage of halogenated flame retardant is gradually decreasing at present.Non- halogenated flame retardant mainly wraps
Include organic phosphorus flame retardant, inorganic fire retardants etc..Wherein organic phosphorus flame retardant on the physical mechanical property of polymer influence compared with
Small and polymer has preferable compatibility, becomes the fire retardant in recent years by favor.But organic phosphates fire retardant is mostly liquid
Body has high volatility, and smoke amount is big, the disadvantage of heat stability difference.Inorganic fire retardants include aluminium hydroxide, magnesium hydroxide,
Red phosphorus, zinc borate, antimony oxide etc., have that stability is good, non-volatile, raw material sources are abundant and the advantages such as environmentally friendly, still
It is big that inorganic fire retardants usually requires loading, and high molecular material poor compatibility, cause resin to be kneaded, molding when poor fluidity,
The processing of synthetic material and mechanical performance decline, so that its application is limited to.
But either halogenated flame retardant is also non-halogenated flame retardant, all only has the effect of that level-one is fire-retardant, works as modeling at present
When material temperature degree constantly increases, flame retardant property can fail with the raising of temperature.As it can be seen that the prior art could be improved and mention
It is high.
Summary of the invention
Place in view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of staged flame retardant plastics and its
Preparation method, it is intended to solve non-halogen system fire proofing dispersibility, poor fluidity in the prior art, multistage flame retardant effect can not be provided
Defect.
In order to achieve the above object, this invention takes following technical schemes:
A kind of staged flame retardant plastics includes following components according to parts by weight:
800~1200 parts of plastics；
30~120 parts of inorganic fire-retarded powder；
3~8 parts of zinc borate；
2~5 parts of silicon powder；
1~2 part of antismoke agent；
1~2 part of calcium carbonate；
0.3~1.2 part of macromolecule dispersing agent；
0.3~2 part of auxiliary agent.
In the staged flame retardant plastics, the plastics are one of PVC, PP, PA, ABS.
In the staged flame retardant plastics, the inorganic fire-retarded powder is prepared by inorganic silicon-aluminum shell-forming material, the nothing
Machine sial shell-forming material includes: according to parts by weight
SiO240~55 parts；
H3BO320~40 parts；
CaCO35~10 parts；
K2CO33~10 parts；
Al2O31~8 part；
NaNO31~5 part；
Na21~5 part of O；
Na2SO40.1~0.5 part；
La2O30.05~0.2 part；
ZrO2 0.05~0.1 part.
In the staged flame retardant plastics, the partial size of the silicon powder is 0.1~0.3 μm, and the silicon that partial size is 0.1 μm is micro-
Powder is no less than 80%.
In the staged flame retardant plastics, the antismoke agent includes Al (OH)3, Mg(OH)2One or both of.
In the staged flame retardant plastics, the macromolecule dispersing agent is epoxy resin modified material, including liquid end
In carboxylic acrylonitrile butadiene rubber modified epoxy resin, liquid hydroxy'terminated butadiene nitrile rubber modified epoxy and modifying epoxy resin by organosilicon
One kind.
In the staged flame retardant plastics, the auxiliary agent includes one of lubricant, plasticizer, heat stabilizer or several
Kind.
In the staged flame retardant plastics, the lubricant includes ethylene bis stearic acid amide, pentaerythritol stearate
One of.
A kind of preparation method of staged flame retardant plastics as described above, which comprises
The preparation of the inorganic fire-retarded powder of step S1.: weighing according to the ratio in inorganic silicon-aluminum shell-forming material in the high temperature converter of each component investment,
It is quenched after high-temperature fusion, obtains broken shape coloured glaze block, inorganic fire-retarded powder is obtained after then grinding coloured glaze block；
The modification of step S2. fire proofing: by inorganic fire-retarded powder, silicon powder and macromolecule dispersing agent obtained in step S1 by matching
Than feeding, inorganic fire-retarded powder and silicon powder is first added in super grinder, macromolecule dispersing agent then is added in grinding, grinds
Fire proofing to 1250~2000 mesh, after must modifying；
The preparation of step S3. composite flame-proof material: fire proofing, zinc borate and the antismoke agent after modifying in step S2 are taken according to the ratio
In blender, it is uniformly mixed to obtain composite flame-proof material；
The preparation of step S4. flame retardant plastics: plastics, composite flame-proof material, lubrication are taken by automatic blend ingredients system according to the ratio
Agent and other auxiliary agents are added batch mixer and mix, then feed the mixture into extruder plastication, then be granulated through pelletizer, obtain ladder
Formula flame retardant plastics particle.
In the preparation method of the staged flame retardant plastics, the step S1 is specifically included: weighing inorganic silicon-aluminum according to the ratio
Each component in shell-forming material, stirs and evenly mixs, then quickly investment in 1100~1200 DEG C of high temperature converter, be warming up to 1200~
1350 DEG C of 1~2h of sintered molten keep the temperature 30~60min, and liquid melts are put into freezing pure water and are quenched, and form broken shape coloured glaze
Block obtains inorganic fire-retarded powder after then grinding coloured glaze block.
