CN103073808B - Low-cost high-flow weather-proof environment-friendly brominated flame retardant ASA material as well as preparation method and application thereof - Google Patents

Low-cost high-flow weather-proof environment-friendly brominated flame retardant ASA material as well as preparation method and application thereof Download PDF

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Publication number
CN103073808B
CN103073808B CN201310022800.9A CN201310022800A CN103073808B CN 103073808 B CN103073808 B CN 103073808B CN 201310022800 A CN201310022800 A CN 201310022800A CN 103073808 B CN103073808 B CN 103073808B
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flame
retardant
polysiloxane
environmental protection
asa material
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CN103073808A (en
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汪炉林
郭涛
王林
程庆
王亮
叶晓光
吴博
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SICHUAN KINGFA TECHNOLOGY DEVELOPMENT CO., LTD.
Kingfa Science and Technology Co Ltd
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MIANYANG CHANGXIN NEW MATERIAL DEVELOPMENT Co Ltd
Kingfa Science and Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92676—Weight
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92828—Raw material handling or dosing, e.g. active hopper or feeding device
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

The invention discloses a low-cost high-flow weather-proof environment-friendly brominated flame retardant ASA (acrylonitrile styrene acrylate) material, which comprises the following components in parts by weight: 15-40 parts of ASA resin, 30-60 parts of styrene-acrylonitrile resin, 8-12 parts of environment-friendly brominated flame retardant, 5-20 parts of chlorinated polyethylene and 2-6 parts of novel environment-friendly flame retardant synergist. A preparation method for the ASA material comprises the steps as follows: adding the components into a high-speed mixer in sequence according to the proportion for uniformly mixing, and adding a mixture into a double screw extruder for mixing, extruding, pulling, water-cooling and dicing to obtain the ASA material. According to the ASA material, the addition amount of the flame retardant is lower than that of other conventional flame-retardant system by more than 1/3; through the test, the flame retardant level reaches UL94@1.0-3.0 mm V-0, the impact intensity is kept more than 10 kJ/m<2>, the melting index exceeds 42 g/10 min, the weather-proof performance is excellent, and the other mechanical performance is balanced; the preparation method is simple and easy to implement; and the ASA material is easy to process and is suitable for popularization and application in the fields of outdoor electronic products and the like.

Description

A kind of low cost height flowing weather resistance environmental protection bromine system flame-retardant ASA material and preparation method thereof and application
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of flame-retardant ASA material, particularly a kind of low cost height flowing weather resistance environmental protection bromine system flame-retardant ASA material and preparation method thereof and application.
Background technology
The ternary graft copolymer that ASA resin is made up of vinylbenzene, acrylate, vinyl cyanide is main chain with polyacrylic ester, the non-crystalline polymer formed with vinyl cyanide, styrene monomer graft copolymerization.ASA realized suitability for industrialized production by BASF AG of Germany first in 1962, and FDAC changes into and also achieves industrialization subsequently.
