CN102827452B - Flame retardant acrylonitrile butadiene styrene (ABS) composition with high heat resistance and high toughness and preparation method and application thereof - Google Patents

Flame retardant acrylonitrile butadiene styrene (ABS) composition with high heat resistance and high toughness and preparation method and application thereof Download PDF

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Publication number
CN102827452B
CN102827452B CN201210340196.XA CN201210340196A CN102827452B CN 102827452 B CN102827452 B CN 102827452B CN 201210340196 A CN201210340196 A CN 201210340196A CN 102827452 B CN102827452 B CN 102827452B
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abs
heat
resisting
composition
retardant
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CN102827452A (en
Inventor
汪炉林
王林
程庆
叶晓光
刘学亮
郭涛
王亮
谢明星
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WUHAN JINFA TECHNOLOGY CO., LTD.
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Kingfa Science and Technology Co Ltd
Tianjin Kingfa Advanced Materials Co Ltd
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Abstract

The invention discloses a flame retardant acrylonitrile butadiene styrene (ABS) composition with high heat resistance and high toughness and a preparation method and the application of the composition; the flame retardant ABS composition comprises the components in parts by weight: 100 parts of high temperature resistant ABS masterbatches, 10-25 parts of environment-friendly brominated flame retardant, 5-10 parts of flame retardant synergist, 0.5-2 parts of maleic anhydride grafting styrene block copolymer (SEBS), 5-15 parts of flexibilizer and 0.5-5 parts of processing agent. The preparation method of the flame retardant ABS composition comprises two steps of: firstly, preparing the high temperature resistant ABS masterbatches; and secondly, mixing the temperature resistant ABS masterbatches, the environment-friendly brominated flame retardant, the flame retardant synergist, the maleic anhydride grafting SEBS, the flexibilizer and the processing agent, adding the mixture into a twin-screw extruder and then carrying out extruding and pelleting to obtain the flame retardant ABS plastic particles with high heat resistance and high toughness. The flame retardant ABS composition with high heat resistance and high toughness has high heat resistance, impact resistance and flame retardant effect as well as excellent stability and mechanical property, thus being widely applied to the fields such as a motor, a blower, a power supply box, a microwave oven, an electric cooker, an extension socket, an automobile instrument, a heat-resistant storage battery and the like.

Description

A kind of high heat-resisting, high tenacity flame-retardant ABS composition and its preparation method and application
Technical field
The invention belongs to functional high molecule material technical field, be specifically related to a kind of high heat-resisting, high tenacity flame-retardant ABS composition and its preparation method and application.
Background technology
Styrene butadiene-vinyl cyanide (ABS) resin is with rigidity and the thermotolerance of vinyl cyanide, the features such as shock resistance of the glossiness of polystyrene and processibility and polyhutadiene, can be widely used in the fields such as household electrical appliance, office equipment, instrument, communications and transportation, material of construction, household utensils and wrapping material.But the oxygen index of ABS resin only has 18, belongs to inflammable material.In order to improve its burning behavior, make it meet the difficult combustion of fire or certainly put out from fire, must carry out flame-retardant modified to ABS.But for electric appliance casing or component such as motor, blower, power pack, microwave oven, electric cooker, socket, fascia, heat-resisting store batteries, except requiring material to have fire-retardant time, also require material to there is certain thermotolerance and certain toughness.
Flame-proof ABS reaches fire-retardant object mainly with adding fire retardant at present, conventional fire retardant mainly contains tetrabromo-bisphenol (TBBPA), brominated epoxy resin (BEO), brominated triazine (BTAC), TDE (DBDPE) etc. and antimonous oxide (SBO) are composite.But the thermotolerance of ABS resin own is not high on the one hand, its heat-drawn wire is 82-84 ℃, ABS resin itself is sea-island structure on the other hand, add above-mentioned fire retardant and can further reduce thermotolerance and the mechanical property of ABS resin, therefore having limited it is not only needing fire-retardant but also is needing the application in the fields such as certain thermotolerance and toughness.
For this reason, some scholars are in order to improve the thermotolerance of flame-proof ABS, conventionally with toughener glass fibre (GF), wollastonite, talcum powder etc., flame-proof ABS is carried out to thermotolerance modification, but this method is in the thermotolerance while of improving flame-proof ABS, can significantly reduce toughness and the mobility of flame-proof ABS, make ABS resin lose high-luster simultaneously, be difficult to apply in appearance component field.Another kind method is by heat-resistant agent, fire retardant and other processing aid blend, by twin screw extruder extruding pelletization, prepare high-temp resistant fire-retarding ABS again, but because heat-resistant agent is different with fire retardant thermotolerance, temperature is lower than under 240 ℃ of conditions, heat-resistant agent disperses uneven, and temperature is higher than 240 ℃, and fire retardant decomposes serious, make the serious flavescence of plastic particles of preparation, do not reach the flame retardant effect of appointment simultaneously.Also has a kind of method by ABS resin and other resin formation alloy, as fire retardation PC/ABS alloy, ABS/SMA alloy etc.Although this type of alloy can improve the thermotolerance of flame-proof ABS resin and keep good appearance simultaneously, the tired energy of its processing, high expensive, is not suitable for large-scale popularization application on market simultaneously.
