CN104479285A - Halogen-free ABS flame-resistant material and preparation method thereof - Google Patents
Halogen-free ABS flame-resistant material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a halogen-free ABS flame-resistant material and a preparation method thereof. The flame-resistant material is prepared from the following components in parts by weight: 100 parts of ABS, 20-33 parts of nano-CG-ATH, 20-32 parts of encapsulated red phosphorous, 15-29 parts of SBS, 0.1-1 part of antioxidant, 0.1-1 part of lubricant; all the materials are mixed evenly and granulated to obtain a raw material for the housings of electric appliances such as computers, televisions and mobile phones; the flame retardant property of the flame-resistant material is at the highest level; besides, the flame-resistant material is excellent in mechanical properties and superior in tenacity and strength.
Description
Technical field
The invention belongs to ABS fire retardant material technical field, be specifically related to a kind of Halogen ABS fire retardant material and preparation method thereof.
Background technology
Acrylonitrile-butadiene-styrene copolymer (ABS) has good mechanical property, electrical insulation capability and processing characteristics, and price is relatively low, be widely used in the field such as household electrical appliance and telecommunication product enclosure, electric elements, furniture, work-at-home decoration, building and traffic.But ABS is ignition very easily, bring potential threat to the people's lives and property.Along with fire safety evaluating comes into one's own and relevant laws and regulations constantly sound day by day, the requirement of people to ABS flame retardant properties is also more and more higher.Current China flame-proof ABS product is fire-retardant based on Halogen, and this product discharges a large amount of dense smoke and corrosive halide when burning, and causes casualties and equipment corrosion.Domestic and international many producers are all being devoted to the exploitation of halogen-free low-smoke flame retardant material, and during this kind of material combustion, the amount of being fuming is few, discharges toxic gas few, little to the injury of human body and plant and instrument.But current developed low smoke halogen-free flame retardant ABS mostly can not take into account mechanical property and the flame retardant properties of material, haves much room for improvement simultaneously.
Summary of the invention
The object of this invention is to provide a kind of Halogen ABS fire retardant material, adopt nano-CG-ATH and encapsulated red phosphorus to carry out synergistic to ABS fire-retardant, utilize SBS to carry out toughness reinforcing to fire retardant material simultaneously, obtain the low smoke halogen-free flame retardant ABS material with excellent mechanical performance.
In order to realize object of the present invention, inventor provide following technical scheme.
A kind of Halogen ABS fire retardant material, its ratio of weight and number consists of: ABS 100 parts, nano-CG-ATH20-33 part, encapsulated red phosphorus 20-32 part, SBS 15-29 part, oxidation inhibitor 0.1-1 part, lubricant 0.1-1 part.
Preferably its ratio of weight and number consists of: ABS 100 parts, nano-CG-ATH 22-30 part, encapsulated red phosphorus 22-29 part, SBS 18-27 part, oxidation inhibitor 0.3-0.8 part, lubricant 0.3-0.8 part.
Preferably its ratio of weight and number consists of further: ABS 100 parts, nano-CG-ATH 24-28 part, encapsulated red phosphorus 23-27 part, SBS 20-23 part, oxidation inhibitor 0.5-0.7 part, lubricant 0.4-0.7 part.
Further preferably its ratio of weight and number consists of: ABS 100 parts, nano-CG-ATH 26 parts, encapsulated red phosphorus 26 parts, SBS 21 parts, 0.6 part, oxidation inhibitor, lubricant 0.5 part.
Above-mentioned Halogen ABS fire retardant material, described oxidation inhibitor is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, 2,6-di-tert-butyl-4-methy phenol, 2,2 '-methylene-bis (4-methyl-6-tert butyl) phenol, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1, any one in 1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane.
Above-mentioned Halogen ABS fire retardant material, described lubricant be selected from stearic acid, lead stearate, Zinic stearas, calcium stearate any one.
Invention also provides the preparation method of above-mentioned bittern-free flame-proof material, comprise following operation steps:
A. batch mixing: take all raw materials, mix, obtain compound;
B. granulation: by steps A gained compound extruding pelletization on forcing machine.
The preparation method of above-mentioned bittern-free flame-proof material, described forcing machine is twin screw extruder.
The preparation method of above-mentioned bittern-free flame-proof material, described forcing machine each section of design temperature is respectively: a district 130-160 DEG C, two district 150-180 DEG C, three district 180-200 DEG C, head 190-220 DEG C.