The polyacrylic ester that have employed without double bond structure due to ASA resin instead of polybutadiene rubber in ABS, therefore becomes one of best kind of weathering resistance in plastics, and its weathering resistance is higher than ABS resin more than 10 times.But ASA resin itself also belongs to inflammable material, therefore the same with ABS resin, when for electronic and electrical equipment, need to carry out flame-retardant modified, to reach fire safety service requirements.Current flame-retardant modified the most effective, that cost is minimum method to thermoplastic is by the bromide fire retardant of interpolation more than more than 20% and the mixture of antimony system fire retarding synergist.Due to ASA resin itself, because it has excellent weather resistance, great majority are for the field of electronics of open air, and the membership that adds of therefore so many bromide fire retardant causes its weathering resistance to worsen seriously, loses its excellent weather resistance feature.As Chinese patent CN101397391 discloses tetrabromo-bisphenol and the antimonous oxide fire retardant as the modification of ASA resins fire retardant, but the weathering resistance of tetrabromo-bisphenol and heat-resistant stability are all poor, it is added to and the weathering resistance of ASA resin can be caused in ASA resin to reduce, and thermostability declines.Chinese patent CN101765635A discloses the ASA modified resin of brominated epoxy as fire retardant, because the weathering resistance of brominated epoxy and heat-resistant stability are all better than tetrabromo-bisphenol, but brominated epoxy resin softening temperature only has about 90 degree, easily lump in blending extrusion process, affect metering system, and and then affect fire-retardant stability and the mechanical property of the finished product.Chinese patent CN102002203A discloses three (three-bromophenyl) cyanurate fire retardant, and to be applied to ASA flame-retardant modified, this fire retardant maintains the physical strength of ASA resin preferably, weathering resistance and thermostability are all better than the flame-proof ABS product of identical flame-retardant system, but because itself and the total addition level of Sb system fire retardant are about 20%, so many addition causes weathering resistance to have deterioration to a certain degree, and the mobility of this system is general, be not optimal selection in forming thin-walled and large size product.Meanwhile, because the price comparison of ASA resin own is high, so many bromo-antimony composite flame-retardant agent add the further raising causing its cost, be difficult to commercially apply.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of high flowing, weather-proof, high-performance, handling ease low cost height flows weather resistance environmental protection bromine system flame-retardant ASA material.
Another object of the present invention is to the preparation method that above-mentioned low cost height flowing weather resistance environmental protection bromine system flame-retardant ASA material is provided.
The present invention is achieved by the following technical solutions:
A kind of low cost height flowing weather resistance environmental protection bromine system flame-retardant ASA material, count by weight, comprise following component:
ASA resin 15-40 part
Styrene-acrylonitrile resin 30-60 part
Environmental protection bromide fire retardant 8-12 part
Chlorinatedpolyethylene 5-20 part
Novel environment friendly fire retarding synergist 2-6 part.
Described ASA resin is for being acrylonitrile-styrene-acrylic ester terpolymer.
Described environmental protection bromide fire retardant is tetrabromo-bisphenol.
The compound that described novel environment friendly fire retarding synergist is made up of antimony compounds, inorganic powder and ultra-high molecular weight polysiloxane, in this compound, the weight percentage of antimony compounds is 20-80%.
Described antimony compounds is antimonous oxide, colloidal antimony pentoxide, sodium antimonate, butter of antimony, antimony pentachloride, and one or more in phosphorous acid antimony, polyphosphoric acid antimony, complexing antimony are composite to be formed.
Described inorganic powder is the mixture of one or more in talcum powder, titanium dioxide, zinc sulfide white, magnesiumcarbonate, barium sulfate, marble dust, mica powder, natural silica, wollastonite powder, kaolin or Feldspar Powder.
Weight-average molecular weight >=30,000 of described ultra-high molecular weight polysiloxane, when temperature is 25 DEG C, its viscosity >=500mPas.
Described ultra-high molecular weight polysiloxane is the mixture of one or more in methyl polysiloxane, phenyl polysiloxane, vinyl polysiloxane, amide group polysiloxane, epoxy group(ing) polysiloxane, isobutyl-polysiloxane, styryl polysiloxane or ring texture polysiloxane.
Material of the present invention also comprises 0.1-0.3 part anti-dripping agent, 0.1-2 part dispersion agent, 0-1 part oxidation inhibitor, 0-1 part photostabilizer or 0-5 part processing aid.
Described anti-dripping agent is tetrafluoroethylene.
Described dispersion agent is stearic acid dispersion agent.
Described oxidation inhibitor is the mixture of Hinered phenols primary antioxidant and phosphorous acid esters auxiliary anti-oxidant composition.
Described photostabilizer is benzophenone, benzotriazole category, triazines, poly-for the mixture of one or more in the fine class of propylene, Oxamides and hindered amines.
Described processing aid is the mixture of one or more in stearylamide series lubricant agent, silicone oil and white mineral oil.