The utility model has the advantages that
The present invention provides a kind of staged flame retardant plastics and preparation method thereof, the plastics pass through addition composite flame-proof material,
Gradual firm fire-resisting protection shell can be being formed under different temperatures and different calcination times, to have multistage fire-retardant
Effect carries out stepped fire-resisting protection to plastic basis material.Compared with prior art, it has the advantages that
(1) zinc borate added is low-melting compound, can form glassy state inorganic expansive coating at low temperature and be covered in polymerization
On object, to block burning, promote polymer at charcoal, the glassy state coating of covering can hinder the evolution of volatile fuel, because
And have the effect of pressing down cigarette, simultaneously as the dehydration of zinc borate, to have the effect of heat absorption, foam and rush dilute combustible；
(2) the inorganic fire-retarded powder added can be effectively isolated in 600 DEG C~800 DEG C formation glassy state shells, glassy state shell
Air makes plastics still have flame-retarding characteristic under the conditions of high temperature, and does not prolong combustion, drippage, to have double fire-retardant effect
Fruit；
(3) calcium carbonate, the silicon powder added has filling effect, and under the high temperature conditions, calcium carbonate can resolve into calcium oxide
And carbon dioxide, calcium oxide and silicon powder can act synergistically with inorganic fire-retarded powder, play fire retardation to charing post-consumer polymer, together
When, the carbon dioxide of generation has the function of fire extinguishing；
(4) macromolecule dispersing agent can be modified inorganic fire-retarded powder and silicon powder, improve inorganic fire-retarded powder and silicon powder
With the compatibility of plastic basis material, inorganic fire-retarded powder and silicon powder is enable to be uniformly dispersed in substrate, had preferably fire-retardant
Effect, meanwhile, macromolecule dispersing agent can make inorganic fire-retarded powder and silicon powder combine closely with plastics, to promote the mechanics of product
Intensity.
Specific embodiment
The present invention provides a kind of staged flame retardant plastics and preparation method thereof, for make the purpose of the present invention, technical solution and
Effect is clearer, clear, and the present invention is described in more detail by the following examples.It should be appreciated that tool described herein
Body embodiment only to explain the present invention, is not intended to limit the present invention.
The present invention provides a kind of staged flame retardant plastics, according to parts by weight includes following components:
800~1200 parts of plastics；
30~120 parts of inorganic fire-retarded powder；
3~8 parts of zinc borate；
2~5 parts of silicon powder；
1~2 part of antismoke agent；
1~2 part of calcium carbonate；
0.3~1.2 part of macromolecule dispersing agent；
0.3~2 part of auxiliary agent.
The staged flame retardant plastics of said ratio is using plastics as substrate, and the plastic basis material includes PVC, PP, PA, ABS
One of, by adding inorganic fire-retarded powder, silicon powder, zinc borate, calcium carbonate, difference can be in 300~470 DEG C, 600~800
DEG C, 955~1100 DEG C form different vitreous shells, the vitreous shell can effectively block burning, and prevent plastics prolongs combustion and drippage,
With staged flame retardant effect.During concrete application, when the staged flame retardant plastics of various substrates is for wire and cable, decoration
When profile plate, furniture section steel plate or advertisement plate, staged flame retardant property can effectively block burning, prevent the powder of material
Change, avoid prolonging combustion drippage, to effectively prevent the sprawling of the intensity of a fire, greatly races against time for escape and fire-fighting rescue.
In said ratio, the zinc borate is minimum platelet, and activity is high, belongs to inorganic based flame retardant, in combustion process
In, when temperature reaches 300 DEG C, zinc borate thermal decomposition releases the crystallization water, plays in heat absorption cooling effect and diluent air
The effect of oxygen.On the other hand, zinc borate decomposes and generates B at high temperature2O3, it is attached to one layer of formation on the surface of polymer and covers
Cap rock, this coating can inhibit imflammable gas generation, and oxidation reaction and thermal decomposition can also be prevented to act on, promote charing.Specifically
Ground, when plastic basis material is PVC, the Cl that zinc borate can also be discharged with PVC generates BCl3, BCl3It acts on and generating with the water in gas phase
HCl has the generation of halogen atom free radical in flame, which can prevent the chain reaction of hydroxyl free radical, to play resistance
Combustion effect.
In said ratio, the inorganic fire-retarded powder can form very thin vitreous shell in polymer surfaces at 600~800 DEG C,
The vitreous shell and zinc borate gather on the surface of polymer, play blanketing effect, and then have flame retardant effect.Inorganic fire-retarded powder
Shelling it is related with glass transition temperature, when inorganic fire-retarded powder component proportion change, glass transition temperature also changes, minimum
Shelling temperature can be down to 600 DEG C, therefore can form continuous protection to polymer in high temperature.
In said ratio, the calcium carbonate and silicon powder have higher melt and hardness, and thermal expansion coefficient is smaller, thermostabilization
Property it is higher, can not only be used for filler to increase the intensity of polymer, and there is preferable flame retardant effect.Calcium carbonate is being higher than 800
DEG C when be easily decomposed into carbon dioxide and calcium oxide, the carbon dioxide of generation has fire extinguishing effect.In specific combustion process, work as temperature
Higher than 800 DEG C, the inorganic fire-retarded powder viscosity of inorganic fire-retarded powder fusing, melting is big, is attached on the charing skeleton of polymer formation,
To form the skeleton with adhesion characteristics, while Decomposition of Calcium Carbonate, the calcium oxide of formation are adhered to charcoal bone together with silicon powder
Frame, the shell for continuing to be formed similar vitreous shell in polymer surfaces play fire-retardant effectiveness in high temperature section to completely cut off air.
Preferably, the partial size of the silicon powder is 0.1~0.3 μm, and the silicon powder that partial size is 0.1 μm is no less than 80%.Institute
Stating silicon powder is both a kind of filler, is capable of the hardness of reinforced plastics, and can adhere to after melting inorganic under the high temperature conditions
Fireproof powder surface forms similar glassy shell, the fire-retardant effect of starvation is played, to further protect plastics base
Material and its product.The partial size of silicon powder is related to its dispersibility in the plastic, therefore more thinner better, in the present invention, described
The particle size range of silicon powder is 0.1~0.3 μm, and the silicon powder that partial size is 0.1 μm is no less than 80%, such silicon powder tool
There is biggish specific surface area, there is preferable dispersion effect, can preferably be combined with the inorganic fire-retarded powder after melting.
