CN103214809A - Method for preparing flame retardant micro encapsulation alloy - Google Patents
Method for preparing flame retardant micro encapsulation alloy Download PDFInfo
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Abstract
The invention provides a method for preparing a flame retardant micro encapsulation alloy, comprising the following steps of: a. adding the following components into a stirred tank and stirring for 5-10min, wherein the components comprise: 66-70% by weight of ammonium polyphosphate, 26-30% by weight of char-forming agent, and 7-9% by weight of synergistic synergist; b. sprinkling atomized polysiloxanes weak solution into the stirred tank for 5-10min, stewing for 10min after stirring, and then forming a microcapsule fire retardant; and c. adding ABS and PC pellets, thoroughly stirring to make the microcapsule fire retardant be adhered onto the ABS and PC pellets, discharging the material, and then drying the material.
Description
Technical field
The present invention relates to the preparation method of flame retardant microcapsule alloy, further, relate to the preparation method of flame retardant microcapsule alloy.
Background technology
ABS resin is the terpolymer of vinyl cyanide (A), divinyl (B), vinylbenzene (S), high-performance in conjunction with three kinds of components, have higher resistance to impact shock, good processing properties and chemical stability, be easy to molded, goods are rich in gloss, and having toughness concurrently, is a kind of general thermoplastic engineering plastic of superior performance.Polycarbonate (PC) resin is a kind of thermoplastic engineering plastic of excellent property, has outstanding impact resistance, and anti-creep and dimensional stability are good, heat-resisting, water-intake rate is low, nontoxic, dielectric properties are good.ABS resin and the two consistency of PC resin are good, prepare the ABS/PC alloy in conjunction with the two advantage and are widely used in industries such as automotive industry, electronic apparatus industry, light industry household electrical appliances, weaving and building with its superior over-all properties.Because the two all is an inflammable material, and discharge a large amount of toxic gases and black smoke during burning, not only cause serious property damage, return people's life security and living environment and bring very big threat, so the ABS/PC alloy need carry out fire-retardant and but cigarette processing in a lot of Application Areass.
The halogenated flame retardant application and development is the widest, the technology comparative maturity, the flame retarding efficiency height, but the halogenated flame retardant goods amount of being fuming increases, burning back produces hydrogen halide and has severe corrosive, and hiding secondary harm may make in the electronic and electrical equipment key part impaired and cause whole plant malfunctioning, and environmental pollution is serious in the recycling process, produces the “ dioxin " etc. carcinogenic gas.According to the RoHS of European Union command request, the Electrical and Electronic product that on July 1st, 2006 was thrown in European Union market later on must not contain 6 kinds of objectionable impuritiess such as lead, mercury, cadmium, sexavalent chrome, Polybrominated biphenyl and Poly Brominated Diphenyl Ethers.China has also put into effect corresponding rules " electronics and IT products pollution control management way ", and in execution on March 1 in 2007.Environmental regulation for the reply RoSH of European Union instruction and various countries' promulgation, the continuous upgrading that, Halogen nontoxic to fire retardant, environmental protection etc. require, various countries research and develop multiple fire retardant in succession, wherein chemically expansible fire retardant (IFR) flame-retardant system flame retardant effect ideal, the complete processing based on phosphorus, nitrogen is simple, cheap, be subjected to people's extensive concern.
Most of IFR are by ammonium polyphosphate (APP, acid source), tetramethylolmethane (PER, charcoal source), the composite formation of trimeric cyanamide (MEL, source of the gas) three components, are mainly used in PF, PP, EVA and elastomeric fire-retardant.When the fire retardant consumption was 25-30wt%, the material oxygen index can reach 30%, and the difficult combustion of UL-94 rank can reach the V-0 level, and almost with not fire retardant material is identical to give birth to the cigarette amount, did not increase living cigarette amount or gave birth to cigarette speed and reduce, and density only improves 10-15% than fire retardant material not.The initial heat decomposition temperature of APP and the compound IFR of PER is between 160-180 ℃, so this system is used for fire retardant polyolefin and thermoplastic elastomer more, and is not used in fire-resistant engineering plastics; Simultaneously, exist the ammonium radical ion to decompose instability problem among the APP, under the strong shearing action of the course of processing, easily deviate from NH
3, the sample part that processes is reddened, the unsettled phenomenon of processing appears in the extruding pelletization process when serious.There is the water absorbability problem in IFR, causes the problem of anti-moving out property difference, can not adapt to open air and humid climate, PER can because of be rich in-wetting ability of OH produces the moisture absorption, transport phenomena, makes product surface " frosting ", generation hickie or tarnish, move out when serious, can cause fire retardant to lose efficacy.Add IFR and will reach the difficult combustion of fire-retardant UL-94 test rank V-0 level and need addition big, and and resin between consistency poor, difficulties in dispersion can cause the IFR flame retarding efficiency to descend, and ABS/PC alloy physics mechanical property is worsened serious.
