CN102786767A - Halogen-free flame retardant ABS with super high flow and preparation method thereof - Google Patents
Halogen-free flame retardant ABS with super high flow and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a halogen-free flame retardant ABS with super high flow and a preparation method thereof. The halogen-free flame retardant ABS is composed of the following components, by weight: 100 parts of an ABS resin, 5-15 parts of aromatic phosphate ester, 0.5-5 parts of a flow modifier, 0-10 parts of a toughening agent, 0.1-1 part of an antioxidant, 0-1 part of a light stabilizer and 0-5 parts of processing agent. The halogen-free flame retardant ABS with super high flow prepared by the invention has advantages of high flow, low cost, high mechanical performance and stable flame resistance compared with existing halogen-free flame retardant ABS materials, and can be widely applied to the fields of thin wall and super large parts, such as office equipment, communications and video multimedia.
Description
Technical field
The present invention relates to polymeric material field, specifically, relate to a kind of halogen-free flame retardant ABS and preparation method thereof.
Background technology
The terpolymer that ABS resin is made up of vinylbenzene, divinyl, vinyl cyanide; The rubber toughness of cinnamic high workability, divinyl and the chemicals-resistant characteristic of vinyl cyanide have been concentrated; Have good processing characteristics, resistance to low temperature, electrical insulation capability, resistance to chemical corrosion and high gloss and excellent plating performance; Have excellent characteristics such as creep resistant is good, dimensional stability is high, molding shrinkage is little simultaneously, use very extensive in fields such as military project, automobile, electronic apparatuss.But the oxygen index of ABS resin has only 18, belongs to inflammable material, therefore when being used for electronic and electrical equipment, need carry out mostly flame-retardant modified, to reach the fire safety request for utilization.And have the burning of halogen flame-proof ABS product the time dense black smoke can occur usually, can produce toxic and harmful simultaneously.Therefore, the non-halogen research to material will become the main flow of flame retardant products from now on.But ABS resin is because its molecular backbone chain lacks aromatic group; With phosphorus flame retardant commonly used at present; Nitrogen flame retardant or inorganic combustion inhibitor can reach the V-2 level but not possess the stable flame-retardant effect; These fire retardants are owing to addition height, each item mechanical property and the processing fluidity of severe exacerbation material simultaneously.And another direction of non-halogen anti-flaming ABS material exploitation is to adopt polycarbonate or polyester and ABS to form alloy; Add halogen-free flame retardants commonly used at present again; Prepare halogen-free flame retardant ABS alloys such as PC/ABS or PET/ABS, its each item performance all than before a kind of method obvious improvement has been arranged, also can reach simultaneously higher flame retardant rating; But the also more common flame-proof ABS of its cost is high a lot; And its mobile deterioration is even more serious, causes the narrower of process window change, and this series products receives restriction to a certain degree in the application in some thin-gage goods and big product field.Therefore, existing market more need develop a kind of be suitable for that thin-gage goods and big product field use have a superelevation mobile halogen-free flame retardant ABS.
The preparation halogen-free flame retardant ABS generally adopts composite (patent No. 200910054786.4) of phosphonium flame retardant and other material, phosphorus-nitrogen combustion inhibitor (patent No. 200810203124.9) at present; Perhaps adopt inorganic combustion inhibitor such as red phosphorus flame-retardant ABS (patent No. 200910163461.X), composite (patent No. 200710172870.7) and other each system inorganic combustion inhibitor of red phosphorus and other char-forming agent.Or with the alloying of composite preparation of other tree resin.Like the alloy (patent No. 200810202918.9) that forms with the halogen-free flame retardant PC/ABS alloy (patent No. 201010524225.9) of the composite preparation of PC and polyester etc.
Summary of the invention
Shortcoming and deficiency in order to overcome prior art the object of the present invention is to provide a kind of superelevation mobile halogen-free flame retardant ABS.
Another object of the present invention is to provide the preparation method of the mobile halogen-free flame retardant ABS of above-mentioned superelevation.