Specifically, the macromolecule dispersing agent is epoxy resin modified material, including liquid nbr carboxyl terminal changes
One of property epoxy resin, liquid hydroxy'terminated butadiene nitrile rubber modified epoxy and modifying epoxy resin by organosilicon.Asphalt mixtures modified by epoxy resin
Lipid modified material is coated on the surface of inorganic fire-retarded powder and silicon powder, can improve the dispersibility of frit and silicon powder in the plastic
And compatibility, while the interface binding power between inorganic fire-retarded powder and silicon powder and plastics is promoted, preparation process is reduced to equipment
Loss, it is most important that, inorganic fire-retarded powder and silicon powder can be made evenly dispersed in the plastic, improve flame retardant of plastic uniformity.
Specifically, the antismoke agent includes Al (OH)3, Mg(OH)2One or both of.Al(OH)3, Mg(OH)2Itself
Fire retardant is also belonged to, while also there is preferable suppression cigarette, smoke elimination performance, adds Al (OH) in plastics3, Mg(OH)2, burned
Cheng Zhongneng obviously inhibit the generation of smog, especially substrate be PVC when.
Specifically, the auxiliary agent includes one or more of lubricant, plasticizer, heat stabilizer.The various of addition help
Agent can improve the processing performance of plastic basis material, enhance its plasticity or thermal stability.Specifically, the lubricant includes that ethylene is double hard
One of resin acid amide, pentaerythritol stearate, the plasticizer include phthalate, stearic acid esters etc.；
The heat stabilizer includes low lead or compound low lead stabilizer, such as one of zinc stearate, calcium stearate or lead stearate or
It is several.
The lubricant ethylene bis stearic acid amide, pentaerythritol stearate can improve the processing performance of plastics, wherein
Ethylene bis stearic acid amide is to lubricate regulator in the later period, and can disperse pigment, has preferable lubricant effect；Pentaerythrite is hard
Resin acid ester belongs to high-temperature lubricant, has good thermal stability and low volatility at high operating temperatures, has preferably lubrication effect
Fruit, and the stabilizer of plastics can be made.Above two lubricant can be added individually, can also compound addition, but be not limited to above-mentioned two
Kind of lubricant, can be replaced according to actual needs or additive amount on change in the specific implementation process can be according to plastics
Component proportion and material property add the lubricant to application to obtain more excellent lubricant effect.
In above-mentioned plastics proportion, the inorganic fire-retarded powder is prepared by inorganic silicon-aluminum shell-forming material, the inorganic silicon-aluminum
Shell-forming material includes following components according to parts by weight:
SiO240~55 parts；
H3BO320~40 parts；
CaCO35~10 parts；
K2CO33~10 parts；
Al2O31~8 part；
NaNO31~5 part；
Na21~5 part of O；
Na2SO40.1~0.5 part；
La2O30.05~0.2 part；
ZrO2 0.05~0.1 part.
It is inorganic can to obtain broken shape by being rapidly fired to and quenching process for the inorganic silicon-aluminum shell-forming material of said ratio
Fireproof powder, the inorganic fire-retarded powder can form glass shell at 600~800 DEG C, so that plastics be made to have flame retardant property.Specifically
In use process, when temperature reaches 300~400 DEG C, surface coated macromolecule dispersing agent is destroyed inorganic fire-retarded powder, inorganic
Fireproof powder progresses into molten condition, bonds to form preliminary shell with polymer charcoal skeleton, protection at charcoal substance will not dusting fall
It falls, when temperature rises to 600~800 DEG C, inorganic fire-retarded powder forms glass shell on polymer charcoal skeleton surface, to completely cut off sky
Gas plays flame retardant effect.
In the inorganic silicon-aluminum shell-forming material of said ratio, SiO2、CaCO3、Al2O3Content it is higher, then inorganic fire-retarded powder
Glass transition temperature is higher, so that it is higher in the temperature that frosting forms vitreous shell, and Na2O、K2CO3、NaNO3's
Content is higher, then glass transition temperature is lower, can form glass shell in plastics at a lower temperature, have lower resistance
Temperature is fired, but cost correspondinglys increase.When inorganic silicon-aluminum shell-forming material is said ratio range, glass transition temperature can be obtained
The inorganic fire-retarded powder that degree is 600~800 DEG C.
A kind of preparation method of staged flame retardant plastics, which comprises
The preparation of the inorganic fire-retarded powder of step S1.: each component in inorganic silicon-aluminum shell-forming material is weighed according to the ratio, is stirred and evenly mixed, then
Quickly investment is in 1100~1200 DEG C of high temperature converter, being warming up to 1200~1350 DEG C of 1~2h of sintered molten, and heat preservation 30~
Liquid melts are put into freezing pure water and are quenched by 60min, form the broken inorganic fire-retarded powder of shape.In order to guarantee quality, preparing
It should be noted in journey: (1) in melting process, need to guarantee that each material needs to dry without dampness and caking phenomenon if any dampness and agglomeration
It can use；(2) before feeding intake, it need to ensure that furnace temperature has reached 1100~1200 DEG C；(3) it needs to be rapidly heated after feeding intake；(4) it keeps the temperature
After need to be quenched, cooling bay keep cold water supplement flow into, inorganic fire-retarded powder need to be allowed to blow broken.