In addition, application number is 201210142259.0 to disclose a kind of ultrahigh heat-resistant flame-retardant ABS composition and its preparation method and application, by two-step approach, solve on the one hand the dispersion of heat-resistant agent in matrix resin, solved on the other hand the contradiction of fire retardant with the different processing temperatures of heat-resistant agent.But by the disclosed technical formula of above-mentioned patent, its toughness is all not high, and adding the raising of toughness of toughner is very limited, too much toughner can cause thermotolerance to reduce simultaneously.
Summary of the invention
Primary and foremost purpose of the present invention is to provide that a kind of height that has high flame retardant effect, high thermotolerance, high tenacity, low cost, mechanical property excellence concurrently is heat-resisting, high tenacity flame-retardant ABS composition.
Another object of the present invention is to provide that above-mentioned height is heat-resisting, the preparation method of high tenacity flame-retardant ABS composition.
The present invention is achieved through the following technical solutions:
High heat-resisting, a high tenacity flame-retardant ABS composition, counts by weight, comprises following component:
100 parts of high heat-proof ABS master batches
Environmental protection bromide fire retardant 10-25 part
Fire retarding synergist 5-10 part
Maleic anhydride graft SEBS 0.5-2 part
Toughner 5-15 part
Processing aid 0.5-5 part.
High heat-proof ABS master batch of the present invention comprises the component of following weight part:
100 parts of ABS resinoids
Heat-proof modifier 12-45 part
Oxidation inhibitor 0.1-1 part
Photostabilizer 0.1-1 part
Processing aid 0.5-5 part.
Preferably, high heat-proof ABS master batch of the present invention comprises the component of following weight part:
100 parts of ABS resinoids
Heat-proof modifier 12-45 part
Toughner 5-20 part
Dispersion agent 0.5-2 part
Oxidation inhibitor 0.1-1 part
Photostabilizer 0.1-1 part
Processing aid 0.5-5 part.
Described ABS resinoid is acrylonitrile-butadiene-phenylethene grafted copolymer ABS, acrylonitrile-styrene-acrylic terpolymer ASA or MBS graft copolymer MBS.This resinoid is known resin, and all can buy and obtain on the market, ABS prepared by the ABS that for example prepared by substance law or emulsion method or their compound, raw material range is extensive, can select different ABS resin according to different demands; Wherein substance law ABS resin for example Shanghai Gaoqiao model be ABS 8434,8391 and 3504 products, emulsion method ABS resin is the HI high impact ABS 745N of Jin Hu company and the HI high impact ABS D-120A of Zhenjiang Guo Heng company for example; The compound of ABS resin prepared by ABS resin prepared by the preferred substance law of the present invention and emulsion method.
Described heat-proof modifier is one or more the mixture in N-sec.-propyl maleimide, N-CYCLOHEXANE maleimide, poly-(N-n-octadecyl maleimide), N-phenylmaleimide and poly-(N-n-butyl maleimide).
Described oxidation inhibitor is comprised of Hinered phenols primary antioxidant and phosphorous acid esters auxiliary anti-oxidant.
Described photostabilizer is one or more the mixture in benzophenone, benzotriazole category, triazines, group-substituted acrylonitrile, Oxamides and hindered amines.
Described processing aid is one or more the mixture in stearylamide series lubricant agent, silicone oil and white mineral oil.
Described toughner is one or more the mixture in styrenic toughner, chlorinatedpolyethylene class toughner and ABS high glue powder.
Described dispersion agent is one or more the mixture in stearic acid dispersion agent.
Described environmental protection bromide fire retardant is one or more the mixture in TDE, brominated epoxy and aggretion type fire retardant FR-Emerald 1000.
The compound that described fire retarding synergist is comprised of antimonous oxide, inorganic powder and ultra-high molecular weight polysiloxane, in this compound, the weight percentage of antimonous oxide is 20-80%.
Described inorganic powder is one or more the mixture in talcum powder, titanium dioxide, zinc sulfide white, magnesiumcarbonate, barium sulfate, marble dust, mica powder, natural silica, wollastonite powder, kaolin and Feldspar Powder.
Described ultra-high molecular weight polysiloxane is with methyl polysiloxane, with phenyl polysiloxane, with vinyl polysiloxane, with amide group polysiloxane, with epoxy based polysiloxane, with isobutyl-polysiloxane, with styryl polysiloxane with one or more the mixture in ring texture polysiloxane.
The molecular weight of described ultra-high molecular weight polysiloxane >=30,000, when temperature is 25 ℃, its viscosity >=500mPas.
Described processing aid is one or more the mixture in stearylamide series lubricant agent, silicone oil and white mineral oil.