The preparation method of low cost height flowing weather resistance environmental protection bromine system of the present invention flame-retardant ASA material, comprises the steps:
A, each component raw material is fully mixed 10-60 minute by proportioning at high-speed mixer;
B, said mixture is transported in twin screw extruder through the pay-off of delicate metering, each section of extruder temperature of forcing machine controls between 170 ~ 220 DEG C, the length-to-diameter ratio of twin screw extruder is 25 ~ 40, screw speed is 200-800 rev/min, screw rod shearing, mixing and conveying under, material is able to abundant fusing, compound, then obtains flame-retardant ASA material through extruding pelletization, drying.
Low cost height flowing weather resistance environmental protection bromine system of the present invention flame-retardant ASA material can be widely used in the outdoor large thin-walled electronic apparatus series products needing weather-proof requirement, is applicable to commercially applying.
The present invention compared with prior art, has following beneficial effect:
1) low cost height flowing weather resistance environmental protection bromine system of the present invention flame-retardant ASA material, the addition of its fire retardant is less than more than 1/3 of other flame-retardant system consumption at present;
2) low cost height flowing weather resistance environmental protection bromine system of the present invention flame-retardant ASA material is through test, and its flame retardant rating reaches UL94@1.0-3.0mmV-0, and shock strength then remains on 10kJ/m 2above, melt index, at more than 42g/10min, under all other mechanical property equilibriums, has certain weathering resistance;
3) low cost height flowing weather resistance environmental protection bromine system flame-retardant ASA material preparation method of the present invention is simple, handling ease, its cost is quite even lower with the flame-proof ABS generally used at present simultaneously, is therefore adapted at outdoor large thin-gage goods field and applies.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
Now following explanation is done to embodiment and comparative example starting material used, but is not limited to these materials:
The A600N of Japanese UMG selected by ASA resin;
Styrene-acrylonitrile resin AS selects the NF2200 of platform;
ABS resin selects the AG15A1 of Taiwan;
Environmental protection macromolecule amount bromide fire retardant selects the CN-3384 of big lake chemical industry;
Tetrabromo-bisphenol selects the FR-1524 of Dead Sea bromine company of Israel;
The CXB-714C that brominated epoxy selects Korea S's space to enter;
Brominated triazine selects the FR-245 of Dead Sea bromine company of Israel;
Chlorinated polyethylene resin selects the CPE 2135 of Shandong AsiaSat company;
Anti-dripping agent selects the SN80-SA7 of Guangzhou Shang Neng company;
Dispersion agent selects the S-74 of Li Yan company and the EBS of Dow Chemical company;
Antimony compounds selects the S-05N of Yunnan Mu Liti industry company limited;
Milan, Nanjing chemical industry photostabilizer HS-770 selected by photostabilizer;
Oxidation inhibitor selects pentaerythritol ester 1010 and the phosphorous acid ester 168 of gas Ba Jinghua;
Processing aid selects white mineral oil No. 70 white oils of Liaoning AoKe Chemical Co., Ltd;
Calcium stearate BS-3818 obtains can buy on the market.
the plant and instrument that the present invention is prepared used by composition has:
The flame-retardant modified twin screw extruder used of thermoplastics is the SHJ-30 produced by Rhea superpolymer Equipment Limited, Nanjing.
The injection moulding machine that flame retardant thermoplastic's test bars adopts is the B-920 type produced by Zhejiang Hai Tian injection moulding machine company limited.
The instrument of test melt flow rate (MFR) is the ZR21452 Melt Flow Rate Measurer that Mei Site industrial system (China) company limited produces.
The T92 type of Tinius Olsenis company of the impact experiment Ji Shi U.S. production of test shock strength.
The universal testing machine of test tensile strength is the H10K-S that Hounsfield company produces.
The UL-94 vertical combustion Yi Shi U.S. ATLAS HVUL-2 that test flame retardant rating uses.
Test weathering resistance uses the xenon lamp aging case JN-HQLH-1581 of UL company.