The modification of step S2. fire proofing: by inorganic fire-retarded powder, silicon powder and macromolecule dispersing agent obtained in step S1
Feeding according to the ratio is first added inorganic fire-retarded powder and silicon powder in super grinder, macromolecule dispersing agent then is added in grinding,
1250~2000 mesh are ground to, fire proofing is obtained.The preparation of fire-retardant powder is ground using super grinder, it is desirable that partial size reaches
1250~2000 mesh, fire-retardant powder is thinner, then dispersibility in the substrate is better.Meanwhile to inorganic resistance during powder processed
Combustion powder and silicon powder are modified, by side edging addition macromolecule dispersing agent during ball milling, so that macromolecule disperses
Agent can be coated on the surface of fire proofing, so as to make fire proofing and plastics have preferable compatibility.
The preparation of step S3. composite flame-proof material: fire proofing, calcium carbonate, boron after modifying in step S2 are taken according to the ratio
Sour zinc and antismoke agent are uniformly mixed to obtain composite flame-proof material in blender.
The preparation of step S4. flame retardant plastics: by automatic blend ingredients system take according to the ratio plastics, composite flame-proof material,
Lubricant, auxiliary agent are added batch mixer and mix, then feed the mixture into extruder plastication, then be granulated through pelletizer, obtain staged
Flame retardant plastics particle.
Above-mentioned preparation method can obtain the plastics with staged flame retardant effect, and the preparation method passes through Flashmelt
Be made the inorganic fire-retarded powder with multistage shelling with the mode of quenching, the inorganic fire-retarded powder with other fire proofings are compound makes
With, there can be a multistage flame retardant effect, and by macromolecule dispersing agent, by composite flame-proof material coating decoration, so as to
It is uniformly dispersed in plastics, makes plastics that there is uniform shelling effect, have better flame resistance.
Embodiment 1
A kind of staged flame retardant plastics, the plastic basis material are PVC, according to parts by weight include following components:
800 parts of PVC；
30 parts of inorganic fire-retarded powder；
3 parts of zinc borate；
2 parts of silicon powder；
Al(OH)31 part；
1 part of calcium carbonate；
0.3 part of macromolecule dispersing agent；
0.3 part of auxiliary agent.
Wherein, the partial size of the silicon powder is 0.1~0.3mm, and the silicon powder that partial size is 0.1 μm is no less than 80%.It is described
Macromolecule dispersing agent is liquid nbr carboxyl terminal modified epoxy.The auxiliary agent is lubricant, and the lubricant is second
Support double stearic amides.The inorganic fire-retarded powder is prepared by inorganic silicon-aluminum shell-forming material, and the inorganic silicon-aluminum shell-forming material is by weight
Measuring number meter includes following components:
SiO240 parts；
H3BO320 parts；
CaCO35 parts；
K2CO33 parts；
Al2O31 part；
NaNO31 part；
Na21 part of O；
Na2SO40.1 part；
La2O30.05 part；
ZrO2 0.05 part.
A kind of preparation method of staged flame retardant plastics, is prepared using above-mentioned material, which comprises
The preparation of the inorganic fire-retarded powder of step S1.: each component in inorganic silicon-aluminum shell-forming material is weighed according to the ratio, is stirred and evenly mixed, then
Quickly in investment to 1100 DEG C of high temperature converter, 1350 DEG C of sintered molten 1h are warming up to, 60min is kept the temperature, liquid melts is put into
It is quenched in freezing pure water, forms broken shape coloured glaze block, inorganic fire-retarded powder is obtained after then grinding coloured glaze block；
The modification of step S2. fire proofing: by inorganic fire-retarded powder, silicon powder and macromolecule dispersing agent obtained in step S1 by matching
Than feeding, inorganic fire-retarded powder and silicon powder is first added in super grinder, macromolecule dispersing agent is added in grinding, is ground to
1250~2000 mesh, the fire proofing after must modifying；
The preparation of step S3 composite flame-proof material: taking fire proofing, zinc borate and the antismoke agent after modifying in step S2 according to the ratio,
It is uniformly mixed to obtain composite flame-proof material；
The preparation of step S4. flame retardant plastics: PVC, composite flame-proof material, lubricant are taken by automatic blend ingredients system according to the ratio
And other auxiliary agents, batch mixer is added and mixes, then feeds the mixture into extruder plastication, then be granulated through pelletizer, obtains staged
Flame-proof PVC material particles.
Staged flame-proof PVC plastics prepared by the present invention, can at a temperature of 300 DEG C, 800 DEG C and 1100 DEG C shelling, tool
There is staged flame retardant effect, specific performance parameter is shown in Table 1.
Embodiment 2
A kind of staged flame retardant plastics, the plastic basis material are PVC, according to parts by weight include following components:
1200 parts of PVC；
120 parts of inorganic fire-retarded powder；
8 parts of zinc borate；
5 parts of silicon powder；
Mg(OH)22 parts；
2 parts of calcium carbonate；
1.2 parts of macromolecule dispersing agent；
2 parts of auxiliary agent.
Wherein, the partial size of the silicon powder is 0.1~0.3 μm, and the silicon powder that partial size is 0.1 μm is no less than 80%.It is described
Macromolecule dispersing agent is liquid hydroxy'terminated butadiene nitrile rubber modified epoxy, and the auxiliary agent includes lubricant and heat stabilizer, institute
State the pentaerythritol stearate that lubricant is 1 part, the compound low lead heat stabilizer that the heat stabilizer is 1 part.It is described inorganic
Fireproof powder is prepared by inorganic silicon-aluminum shell-forming material, and the inorganic silicon-aluminum shell-forming material includes: according to parts by weight
SiO255 parts；
H3BO340 parts；
CaCO310 parts；
K2CO310 parts；
Al2O38 parts；
NaNO35 parts；
Na25 parts of O；
Na2SO40.5 part；
La2O30.2 part；
ZrO2 0.1 part.