Nano-CG-ATH of the present invention refers to high-performance nano aluminium hydroxide, and SBS refers to styrene-butadiene-styrene block copolymer, and ERP refers to encapsulated red phosphorus.
Described per-cent, except special mark, all refers to weight percent.
Contriver investigates the impact of composition on material combustion performance in ABS bittern-free flame-proof material prescription in the process of research:
(1) nano-CG-ATH is on the impact of fire retardant material combustionproperty
The amount of fixing ERP is 15% of total amount.
Table 1nano-CG-ATH is on the impact of fire retardant material combustionproperty
The consumption of note: nano-CG-ATH is that it accounts for the per-cent of ABS, ERP and nano-CG-ATH tri-kinds of material gross weights.
As can be seen from Table 1, when the consumption of nano-CG-ATH is the encapsulated red phosphorus only adding 15% in 0, ABS, the horizontal firing grade of fire retardant material is FH-2 level, after adding the nano-CG-ATH of 3%, the horizontal firing grade of fire retardant material reaches the highest FH-1 level of horizontal firing.Afterwards, along with the increase of nano-CG-ATH consumption, the horizontal firing grade of fire retardant material keeps the highest FH-1 level of horizontal firing always.It can also be seen that from table, when only adding the encapsulated red phosphorus of 15% in ABS, the combustionproperty of matrix material does not reach the judgment criteria of vertical combustion; When in ABS/ encapsulated red phosphorus fire retardant material, the consumption of nano-CG-ATH is equal to or less than 6%, the combustionproperty of fire retardant material still can not meet the judgment criteria of vertical combustion; When the consumption of nano-CG-ATH reaches 9%, the combustionproperty of fire retardant material reaches the judgment criteria of vertical combustion, is FV-1 level, and when the consumption of nano-CG-ATH is 15%, the combustionproperty of fire retardant material reaches the highest FV-0 level of vertical combustion.From analyzing above, along with the increase of nano-CG-ATH consumption, the flame retardant properties of fire retardant material presents the trend of increase.
(2) nano-CG-ATH is on the impact of fire retardant material mechanical property
Nano-CG-ATH consumption to the influence curve figure of fire retardant material shock strength and tensile strength as shown in Figure 1.
From accompanying drawing 1, along with the increase of nano-CG-ATH consumption, the shock strength of fire retardant material constantly declines.When nano-CG-ATH consumption is increased to 15% from 0, shock strength is from 10.54kJ/m
2drop to 5.92kJ/m
2, fall reaches 43.83%.Elastic body toughening is that rubber grain brings out matrix shear yielding and crazing, absorbs plasticity energy, does not have particular requirement to the toughness of body material.Rigid inorganic filler toughening is different from elastic body toughening, its toughening mechanism is: rigid particles adds rear as focal point of stress, cause a large amount of crazings, when its consumption reaches threshold value, violent interaction between stress field impels base material that surrender and plastic deformation and absorb energy occur, this just requires that base material itself has the ability of plastic deformation, namely requires that base material has certain toughness.In the present invention, due to base material, (base material is ABS, ERP herein, toughness as shown in Figure 1) is poor, shock strength only has 10.54kJ/m2, so adding of nano-CG-ATH can not make the toughness of base material increase, on the contrary, along with the toughness of the increase base material of its consumption can worse and worse, thus cause the shock strength of fire retardant material constantly to decline.Therefore, under ensureing that the flame retardant properties of fire retardant material meets the requirements of prerequisite, the add-on of nano-CG-ATH is more few better.
The tensile strength of fire retardant material, along with the increase of nano-CG-ATH consumption, present downward trend after first rising, but rangeability is little.When nano-CG-ATH consumption is less than 3%, tensile strength constantly increases, and when nano-CG-ATH consumption is 3wt%, tensile strength reaches maximum, is 36.73MPa.Afterwards, along with the increase of nano-CG-ATH consumption, tensile strength constantly declines, and when its consumption is 15%, tensile strength reduces to 34.85MPa.Visible, in this system, when addition is less, nano-CG-ATH has certain enhancement to fire retardant material.And after nano-CG-ATH consumption exceeds 3%, be deteriorated due to dispersed in the polymer, particle generation diffuse phase transition, changed to grand farmland by microdomain, cause particle diameter to increase, agglomeration is serious, thus in body material, introduce more defect, under the effect of tensile stress, easily there is slippage and the propagation of dislocation, its mechanical property is reduced.