Test atmospheric exposure test condition: black mark temperature: 65 DEG C; Relative humidity: 65%; Irradiance: 0.50W/m 2@340nm; Loop cycle: continuous illumination, 102min does not spray, and 18min sprays; Test period: 800h
the preparation of novel environment friendly fire retarding synergist XX:
By talcum powder 68 grams, dimethyl polysiloxane 12 grams, antimonous oxide 20 grams, high-speed mixer and mixing 20 minutes, can prepare novel environment friendly fire retarding synergist XX 1, the weight-average molecular weight of described dimethyl polysiloxane is 30000, and its viscosity is 500PaS.
By talcum powder 18 grams, dimethyl polysiloxane 2 grams, antimonous oxide 80 grams, high-speed mixer and mixing 20 minutes, can prepare novel environment friendly fire retarding synergist XX 2, the weight-average molecular weight of described dimethyl polysiloxane is 30000, and its viscosity is 500PaS.
By talcum powder 44 grams, dimethyl polysiloxane 6 grams, antimonous oxide 50 grams, high-speed mixer and mixing 20 minutes, can prepare novel environment friendly fire retarding synergist XX 3, the weight-average molecular weight of described dimethyl polysiloxane is 30000, and its viscosity is 500PaS.
the flame-retardant ASA material preparation of low cost height flowing weather resistance environmental protection bromine system:
First each component of each comparative example/embodiment is successively added in high-speed mixer by proportioning and carries out Homogeneous phase mixing, then said mixture is sent into mixing in twin screw extruder, extrude, tie rod, water-cooled, pelletizing; Wherein, the length-to-diameter ratio of twin screw extruder is 25-40; Barrel temperature is set as: district's temperature 170 DEG C, two district's temperature 180 DEG C, three district's temperature 190 DEG C, four district's temperature 200 DEG C, five district's temperature 200 DEG C, six district's temperature 200 DEG C, seven district's temperature 200 DEG C, eight district's temperature 200 DEG C, nine district's temperature 200 DEG C, ten district's temperature 200 DEG C, head temperature 210 DEG C; Screw speed is 200-800 rev/min.Plastic particles obtained by above-mentioned each example is injection molded into the standard batten of test by standard size, and carries out each performance test by testing standard; The performance test data of each routine sample is in Table 1-3.
Properties testing standard
Test event Unit Testing standard
Tensile strength TS Mpa ISO 527
Elongation at break EL % ISO 527
Izod notched impact strength NIS kJ/m 2 ISO 180, breach type is A type breach
Flexural strength FS Mpa ISO 178
Modulus in flexure FM Mpa ISO 178
Melting index MI 10g/min ISO 1133
Burning UL94 class UL94
Weathering resistance WR GB/T 16422.2
Heat-drawn wire H.D.T. ℃ ISO 75
the concrete proportioning of each component and performance test data in table 1 embodiment and comparative example
　 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Embodiment 1 Embodiment 2 Embodiment 3
A600N 25 25 25 25 25 25 25 25
AS 65 47 47 47 47 47 49 50
AG15A1 72
FR-1524 15 15 12 10 8
CXB-714C 15
FR-245 15
CN-3384 　 　 　 15　 　 　
CPE 2135 10　 10 10 10 10 10 10　 10 10
XX 1 　 　 　 　 　 6 5　 5
S-05N 3 3 3 3 3
SN80-SA7 0.1 0.1 0.1 0.1 0.1 0.1 0.2 0.3
S-74 0.5 0.5 0.5 0.5 0.5 0.5 1 2