The step of preparation method of the staged flame-proof PVC material of the present embodiment is with embodiment 1 is identical, only in parameter
Changing, specific steps are not described in detail here referring to embodiment 1, difference technology is only listed below:
The preparation of the inorganic fire-retarded powder of step S1.: each component in inorganic silicon-aluminum shell-forming material is weighed according to the ratio, is stirred and evenly mixed, then
Quickly in investment to 1200 DEG C of high temperature converter, 1200 DEG C of sintered molten 2h are warming up to, 60min is kept the temperature, liquid melts is put into
It is quenched in freezing pure water, forms the broken inorganic fire-retarded powder of shape.
Staged flame-proof PVC plastics prepared by the present invention, can at a temperature of 300 DEG C, 600 DEG C and 955 DEG C shelling, have
Staged flame retardant effect, specific performance parameter are shown in Table 1.
Embodiment 3
A kind of preferably staged flame retardant plastics, the plastic basis material are polyvinyl chloride resin, according to parts by weight include following components:
1000 parts of PVC；
100 parts of inorganic fire-retarded powder；
5 parts of zinc borate；
3 parts of silicon powder；
1.57 parts of antismoke agent；
0.5 part of macromolecule dispersing agent；
1.5 parts of calcium carbonate；
0.5 part of auxiliary agent.
Wherein, the partial size of the silicon powder is 0.1~0.3 μm, and the silicon powder that partial size is 0.1 μm is no less than 80%.It is described
The Al (OH) that antismoke agent is 0.57 part3With 1.0 parts of Mg(OH)2, the macromolecule dispersing agent is modifying epoxy resin by organosilicon.
The auxiliary agent includes 0.3 part of lubricant, 0.1 part of plasticizer and 0.1 part of heat stabilizer.The lubricant is that ethylene is double hard
Resin acid amide, the plasticizer are phthalate compound, and the heat stabilizer is compound low lead stabilizer.
The inorganic silicon-aluminum shell-forming material includes: according to parts by weight
SiO250 parts；
H3BO330 parts；
CaCO38 parts；
K2CO37 parts；
Al2O36 parts；
NaNO33 parts；
Na23 parts of O；
Na2SO40.3 part；
La2O30.1 part；
ZrO2 0.08 part.
The step of preparation method of the staged flame-proof PVC material of the present embodiment is with embodiment 1 is identical, only in parameter
Changing, specific steps are not described in detail here referring to embodiment 1, difference technology is only listed below:
The preparation of the inorganic fire-retarded powder of step S1.: each component in inorganic silicon-aluminum shell-forming material is weighed according to the ratio, is stirred and evenly mixed, then
Quickly in investment to 1150 DEG C of high temperature converter, 1300 DEG C of sintered molten 1.5h are warming up to, 40min is kept the temperature, liquid melts is thrown
Enter to freeze in pure water and be quenched, forms the broken inorganic fire-retarded powder of shape.
Staged flame-proof PVC plastics prepared by the present invention, can at a temperature of 300 DEG C, 690 DEG C and 1000 DEG C shelling, tool
There is staged flame retardant effect, specific performance parameter is shown in Table 1.
Embodiment 4
A kind of staged flame retardant plastics, the plastic basis material are ABS, according to parts by weight include following components:
1000 parts of ABS；
80 parts of inorganic fire-retarded powder；
6 parts of zinc borate；
4 parts of silicon powder；
Mg(OH)21.3 part；
1 part of calcium carbonate；
0.5 part of macromolecule dispersing agent；
0.8 part of auxiliary agent.
Wherein, the partial size of the silicon powder is 0.1~0.3 μm, and the silicon powder that partial size is 0.1 μm is no less than 80%.It is described
Macromolecule dispersing agent is modifying epoxy resin by organosilicon.The auxiliary agent includes 0.3 part of lubricant, 0.3 part of plasticizer and 0.2
The heat stabilizer of part.The lubricant is ethylene bis stearic acid amide, and the plasticizer is phthalate compound, institute
Stating heat stabilizer is compound low lead stabilizer.
The inorganic silicon-aluminum shell-forming material includes: according to parts by weight
SiO244 parts；
H3BO335 parts；
CaCO36 parts；
K2CO38 parts；
Al2O36 parts；
NaNO34 parts；
Na23 parts of O；
Na2SO40.3 part；
La2O30.12 part；
ZrO2 0.06 part.
The step of preparation method of the staged anti-flaming ABS material of the present embodiment is with embodiment 1 is identical, only in parameter
Changing, specific steps are not described in detail here referring to embodiment 1, difference technology is only listed below:
The preparation of the inorganic fire-retarded powder of step S1.: each component in inorganic silicon-aluminum shell-forming material is weighed according to the ratio, is stirred and evenly mixed, then
Quickly in investment to 1200 DEG C of high temperature converter, 1250 DEG C of sintered molten 2h are warming up to, 40min is kept the temperature, liquid melts is put into
It is quenched in freezing pure water, forms the broken inorganic fire-retarded powder of shape.
Staged flame-proof ABS plastics prepared by the present invention, can at a temperature of 300 DEG C, 620 DEG C and 980 DEG C shelling, have
Staged flame retardant effect, specific performance parameter are shown in Table 1.
Embodiment 5
A kind of staged flame retardant plastics, the plastic basis material are ABS, according to parts by weight include following components:
900 parts of ABS；
100 parts of inorganic fire-retarded powder；
4 parts of zinc borate；
5 parts of silicon powder；
Al(OH)31.1 part；
2 parts of calcium carbonate；
1.0 parts of macromolecule dispersing agent；
1.3 parts of auxiliary agent.