The object of the invention is realized through following technical proposals:
A kind of superelevation halogen-free flame retardant ABS that flows is prepared by following compositions in portion by weight:
ABS resinoid: 100 parts
Aromatic phosphoric ester 5-15 part
Flow ability modifying agent 0.5-5 part
Toughner 0-10 part
Oxidation inhibitor 0.1-1 part
Photostabilizer 0-1 part
Processing aid 0-5 part;
Described ABS resinoid is acrylonitrile-butadiene-phenylethene grafted copolymer (ABS), acrylonitrile-styrene-acrylic terpolymer (ASA) or TEB 3K-butadiene-styrene graft copolymer (MBS);
Said aromatic phosphoric ester comprises that Resorcinol two (diphenylphosphoric acid fat) (RDP) and polycondensate; Dihydroxyphenyl propane two (diphenyl phosphoesters) (BDP) and polycondensate; Metaphenylene four (xylyl) biphosphonate (RXDP); Triphenylphosphate (TPP); Di(2-ethylhexyl)phosphate benzene toluene ester (DPTP); Phosphoric acid hexichol (YLENE) ester (DPXP); Phosphoric acid hexichol isopropyl benzene ester (DPPP); Diphenyl 2 ethylhexyl phosphate (DPOP); Phosphate diphenyl isodecyl ester (DPDP); Tricresyl phosphate (toluene) ester (TTP); Tricresyl phosphate (YLENE) ester (TXP); Phosphoric acid phenyl trimethylphenylmethane base ester (TBPPP); Alkane phenyl biphosphonate (phenyl is by alkane phenyl substituent among BDP and the RDP); Contain in the biphosphonate etc. of naphthenic base one or more.
Said flow ability modifying agent comprises 2,3-dimethyl--2, one or more in 3-diphenyl butane (Dicumene), amides lubricant, silicone lubricant, stearic acid lubricant, illiteracy dawn ester series lubricant agent, the polyalcohols lubricant.
Said toughner is one or more the mixture in esters of acrylic acid toughner, silicone based toughner and the ABS high glue powder.
Said oxidation inhibitor comprises Hinered phenols primary antioxidant and phosphorous acid esters auxiliary anti-oxidant composition.
Said photostabilizer comprises benzophenone, benzotriazole category, triazines, gather in the fine class of propylene, Oxamides, the hindered amines one or more.
Said processing aid is one or more the mixture in silicone oil, white mineral oil, the lubrication prescription.
The preparation method of above-mentioned halogen-free flame retardant ABS comprises the steps:
A, with each component raw material by proportioning high-speed mixer thorough mixing 10-60 minute;
B, said mixture is transported in the twin screw extruder through the pay-off of delicate metering; Each of forcing machine section extruder temperature is controlled between 170 ~ 230 ℃; The length-to-diameter ratio of twin screw extruder is 20 ~ 35, and screw speed is 200-800 rev/min, the shearing of screw rod, mixing and carry under; Material is able to abundant fusing, compound, obtains the halogen-free flame retardant ABS particle through extruding pelletization, drying again;
C, the halogen-free flame retardant ABS particle joined be processed into required test bars in the injection moulding machine; Said injecting condition is: barrel temperature 180-220 ℃, and 50 ~ 70 ℃ of die temperatures, injection pressure 6-10MPa.The present invention compared with prior art has following beneficial effect:
(1) the mobile halogen-free flame retardant ABS of superelevation disclosed by the invention is based on the further investigation of V-2 fire retardant mechanism; Adopt aromatic phosphoric ester and the composite halogen-free flame retardant ABS for preparing of flow ability modifying agent; Therefore under the very low situation of its addition; Flame retardant rating reaches UL941.0mm-3.0mm thickness and stablizes V-2, and its each item mechanical property is compared conservation rate more than 90% with matrix resin ABS.
(2) superelevation of the present invention flows halogen-free flame retardant ABS because its flowability significantly improves, and therefore can be widely used in thin-walled and super large product field, like office equipment, communication, video display multi-media etc.