Nano-CG-ATH consumption on the impact of fire retardant material modulus in flexure as shown in Figure 2.
From accompanying drawing 2, along with the increase of nano-CG-ATH consumption, the modulus in flexure of fire retardant material presents the trend significantly risen.When nano-CG-ATH consumption is increased to 15% from 0, modulus in flexure is increased to 2472MPa from 1830MPa, and increasing degree reaches 35.08%.As can be seen here, nano-CG-ATH add the increase contributing to fire retardant material rigidity.
(3) encapsulated red phosphorus is on the impact of fire retardant material combustionproperty
Red phosphorus is relatively applicable to being applied to containing oxygen superpolymer, and not ideal to polyolefinic flame retardant effect, must use just can reach good flame retardant effect with the fire retardant such as aluminium hydroxide and magnesium hydroxide synergistic.The present invention, using the synergistic flame retardant of encapsulated red phosphorus as nano-CG-ATH, achieves good flame retardant effect.
Keep nano-CG-ATH consumption to be 15%, change the consumption of encapsulated red phosphorus, investigate its impact of change on fire retardant material combustionproperty, the results are shown in Table 2
Table 2 encapsulated red phosphorus is on the impact of fire retardant material combustionproperty
Note: the consumption of encapsulated red phosphorus is that it accounts for the per-cent of ABS, ERP and nano-CG-ATH tri-kinds of material gross weights.
As can be seen from Table 2, when only adding the nano-CG-ATH of 15% in ABS, the horizontal firing grade of fire retardant material is FH-4 level, and horizontal firing speed is 50.16mm/min; After adding the encapsulated red phosphorus of 3%, the horizontal firing grade of fire retardant material does not change, but its horizontal firing speed reduces to 41.67mm/min; When in ABS/nano-CG-ATH fire retardant material, the consumption of encapsulated red phosphorus is 6%, the horizontal firing grade of fire retardant material becomes FH-3 level from FH-4 level, when the consumption of encapsulated red phosphorus is 9%, the horizontal firing grade of fire retardant material is still FH-3 level, but its horizontal firing speed reduces to 27.27mm/min by 35.71mm/min; When the consumption of encapsulated red phosphorus is 12%, the horizontal firing grade of fire retardant material reaches the highest FH-1 level of horizontal firing, and afterwards, along with the increase of coated consumption, the horizontal firing grade of fire retardant material keeps the highest FH-1 level of horizontal firing always.It can also be seen that from table, when only adding the nano-CG-ATH of 15% in ABS, the combustionproperty of matrix material does not reach the judgment criteria of vertical combustion; When in ABS/nano-CG-ATH fire retardant material, the consumption of encapsulated red phosphorus is equal to or less than 9%, the combustionproperty of fire retardant material still can not meet the judgment criteria of vertical combustion; When the consumption of encapsulated red phosphorus reaches 12%, the combustionproperty of fire retardant material reaches the judgment criteria of vertical combustion, is FV-1 level, and when the consumption of encapsulated red phosphorus is 15%, the combustionproperty of fire retardant material reaches the highest FV-0 level of vertical combustion.Be not difficult to find out by analyzing above, along with the increase of encapsulated red phosphorus consumption, the flame retardant properties of fire retardant material presents the trend of increase.
If when only adding nano-CG-ATH in ABS matrix, its addition at least should reach 50% just can make the vertical combustion of ABS base fire retardant material meet the requirement of FV-0 level.As can be seen here, good synergistic flame retardant effect is had between encapsulated red phosphorus and nano-CG-ATH.