Wherein, the partial size of the silicon powder is 0.1~0.3 μm, and the silicon powder that partial size is 0.1 μm is no less than 80%.It is described
Macromolecule dispersing agent is liquid nbr carboxyl terminal modified epoxy.The auxiliary agent include 1.1 parts lubricant, 0.1 part
Plasticizer and 0.1 part of heat stabilizer.The lubricant is pentaerythritol stearate, and the plasticizer is phthalic acid
Ester type compound, the heat stabilizer are compound low lead stabilizer.
The inorganic silicon-aluminum shell-forming material includes: according to parts by weight
SiO248 parts；
H3BO332 parts；
CaCO37 parts；
K2CO35 parts；
Al2O35 parts；
NaNO33 parts；
Na23 parts of O；
Na2SO40.1 part；
La2O30.17 part；
ZrO2 0.08 part.
The step of preparation method of the staged anti-flaming ABS material of the present embodiment is with embodiment 1 is identical, only in parameter
Changing, specific steps are not described in detail here referring to embodiment 1, difference technology is only listed below:
The preparation of the inorganic fire-retarded powder of step S1.: each component in inorganic silicon-aluminum shell-forming material is weighed according to the ratio, is stirred and evenly mixed, then
Quickly in investment to 1180 DEG C of high temperature converter, 1220 DEG C of sintered molten 2h are warming up to, 50min is kept the temperature, liquid melts is put into
It is quenched in freezing pure water, forms the broken inorganic fire-retarded powder of shape.
Staged flame-proof ABS plastics prepared by the present invention, can at a temperature of 330 DEG C, 680 DEG C and 960 DEG C shelling, have
Staged flame retardant effect, specific performance parameter are shown in Table 1.
Embodiment 6
A kind of staged flame retardant plastics, the substrate are PA plastics, according to parts by weight include following components:
1100 parts of PA；
70 parts of inorganic fire-retarded powder；
8 parts of zinc borate；
5 parts of silicon powder；
Al(OH)31.3 part；
1.0 parts of calcium carbonate；
0.4 part of macromolecule dispersing agent；
0.4 part of auxiliary agent.
Wherein, the partial size of the silicon powder is 0.1~0.3 μm, and the silicon powder that partial size is 0.1 μm is no less than 80%.It is described
Macromolecule dispersing agent is liquid hydroxy'terminated butadiene nitrile rubber modified epoxy.The auxiliary agent include 0.2 part lubricant and 0.2 part
Heat stabilizer.The lubricant is ethylene bis stearic acid amide, and the heat stabilizer is compound low lead stabilizer.
The inorganic silicon-aluminum shell-forming material includes: according to parts by weight
SiO250 parts；
H3BO340 parts；
CaCO36 parts；
K2CO36 parts；
Al2O37 parts；
NaNO32 parts；
Na22 parts of O；
Na2SO40.4 part；
La2O30.05 part；
ZrO2 0.08 part.
The step of preparation method of the fire-retardant PA plastics of the staged of the present embodiment is with embodiment 1 is identical, only in parameter
Changing, specific steps are not described in detail here referring to embodiment 1, difference technology is only listed below:
The preparation of the inorganic fire-retarded powder of step S1.: each component in inorganic silicon-aluminum shell-forming material is weighed according to the ratio, is stirred and evenly mixed, then
Quickly in investment to 1200 DEG C of high temperature converter, 1280 DEG C of sintered molten 2h are warming up to, 60min is kept the temperature, liquid melts is put into
It is quenched in freezing pure water, forms the broken inorganic fire-retarded powder of shape.
The fire-retardant PA plastics of staged prepared by the present invention, can at a temperature of 300 DEG C, 700 DEG C and 1100 DEG C shelling, have
Staged flame retardant effect, specific performance parameter are shown in Table 1.
Embodiment 7
A kind of staged flame retardant plastics, the substrate are PA plastics, according to parts by weight include following components:
1100 parts of PA；
70 parts of inorganic fire-retarded powder；
8 parts of zinc borate；
5 parts of silicon powder；
Mg(OH)21.3 part；
1.0 parts of calcium carbonate；
0.4 part of macromolecule dispersing agent；
0.4 part of auxiliary agent.
Wherein, the partial size of the silicon powder is 0.1~0.3 μm, and the silicon powder that partial size is 0.1 μm is no less than 80%.It is described
Macromolecule dispersing agent is liquid hydroxy'terminated butadiene nitrile rubber modified epoxy.The auxiliary agent include 0.2 part lubricant and 0.2 part
Heat stabilizer.The lubricant is ethylene bis stearic acid amide, and the heat stabilizer is compound low lead stabilizer.
The inorganic silicon-aluminum shell-forming material includes: according to parts by weight
SiO250 parts；
H3BO340 parts；
CaCO36 parts；
K2CO36 parts；
Al2O37 parts；
NaNO32 parts；
Na22 parts of O；
Na2SO40.4 part；
La2O30.05 part；
ZrO2 0.08 part.
The step of preparation method of the fire-retardant PA plastics of the staged of the present embodiment is with embodiment 1 is identical, only in parameter
Changing, specific steps are not described in detail here referring to embodiment 1, difference technology is only listed below:
The preparation of the inorganic fire-retarded powder of step S1.: each component in inorganic silicon-aluminum shell-forming material is weighed according to the ratio, is stirred and evenly mixed, then
Quickly in investment to 1200 DEG C of high temperature converter, 1280 DEG C of sintered molten 2h are warming up to, 60min is kept the temperature, liquid melts is put into
It is quenched in freezing pure water, forms the broken inorganic fire-retarded powder of shape.
The fire-retardant PA plastics of staged prepared by the present invention, can at a temperature of 300 DEG C, 700 DEG C and 1100 DEG C shelling, have
Staged flame retardant effect, specific performance parameter are shown in Table 1.