Height of the present invention is heat-resisting, the preparation method of high tenacity flame-retardant ABS composition, comprises the steps:
A, prepare high heat-proof ABS master batch: each component is added in high-speed mixer and be mixed to get pre-composition according to the above ratio, pre-composition is dropped into twin screw extruder and carry out extruding pelletization, obtain high heat-proof ABS master batch;
B, above-mentioned high heat-proof ABS master batch is dried, then by 100 parts of high heat-proof ABS master batches; Environmental protection bromide fire retardant 10-25 part; Fire retarding synergist 5-10 part; Maleic anhydride graft SEBS 0.5-2 part; Toughner 5-20 part; Processing aid 0.5-5 part adds in high-speed mixer carries out premix, above-mentioned pre-composition is dropped into twin screw extruder and carry out extruding pelletization, obtains high heat-resisting, high tenacity flame-retardant ABS composition.
In step a, twin-screw extrusion machine barrel temperature is preferably 240 ℃-270 ℃, engine speed 500-1500r/min, feeding rotating speed 200-800 r/min.
In step b, twin-screw extrusion machine barrel temperature is preferably 180 ℃-210 ℃, engine speed 500-1500r/min, feeding rotating speed 200-800r/min.
Described in step a and step b, high-speed mixer mixes 2-10min under the rotating speed of 200-800r/min, then mixes 1-5min under the rotating speed of 500-1500r/min.
Preparation method of the present invention carries out in two steps, because heat-proof modifier is different with fire retardant thermotolerance, temperature is lower than under 240 ℃ of conditions, heat-resistant agent disperses uneven, temperature is higher than 240 ℃, fire retardant decomposes serious, therefore the present invention joins twin screw extruder and carries out extruding pelletization and prepare high heat-proof ABS master batch, preferably 240 ℃-270 ℃ of twin-screw extrusion machine barrel temperature after first ABS resinoid, heat-proof modifier, oxidation inhibitor, photostabilizer and processing aid being joined by a certain percentage and mixing in high-speed mixer; Again above-mentioned high heat-proof ABS master batch, environmental protection bromide fire retardant, fire retarding synergist, maleic anhydride graft SEBS, toughner and other processing aid are carried out to blend by a certain percentage, and then by twin screw extruder in carrying out extruding pelletization, prepare high heat-resisting, high tenacity flame-retardant ABS composition, in this step, twin-screw extrusion machine barrel temperature is preferably 180 ℃-210 ℃.Adopt such two-step approach to solve on the one hand the scattering problem of heat-proof modifier in matrix resin, met on the other hand fire retardant to processing temperature sensitive question.Again on the one hand, the introducing of the SEBS by maleic anhydride graft, can significantly improve the toughening efficiency of toughner.Meanwhile, utilize the feature of the sea-island structure of ABS resin itself, so the high thermotolerance heat-resisting, high tenacity flame-retardant ABS composition of preparation is high, and high heat distortion temperature surpasses 115 degree, and ball impression temperature surpasses 125 degree, and its shock strength can be accomplished 25kJ/m simultaneously 2above.
The preferred DBDPE of environmental protection bromide fire retardant of the present invention, CXB-2000 and aggretion type fire retardant FR-Emerald 1000, fire retardant fusing point is high, and substantially insoluble in resin, so add in resin, there is higher heat-drawn wire and unsuitable frosting, can recycling use be conducive to energy-conserving and environment-protective, the unconventional antimonous oxide of fire retarding synergist of introducing, but a small amount of antimonous oxide, the compound of inorganic powder and ultra-high molecular weight polysiloxane, the introducing that concrete is exactly by ultra-high molecular weight polysiloxane and inorganic powder makes the high temperature that produces in combustion processes delay because condensed phase is fire-retardant to the speed of material internal transmission, because condensed phase is fire-retardant, at material surface, form one deck protection charcoal layer simultaneously, can further reduce the supply of fuel to material internal, flame temperature is reduced, thereby the inner bromo-antimony gaseous phase free radical of protective layer being flutterred catch mechanism is able to effective performance, so fire-retardant being achieved of synergistic between them, reaching under the prerequisite of required flame retardant rating, can significantly reduce antimonous oxide and bromide fire retardant consumption, in addition, the thermotolerance of ultra-high molecular weight polysiloxane itself is just very high, in system, jointly disperse the interpolation auxiliary agents such as fire retardant with dispersion agent simultaneously, fire retardant effect and stability have further been brought into play thus, and improved system thermotolerance.Meanwhile, the SEBS of maleic anhydride graft can bring into play the toughening efficiency of toughner, in the stable on heating while of guarantee system, can significantly improve the toughness of system.
Height of the present invention is heat-resisting, the test of high tenacity flame-retardant ABS plastic particle process, meeting under mechanical property prerequisite, its every mechanical property all keeps optimum balance, can be widely used in the fields such as motor, blower, power pack, microwave oven, electric cooker, socket, fascia, heat-resisting store battery.
Preparation method of the present invention is simple, handling ease, and cost, far below fire retardation PC/ABS alloy and fire retardation PC, is applicable to substituting the large-scale popularization application on market of fire retardation PC/ABS alloy and fire retardation PC.