Generate phosphorus oxide during red phosphorus burning, the steam reaction of releasing can be decomposed with nano-CG-ATH, promote the thermal endothermic decomposition of nano-CG-ATH, stop the carrying out of burning.And the reaction that the quickening of nano-CG-ATH decomposition rate is generation phosphoric acid provides enough water vapors, accelerate the formation speed of phosphoric acid, phosphoric acid can dewater generation metaphosphoric acid further, and then aggregate into poly-metaphosphoric acid glassy mass, this material covers polymer surfaces, play the effect of starvation and inflammable gas, thus effectively prevent the carrying out of burning.Therefore, red phosphorus and nano-CG-ATH have synergistic fire retardation.In addition, when fire retardant material containing encapsulated red phosphorus burns, phosphorus has wherein changed into phosphoric acid and poly-metaphosphoric acid, the one-tenth charcoal reaction of these strongly-acid substance catalytic resin cured articles, be conducive to its split product and condense the graphite-like charcoal carbonizing into difficult combustion, phosphorus then major part residues in layer of charcoal.The combustion of this graphite-like layer of charcoal difficulty, heat insulation, oxygen barrier, burning is suffocated, meanwhile, this layer of charcoal heat conductivility is poor, and the heat being delivered to base material is reduced, and the thermolysis of base material slows down, thus performance condensed phase fire retardation.
(4) encapsulated red phosphorus is on the impact of fire retardant material mechanical property
The consumption of encapsulated red phosphorus on the impact of fire retardant material shock strength and tensile strength as shown in Figure 3.
As shown in Figure 3, along with the increase of encapsulated red phosphorus consumption, the shock strength of fire retardant material sharply declines, and when its consumption increases to 15% from 0, the shock strength of fire retardant material is from 15.10kJ/m
2drop to 5.92kJ/m
2, fall is 60.79%.As can be seen here, the toughness adding grievous injury fire retardant material of encapsulated red phosphorus.Trace it to its cause, the poor compatibility of encapsulated red phosphorus and ABS, its membership that adds makes to produce numerous focal point of stress in ABS matrix, outside under stress, phase interface place very easily peels off, and it is thick to add red phosphorus particle, also large because peeling off the hole produced, thus initiation crack, cause the brittle rupture of material.
Along with the increase of encapsulated red phosphorus consumption, the tensile strength of fire retardant material first rises and declines afterwards.When encapsulated red phosphorus consumption is less than 9%, tensile strength constantly increases, and when encapsulated red phosphorus consumption is 9%, tensile strength reaches maximum, is 35.65MPa.Afterwards, along with the increase of encapsulated red phosphorus consumption, tensile strength constantly declines, and when its consumption is 15%, tensile strength reduces to 34.85MPa.Visible, in this system, when addition is less, encapsulated red phosphorus has certain enhancement to fire retardant material.When addition is less, red phosphorus masterbatch can be dispersed in fire retardant material, effective filling has been carried out to body material, improve the density of material, and then improve the tensile strength of material, and when addition increases further, encapsulated red phosphorus is difficult to be uniformly dispersed in the base, under shearing stress effect, material surface is easy to produce crack, causes material damage.
The consumption of encapsulated red phosphorus on the impact of fire retardant material modulus in flexure as shown in Figure 4.
As shown in Figure 4, along with the increase of encapsulated red phosphorus consumption, the modulus in flexure of fire retardant material significantly increases, and when its consumption increases to 15% from 0, the modulus in flexure of fire retardant material is increased to 2472MPa from 1994MPa, and increasing degree reaches 23.97%.As can be seen here, the increase adding the rigidity contributing to fire retardant material of encapsulated red phosphorus.
(5) different toughner is on the impact of fire retardant material combustionproperty
Have studied the consumption of SBS, POE, EPDM tri-kinds of toughner respectively to the impact of fire retardant material combustionproperty, concrete outcome is as shown in table 3.
POE is ethylene octane multipolymer, and EPDM is terpolymer EP rubber.
Table 3 toughner consumption is on the impact of fire retardant material combustionproperty
As shown in Table 3, toughner add the horizontal firing performance not affecting flame-proof ABS, the horizontal firing grade of different toughner sample is FH-1 level.
When taking SBS as toughner, the vertical combustion grade of fire retardant material does not reduce with the increase of toughner consumption, can reach FV-0 level.This is because the combustionproperty of SBS and the combustionproperty of ABS are more or less the same, and their consistency is good, and dispersed phase particles is good with the interface adhesion between base material, is uniformly dispersed.
When taking POE as toughner, when its consumption is less than 9%, the vertical combustion grade of fire retardant material can meet the requirement of FV-0 level, and after the consumption of POE meets or exceeds 9%, the vertical combustion grade of fire retardant material reduces to FV-1 level.
When taking EPDM as toughner, when its consumption is less than 15%, the vertical combustion grade of fire retardant material can reach FV-0 level, and after the consumption of EPDM meets or exceeds 15%, the vertical combustion grade of fire retardant material reduces to FV-1.
