CN102786767B - 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
- Publication number
- CN102786767B CN102786767B CN201210149605.8A CN201210149605A CN102786767B CN 102786767 B CN102786767 B CN 102786767B CN 201210149605 A CN201210149605 A CN 201210149605A CN 102786767 B CN102786767 B CN 102786767B
- Authority
- CN
- China
- Prior art keywords
- weight part
- flame retardant
- halogen
- abs
- free flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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 are concentrated, there is good processing characteristics, resistance to low temperature, electrical insulation capability, resistance to chemical corrosion and high gloss and excellent plating performance, there is the excellent characteristics such as creep resistant is good, dimensional stability is high, molding shrinkage is little simultaneously, very extensive in field application such as military project, automobile, electronic apparatuss.But the oxygen index of ABS resin only has 18, belongs to inflammable material, therefore when for electronic and electrical equipment, mostly need to carry out flame-retardant modified, to reach fire safety service requirements.And conventionally have the burning of halogen flame-proof ABS product time to there will be dense black smoke, can produce toxic and harmful simultaneously.Therefore, will become the main flow of flame retardant products from now on to the non-halogen research of material.But ABS resin is because its molecular backbone chain lacks aromatic group, with current conventional phosphorus flame retardant, nitrogenated flame retardant or inorganic combustion inhibitor can reach V-2 level but not possess stable flame-retardant effect, simultaneously these fire retardants are because addition is high, every mechanical property and the processing fluidity of severe exacerbation material.And another direction of non-halogen anti-flaming ABS material exploitation is to adopt polycarbonate or polyester and ABS to form alloy, add again conventional halogen-free flame retardants at present, prepare the halogen-free flame retardant ABS such as PC/ABS or PET/ABS alloy, its properties all a kind of front method has had obvious improvement, also can reach higher flame retardant rating simultaneously, but its cost also more common flame-proof ABS is high a lot, and its mobility worsens even more serious, cause the narrower of process window change, this series products is subject to restriction to a certain extent in the application in some thin-gage goods and large product field.Therefore, existing market more need to develop a kind of be suitable for thin-gage goods and the application of large product field there is the mobile halogen-free flame retardant ABS of superelevation.
Prepare at present composite (patent No. 200910054786.4) that halogen-free flame retardant ABS generally adopts phosphonium flame retardant and other material, phosphorus-nitrogen combustion inhibitor (patent No. 200810203124.9); Or adopt inorganic combustion inhibitor 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 set the alloying of the composite preparation of resin with other.As with halogen-free flame retardant PC/ABS alloy (patent No. 201010524225.9) of the composite preparation of PC, and the alloy (patent No. 200810202918.9) that forms of polyester etc.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, the object of the present invention is to provide the mobile halogen-free flame retardant ABS of a kind of superelevation.
Another object of the present invention is to provide the preparation method of the mobile halogen-free flame retardant ABS of above-mentioned superelevation.
Object of the present invention is achieved through the following technical solutions:
The mobile halogen-free flame retardant ABS of a kind of superelevation, is prepared by the composition of following parts 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 MBS graft copolymer (MBS);
Described aromatic phosphoric ester comprises 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 (dimethylbenzene) 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 (dimethylbenzene) ester (TXP), phosphoric acid phenyl trimethylphenylmethane base ester (TBPPP), alkane phenyl biphosphonate (in BDP and RDP, phenyl is by alkane phenyl substituent), containing one or more in the biphosphonate of cycloalkyl etc.
Described 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 lubricant, polyalcohols lubricant.
Described toughner is one or more the mixture in esters of acrylic acid toughner, silicone based toughner and ABS high glue powder.
Described oxidation inhibitor comprises Hinered phenols primary antioxidant and phosphorous acid esters auxiliary anti-oxidant composition.
Described photostabilizer comprises benzophenone, benzotriazole category, triazines, poly-one or more in the fine class of propylene, Oxamides, hindered amines.
Described processing aid is one or more the mixture in silicone oil, white mineral oil, lubrication prescription.
The preparation method of above-mentioned halogen-free flame retardant ABS comprises the steps:
A, each component raw material is fully mixed to 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 is controlled between 170 ~ 230 DEG C, the length-to-diameter ratio of twin screw extruder is 20 ~ 35, screw speed is 200-800 rev/min, the shearing of screw rod, mixing and carry under, material is able to abundant fusing, compound, then through extruding pelletization, the dry halogen-free flame retardant ABS particle that obtains;
C, halogen-free flame retardant ABS particle is joined and in injection moulding machine, is processed into required test bars; Described injecting condition is: barrel temperature 180-220 DEG C, 50 ~ 70 DEG C 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 the further investigation based on V-2 fire retardant mechanism, adopt aromatic phosphoric ester and the composite halogen-free flame retardant ABS of preparing of flow ability modifying agent, therefore in the situation that its addition is very low, flame retardant rating reaches [email protected] thickness and stablizes V-2, and its every 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 mobility significantly improves, and therefore can be widely used in thin-walled and super large product field, as 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 is suitable in the market, is adapted at wideling popularize on market application.