Embodiment 8
A kind of staged flame retardant plastics, the substrate are PP plastics, according to parts by weight include following components:
800 parts of PP；
60 parts of inorganic fire-retarded powder；
4 parts of zinc borate；
3 parts of silicon powder；
Al(OH)31 part；
1.0 parts of calcium carbonate；
0.5 part of macromolecule dispersing agent；
1.0 parts of auxiliary agent.
Wherein, the partial size of the silicon powder is 0.1~0.3 μm, and the silicon powder that partial size is 0.1 μm is no less than 80%.It is described
Macromolecule dispersing agent is modifying epoxy resin by organosilicon.The auxiliary agent includes 0.5 part of lubricant and 0.5 part of heat stabilizer.
The lubricant is ethylene bis stearic acid amide, and the heat stabilizer is compound low lead stabilizer.
The inorganic silicon-aluminum shell-forming material includes: according to parts by weight
SiO250 parts；
H3BO340 parts；
CaCO36 parts；
K2CO36 parts；
Al2O37 parts；
NaNO32 parts；
Na22 parts of O；
Na2SO40.4 part；
La2O30.05 part；
ZrO2 0.08 part.
The step of preparation method of the staged Flame-retardant PP of the present embodiment is with embodiment 1 is identical, only in parameter
Changing, specific steps are not described in detail here referring to embodiment 1, difference technology is only listed below:
The preparation of the inorganic fire-retarded powder of step S1.: each component in inorganic silicon-aluminum shell-forming material is weighed according to the ratio, is stirred and evenly mixed, then
Quickly in investment to 1100 DEG C of high temperature converter, 1300 DEG C of sintered molten 2h are warming up to, 30min is kept the temperature, liquid melts is put into
It is quenched in freezing pure water, forms the broken inorganic fire-retarded powder of shape.
Staged Flame-retardant PP prepared by the present invention, can at a temperature of 300 DEG C, 800 DEG C and 1020 DEG C shelling, have
Staged flame retardant effect, specific performance parameter are shown in Table 1.
Embodiment 9
A kind of staged flame retardant plastics, the substrate are PP plastics, according to parts by weight include following components:
1200 parts of PP；
100 parts of inorganic fire-retarded powder；
6 parts of zinc borate；
5 parts of silicon powder；
Mg(OH)21.5 part；
2.0 parts of calcium carbonate；
0.8 part of macromolecule dispersing agent；
2 parts of auxiliary agent.
Wherein, the partial size of the silicon powder is 0.1~0.3 μm, and the silicon powder that partial size is 0.1 μm is no less than 80%.It is described
Macromolecule dispersing agent is liquid hydroxy'terminated butadiene nitrile rubber modified epoxy.The auxiliary agent include 1 part lubricant, 0.5 part
Plasticizer and 0.5 part of heat stabilizer.The lubricant is pentaerythritol stearate, and the plasticizer is phthalic acid ester
Class compound, the heat stabilizer are compound low lead stabilizer.
The inorganic silicon-aluminum shell-forming material includes: according to parts by weight
SiO240 parts；
H3BO338 parts；
CaCO310 parts；
K2CO310 parts；
Al2O34 parts；
NaNO35 parts；
Na25 parts of O；
Na2SO40.1 part；
La2O30.2 part；
ZrO2 0.05 part.
The step of preparation method of the staged Flame-retardant PP of the present embodiment is with embodiment 1 is identical, only in parameter
Changing, specific steps are not described in detail here referring to embodiment 1, difference technology is only listed below:
The preparation of the inorganic fire-retarded powder of step S1.: each component in inorganic silicon-aluminum shell-forming material is weighed according to the ratio, is stirred and evenly mixed, then
Quickly in investment to 1180 DEG C of high temperature converter, 1280 DEG C of sintered molten 1.8h are warming up to, 50min is kept the temperature, liquid melts is thrown
Enter to freeze in pure water and be quenched, forms the broken inorganic fire-retarded powder of shape.
Staged Flame-retardant PP prepared by the present invention, can at a temperature of 300 DEG C, 620 DEG C and 1080 DEG C shelling, have
Staged flame retardant effect, specific performance parameter are shown in Table 1.
Material properties test
By above-described embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6, embodiment 7, embodiment 8, reality
Applying staged flame retardant plastics number consecutively made from example 9 is 1#, 2#, 3#, 4#, 5#, 6#, 7#, 8#, 9#, carries out combustion test
Test, testing standard is according to GB/T 2408-2008 " the measurement Horizontal Bridgman Method and normal beam technique of Plastics Combustion performance ", GB/T
8627-2007 " the smoke density test method of construction material burning or decomposition ", GB/T 2406.2-2009 " plastics oxygen index (OI)
Method measures burning behavior part 2: room temperature test ", GB/T 19666-2005 " fire-retardant and fire-resistant wire and cable general rule " standard
Execute, and for GB/T 19666-2005 " fire-retardant and fire-resistant wire and cable general rule " standard by 1#, 2#, 3#, 4#, 5#, 6#, 7#,
8#, 9# flame retardant plastics be prepared into it is cable-shaped, shown in test result table 1.
The performance test results table of 1. staged flame retardant plastics of table
As known from Table 1,1#, 2#, 3#, 4#, 5#, 6#, 7#, 8#, 9# all have preferable anti-flammability, in horizontal firing performance and hang down
Direct combustion burns in performance test and puts out from fire, and in oxygen index (OI) test, oxygen concentration OI is greater than or equal to 32, and combustion state is shown as
Non-ignitable shelling, smoke density grade SDR is far smaller than 75, in high fire combustion testing, shows as char length and is lower than 2.5m,
Stop for the flaming combustion time on sample after fire being 10~20s, is no more than 60s far below standard requirements, has preferable
Flame retardant effect.