Think after analysis, when POE or EPDM is toughner, the flame retardant properties of fire retardant material can be reduced, and when being toughner with SBS, can not have a negative impact to the flame retardant properties of fire retardant material.
(6) different toughner is on the impact of fire retardant material mechanical property
The membership that adds of inorganic combustion inhibitor makes the shock strength of ABS significantly decline, and must carry out toughening modifying to make it have good over-all properties.
First, contriver carries out blended with SBS, POE, EPDM and ABS respectively, and investigate toughner consumption to the impact of fire retardant material shock strength, result as shown in Figure 5.
As can be seen from Figure 5, the shock strength of fire retardant material increases with the increase of SBS consumption, its consumption lower than 3% time, shock strength change is relatively mild, its consumption more than 3% after, shock strength significantly increases with the increase of SBS consumption, its consumption more than 12% after, the increasing degree of shock strength obviously slows down, and when its consumption is 12%, shock strength can reach 13.80kJ/m
2, add 7.88kJ/m compared with the shock strength without toughening modifying fire retardant material
2, increasing degree reaches 133.11%.And with POE or EPDM for toughner time, the shock strength of obtained flame-retardant material all presents the trend of first increases and then decreases, and its maximum impact intensity is respectively 7.55kJ/m
2and 8.90kJ/m
2.
Dispersed phase particles is reach one of excellent toughening effect prerequisite with interfacial adhesion good between base material.Because can mesophase spherule be formed in this kind of two-phase system, change the feature of molecular motion, be conducive to transmission and the waste of energy of stress.
SBS is segmented copolymer, and S section is at macromolecular two ends, and it forms a phase with the S segment in ABS matrix, and divinyl rubber segment part B forms a phase with the B segment in ABS matrix.Therefore, SBS and ABS substrate have good interface adhesion, and it by firm earth anchor in the substrate.When sample is subject to External Force Acting, SBS has the effect causing and stop crazing, and external influence can be made in system to obtain well transmission and dispersion.Therefore, when taking SBS as toughner, the matrix material had compared with high impact can be obtained.
In the matrix material that POE or EPDM is toughness reinforcing, two touching positions almost exist without mesophase spherule, and the interface adhesion between dispersed phase particles and ABS substrate is poor.So comparatively use the shock strength of SBS toughness reinforcing obtained flame-retardant material poor by the shock strength of POE or EPDM toughness reinforcing obtained flame-retardant material.
In addition, because the molecular structure difference of the molecular structure of POE and EPDM and ABS is comparatively large, the poor compatibility of they and ABS.So in the fire retardant material that POE or EPDM is toughness reinforcing, after toughner consumption exceeds 9%, the dispersiveness of toughner in fire retardant material will worse and worse, and toughner particle also will be increasing, and the performance of toughner particle to ABS of oversized dimensions is extremely harmful.Because under the condition that φ d (volume fraction of disperse phase) is identical, macroparticle can make the T (distance between two adjacent rubber particles, also known as base material ligament thickness) value change is greatly, the n number of dispersed phase particles (in the unit volume) value diminishes, and then makes the deteriorated impact toughness of material.On the other hand, because dispersed phase particles is different with the thermal expansivity of base material, in addition the thermal conductivity that macromolecular material is poor, when cooling from melt to room temperature, large toughner particle will bear larger stress and forced deformation, easily become the nucleator of stress raiser and material generation breach and destruction, cause material property to become bad.So during with POE or EPDM for toughner, the shock strength of obtained flame-retardant material all presents the trend of first increases and then decreases.
Secondly, contriver carries out blended with SBS, POE, EPDM and flame-proof ABS respectively, and investigate toughner consumption to the impact of fire retardant material tensile strength, result as shown in Figure 6.
As can be seen from Figure 6, along with the increase of toughner consumption, the fire retardant material tensile strength of three kinds of toughened systems all presents downward trend.For the mechanical property except shock strength, can illustrate that it changes with mixing principle.In the matrix material that toughner/flame-proof ABS is formed, by mixing principle, the mechanical property (except shock strength) of material is σ=σ pVp-σ rVr, wherein σ is the mechanical property of blend, σ p, Vp are mechanical property and the content in the blend thereof of flame-proof ABS, and σ r, Vr are mechanical property and the content of toughner.With the increase of Vr, Vp reduces, and σ inevitably trends towards σ r from σ p.And σ r is far below σ p, therefore the tensile strength of fire retardant material presents increases and downward trend with toughner content.