Number of patent application: CN200410051777, disclose a kind of novel flame-retardant PC/ABS alloy, according to weight percent meter, this alloy comprises the brominated polycarbonate oligopolymer of ABS, 1%-30% of PC, the 10%-80% of 10%-80%, the Sb2O3 of 1%-10%, the tetrafluoroethylene of 0.1%-5% and optional stabilizer, toughener, pigment, other additive such as weighting material.During manufacturing, at first raw material was toasted 4-6 hour down at 90-100 ℃, drop in proportion then in the high-speed mixer and mixed 5-10 minute, then carry out mixing granulation in dual-screw-stem machine, prilling temperature is 240-260 ℃.This novel PC/ABS alloy has excellent mechanical property, thermal property and flame retardant resistance.Its shortcoming is that the flame retardant brominated polycarbonate oligomer that is adopted still contains halogen, collaborative and the usefulness with Sb2O3 still can cause the PC/ABS alloy system amount of being fuming to increase, and the hydrogen halide that the burning back produces has severe corrosive, hiding secondary harm is unfavorable for MAT'L recycling.
Number of patent application: CN201010125980, disclose a kind of electric works flame-proof ABS/PC alloy material and preparation method thereof, various components of described alloy and content are expressed as with weight part: 55～63 parts of acrylonitrile-butadiene-styrene copolymers (ABS), 21～34 parts of polycarbonate (PC), 2～7 parts of maleic anhydride grafted ABS compatilizers, 7～15 parts of organophosphate based flame retardants, 1.0～3.0 parts of 0.1～0.5 part of anti-dripping agent FA500B, organosilicon Dymgard, 0.2～0.5 part of composite antioxidant.The preparation method is for adopting the production of the disposable mixing plasticizing of twin screw/single screw rod two steps type forcing machine extruding pelletization, and the product over-all properties satisfies the storage battery dedicated shell performance requriements in subway engineering, electric locomotive and mobile base station.Its shortcoming is that the socle girder notched Izod impact strength of the finished product is at 12.1-17.1kJ/m
2Between, do not give full play to the outstanding impact resistance of PC, because the ABS addition is higher than PC, PC is not an external phase, the relative PC resin of the intensity that impacts is lower.
Number of patent application: CN200710074852 discloses a kind of halogen-free phosphorus-free inflaming retarding PC/ABS alloy material, and its component and content are: polycarbonate 65.5%-91.2%; Acrylonitrile-butadiene-styrene terpolymer 6%-17%; Compatilizer 1%-4%; Fire retardant tetrafluoroethylene 0.3%-1.5%; Organic silicon fibre retardant 1.0%-8.0%; Sulfobenzide sulfonate 0.1%-1.0%; Oxidation inhibitor 0.1%-1.0%; Lubricant 0.2%-2.0%; Above percentage ratio is weight percent.This patent also proposes the preparation method of described alloy material.Described alloy material can be widely used in the high automotive industry of environmental requirement, electric industry, mechanical industry.Its shortcoming is that the fire retardant sulfobenzide sulfonate that is adopted is relatively poor for the PC stability to hydrolysis, generally is not used in to make the thin-walled original paper.
Summary of the invention
Technical problem to be solved by this invention is the preparation method of flame retardant microcapsule alloy, this alloy has Heat stability is good, course of processing fluidity of molten is good, while flame retarding efficiency height, be difficult for the moisture absorption, be difficult for migration, the characteristics that product size stability is high can be applicable to injection molding and make electric appliance casing, automobile instrument panel, fan, secondary battery etc.