Embodiment
Below by embodiment, the present invention is described, but is not limited to this.
The high high-speed mixer heat-resisting, that high tenacity flame-retardant ABS composition is used of preparation is the SHR-100A that Zhangjagang City, Jiangsu Kodak Machinery Co., Ltd. produces; The high twin screw extruder heat-resisting, that high tenacity flame-retardant ABS composition is used of preparation is the SHJ-30 being produced by Rhea superpolymer Equipment Limited, Nanjing; The high injection moulding machine heat-resisting, that high tenacity flame-retardant ABS composition test bars adopts of preparation is the B-920 type of being produced by Zhejiang Hai Tian injection moulding machine company limited; The T92 type that the impact experiment Ji Shi U.S. Tinius Olsenis company that test shock strength is used produces; The universal testing machine that test tensile strength is used is the H10K-S that Hounsfield company produces;
The thermal distortion dimension card tester that test heat resisting temperature is used is the 40-197-006 that German COESFELD produces;
The ball pressure tester that test ball impression temperature is used is the OJN-9414 that Shenzhen Ou Jienuo Science and Technology Ltd. produces; The ATLAS HVUL-2 that the vertical combustion Yi Shi U.S. UL company that test flame retardant effect is used produces.
In following examples, wherein to select respectively Shanghai Gaoqiao model be ABS 8434,8391 and 3504 products to substance law ABS resin, and emulsion method ABS resin is selected the HI high impact ABS 745N of Jin Hu company and the HI high impact ABS D-120A of Zhenjiang Guo Heng company; The CXB-2000 that environmental protection bromide fire retardant selects Korea S's space to enter, 4010 of Albemarle Corporation, one or more in the FR-Emerald 1000 of big lake chemical industry; Fire retarding synergist is selected the KF-100 of golden hair company; Heat-proof modifier is selected AS-MS-NA, the AS-MS-NB of Japanese electrochemical company; Toughner is selected the HR181 of Jin Hu company; The SEBS of maleic anhydride graft selects the SEBS 7131 of Tai Xiang company; Dispersion agent is selected the S-74 of Li Yan company; Oxidation inhibitor is selected Irganox 1010 and the Irganox 168 of gas Ba Jinghua; Photostabilizer is selected the UV-P of gas Ba Jinghua; Processing aid is selected general commodity in the market.
embodiment 1
(1) weight part of each component of high heat-proof ABS master batch (HRM1) is as follows:
ABS resin: 100 weight parts
Heat-proof modifier (AS-MS-NB): 12 weight parts
Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) 0.2+ 0.4 weight part
Photostabilizer (UV-P) 0.2 weight part
Processing aid (EBS+70 white oil): 0.5 weight part
(2) its preparation method is as follows:
The each component of above-mentioned designated ratio is added in high-speed mixer and mix 2-10min under the rotating speed of 200-800r/min, under the rotating speed of 500-1500r/min, mix 1-5min again and obtain pre-composition, above-mentioned pre-composition is dropped into twin screw extruder and carry out extruding pelletization, twin-screw extrusion machine barrel temperature is divided 10 sections of controls, temperature is controlled at 240-270 ℃, engine speed 500-1500r/min, feeding rotating speed 200-800 r/min, and extruding pelletization is prepared high heat-proof ABS master batch.Above-mentioned particle is joined in injection moulding machine and is processed into required batten, and injecting condition is: 220 ℃ of barrel temperatures, die temperature 60-70 ℃, injection pressure 8MPa.Data measured is as shown in table 2.
embodiment 2
(1) weight part of each component of high heat-proof ABS master batch (HRM2) is as follows:
ABS resin: 100 weight parts
Heat-proof modifier (AS-MS-NB): 18 weight parts
Toughner (HR181): 5 weight parts
Dispersion agent (S-74): 1 weight part
Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) 0.2+ 0.4 weight part
Photostabilizer (UV-P) 0.2 weight part
Processing aid (EBS+70 white oil): 0.5 weight part
(2) its preparation technology is with embodiment 1, and data measured is as shown in table 2.
embodiment 3
(1) weight part of each component of high heat-proof ABS master batch (HRM3) is as follows:
ABS resin: 100 weight parts
Heat-proof modifier (AS-MS-NB): 24 weight parts
Toughner (HR181): 10 weight parts
Dispersion agent (S-74): 1 weight part
Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) 0.2+ 0.4 weight part
Photostabilizer (UV-P) 0.2 weight part
Processing aid (EBS+70 white oil): 0.5 weight part
(2) its preparation technology is with embodiment 1, and data measured is as shown in table 2.
embodiment 4
(1) weight part of each component of high heat-proof ABS master batch (HRM4) is as follows:
ABS resin: 100 weight parts
Heat-proof modifier (AS-MS-NB): 30 weight parts
Toughner (HR181): 15 weight parts
Dispersion agent (S-74): 1.5 weight part
Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) 0.2+ 0.4 weight part
Photostabilizer (UV-P) 0.2 weight part
Processing aid (EBS+70 white oil): 0.5 weight part
(2) its preparation technology is with embodiment 1, and data measured is as shown in table 2.