Embodiment
Below by embodiment, the present invention is described, but is not limited to this.
The mobile halogen-free flame retardant ABS twin screw extruder used of preparation superelevation is the SHJ-30 being produced by Rhea superpolymer Equipment Limited, Nanjing.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 Zhejiang Hai Tian injection moulding machine company limited.The T92 type that the Tinius Olsenis company of the impact experiment Ji Shi U.S. 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 UL-94 vertical combustion Yi Shi U.S. ATLAS HVUL-2 that test UL94 uses.
In following examples, wherein ABS resin is selected respectively the ABS D670 of Guo Qiao company and the HI high impact ABS D-120A of Zhenjiang Guo Heng company, ASA selects 7045 of Jin Hu company, MBS selects the TH-21 of NEC chemistry, aromatic phosphoric ester is selected the Fyrolflex sol-DP of ICL International Computer Limited, the TPP of Akzo Nobel N.V. and RDP, flow ability modifying agent is selected the Dicumene of SI Group company and the EBS of the sharp chemical industry of speeding; Toughner is selected the KRISTALEX 5140 of Yi Shi Man of the U.S. and the HR181 of Korea S Jin Hu, oxidation inhibitor is selected Irganox 1010 and the Irganox 168 of gas Ba Jinghua, photostabilizer is selected 770 and the UV-P of gas Ba Jinghua, and other NM various processing aids are commercially available general commodity.
embodiment 1
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 as follows:
Above-mentioned each component raw material is added in mixing machine to blending 15 minutes in proportion, pay-off through delicate metering is transported in twin screw extruder, the length-to-diameter ratio of twin screw extruder is 30, each section of extruder temperature of forcing machine is controlled between 220 DEG C, screw speed is 400 revs/min, the shearing of screw rod, mixing and carry under, material is able to abundant fusing, compound, pass through again extruding pelletization, the dry mobile halogen-free flame retardant ABS particle of superelevation that obtains for 4 hours at 80 DEG C; Then flame-proof ABS particle is joined in injection moulding machine and is processed into required batten, injecting condition is: 200 DEG C of barrel temperatures, die temperature 60-70 DEG C, injection pressure 8MPa.Data measured is as shown in table 2.
embodiment 2
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 2.
embodiment 3
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+ASA 7054): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 2.
embodiment 4
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+MBS TH-21): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 2.
embodiment 5
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+ASA 7054): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 2.
embodiment 6
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 2.
embodiment 7
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 3.
embodiment 8
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 3.
embodiment 9
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 3.
embodiment 10
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 3.
embodiment 11
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 2.
embodiment 12
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 3.
embodiment 13
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 4.
embodiment 14
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 4.
embodiment 15
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 4.
embodiment 16
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 5+5 weight part |
| Flow ability modifying agent (Dicumene+EBS): | 3+2.0 weight part |
| Toughner (KRISTALEX 5140+HR181): | 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 data measured is as shown in table 4.
embodiment 17
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 4.
embodiment 18
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 4.
embodiment 19
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+TPP): | 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 data measured is as shown in table 5.
embodiment 20
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP+RDP): | 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 data measured is as shown in table 5.
embodiment 21
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (RDP+TPP): | 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 data measured is as shown in table 5.
embodiment 22
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (Fyrolflex sol-DP): | 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 data measured is as shown in table 5.
embodiment 23
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (TPP): | 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 data measured is as shown in table 5.
embodiment 24
(1) weight part of the mobile each component of halogen-free flame retardant ABS of superelevation is as follows:
| ABS resin (ABS D670+D-120A): | 70+30 weight part |
| Aromatic phosphoric ester (RDP): | 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 data measured is as shown in table 5.