The preparation method of flame retardant microcapsule alloy of the present invention contains following component and mass percent:
Acrylonitrile-butadiene-styrene (ABS) (ABS) 10%-40%
Polycarbonate (PC) 40%-70%
Microcapsule flame retardant 10%-14%
Phenyl-boron dihydroxide compound 0%-4%
Nano imvite 0%-4%.
Described microcapsule flame retardant is that mixing in each component input stirring tank of following mass parts was stirred 5-10 minute: ammonium polyphosphate 66-70, char-forming agent 26-30, synergetic effect additive 7-9, liquid organopolysiloxane (being commonly called as silicone oil) dilution through spraying atomizing 5-10 minute, leave standstill the exhaust of 10 minutes unlatching stirring kettle covers after waiting to stir end, add ABS then and the PC pellet fully stirs for some time, microcapsule stick on ABS and the PC pellet, discharge compound then, oven dry is 2 hours in 60-80 ℃ of baking oven.
Described microcapsule flame retardant component ammonium polyphosphate, nonpoisonous and tasteless, do not produce corrosive gases, the thermostability height, water absorbability is little, preferably adopts the II type APP of polymerization degree n＞1500, and initial heat decomposition temperature reaches more than 275 ℃, solubleness is reduced to 0.2g/100mL in the water, and pH value (10% suspension) is between 6-7.
Described microcapsule flame retardant component char-forming agent is that tetramethylolmethane (PER), dipentaerythritol (DPER), starch etc. contain the organism than poly-hydroxy, preferred DPER.
Described microcapsule flame retardant component synergetic effect additive is Nano-class zinc oxide (ZnO), silicon-dioxide (SiO2), the titanium dioxide metal oxides such as (TiO2s) of particle diameter below 100nm, have and promote IFR to become the effect of charcoal, and more densification and the high resilience of charcoal layer structure that forms, this structure is difficult for breaking, preferred ZnO.Described synergetic effect additive has played the synergy fire retardation, the zn cpds that a small amount of ZnO and APP reaction produce forms bridged bond between APP, make the model that is similar to " track " that forms ordering between the APP molecular chain, this regular " track " in order promoted the esterification of char-forming agent and APP, reduce reaction activity, phosphoric acid ester model compound defective is tailed off, and the final charcoal layer that forms is fine and close, regular more, and we claim that this effect is " trackization " effect.
Described microcapsule flame retardant component fluids organopolysiloxane is polydimethylsiloxane, poly-aminosiloxane, silicone resin etc., and viscosity (25 ℃) is 2000-3500 (mPa.s), flash-point 〉=310 ℃.Liquid organopolysiloxane addition accounts for the 6%-8% of microcapsule flame retardant total amount, is dissolved in preparation silicone oil diluent in amount of acetone or the dehydrated alcohol.Adopt the composite expansion flame-retardant agent of atomizing nozzle in stirring to spray atomized liquid organopolysiloxane diluent, after treating diluting solvent volatilization, organopolysiloxane evenly is coated on composite expansion flame-retardant agent surface, and with the APP bonding, have strong bonding force, microcapsule have high thermal stability.Organopolysiloxane is water insoluble, forms the microcapsule of surface hydrophobicity, makes its humidity environment, is difficult for migration.
Described phenyl-boron dihydroxide compound is the phenyl-boron dihydroxide of aligning structure, is mainly the condensed phase fire retardant mechanism, can change the direction of polymer unwinds reaction, promotes to form surface protection charcoal layer, reduces and gives birth to cigarette amount and CO and CO
2Burst size.After described phenyl-boron dihydroxide compound added PC, dehydration at a certain temperature formed network structure, and when material combustion decomposed, this structure formed layer protective layer at material surface, played the heat insulation oxygen effect that presses down, and stoped material to burn away, and reduced the cigarette amount of giving birth to.It adds content is 4% o'clock, and the charring rate of PC is 30%, and heat decomposition temperature can reach 450 ℃.Can replace the phenyl-boron dihydroxide compound with nano imvite, nano imvite and microcapsule composite flame-retardant agent have synergy, mainly play the heat insulation oxygen effect that presses down by the migration of nanometer sheet course material surface, have the effect that promotes PC one-tenth charcoal simultaneously, reduce the cigarette amount of giving birth to, comparatively speaking, the independent time spent of nano imvite can effectively be reduced living cigarette amount, increase neat coal amout, but oxygen index is not high, vertical combustion test grade does not reach the V-0 level; The microcapsule composite flame-retardant agent uses separately, and charring rate is low, and charcoal layer structure is easily destroyed, vertical combustion test grade does not reach the V-0 level yet, and the two is with having synergy, and mechanical property improves, shock strength is brought up to 45.7kJ/m-2 from 39.2kJ/m-2, and flame retardant properties is almost constant.