embodiment 5
1) weight part of each component of high heat-proof ABS master batch (HRM5) is as follows:
ABS resin: 100 weight parts
Heat-proof modifier (AS-MS-NB): 38 weight parts
Toughner (HR181): 15 weight parts
Dispersion agent (S-74): 1.5 weight part
Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) 0.2+ 0.4 weight part
Photostabilizer (UV-P) 0.2 weight part
Processing aid (EBS+70 white oil): 0.5 weight part
(2) its preparation technology is with embodiment 1, and data measured is as shown in table 2.
embodiment 6
(1) weight part of each component of high heat-proof ABS master batch (HRM6) is as follows:
ABS resin: 100 weight parts
Heat-proof modifier (AS-MS-NB): 45 weight parts
Toughner (HR181): 20 weight parts
Dispersion agent (S-74): 2 weight parts
Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) 0.2+ 0.4 weight part
Photostabilizer (UV-P) 0.2 weight part
Processing aid (EBS+70 white oil): 0.5 weight part
(2) its preparation technology is with embodiment 1, and data measured is as shown in table 2.
embodiment 7
(1) high weight part heat-resisting, each component of high tenacity flame-proof ABS (FRM1) is as follows:
Ultrahigh heat-resistant ABS master batch (HRM1): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 1 weight part
HR181 8 weight parts
Processing aid (EBS): 0.5 weight part
(2) during being added to high-speed mixer in proportion with above-mentioned each component after 80 ℃ of dry 4h, high heat-proof ABS master batch mixes 2-10min under the rotating speed of 200-800r/min, under the rotating speed of 500-1500r/min, mix 1-5min again and obtain pre-composition, above-mentioned pre-composition is dropped into twin screw extruder and carry out extruding pelletization, twin-screw extrusion machine barrel temperature is divided 10 sections of controls, temperature is controlled at 180-210 ℃, engine speed 500-1500r/min, feeding rotating speed 200-800r/min, extruding pelletization obtains high heat-resisting, high tenacity flame-retardant ABS composition.Above-mentioned particle is joined in injection moulding machine and is processed into required batten, and injecting condition is: 220 ℃ of barrel temperatures, die temperature 60-70 ℃, injection pressure 8MPa.Data measured is as shown in table 3.
comparative example 1
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM1): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 3.
comparative example 2
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM1): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
HR181 8 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 3.
comparative example 3
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM1): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 1 weight part
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 3.
embodiment 8
(1) high weight part heat-resisting, each component of high tenacity flame-proof ABS (FRM2) is as follows:
High heat-proof ABS master batch (HRM2): 100 weight parts
Environmental protection bromide fire retardant (4010): 10 weight parts
Fire retarding synergist (KF-100): 10 weight parts
SEBS 7131 1 weight part
HR181 8 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 3.
comparative example 4
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM2): 100 weight parts
Environmental protection bromide fire retardant (4010): 10 weight parts
Fire retarding synergist (KF-100): 10 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 3.
comparative example 5
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM2): 100 weight parts
Environmental protection bromide fire retardant (4010): 10 weight parts
Fire retarding synergist (KF-100): 10 weight parts
HR181 8 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 3.
comparative example 6
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM2): 100 weight parts
Environmental protection bromide fire retardant (4010): 10 weight parts
Fire retarding synergist (KF-100): 10 weight parts
SEBS 7131 1 weight part
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 3.
embodiment 9
(1) high weight part heat-resisting, each component of high tenacity flame-proof ABS (FRM3) is as follows:
High heat-proof ABS master batch (HRM3): 100 weight parts
Environmental protection bromide fire retardant (4010): 25 weight parts
Fire retarding synergist (KF-100): 5 weight parts
SEBS 7131 1 weight part
HR181 8 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 4.
comparative example 7
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM3): 100 weight parts
Environmental protection bromide fire retardant (4010): 25 weight parts
Fire retarding synergist (KF-100): 5 weight parts
HR181 8 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 4.
comparative example 8
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM3): 100 weight parts
Environmental protection bromide fire retardant (4010): 25 weight parts
Fire retarding synergist (KF-100): 5 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 4.
comparative example 9
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM3): 100 weight parts
Environmental protection bromide fire retardant (4010): 25 weight parts
Fire retarding synergist (KF-100): 5 weight parts
SEBS 7131 1 weight part
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 4.
embodiment 10
(1) high weight part heat-resisting, each component of high tenacity flame-proof ABS (FRM4) is as follows:
High heat-proof ABS master batch (HRM4): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 1 weight part
HR181 8 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 4.
comparative example 10
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM4): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
HR181 8 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 4.
comparative example 11
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM4): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 4.
comparative example 12
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM4): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 1 weight part
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 4.
embodiment 11
(1) high weight part heat-resisting, each component of high tenacity flame-proof ABS (FRM5) is as follows:
High heat-proof ABS master batch (HRM5): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 1 weight part
HR181 8 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 5.
comparative example 13
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM5): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
HR181 8 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 5.
comparative example 14
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM5): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 5.