Composition prepared by each embodiment is injection molded into the standard batten of test use by standard size, the physicochemical property in each embodiment is pressed respectively CNS and U.S. UL standard testing, 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 |
| Izod notched Izod impact strength | NIS(kJ/m 2) | GB1843 |
| Flexural strength | FS(MPa) | GB9341 |
| Modulus in flexure | FM(MPa) | GB9341 |
| Molten finger | MFI(g/10min) | GB3682 |
| Proportion | SG(g/cm 3) | GB1033 |
| Burning | UL94@(mm) | UL94 |
The physicochemical property data that 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 |
| [email protected] | V-2 | V-2 | V-2 | V-2 | V-2 | V-2 |
| [email protected] | V-2 | V-2 | V-2 | V-2 | V-2 | V-2 |
| [email protected] | ? | V-2 | V-2 | V-2 | V-2 | V-2 |
| [email protected] | ? | ? | V-2 | V-2 | V-2 | V-2 |
| [email protected] | ? | ? | V-2 | V-2 | V-2 | V-2 |
The physicochemical property data that 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 |
| [email protected] | ? | V-2 | V-2 | V-2 | V-2 | V-2 |
| [email protected] | ? | V-2 | V-2 | V-2 | V-2 | V-2 |
| [email protected] | ? | V-2 | V-2 | V-2 | V-2 | V-2 |
| [email protected] | ? | ? | V-2 | V-2 | V-2 | V-2 |
| [email protected] | ? | ? | V-2 | V-2 | V-2 | V-2 |
The physicochemical property data that 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 |
| [email protected] | V-2 | V-2 | V-2 | V-2 | V-2 | V-2 |
| [email protected] | V-2 | V-2 | V-2 | V-2 | V-2 | V-2 |
| [email protected] | V-2 | V-2 | V-2 | V-2 | V-2 | V-2 |
| [email protected] | V-2 | V-2 | V-2 | V-2 | V-2 | V-2 |
| [email protected] | V-2 | V-2 | V-2 | ? | V-2 | ? |
The physicochemical property data that 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 |
| [email protected] | V-2 | V-2 | V-1 | V-2 | V-1 | V-1 |
| [email protected] | V-2 | V-2 | ? | V-2 | ? | ? |
| [email protected] | V-2 | V-2 | ? | V-2 | ? | ? |
| [email protected] | V-2 | V-2 | ? | V-2 | ? | ? |
| [email protected] | 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 reaches after 10 parts when its total content, and flame retardant rating remains unchanged, and mobility continues to improve, but shock strength is in a slight decrease.
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 membership and obviously improve the mobility of material.
3. the increase of toughner, flame retardant effect is not had a significant effect, and impact intensity has lasting synergistic effect, has a synergistic toughening effect and KRISTALEX 5140 and HR181 are composite, but tensile strength and flexural strength, along with the increase of toughner, reduce also quite obvious.
4. the composite combination flow ability modifying agent Dicumene of aromatic phosphoric ester sol-DP and TPP or RDP is very effective to stablizing the ABS of V-2 flame retardant rating, and sol-DP is significantly less than TPP or RDP to the Effect on Mechanical Properties of matrix resin simultaneously.
Claims (7)
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 resin
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 flow ability modifying agent is 2,3-dimethyl-2, the mixture of 3-diphenyl butane and EBS; Described 2,3-dimethyl-2,3-diphenyl butane is at least 0.5 part;
Described aromatic phosphoric ester is the mixture of Fyrolflexsol-DP and TPP or RDP.
2. halogen-free flame retardant ABS according to claim 1, is characterized in that: described ABS resinoid is acrylonitrile-butadiene-phenylethene grafted copolymer, acrylonitrile-styrene-acrylic terpolymer or MBS graft copolymer.
3. halogen-free flame retardant ABS according to claim 1, is characterized in that: described toughner is one or more the mixture in esters of acrylic acid toughner, silicone based toughner and ABS high glue powder.
4. halogen-free flame retardant ABS according to claim 1, is characterized in that: described oxidation inhibitor is made up of Hinered phenols primary antioxidant and phosphorous acid esters auxiliary anti-oxidant.
5. halogen-free flame retardant ABS according to claim 1, is characterized in that: described photostabilizer is benzophenone, benzotriazole category, triazines, poly-one or more in vinyl cyanide, Oxamides, hindered amines.
6. halogen-free flame retardant ABS according to claim 1, is characterized in that: described processing aid is one or more the mixture in silicone oil, white mineral oil, lubrication prescription.