Described flame-proof ABS/PC alloy course of processing is with blended under agitation such as the ABS of above-mentioned adhesion microcapsule flame retardant and PC pellet and other auxiliary material auxiliary agents, be added in the twin screw extruder, 200 ℃ of-240 ℃ of following blend granulations, the flame-retardant alloy particle descended dry 6-8 hour at 80 ℃-100 ℃.
Embodiment
The preparation method of flame retardant microcapsule alloy of the present invention, this alloy fire retardant good thermal stability does not decompose in the course of processing, and granulation is extracted out smooth and easy, and surface hydrophobicity is easily dry; Product surface is smooth, and fire retardant humidity environment is difficult for migration precipitation, and physical and mechanical properties is good, particularly has good shock resistance; Flame retardant properties is good, and oxygen index can reach more than 37%, and the vertical combustion grade can reach the V-0 level of UL-94 standard, and the increase of carbon residue amount, gives birth to the cigarette amount and more helps reducing fire hazard less.
The oxygen index test execution GB/T2406 of the embodiment of the invention; Vertical combustion test execution standard GB/T2508-1996 " plastics combustionproperty experimental technique-level and normal beam technique " or U.S. UL-94 testing standard; Give birth to cigarette test (PSPR) and carry out ISO 5660 standards " Reaction-to-fire tests--Heatrelease, smoke production and mass loss rate ", CR is final carbon residue amount; Socle girder notched Izod impact strength operative norm GB/T1843; Tensile strength operative norm GB/T1040; Melt mass flow rate operative norm GB/T3682-2000.
Embodiment 1
The preparation method of flame retardant microcapsule alloy may further comprise the steps:
Mix in a each component input stirring tank and stirred 5-10 minute: ammonium polyphosphate 66, char-forming agent 26, synergetic effect additive 7 following mass parts;
B sprays organopolysiloxane diluent 5-10 minute of atomizing in stirring tank, wait to stir to leave standstill 10 minutes after finishing, and forms microcapsule flame retardant;
C adds ABS and the PC pellet fully stirs, and microcapsule flame retardant is sticked on ABS and the PC pellet, and discharge is dried then.
Above-mentioned ammonium polyphosphate is the II type APP of polymerization degree n=2000; Above-mentioned char-forming agent is a tetramethylolmethane; Above-mentioned synergetic effect additive is the Nano-class zinc oxide of particle diameter below 100nm; Above-mentioned organopolysiloxane is a polydimethylsiloxane, and its addition accounts for the 6%-8% of microcapsule flame retardant total amount, is dissolved in and forms the silicone oil diluent in the acetone.ABS after the step c oven dry and PC pellet are added in the twin screw extruder 230 ℃ of following blend granulations, with flame-proof ABS/PC alloy particle of obtaining 90 ℃ dry 7 hours down.Described micro encapsulation flame-proof ABS/PC alloy contains following component and mass percent:
Acrylonitrile-butadiene-styrene (ABS) (ABS) 20%
Polycarbonate (PC) 70%
Microcapsule flame retardant 10%.
Embodiment 2
Repeat embodiment 1, difference is that each constituent mass part of microcapsule flame retardant is ammonium polyphosphate 70, char-forming agent 30, synergetic effect additive 8; In step c, also add the phenyl-boron dihydroxide compound; Described char-forming agent is a dipentaerythritol; Described synergetic effect additive is the nanometer grade silica of particle diameter below 100nm; Described organopolysiloxane is poly-aminosiloxane, is dissolved in the dehydrated alcohol.