(3) preparation method of the present invention is simple, handling ease, and simultaneously its cost and tetrabromo flame-proof ABS on sale in the market are suitable, are adapted at wideling popularize on the market application.
Embodiment
Through embodiment the present invention is described below, but is not limited to this.
The mobile used twin screw extruder of halogen-free flame retardant ABS of preparation superelevation is the SHJ-30 that is produced by Nanjing Rhea superpolymer equipment ltd.The injection moulding machine that the mobile halogen-free flame retardant ABS test bars of preparation superelevation adopts is the B-920 type of being produced by sea, Zhejiang sky injection moulding machine ltd.The impact experiment machine that the test shock strength is used is the T92 type that U.S. Tinius Olsenis company produces.The universal testing machine that test tensile strength is used is the H10K-S that Hounsfield company produces.The UL-94 vertical combustion appearance that test UL94 uses is U.S. ATLAS HVUL-2.
In following examples; Wherein ABS resin is selected the HI high impact ABS D-120A of the prosperous company of ABS D670 and Zhenjiang state of the tall company of state respectively for use; ASA selects 7045 of bright and beautiful lake company for use, and MBS selects the TH-21 of NEC chemistry for use, and aromatic phosphoric ester is selected the Fyrolflex sol-DP of ICL International Computer Limited for use; TPP of Akzo Nobel N.V. and RDP, flow ability modifying agent select the Dicumene of SI Group company and the EBS of the sharp chemical industry of speeding for use; Toughner is selected the KRISTALEX 5140 of U.S. Yi Shi Man and the HR181 of Korea S Jin Hu for use; Oxidation inhibitor is selected the Irganox 1010 and Irganox 168 of gas Ba Jinghua for use; Photostabilizer is selected 770 and the UV-P of gas Ba Jinghua for use, and other NM various processing aids are commercially available general commodity.
Embodiment 1
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 3+3 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 2+0.5 weight part |
| Toughner (KRISTALEX 5140): | 5 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550+O-W01): | 0.4+0.1 weight part |
(2) its preparation method is following:
Above-mentioned each component raw material was added in the mixing machine blending 15 minutes in proportion, is transported in the twin screw extruder through the pay-off of delicate metering, the length-to-diameter ratio of twin screw extruder is 30; Each of forcing machine section extruder temperature is controlled between 220 ℃; Screw speed is 400 rev/mins, the shearing of screw rod, mixing and carry under, material is able to abundant fusing, compound; Pass through extruding pelletization again, obtained the mobile halogen-free flame retardant ABS particle of superelevation down in dry 4 hours at 80 ℃; Then the flame-proof ABS particle is joined and be processed into required batten in the injection moulding machine, injecting condition is: 200 ℃ of barrel temperatures, die temperature 60-70 ℃, injection pressure 8MPa.It is as shown in table 2 to record data.
Embodiment 2
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 4+4 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 2+0.5 weight part |
| Toughner (KRISTALEX 5140): | 5 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550+O-W01): | 0.4+0.1 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 2 to record data.
Embodiment 3
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+ASA 7054): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 2+0.5 weight part |
| Toughner (KRISTALEX 5140): | 5 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.1 weight part |
| Processing aid (PH550+O-W01): | 0.4+0.1 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 2 to record data.
Embodiment 4
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+MBS TH-21): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 6+6 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 2+0.5 weight part |
| Toughner (KRISTALEX 5140): | 5 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550+O-W01): | 0.4+0.1 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 2 to record data.
Embodiment 5
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+ASA 7054): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 7+7 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 2+0.5 weight part |
| Toughner (KRISTALEX 5140): | 5 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.1 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 2 to record data.
Embodiment 6
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 8+7 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 2+0.5 weight part |
| Toughner (KRISTALEX 5140): | 5 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (O-W01): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 2 to record data.
Embodiment 7
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 0+0.5 weight part |
| Toughner (KRISTALEX 5140): | 5 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 3 to record data.
Embodiment 8
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 0.5+0.5 weight part |
| Toughner (KRISTALEX 5140): | 5 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 3 to record data.