Antioxidant 1010+168 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.6 1
HS-770 0.5 0.5 0.5 0.5 0.5 0.1 0.1 0.7 1
BS 3818+70 white oil 1 1 1 1 1 1 1 3 5
TS 43 40 38 38 42 40 40 41 42
EL 5 5 5 5 5 5 5 5 5
NIS 16 10 7 12 12 12 14 15 16
FS 62 65 63 66 66 61 62 63 64
FM 2200 2500 2300 2500 2450 2200 2200 2350 2450
MI 18 45 39 30 14 45 58 53 48
UL94@1.0mm / V-0 V-0 V-0 V-0 V-0 V-0 V-0 /
UL94@1.5mm / V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
UL94@2.0mm / V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
UL94@2.5mm / V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
UL94@3.0mm / V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
H.D.T 82 74 78 77 80 74 75 76 77
WR 3.58 15.51 9.17 9.05 7.35 29.95 13.35 10.98 8.66
the concrete proportioning of each component and test performance thereof in each embodiment of table 2
　 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11
A600N 15 20 25 30 35 40 39 34
AS 55 50 45 40 35 30 40 40
FR-1524 10　 12　 10　 10　 10　 10　 10　 10　
CPE 2135 14 14　 14 14 14 14　 5 10
XX 2 5　 5 5　 5 5　 5 5　 5
SN80-SA7 0.1 0.1 0.2 0.3 0.1 0.1 0.2 0.3
S-74 0.5 0.5 1 2 0.5 0.5 1 2
Antioxidant 1010+168 0.4 0.4 0.6 1 0.4 0.4 0.6 1
HS-770 0.5 0.1 0.7 1 0.5 0.1 0.7 1
BS 3818+70 white oil 1 1 1 1 1 1 1 1
TS 42 41 40 39 37 36 40 39
EL 5 5 5 5 5 5 5 5
NIS 14 15 16 17 18 19 13 14
FS 64 63 62 60 58 57 63 61
FM 2400 2350 2250 2050 1950 1850 2450 2150
MI 65 60 57 54 49 42 45 43
UL94@1.0mm V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
UL94@1.5mm V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
UL94@2.0mm V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
UL94@2.5mm V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
UL94@3.0mm V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
H.D.T 76 75 75 75 74 74 75 75
WR 7.57 8.85 9.54 10.51 11.80 12.76 13.03 12.86
the concrete proportioning of each component and test performance thereof in each embodiment of table 3
　 Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20
A600N 29 24 25 25 25 25 25 25 15
AS 40 40 50 50 50 50 50 50 60
FR-1524 10　 10　 12　 11　 11　 10　 9　 8　 8
CPE 2135 15 20 10 10 10 10 10 10 10
XX 3 5 5 2　 2　 3　 4　 5　 6　 6
SN80-SA7 0.3 0.3 0.2 0.2 0.2 0.2 0.2 0.2 0.2
S-74 2 2 1 1 1 1 1 1 1
Antioxidant 1010+168 1 1 0.6 0.6 0.6 0.6 0.6 0.6 0.6
HS-770 1 1 0.7 0.7 0.7 0.7 0.7 0.7 0.7
BS 3818+70 white oil 1 1 1 1 1 1 1 1 1
TS 37 35 40 41 41 40 40 39 42
EL 5 5 5 5 5 5 5 5 5
NIS 19 21 12 13 15 16 17 17 12
FS 58 57 62 63 63 62 61 60 63
FM 1900 1790 2250 2390 2350 2350 2490 2560 2350
MI 47 42 44 48 52 55 57 61 66
UL94@1.0mm V-0 V-0 / / / / V-0 V-0 V-0
UL94@1.5mm V-0 V-0 / / / V-0 V-0 V-0 V-0
UL94@2.0mm V-0 V-0 / / V-0 V-0 V-0 V-0 V-0
UL94@2.5mm V-0 V-0 / V-0 V-0 V-0 V-0 V-0 V-0
UL94@3.0mm V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
H.D.T 74 74 76 76 75 75 75 75 75
WR 11.02 8.66 12.53 11.89 11.00 10.89 10.58 10.78 8.60
As can be seen from the performance comparison of above-described embodiment and comparative example, by adding suitable species and properly mixed fire retardant and novel environment friendly fire retarding synergist thereof, ASA material has excellent flame retardant properties and mobility, the mechanical property of superelevation, simultaneously, compare with flame-proof ABS, under the same terms, its weathering resistance improves more than 1 times.