comparative example 15
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM5): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 1 weight part
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 5.
embodiment 12
(1) high weight part heat-resisting, each component of high tenacity flame-proof ABS (FRM6) is as follows:
High heat-proof ABS master batch (HRM6): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 1 weight part
HR181 8 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 5.
comparative example 16
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM6): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
HR181 8 weight parts
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 5.
comparative example 17
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM6): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
Processing aid (EBS): 0.5 weight part
(3) its preparation method is with embodiment 7, and data measured is as shown in table 5.
comparative example 18
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM6): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 1 weight part
Processing aid (EBS): 0.5 weight part
(2) its preparation method is with embodiment 7, and data measured is as shown in table 5.
embodiment 13
(1) high weight part heat-resisting, each component of high tenacity flame-proof ABS (FRM7) is as follows:
High heat-proof ABS master batch (HRM6): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 0.5 weight part
HR181 8 weight parts
Processing aid (EBS): 2 weight parts
(2) its preparation method is with embodiment 7, and data measured is as shown in table 6.
embodiment 14
(1) high weight part heat-resisting, each component of high tenacity flame-proof ABS (FRM7) is as follows:
High heat-proof ABS master batch (HRM6): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 1.5 weight part
HR181 8 weight parts
Processing aid (EBS): 2 weight parts
(2) its preparation method is with embodiment 7, and data measured is as shown in table 6.
embodiment 15
(1) high weight part heat-resisting, each component of high tenacity flame-proof ABS (FRM7) is as follows:
High heat-proof ABS master batch (HRM6): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 2 weight parts
HR181 8 weight parts
Processing aid (EBS): 2 weight parts
(2) its preparation method is with embodiment 7, and data measured is as shown in table 6.
embodiment 16
(1) high weight part heat-resisting, each component of high tenacity flame-proof ABS (FRM7) is as follows:
High heat-proof ABS master batch (HRM6): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 1 weight part
HR181 5 weight parts
Processing aid (EBS): 2 weight parts
(2) its preparation method is with embodiment 7, and data measured is as shown in table 6.
embodiment 17
(1) high weight part heat-resisting, each component of high tenacity flame-proof ABS (FRM7) is as follows:
High heat-proof ABS master batch (HRM6): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 1 weight part
HR181 10 weight parts
Processing aid (EBS): 2 weight parts
(2) its preparation method is with embodiment 7, and data measured is as shown in table 6.
embodiment 18
(1) high weight part heat-resisting, each component of high tenacity flame-proof ABS (FRM7) is as follows:
High heat-proof ABS master batch (HRM6): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 1 weight part
HR181 15 weight parts
Processing aid (EBS): 2 weight parts
(2) its preparation method is with embodiment 7, and data measured is as shown in table 6.
comparative example 19
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM6): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 3 weight parts
HR181 15 weight parts
Processing aid (EBS): 2 weight parts
(2) its preparation method is with embodiment 7, and data measured is as shown in table 6.
comparative example 20
(1) weight part of each component is as follows:
High heat-proof ABS master batch (HRM6): 100 weight parts
Environmental protection bromide fire retardant (4010): 15 weight parts
Fire retarding synergist (KF-100): 8 weight parts
SEBS 7131 5 weight parts
HR181 15 weight parts
Processing aid (EBS): 2 weight parts
(2) its preparation method is with embodiment 7, and data measured is as shown in table 6.
Composition prepared by each embodiment is injection molded into the standard batten of test use by standard size, the following standard testing respectively of the performance in each embodiment is as shown in table 1.
Table 1 testing standard
1. melting index test condition: 220 ℃/10KG
2. heat-drawn wire test condition: 6.4mm/1.82MPa
The physicochemical property data of table 2 embodiment 1-6 tests
Test event Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
TS 46 49 51 52 55 58
EL 9 8 8 8 9 10
NIS 19 18 17 17 16 15
FS 67 70 74 77 78 80
FM 2250 2339 2420 2510 2607 2815
MFI 10.5 8.3 6.5 4.8 3.5 2.2
SG 1.08 1.08 1.08 1.08 1.08 1.09
H.D.T 86 92 101 109 113 122
B.P.T 95 101 111 117 122 131
The physicochemical property data of table 3 embodiment 7-8 and comparative example 1-6 test