Embodiment 9
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 1+0.5 weight part |
| Toughner (KRISTALEX 5140): | 5 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 3 to record data.
Embodiment 10
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 1.5+0.5 weight part |
| Toughner (KRISTALEX 5140): | 5 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 3 to record data.
Embodiment 11
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 2.5+0.5 weight part |
| Toughner (HR181): | 5 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 2 to record data.
Embodiment 12
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 3+0.5 weight part |
| Toughner (HR181): | 5 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 3 to record data.
Embodiment 13
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 1+0.5 weight part |
| Toughner (HR181): | 5 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 4 to record data.
Embodiment 14
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 1+0.5 weight part |
| Toughner (HR181): | 5 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 4 to record data.
Embodiment 15
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 3+1.5 weight part |
| Toughner (KRISTALEX 5140+HR181): | 2.5+2.5 weight part |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 4 to record data.
Embodiment 16
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 3+2.0 weight part |
| Toughner (KRISTALEX 5140+HR181): | The 5+5 weight part |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 4 to record data.
Embodiment 17
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 1+0.5 weight part |
| Toughner (KRISTALEX 5140): | 0 weight part |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 4 to record data.
Embodiment 18
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 1+0.5 weight part |
| Toughner (KRISTALEX 5140): | 10 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 4 to record data.
Embodiment 19
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 1+0.5 weight part |
| Toughner (HR181): | 3 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 5 to record data.
Embodiment 20
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+RDP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 1+0.5 weight part |
| Toughner (HR181): | 3 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.5 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 5 to record data.
Embodiment 21
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (RDP+TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 1+0.5 weight part |
| Toughner (HR181): | 3 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 5 to record data.
Embodiment 22
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 1+0.5 weight part |
| Toughner (HR181): | 3 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550+O-W01): | 0.4+0.1 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 5 to record data.
Embodiment 23
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (TPP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 1+0.5 weight part |
| Toughner (HR181): | 3 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550): | 0.4 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 5 to record data.
Embodiment 24
(1) weight part of mobile each component of halogen-free flame retardant ABS of superelevation is following:
| ABS resin (ABS D670+D-120A): | The 70+30 weight part |
| Aromatic phosphoric ester (RDP): | The 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 1+0.5 weight part |
| Toughner (HR181): | 3 weight parts |
| Oxidation inhibitor (primary antioxidant 1010+ auxiliary anti-oxidant 168) | 0.1+ 0.2 weight part |
| Photostabilizer (UV-P) | 0.3 weight part |
| Processing aid (PH550: | 0.4+0.1 weight part |
(2) its preparation method is with embodiment 1, and it is as shown in table 5 to record data.
The compsn of each embodiment preparation is injection molded into the standard batten of testing usefulness by standard size, and the physicochemical property among each embodiment is pressed CNS and U.S. UL standard testing respectively, and is as shown in table 1.