Claims (9)

1. a low cost height flowing weather resistance environmental protection bromine system flame-retardant ASA material, is characterized in that, count by weight, be made up of following component:
ASA resin 15-40 part
Styrene-acrylonitrile resin 30-60 part
Environmental protection bromide fire retardant 8-11 part
Chlorinatedpolyethylene 5-20 part
Novel environment friendly fire retarding synergist 2-6 part
Wherein, described environmental protection bromide fire retardant is tetrabromo-bisphenol;
The compound that described novel environment friendly fire retarding synergist is made up of antimony compounds, inorganic powder and ultra-high molecular weight polysiloxane, in this compound, the weight percentage of antimony compounds is 20-80%.
2. low cost height flowing weather resistance environmental protection bromine system according to claim 1 flame-retardant ASA material, it is characterized in that, described antimony compounds is antimonous oxide, colloidal antimony pentoxide, sodium antimonate, butter of antimony, antimony pentachloride, and one or more in phosphorous acid antimony, polyphosphoric acid antimony, complexing antimony are composite to be formed.
3. low cost height flowing weather resistance environmental protection bromine system according to claim 1 flame-retardant ASA material, it is characterized in that, described inorganic powder is the mixture of one or more in talcum powder, titanium dioxide, zinc sulfide white, magnesiumcarbonate, barium sulfate, marble dust, mica powder, natural silica, wollastonite powder, kaolin and Feldspar Powder.
4. low cost height flowing weather resistance environmental protection bromine system according to claim 1 flame-retardant ASA material, is characterized in that, weight-average molecular weight >=30,000 of described ultra-high molecular weight polysiloxane, when temperature is 25 DEG C, and its viscosity >=500mPas.
5. low cost height flowing weather resistance environmental protection bromine system according to claim 1 flame-retardant ASA material, it is characterized in that, described ultra-high molecular weight polysiloxane is the mixture of one or more in methyl polysiloxane, phenyl polysiloxane, vinyl polysiloxane, amide group polysiloxane, epoxy group(ing) polysiloxane, isobutyl-polysiloxane, styryl polysiloxane or ring texture polysiloxane.
6. low cost height flowing weather resistance environmental protection bromine system according to claim 1 flame-retardant ASA material, is characterized in that, also comprise 0.1-0.3 part anti-dripping agent, 0.1-2 part dispersion agent, 0-1 part oxidation inhibitor, 0-1 part photostabilizer or 0-5 part processing aid.
7. low cost height flowing weather resistance environmental protection bromine system according to claim 6 flame-retardant ASA material, it is characterized in that, described anti-dripping agent is tetrafluoroethylene; Described dispersion agent is stearic acid dispersion agent; Described oxidation inhibitor is the mixture of Hinered phenols primary antioxidant and phosphorous acid esters auxiliary anti-oxidant composition; Described photostabilizer is benzophenone, benzotriazole category, triazines, the poly-mixture for one or more in vinyl cyanide, Oxamides and hindered amines; Described processing aid is the mixture of one or more in stearylamide series lubricant agent, silicone oil and white mineral oil.
8. the preparation method of the low cost height flowing weather resistance environmental protection bromine system flame-retardant ASA material described in any one of claim 1-7, is characterized in that, comprise the steps:
A, each component raw material is fully mixed 10-60 minute by proportioning at high-speed mixer;
B, said mixture is transported in twin screw extruder through the pay-off of delicate metering, each section of extruder temperature of forcing machine controls between 170 ~ 220 DEG C, the length-to-diameter ratio of twin screw extruder is 25 ~ 40, screw speed is 200-800 rev/min, screw rod shearing, mixing and conveying under, material is able to abundant fusing, compound, then obtains flame-retardant ASA material through extruding pelletization, drying.
9. the application of the low cost height flowing weather resistance environmental protection bromine system flame-retardant ASA material described in any one of claim 1-7 out of doors in field of electronics.
CN201310022800.9A 2013-01-22 2013-01-22 Low-cost high-flow weather-proof environment-friendly brominated flame retardant ASA material as well as preparation method and application thereof Active CN103073808B (en)

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