Test event Embodiment 7 Comparative example 1 Comparative example 2 Comparative example 3 Embodiment 8 Comparative example 4 Comparative example 5 Comparative example 6
TS 37 37 38 36 37 37 39 36
EL 15 10 10 10 18 9 10 10
NIS 22 18 17 17 22 17 16 17
FS 63 62 65 61 63 62 68 60
FM 2100 2110 2210 2110 2199 2151 2287 2106
MFI 25.5 18.5 22.5 18.5 24.8 17.5 19.3 18
SG 1.17 1.17 1.18 1.18 1.17 1.17 1.18 1.17
H.D.T 84 83 85 83 90 88 91 87
B.P.T 94 93 96 93 100 99 102 98
UL94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
The physicochemical property data of table 4 embodiment 9-10 and comparative example 7-12 test
Test event Embodiment 9 Comparative example 7 Comparative example 8 Comparative example 9 Embodiment 10 Comparative example 10 Comparative example 11 Comparative example 12
TS 38 38 39 37 39 39 40 38
EL 17 10 11 10 19 9 10 10
NIS 20 15 14 15 22 14 15 13
FS 68 66 70 65 69 67 72 66
FM 2187 2110 2390 2108 2209 2191 2410 2178
MFI 18.9 11.3 15.5 11.5 15.4 8.8 10.8 9.1
SG 1.17 1.17 1.18 1.17 1.17 1.17 1.18 1.17
H.D.T 94 93 96 92 100 99 102 98
B.P.T 107 106 109 105 109 108 111 107
UL94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
The physicochemical property data of table 5 embodiment 11-12 and comparative example 13-18 test
Test event Embodiment 11 Comparative example 13 Comparative example 14 Comparative example 15 Embodiment 12 Comparative example 16 Comparative example 17 Comparative example 18
TS 39 38 41 37 40 39 42 38
EL 20 10 10 10 19 9 10 9
NIS 20 15 14 15 23 13 12 13
FS 72 71 75 69 73 71 76 70
FM 2330 2270 2407 2265 2389 2255 2515 2210
MFI 13.8 5.1 6.5 5.0 9.7 2.9 4.2 2.8
SG 1.17 1.17 1.18 1.17 1.17 1.17 1.18 1.17
H.D.T 107 106 109 105 114 112 115 110
B.P.T 115 113 117 112 123 121 125 120
UL94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
The physicochemical property data of table 6 embodiment 13-18 and comparative example 19-20 test
Test event Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18 Comparative example 19 Comparative example 20
TS 41 38 35 41 39 37 33 23
EL 15 21 20 16 17 20 25 30
NIS 20 25 27 20 25 28 30 31
FS 75 70 66 74 71 69 55 41
FM 2450 2210 2081 2401 2299 2200 1987 1599
MFI 8.1 11.2 13.4 10.5 8.9 7.5 7.0 7.1
SG 1.17 1.17 1.17 1.17 1.17 1.17 1.17 1.17
H.D.T 114 114 111 114 113 110 108 105
B.P.T 124 123 120 124 122 120 118 116
UL94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
From the test result of above-described embodiment 7-8 and comparative example 1-6, embodiment 9-10 and comparative example 7-12, embodiment 11-12 and comparative example 13-18, can find out, add separately toughner or add separately maleic anhydride graft SEBS or both do not add simultaneously,
Its shock strength is 13-18 kJ/m 2and the present invention adds toughner and the prepared height of maleic anhydride graft SEBS is heat-resisting, high tenacity flame-retardant ABS composition simultaneously, there is ultrahigh heat-resistant, high heat distortion temperature surpasses 110 degree, ball impression temperature surpasses 120 degree, compared with prior art, at least improves 10 degree; And have high toughness, its high impact can surpass 28kJ/m 2, improve on the basis of existing technology 50%.In addition, meeting under mechanical property prerequisite, reaching flame retardant effect and stability is more excellent, all other mechanical properties all keep optimum balance.

Claims (18)

1. high heat-resisting, a high tenacity flame-retardant ABS composition, is characterized in that: meter by weight, comprises following component:
100 parts of high heat-proof ABS master batches
Environmental protection bromide fire retardant 10-25 part
Fire retarding synergist 5-10 part
Maleic anhydride graft SEBS 0.5-2 part
Toughner 5-15 part
Processing aid 0.5-5 part
Described high heat-proof ABS master batch comprises the component of following weight part:
100 parts of ABS resinoids
Heat-proof modifier 12-45 part
Oxidation inhibitor 0.1-1 part
Photostabilizer 0.1-1 part
Processing aid 0.5-5 part
Described ABS resinoid is acrylonitrile-butadiene-phenylethene grafted copolymer ABS, acrylonitrile-styrene-acrylic terpolymer ASA or MBS graft copolymer MBS;
or,described high heat-proof ABS master batch comprises the component of following weight part:
100 parts of ABS resinoids
Heat-proof modifier 12-45 part
Toughner 5-20 part
Dispersion agent 0.5-2 part
Oxidation inhibitor 0.1-1 part
Photostabilizer 0.1-1 part
Processing aid 0.5-5 part
Described ABS resinoid is acrylonitrile-butadiene-phenylethene grafted copolymer ABS, acrylonitrile-styrene-acrylic terpolymer ASA or MBS graft copolymer MBS.
2. heat-resisting, the high tenacity flame-retardant ABS composition of height according to claim 1, is characterized in that: described ABS resinoid is one or more compounds in the ABS resin prepared of the ABS resin prepared of substance law or emulsion method.
3. heat-resisting, the high tenacity flame-retardant ABS composition of height according to claim 1, is characterized in that: described heat-proof modifier is one or more the mixture in N-sec.-propyl maleimide, N-CYCLOHEXANE maleimide, poly-(N-n-octadecyl maleimide), N-phenylmaleimide and poly-(N-n-butyl maleimide).