Table 1 testing standard
| Test event | Project abbreviation and unit | Testing standard |
| Tensile strength | TS(MPa) | GB1040 |
| Elongation at break | TS%(%) | GB1040 |
| The Izod notched Izod impact strength | NIS(kJ/m 2) | GB1843 |
| Flexural strength | FS(MPa) | GB9341 |
| Modulus in flexure | FM(MPa) | GB9341 |
| The molten finger | MFI(g/10min) | GB3682 |
| Proportion | SG(g/cm 3) | GB1033 |
| Burning | UL94(mm) | UL94 |
The physicochemical property data of table 2 embodiment 1-embodiment 6 tests
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| TS | 41.6 | 40.8 | 39.2 | 37.3 | 35.8 | 33.5 |
| TS% | 8 | 8 | 7 | 9 | 8 | 7 |
| NIS | 25.7 | 23.5 | 21.7 | 20.3 | 18.9 | 18.1 |
| FS | 63.8 | 61.7 | 60.8 | 58.9 | 57.3 | 57.1 |
| FM | 2487 | 2369 | 2317 | 2239 | 2105 | 2013 |
| MFI | 15.5 | 17.1 | 20.3 | 24.7 | 28.9 | 29.1 |
| SG | 1.061 | 1.059 | 1.054 | 1.051 | 1.053 | 1.054 |
| UL941.0mm | V-2 | V-2 | V-2 | V-2 | V-2 | V-2 |
| UL941.5mm | V-2 | V-2 | V-2 | V-2 | V-2 | V-2 |
| UL942.0mm | ? | V-2 | V-2 | V-2 | V-2 | V-2 |
| UL942.5mm | ? | ? | V-2 | V-2 | V-2 | V-2 |
| UL943.0mm | ? | ? | V-2 | V-2 | V-2 | V-2 |
The physicochemical property data of table 3 embodiment 7-embodiment 12 tests
| Test event | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 |
| TS | 39.3 | 39.5 | 39.2 | 37.3 | 35.8 | 33.5 |
| TS% | 8 | 8 | 7 | 9 | 8 | 7 |
| NIS | 21.5 | 21.2 | 21.0 | 19.3 | 18.3 | 16.3 |
| FS | 61.5 | 61.9 | 60.5 | 59.7 | 58.8 | 57.4 |
| FM | 2298 | 2254 | 2219 | 2203 | 2159 | 2113 |
| MFI | 16.7 | 19.9 | 21.5 | 23.2 | 25.6 | 27.8 |
| SG | 1.055 | 1.057 | 1.057 | 1.055 | 1.055 | 1.056 |
| UL941.0mm | ? | V-2 | V-2 | V-2 | V-2 | V-2 |
| UL941.5mm | ? | V-2 | V-2 | V-2 | V-2 | V-2 |
| UL942.0mm | ? | V-2 | V-2 | V-2 | V-2 | V-2 |
| UL942.5mm | ? | ? | V-2 | V-2 | V-2 | V-2 |
| UL943.0mm | ? | ? | V-2 | V-2 | V-2 | V-2 |
The physicochemical property data of table 4 embodiment 13-embodiment 18 tests
| Test event | Embodiment 13 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 |
| TS | 39.5 | 40.5 | 40.2 | 36.4 | 41.8 | 34.8 |
| TS% | 7 | 8 | 8 | 9 | 9 | 9 |
| NIS | 21.3 | 21.7 | 22.5 | 25.7 | 18.5 | 24.6 |
| FS | 60.9 | 61.4 | 61.0 | 58.1 | 62.4 | 57.8 |
| FM | 2212 | 2269 | 2228 | 2009 | 2399 | 1995 |
| MFI | 21.4 | 20.9 | 21.1 | 18.5 | 23.1 | 19.2 |
| SG | 1.057 | 1.057 | 1.055 | 1.054 | 1.053 | 1.055 |
| UL941.0mm | V-2 | V-2 | V-2 | V-2 | V-2 | V-2 |
| UL941.5mm | V-2 | V-2 | V-2 | V-2 | V-2 | V-2 |
| UL942.0mm | V-2 | V-2 | V-2 | V-2 | V-2 | V-2 |
| UL942.5mm | V-2 | V-2 | V-2 | V-2 | V-2 | V-2 |
| UL943.0mm | V-2 | V-2 | V-2 | ? | V-2 | ? |
The physicochemical property data of table 5 embodiment 19-embodiment 24 tests
| Test event | Embodiment 13 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 |
| TS | 41.5 | 40.8 | 38.2 | 43.2 | 38.8 | 37.9 |
| TS% | 8 | 8 | 9 | 8 | 8 | 7 |
| NIS | 20.5 | 21.2 | 16.7 | 25.4 | 16.1 | 16.5 |
| FS | 62.4 | 62.1 | 60.0 | 64.2 | 58.3 | 57.7 |
| FM | 2338 | 2361 | 2217 | 2434 | 2165 | 2019 |
| MFI | 15.5 | 23.2 | 22.1 | 17.7 | 28.9 | 20.7 |
| SG | 1.055 | 1.055 | 1.054 | 1.056 | 1.055 | 1.053 |
| UL941.0mm | V-2 | V-2 | V-1 | V-2 | V-1 | V-1 |
| UL941.5mm | V-2 | V-2 | ? | V-2 | ? | ? |
| UL942.0mm | V-2 | V-2 | ? | V-2 | ? | ? |
| UL942.5mm | V-2 | V-2 | ? | V-2 | ? | ? |
| UL943.0mm | V-2 | V-2 | ? | V-2 | ? | ? |
Associative list 2-table 5 can draw following some conclusion:
1. along with the increase of aromatic phosphoric ester total content, flame retardant rating improves thereupon, but after its total content reached 10 parts, flame retardant rating remained unchanged, and mobile continuing improved, but shock strength has reduction slightly.