Fig. 6 also shows, and in three kinds of toughner, EPDM has the greatest impact to fire retardant material tensile strength, and POE is slightly little on the impact of fire retardant material tensile strength, and the impact of SBS on fire retardant material tensile strength is minimum.When toughner consumption is increased to 15% from 0, the tensile strength of EPDM toughening flame-proof material reduces to 25.69MPa from 34.85MPa, and fall is 26.28%; The tensile strength of POE toughening flame-proof material reduces to 26.94MPa from 34.85MPa, and fall is 22.70%; The tensile strength of SBS toughening flame-proof material reduces to 30.83MPa from 34.85MPa, and fall is 11.54%.This is mainly because SBS and ABS consistency is good, and dispersed phase particles is with there being good interface adhesion between base material.
Then, contriver carries out blended with SBS, POE, EPDM and ABS respectively, and investigate toughner consumption to the impact of fire retardant material bending property, result as shown in Figure 7.
As can be seen from Figure 7, the fire retardant material modulus in flexure of three kinds of toughened systems is all along with the increase of toughner consumption presents downward trend.This is mainly because the modulus in flexure of three kinds of toughner self is all lower than flame-proof ABS.SBS and ABS structural similitude, consistency is good, and dispersed phase particles, with there being good interfacial adhesion between base material, is compared with POE with EPDM, and it is less on the bending property impact of fire retardant material.When toughner consumption is increased to 15% from 0, the modulus in flexure of SBS toughening flame-proof material reduces to 2093Mpa from 2472Mpa, and fall is 15.33%; The modulus in flexure of POE toughening composition reduces to 1871Mpa from 2472Mpa, and fall is 24.31%; The modulus in flexure of EPDM toughening composition reduces to 1720Mpa from 2472Mpa, and fall is 30.42%.
Therefore, when taking SBS as toughner, ABS fire retardant material has best shock strength, and the disadvantageous effect that SBS produces the tensile strength of ABS fire retardant material and modulus in flexure is minimum.
In sum, by the investigation to each component, contriver has drawn technical scheme of the present invention, uses nano-CG-ATH and encapsulated red phosphorus to carry out synergistic to ABS fire-retardant, utilize SBS to carry out toughness reinforcing to fire retardant material simultaneously, obtain the low smoke halogen-free flame retardant ABS material with excellent mechanical performance.Horizontal firing grade is FH-1 level, and vertical combustion grade is FV-0 level; Shock strength 13-16kJ/m2, tensile strength 30-32MPa, modulus in flexure 2100-2200MPa.Fire retardant material good flame resistance of the present invention, toughness is large, intensity is high, flame retardant properties and excellent in mechanical performance, is suitable for the starting material being used as the multiple casing for electric appliances such as computer, televisor, mobile phone.
Accompanying drawing explanation
Fig. 1 is the graphic representation that nano-CG-ATH consumption affects fire retardant material shock strength and tensile strength.
Fig. 2 is the graphic representation that nano-CG-ATH consumption affects fire retardant material modulus in flexure.
Fig. 3 is the graphic representation that the consumption of encapsulated red phosphorus affects fire retardant material shock strength and tensile strength.
Fig. 4 is the graphic representation that the consumption of encapsulated red phosphorus affects fire retardant material modulus in flexure.
Fig. 5 is the graphic representation that the consumption of toughner affects fire retardant material shock strength.
Fig. 6 is that the consumption of toughner is to the graphic representation of fire retardant material stretching slight effect.
Fig. 7 is the graphic representation that the consumption of toughner affects fire retardant material modulus in flexure.
Embodiment
Below in conjunction with specific embodiment, content of the present invention is described in further detail.
Embodiment 1
Take ABS 100g, nano-CG-ATH 26g, encapsulated red phosphorus 26g, SBS 21g, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.6g, calcium stearate 0.5g.
Fully mixed by above-mentioned material, on the twin screw extruder extruding pelletization, forcing machine each section of design temperature is respectively: 130 DEG C, a district ~ 160 DEG C, two 150 DEG C, districts ~ 180 DEG C, three 180 DEG C, districts ~ 200 DEG C, head 190 DEG C ~ 220 DEG C; Gained pellet is processed into test bars in injector, and injector each section of design temperature is respectively: 180 DEG C, a district ~ 210 DEG C, two 190 DEG C, districts ~ 220 DEG C, nozzle 190 DEG C ~ 220 DEG C.