Described micro encapsulation flame-proof ABS/PC alloy contains following component and mass percent:
Acrylonitrile-butadiene-styrene (ABS) (ABS) 70%
Polycarbonate (PC) 13%
Microcapsule flame retardant 14%
Phenyl-boron dihydroxide compound 3%.
Embodiment 3
Repeat embodiment 1, difference is that each constituent mass part of microcapsule flame retardant is ammonium polyphosphate 68, char-forming agent 28, synergetic effect additive 9; In step c, also add nano imvite; Described char-forming agent is a starch; Described synergetic effect additive is the Nano titanium dioxide of particle diameter below 100nm; Described organopolysiloxane is the silicone resin, is dissolved in the dehydrated alcohol.
Described micro encapsulation flame-proof ABS/PC alloy contains following component and mass percent:
Acrylonitrile-butadiene-styrene (ABS) (ABS) 25%
Polycarbonate (PC) 60%
Microcapsule flame retardant 12%
Nano imvite 3%.
Claims (10)
1. the preparation method of flame retardant microcapsule alloy may further comprise the steps:
Mix in a each component input stirring tank and stirred 5-10 minute: ammonium polyphosphate 66-70, char-forming agent 26-30, synergetic effect additive 7-9 following mass parts;
B sprays organopolysiloxane diluent 5-10 minute of atomizing in stirring tank, wait to stir to leave standstill 10 minutes after finishing, and forms microcapsule flame retardant;
C adds ABS and the PC pellet fully stirs, and microcapsule flame retardant is sticked on ABS and the PC pellet, and discharge is dried then.
2. according to the preparation method of the described flame retardant microcapsule alloy of claim 1, it is characterized in that, also add phenyl-boron dihydroxide compound or nano imvite among the described step c.
3. according to the preparation method of the described flame retardant microcapsule alloy of claim 2, it is characterized in that described micro encapsulation flame-proof ABS/PC alloy contains following component and mass percent
Acrylonitrile-butadiene-styrene (ABS) (ABS) 10%-40%
Polycarbonate (PC) 40%-70%
Microcapsule flame retardant 10%-14%
Phenyl-boron dihydroxide compound 0%-4%
Nano imvite 0%-4%.
4. according to the preparation method of the described flame retardant microcapsule alloy of claim 1, it is characterized in that described ammonium polyphosphate is the II type APP of polymerization degree n＞1500, initial heat decomposition temperature is higher than 275 ℃, solubleness 0.2g/100mL in the water, the pH value of 10% suspension are 6-7.
5. according to the preparation method of the described flame retardant microcapsule alloy of claim 1, it is characterized in that described char-forming agent is tetramethylolmethane (PER), dipentaerythritol (DPER) or starch.
6. according to the preparation method of the described flame retardant microcapsule alloy of claim 5, it is characterized in that described char-forming agent is a dipentaerythritol.
7. according to the preparation method of the described flame retardant microcapsule alloy of claim 1, it is characterized in that described synergetic effect additive is Nano-class zinc oxide (ZnO), silicon-dioxide (SiO2) or the titanium dioxide (TiO2) of particle diameter below 100nm.
8. according to the preparation method of the described flame retardant microcapsule alloy of claim 7, it is characterized in that described synergetic effect additive is a Nano-class zinc oxide.
9. according to the preparation method of the described flame retardant microcapsule alloy of claim 1, it is characterized in that, described organopolysiloxane is polydimethylsiloxane, poly-aminosiloxane or silicone resin, its viscosity (25 ℃) is 2000-3500 (mPa.s), flash-point 〉=310 ℃, the organopolysiloxane addition accounts for the 6%-8% of microcapsule flame retardant total amount, is dissolved in and forms the silicone oil diluent in acetone or the dehydrated alcohol.
10. according to the preparation method of the described flame retardant microcapsule alloy of claim 1, it is characterized in that, ABS after the step c oven dry and PC pellet are added in the twin screw extruder 200 ℃ of-240 ℃ of following blend granulations, with flame-proof ABS/PC alloy particle of obtaining 80 ℃-100 ℃ dry 6-8 hour down.
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Application publication date: 20130724 |