2. the raising of flow ability modifying agent Dicumene content is not only most important to accomplishing to stablize V-2 level flame retardant rating, and it adds the flowability that affiliation obviously improves material.
3. the increase of toughner; To not obviously influence of flame retardant effect, impact intensity has lasting synergistic effect, has a synergistic toughening effect and KRISTALEX 5140 and HR181 are composite; But tensile strength and flexural strength reduce also quite obvious along with the increase of toughner.
4. the composite combination flow ability modifying agent Dicumene of aromatic phosphoric ester sol-DP and TPP or RDP is very effective to the ABS that stablizes the V-2 flame retardant rating, and sol-DP is significantly less than TPP or RDP to the mechanical property influence of matrix resin simultaneously.
Claims (9)
1. a halogen-free flame retardant ABS is characterized in that in parts by weight, is made up of the component of following parts by weight:
100 parts of ABS resins
Aromatic phosphoric ester 5-15 part
Flow ability modifying agent 0.5-5 part
Toughner 0-10 part
Oxidation inhibitor 0.1-1 part
Photostabilizer 0-1 part
Processing aid 0-5 part.
2. halogen-free flame retardant ABS according to claim 1 is characterized in that: said ABS resinoid is acrylonitrile-butadiene-phenylethene grafted copolymer, acrylonitrile-styrene-acrylic terpolymer or TEB 3K-butadiene-styrene graft copolymer.
3. halogen-free flame retardant ABS according to claim 1 is characterized in that: said aromatic phosphoric ester is Resorcinol two (diphenylphosphoric acid fat) and polycondensates thereof, dihydroxyphenyl propane two (diphenyl phosphoester) and polycondensate thereof, metaphenylene four (xylyl) biphosphonate, triphenylphosphate, di(2-ethylhexyl)phosphate benzene toluene ester, phosphoric acid hexichol (YLENE) ester, phosphoric acid hexichol isopropyl benzene ester, diphenyl 2 ethylhexyl phosphate, phosphate diphenyl isodecyl ester, tricresyl phosphate (toluene) ester, tricresyl phosphate (YLENE) ester, phosphoric acid phenyl trimethylphenylmethane base ester, alkane phenyl biphosphonates, contain in the biphosphonate of naphthenic base one or more.
4. halogen-free flame retardant ABS according to claim 1; It is characterized in that: said flow ability modifying agent is 2; 3-dimethyl--2, one or more in 3-diphenyl butane, amides lubricant, silicone lubricant, stearic acid lubricant, illiteracy dawn ester series lubricant agent, the polyalcohols lubricant.
5. halogen-free flame retardant ABS according to claim 1 is characterized in that: said toughner is one or more the mixture in esters of acrylic acid toughner, silicone based toughner and the ABS high glue powder.
6. halogen-free flame retardant ABS according to claim 1 is characterized in that: said oxidation inhibitor is made up of Hinered phenols primary antioxidant and phosphorous acid esters auxiliary anti-oxidant.
7. halogen-free flame retardant ABS according to claim 1 is characterized in that: said photostabilizer is benzophenone, benzotriazole category, triazines, gather in the fine class of propylene, Oxamides, the hindered amines one or more.
8. halogen-free flame retardant ABS according to claim 1 is characterized in that: said processing aid is one or more the mixture in silicone oil, white mineral oil, the lubrication prescription.