It, can according to the technique and scheme of the present invention and its hair it is understood that for those of ordinary skills
Bright design is subject to equivalent substitution or change, and all these changes or replacement all should belong to the guarantor of appended claims of the invention
Protect range.
Claims (10)
1. a kind of staged flame retardant plastics, which is characterized in that according to parts by weight include following components:
800~1200 parts of plastics；
30~120 parts of inorganic fire-retarded powder；
3~8 parts of zinc borate；
2~5 parts of silicon powder；
1~2 part of antismoke agent；
1~2 part of calcium carbonate；
0.3~1.2 part of macromolecule dispersing agent；
0.3~2 part of auxiliary agent.
2. staged flame retardant plastics according to claim 1, which is characterized in that the plastics are in PVC, PP, PA, ABS
One kind.
3. staged flame retardant plastics according to claim 1, which is characterized in that the inorganic fire-retarded powder by inorganic silicon-aluminum at
Shell material is prepared, and the inorganic silicon-aluminum shell-forming material includes: according to parts by weight
SiO240~55 parts；
H3BO320~40 parts；
CaCO35~10 parts；
K2CO33~10 parts；
Al2O31~8 part；
NaNO31~5 part；
Na21~5 part of O；
Na2SO40.1~0.5 part；
La2O30.05~0.2 part；
ZrO2 0.05~0.1 part.
4. staged flame retardant plastics according to claim 1, which is characterized in that the partial size of the silicon powder is 0.1~0.3
μm, and the silicon powder that partial size is 0.1 μm is no less than 80%.
5. staged flame retardant plastics according to claim 1, which is characterized in that the antismoke agent includes Al (OH)3、Mg
(OH)2One or both of.
6. staged flame retardant plastics according to claim 1, which is characterized in that the macromolecule dispersing agent is epoxy resin
Class modified material, including liquid nbr carboxyl terminal modified epoxy, liquid hydroxy'terminated butadiene nitrile rubber modified epoxy
And one of modifying epoxy resin by organosilicon.
7. staged flame retardant plastics according to claim 1, which is characterized in that the auxiliary agent include lubricant, plasticizer,
One or more of heat stabilizer.
8. staged flame retardant plastics according to claim 7, which is characterized in that the lubricant includes the double stearic acid of ethylene
One of amide, pentaerythritol stearate.
9. the preparation method of staged flame retardant plastics according to claim 1-8, which is characterized in that the method
Include:
The preparation of the inorganic fire-retarded powder of step S1.: weighing according to the ratio in inorganic silicon-aluminum shell-forming material in the high temperature converter of each component investment,
It is quenched after high-temperature fusion, obtains broken shape coloured glaze block, inorganic fire-retarded powder is obtained after then grinding coloured glaze block；
The modification of step S2. fire proofing: by inorganic fire-retarded powder, silicon powder and macromolecule dispersing agent obtained in step S1 by matching
Than feeding, inorganic fire-retarded powder and silicon powder is first added in super grinder, macromolecule dispersing agent then is added in grinding, grinds
Fire proofing to 1250~2000 mesh, after must modifying；
The preparation of step S3. composite flame-proof material: fire proofing, zinc borate and the antismoke agent after modifying in step S2 are taken according to the ratio
In blender, it is uniformly mixed to obtain composite flame-proof material；
The preparation of step S4. flame retardant plastics: plastics, composite flame-proof material, lubrication are taken by automatic blend ingredients system according to the ratio
Agent and other auxiliary agents are added batch mixer and mix, then feed the mixture into extruder plastication, then be granulated through pelletizer, obtain ladder
Formula flame retardant plastics particle.
10. the preparation method of staged flame retardant plastics according to claim 9, which is characterized in that the step S1 is specific
Include: to weigh each component in inorganic silicon-aluminum shell-forming material according to the ratio, stir and evenly mix, then quickly puts into 1100~1200 DEG C
In high temperature converter, 1200~1350 DEG C of 1~2h of sintered molten are warming up to, keep the temperature 30~60min, liquid melts investment freezing is pure
It is quenched in water, forms broken shape coloured glaze block, inorganic fire-retarded powder is obtained after then grinding coloured glaze block.
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| CN111057302A (en) * | 2019-12-30 | 2020-04-24 | 广东国珑新材料科技有限公司 | Composite inorganic flame-retardant master batch and preparation method thereof |
| CN111219131A (en) * | 2020-01-14 | 2020-06-02 | 营口暖万佳科技开发有限公司 | Flame-retardant warm edge spacing strip, flame-retardant composite material adopted by same and preparation method of flame-retardant warm edge spacing strip |
| CN111346325A (en) * | 2020-03-09 | 2020-06-30 | 深圳市沃尔核材股份有限公司 | Fireproof blanket capable of controlling temperature and preventing fire in different temperature areas, preparation method thereof, cable and cable connector |
| CN111346325B (en) * | 2020-03-09 | 2022-01-11 | 深圳市沃尔核材股份有限公司 | Fireproof blanket capable of controlling temperature and preventing fire in different temperature areas, preparation method thereof, cable and cable connector |
| CN111446040A (en) * | 2020-03-26 | 2020-07-24 | 深圳市沃尔核材股份有限公司 | Cable fireproof method |
| CN111446040B (en) * | 2020-03-26 | 2022-04-15 | 深圳市沃尔核材股份有限公司 | Cable fireproof method |
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| CN110028740B (en) | 2019-10-18 |
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Application publication date: 20190719 Assignee: Guangdong Guolong New Material Technology Co.,Ltd. Assignor: GUANGXUN TESTING (GUANGDONG) Co.,Ltd. Contract record no.: X2019440000051 Denomination of invention: Stepped flame retardant plastic and preparation method thereof Granted publication date: 20191018 License type: Exclusive License Record date: 20191223 |
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