7. the preparation method of the halogen-free flame retardant ABS described in claim 1 ~ 6 any one, is characterized in that comprising the steps:
A, each component raw material is fully mixed to 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 is controlled between 170 ~ 230 DEG C, the length-to-diameter ratio of twin screw extruder is 20 ~ 35, screw speed is 200-800 rev/min, the shearing of screw rod, mixing and carry under, material is able to abundant fusing, compound, then through extruding pelletization, the dry mobile halogen-free flame retardant ABS particle of superelevation that obtains;
C, the superelevation halogen-free flame retardant ABS particle that flows is joined and in injection moulding machine, is processed into required test bars; Described injecting condition is: barrel temperature 180-220 DEG C, 50 ~ 70 DEG C of die temperatures, injection pressure 6-10MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210149605.8A CN102786767B (en) | 2012-05-15 | 2012-05-15 | Halogen-free flame retardant ABS with super high flow and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210149605.8A CN102786767B (en) | 2012-05-15 | 2012-05-15 | Halogen-free flame retardant ABS with super high flow and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102786767A CN102786767A (en) | 2012-11-21 |
| CN102786767B true CN102786767B (en) | 2014-11-26 |
Family
ID=47152366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210149605.8A Active CN102786767B (en) | 2012-05-15 | 2012-05-15 | Halogen-free flame retardant ABS with super high flow and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102786767B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| KR20200143702A (en) | 2018-04-16 | 2020-12-24 | 이네오스 스티롤루션 그룹 게엠베하 | Ultra High Flow Acrylonitrile Butadiene Styrene Copolymer Composition |
| EP3781627B1 (en) | 2018-04-16 | 2022-02-23 | INEOS Styrolution Group GmbH | Ultra-high flow styrene acrylonitrile 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230569A (en) * | 1998-04-01 | 1999-10-06 | 大八化学工业株式会社 | Flame-retarded resin composition |
| CN1989188A (en) * | 2004-07-19 | 2007-06-27 | 溴化物有限公司 | Novel flame-retardant polystyrenes |
| CN101870810A (en) * | 2010-03-29 | 2010-10-27 | 金发科技股份有限公司 | Heat-resistant polyamide composition |
-
2012
- 2012-05-15 CN CN201210149605.8A patent/CN102786767B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230569A (en) * | 1998-04-01 | 1999-10-06 | 大八化学工业株式会社 | Flame-retarded resin composition |
| CN1989188A (en) * | 2004-07-19 | 2007-06-27 | 溴化物有限公司 | Novel flame-retardant polystyrenes |
| CN101870810A (en) * | 2010-03-29 | 2010-10-27 | 金发科技股份有限公司 | Heat-resistant polyamide composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102786767A (en) | 2012-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102690491B (en) | Heat-resistant, halogen-free and flame-retardant ABS (acrylonitrile butadiene styrene) resin composite and preparation method thereof | |
| CN103102669B (en) | Thermal-resistant light-smoke halogen-free flame-retardant PC/ABS alloy material and preparation method thereof | |
| CN102786767B (en) | Halogen-free flame retardant ABS with super high flow and preparation method thereof | |
| CN101092501A (en) | PA6 / ABS alloy material, and preparation method | |
| CN101397396A (en) | Polycarbonate and acrylic nitrile-butadiene-phenylethylene grafted copolymer heat resisting and flame-retardant alloy | |
| CN101469113A (en) | Halogen-free flame-retardant toughened polycarbonate composition | |
| CN103694623B (en) | Based on the flame-retardant and anti-static polyformaldehyde resin of composite halogen-free flame-retardant system | |
| CN102061077B (en) | Halogen-free inflaming retarding PC/ABS (Polycarbonate/Acrylonitrile Butadiene Styrene) alloy | |
| CN100543081C (en) | Polyformaldehyde resin of a kind of halogen-free environment-friendly flame-proof and preparation method thereof | |
| CN103374214A (en) | High-impact environment-friendly flame-retardant PC (Polycarbonate)/ABS (Acrylonitrile Butadiene Styrene) alloy material and preparation technology thereof | |
| CN103289293B (en) | Transparent flame-retardant antistatic ABS material, preparation method and application thereof | |
| CN102516732A (en) | Polycarbonate (PC) resin/acrylonitrile-butadiene-styrene (ABS) alloy and preparation method thereof | |
| CN104086943A (en) | Flame-retardant acrylonitrile butadiene styrene (ABS) resin with excellent surface glossiness and high blackness and preparation method of ABS resin | |
| CN104086970A (en) | High-efficiency bromine-silicon flame-retardant weather-resistant polycarbonate composite material and preparation method thereof | |
| CN103724968A (en) | High-heat-resistant high-rigidity halogen-free flame-retardant scratch-resistant PC-ABS (polycarbonate-acrylonitrile-butadiene-styrene) alloy material and preparation method thereof | |
| CN106366610A (en) | High-glowing filament scratch-resistant PC material suitable for tablet computer shell and preparation method thereof | |
| CN101570632A (en) | Halogen-free fire retardation thermoplastic polyurethane plastic and preparation method thereof | |
| CN102101941B (en) | Flame-retarding polyphenyl ether composite, and preparation method and use thereof | |
| CN110591350A (en) | Smoke-inhibiting polyamide composition and preparation method thereof | |
| CN101974216A (en) | Halogen-free flame-retardant PC/ABS alloy | |
| WO2023179555A1 (en) | Halogen-free flame-retardant polycarbonate/styrene resin alloy, and preparation method therefor and use thereof | |
| CN104629285A (en) | Halogen-free flame-retardant high toughness modified polycarbonate composition | |
| CN104448672A (en) | Antioxidant, high flow, halogen-free and flame retardant ABS and preparation process thereof | |
| CN101759949B (en) | Halogen-free flame-retardant ABS composition | |
| CN103694695B (en) | A kind of fiber glass reinforced halogen-free flame retardant PA6/PS alloy material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
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. |