4. heat-resisting, the high tenacity flame-retardant ABS composition of height according to claim 1, is characterized in that: described oxidation inhibitor is comprised of Hinered phenols primary antioxidant and phosphorous acid esters auxiliary anti-oxidant.
5. heat-resisting, the high tenacity flame-retardant ABS composition of height according to claim 1, is characterized in that: described photostabilizer is one or more the mixture in benzophenone, benzotriazole category, triazines, group-substituted acrylonitrile, Oxamides and hindered amines.
6. heat-resisting, the high tenacity flame-retardant ABS composition of height according to claim 1, is characterized in that: described processing aid is one or more the mixture in stearylamide series lubricant agent, silicone oil and white mineral oil.
7. heat-resisting, the high tenacity flame-retardant ABS composition of height according to claim 1, is characterized in that: described toughner is one or more the mixture in styrenic toughner, chlorinatedpolyethylene class toughner and ABS high glue powder.
8. heat-resisting, the high tenacity flame-retardant ABS composition of height according to claim 1, is characterized in that: described dispersion agent is one or more the mixture in stearic acid dispersion agent.
9. heat-resisting, the high tenacity flame-retardant ABS composition of height according to claim 1, is characterized in that: described environmental protection bromide fire retardant is one or more the mixture in TDE, brominated epoxy and aggretion type fire retardant FR-Emerald 1000.
10. heat-resisting, the high tenacity flame-retardant ABS composition of height according to claim 1, it is characterized in that: the compound that described fire retarding synergist is comprised of antimonous oxide, inorganic powder and ultra-high molecular weight polysiloxane, in this compound, the weight percentage of antimonous oxide is 20-80%.
11. height according to claim 10 are heat-resisting, high tenacity flame-retardant ABS composition, it is characterized in that: described inorganic powder is one or more the mixture in talcum powder, titanium dioxide, zinc sulfide white, magnesiumcarbonate, barium sulfate, marble dust, mica powder, natural silica, wollastonite powder, kaolin and Feldspar Powder.
12. height according to claim 10 are heat-resisting, high tenacity flame-retardant ABS composition, it is characterized in that: described ultra-high molecular weight polysiloxane is with methyl polysiloxane, with phenyl polysiloxane, with vinyl polysiloxane, with amide group polysiloxane, with isobutyl-polysiloxane, with styryl polysiloxane with one or more the mixture in ring texture polysiloxane.
13. height according to claim 12 are heat-resisting, high tenacity flame-retardant ABS composition, it is characterized in that: described band ring texture polysiloxane is band epoxy based polysiloxane.
14. height according to claim 12 are heat-resisting, high tenacity flame-retardant ABS composition, it is characterized in that: the molecular weight of described ultra-high molecular weight polysiloxane >=30,000, and when temperature is 25 ℃, its viscosity >=500mPas.
Height described in 15. claim 1 ~ 14 any one is heat-resisting, the preparation method of high tenacity flame-retardant ABS composition, it is characterized in that: comprise the steps:
A, prepare high heat-proof ABS master batch: each component is added in high-speed mixer and be mixed to get pre-composition according to the above ratio, pre-composition is dropped into twin screw extruder and carry out extruding pelletization, obtain high heat-proof ABS master batch;
B, above-mentioned high heat-proof ABS master batch is dried, then by 100 parts of high heat-proof ABS master batches; Environmental protection bromide fire retardant 10-25 part; Fire retarding synergist 5-10 part; Maleic anhydride graft SEBS 0.5-2 part; Toughner 5-15 part; Processing aid 0.5-5 part adds in high-speed mixer carries out premix, above-mentioned pre-composition is dropped into twin screw extruder and carry out extruding pelletization, obtains high heat-resisting, high tenacity flame-retardant ABS composition.
16. height according to claim 15 are heat-resisting, the preparation method of high tenacity flame-retardant ABS composition, it is characterized in that: in step a, twin-screw extrusion machine barrel temperature is controlled at 240 ℃-270 ℃, engine speed 500-1500r/min, feeding rotating speed 200-800 r/min; In step b, twin-screw extrusion machine barrel temperature is controlled at 180 ℃-210 ℃, engine speed 500-1500r/min, feeding rotating speed 200-800r/min.
17. height according to claim 15 are heat-resisting, the preparation method of high tenacity flame-retardant ABS composition, it is characterized in that: described in step a and step b, high-speed mixer mixes 2-10min under the rotating speed of 200-800r/min, then mixes 1-5min under the rotating speed of 500-1500r/min.
Height described in 18. claim 1 ~ 14 any one is heat-resisting, the application of high tenacity flame-retardant ABS composition in motor, blower, power pack, microwave oven, electric cooker, socket, fascia, heat-resisting store battery field.
CN201210340196.XA 2012-09-14 2012-09-14 Flame retardant acrylonitrile butadiene styrene (ABS) composition with high heat resistance and high toughness and preparation method and application thereof Expired - Fee Related CN102827452B (en)

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