9. the preparation method of each described halogen-free flame retardant ABS of claim 1 ~ 8 is characterized in that comprising the steps:
A, with each component raw material by proportioning high-speed mixer thorough mixing 10-60 minute;
B, said mixture is transported in the twin screw extruder through the pay-off of delicate metering; Each of forcing machine section extruder temperature is controlled between 170 ~ 230 ℃; The length-to-diameter ratio of twin screw extruder is 20 ~ 35, and screw speed is 200-800 rev/min, the shearing of screw rod, mixing and carry under; Material is able to abundant fusing, compound, obtains the mobile halogen-free flame retardant ABS particle of superelevation through extruding pelletization, drying again;
C, the superelevation halogen-free flame retardant ABS particle that flows is joined and is processed into required test bars in the injection moulding machine; Said injecting condition is: barrel temperature 180-220 ℃, and 50 ~ 70 ℃ of die temperatures, injection pressure 6-10MPa.
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| CN103788558A (en) * | 2014-01-23 | 2014-05-14 | 金发科技股份有限公司 | Halogen-free flame retardant HIPS (High Impact Polystyrene) resin as well as preparation method and application thereof |
| CN104448672A (en) * | 2013-09-12 | 2015-03-25 | 黑龙江鑫达企业集团有限公司 | Antioxidant, high flow, halogen-free and flame retardant ABS and preparation process thereof |
| WO2019201782A1 (en) | 2018-04-16 | 2019-10-24 | Ineos Styrolution Group Gmbh | Ultra-high flow styrene acrylonitrile copolymer compositions |
| WO2019201784A1 (en) | 2018-04-16 | 2019-10-24 | Ineos Styrolution Group Gmbh | Ultra-high flow acrylonitrile butadiene styrene copolymer compositions |
| CN110511554A (en) * | 2019-09-17 | 2019-11-29 | 四川长虹电器股份有限公司 | Halogen-free flameproof nitrogen phosphorus Si modification graphene/polycarbonate/ABS alloy material and preparation method thereof |
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| CN104448672A (en) * | 2013-09-12 | 2015-03-25 | 黑龙江鑫达企业集团有限公司 | Antioxidant, high flow, halogen-free and flame retardant ABS and preparation process thereof |
| CN103788558A (en) * | 2014-01-23 | 2014-05-14 | 金发科技股份有限公司 | Halogen-free flame retardant HIPS (High Impact Polystyrene) resin as well as preparation method and application thereof |
| WO2019201782A1 (en) | 2018-04-16 | 2019-10-24 | Ineos Styrolution Group Gmbh | Ultra-high flow styrene acrylonitrile copolymer compositions |
| WO2019201784A1 (en) | 2018-04-16 | 2019-10-24 | Ineos Styrolution Group Gmbh | Ultra-high flow acrylonitrile butadiene styrene copolymer compositions |
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| US11390736B2 (en) | 2018-04-16 | 2022-07-19 | Ineos Styrolution Group Gmbh | Ultra-high flow acrylonitrile butadiene styrene copolymer compositions |
| CN110511554A (en) * | 2019-09-17 | 2019-11-29 | 四川长虹电器股份有限公司 | Halogen-free flameproof nitrogen phosphorus Si modification graphene/polycarbonate/ABS alloy material and preparation method thereof |
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Address after: 510520 Guangdong city of Guangzhou province high tech Industrial Development Zone No. 33 Ke Feng Lu Patentee after: Kingfa Technology Co., Ltd. Patentee after: Shanghai Kingfa Science and Technology Development Co., Ltd. Patentee after: SICHUAN KINGFA TECHNOLOGY DEVELOPMENT CO., LTD. Address before: 510520 Guangdong city of Guangzhou province high tech Industrial Development Zone No. 33 Ke Feng Lu Patentee before: Kingfa Technology Co., Ltd. Patentee before: Shanghai Kingfa Science and Technology Development Co., Ltd. Patentee before: Mianyang Changxin New Material Development Co., Ltd. |