Embodiment 2
Take ABS 100g, nano-CG-ATH 20g, encapsulated red phosphorus 20g, SBS 15g, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester 0.1g, stearic acid 0.1g.
Preparation method is with embodiment 1.
Embodiment 3
Take ABS 100g, nano-CG-ATH 33g, encapsulated red phosphorus 32g, SBS 29g, 2,6 di tert butyl 4 methyl phenol 1g, lead stearate 1g.
Preparation method is with embodiment 1.
Embodiment 4
Take ABS 100g, nano-CG-ATH 22g, encapsulated red phosphorus 29g, SBS 18g, 2,2 '-methylene-bis (4-methyl-6-tert butyl) phenol 0.3g, Zinic stearas 0.3g.
Preparation method is with embodiment 1.
Embodiment 5
Take ABS 100g, nano-CG-ATH 30g, encapsulated red phosphorus 23g, SBS 23g, 2,2 '-methylene-bis (4-methyl-6-tert butyl) phenol 0.8g, calcium stearate 0.8g.
Preparation method is with embodiment 1.
Embodiment 6
Take ABS 100g, nano-CG-ATH 28g, encapsulated red phosphorus 22g, SBS 20g, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene 0.4g, calcium stearate 0.7g.
Preparation method is with embodiment 1.
Embodiment 7
Take ABS 100g, nano-CG-ATH 24g, encapsulated red phosphorus 27g, SBS 27g, 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane 0.7g, stearic acid 0.4g.
Preparation method is with embodiment 1.
Embodiment 8
Contriver detects the test of embodiment 1-7 gained, and concrete outcome is as shown in table 4.
Table 4
Claims (9)
1. a Halogen ABS fire retardant material, is characterized in that, its ratio of weight and number consists of: ABS 100 parts, nano-CG-ATH 20-33 part, encapsulated red phosphorus 20-32 part, SBS 15-29 part, oxidation inhibitor 0.1-1 part, lubricant 0.1-1 part.
2. a kind of Halogen ABS fire retardant material according to claim 1, it is characterized in that, its ratio of weight and number consists of: ABS 100 parts, nano-CG-ATH 22-30 part, encapsulated red phosphorus 22-29 part, SBS18-27 part, oxidation inhibitor 0.3-0.8 part, lubricant 0.3-0.8 part.
3. a kind of Halogen ABS fire retardant material according to claim 1, it is characterized in that, its ratio of weight and number consists of: ABS 100 parts, nano-CG-ATH 24-28 part, encapsulated red phosphorus 23-27 part, SBS20-23 part, oxidation inhibitor 0.5-0.7 part, lubricant 0.4-0.7 part.
4. a kind of Halogen ABS fire retardant material according to claim 1, it is characterized in that, its ratio of weight and number consists of: ABS 100 parts, nano-CG-ATH 26 parts, encapsulated red phosphorus 26 parts, SBS 21 parts, 0.6 part, oxidation inhibitor, lubricant 0.5 part.
5. a kind of Halogen ABS fire retardant material according to claim 1-4 any one, it is characterized in that, described oxidation inhibitor is selected from four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, 2, 6-di-tert-butyl-4-methy phenol, 2, 2 '-methylene-bis (4-methyl-6-tert butyl) phenol, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1, 1, any one in 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane.
6. a kind of Halogen ABS fire retardant material according to claim 1-4 any one, is characterized in that, described lubricant be selected from stearic acid, lead stearate, Zinic stearas, calcium stearate any one.
7. the preparation method of a kind of bittern-free flame-proof material as claimed in claim 1, is characterized in that, comprises following operation steps:
A. batch mixing: take all raw materials, mix, obtain compound;
B. granulation: by steps A gained compound extruding pelletization on forcing machine.
8. the preparation method of a kind of bittern-free flame-proof material according to claim 7, is characterized in that, described forcing machine is twin screw extruder.
9. the preparation method of a kind of bittern-free flame-proof material according to claim 7, is characterized in that, described forcing machine each section of design temperature is respectively: a district 130-160 DEG C, two district 150-180 DEG C, three district 180-200 DEG C, head 190-220 DEG C.
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