CN102010563B - Nano clay compounded flame-retardant ABS resin - Google Patents
Nano clay compounded flame-retardant ABS resin Download PDFInfo
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- CN102010563B CN102010563B CN2010105515928A CN201010551592A CN102010563B CN 102010563 B CN102010563 B CN 102010563B CN 2010105515928 A CN2010105515928 A CN 2010105515928A CN 201010551592 A CN201010551592 A CN 201010551592A CN 102010563 B CN102010563 B CN 102010563B
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- nano clay
- retardant
- abs resin
- flame
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 41
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 36
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000012802 nanoclay Substances 0.000 title claims abstract description 20
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 3
- 239000011347 resin Substances 0.000 claims abstract description 3
- 239000003112 inhibitor Substances 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 238000012661 block copolymerization Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 239000000138 intercalating agent Substances 0.000 claims description 2
- 125000004402 polyphenol group Chemical group 0.000 claims description 2
- 235000013824 polyphenols Nutrition 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000005469 granulation Methods 0.000 abstract description 3
- 230000003179 granulation Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 238000005303 weighing Methods 0.000 abstract description 2
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a nano clay compound flame-retardant ABS resin, which is prepared by blending the following components in parts by weight: 40-60 parts of acrylonitrile-butadiene-styrene, 20-30 parts of a compound flame retardant, 1-5 parts of nano clay, 3-10 parts of a compatilizer, 10-30 parts of a flexibilizer and 0.1-2 parts of an antioxidant. Weighing raw materials according to a formula ratio, premixing ABS and nano clay in a medium-speed mixer for 2-5 minutes, and then adding other raw materials to mix for 5-10 minutes; and putting the mixed raw materials into a double screw machine, and performing melt extrusion and granulation to obtain the nano clay compounded flame-retardant ABS resin. The resin can reach UL94-V0 level, has stable processing performance and mechanical performance, does not have micromolecule flame retardant exudation in the using process, is environment-friendly, and can be widely used in the fields of electronics, electric appliances, automobile industry and the like.
Description
Technical field
The invention belongs to the environment-friendly flame-resistant ABS resin technical field, especially relate to a kind of nano clay compositional flame-retardant ABS resin.
Background technology
ABS resin is a kind of general thermoplastic engineering plastic, is the terpolymer of vinyl cyanide (A), divinyl (B), vinylbenzene (S).Therefore it has coordinated the high-performance of three kinds of components, has higher resistance to impact shock, good processing properties and chemicalstability, is easy to moldedly, is widely used at aspects such as residential building, household electrical appliances, pipelines.Yet ABS is a kind of inflammable macromolecular material, and combustionvelocity is very fast, produces a large amount of black smokes during burning, still burn away behind the fire, this drawbacks limit its range of application.
At present; The fire retardant that is used for ABS resin both at home and abroad is commonly PBDE etc.; Though have very high flame retardant effect and lower price like the compound flame retardant of mentioning among CN1962751, CN1412238A, the CN1765985; But the objectionable impurities for clearly forbidding in European Union's announced " about in electronic electric equipment, banning use of some objectionable impurities instruction " (abbreviation " RoHS instruction ") to use such as PBDE, this just makes the ABS resin that uses this based flame retardant on using, receive very big impact.
In addition; Also there is the inorganic combustion inhibitor of use to prepare ABS resin; Main inorganic combustion inhibitor is Marinco H and white lake etc.; But the flame retardant properties of this based flame retardant is not obvious, only when heavy addition, just can obtain certain flame retardant effect, though and heavy addition has satisfied mechanical property and the processing characteristics severe exacerbation that flame retardant effect can make ABS.
In addition; The use phosphorus flame retardant is also arranged at present; But this based flame retardant kind, comparatively small amt; And majority is liquid and low melting component, and as disclosing ABS resin forming process temperature among CN1616545A, the US64621125 more than 200 ℃, so phosphorus flame retardant uses in high-temperature molding and receives very big restriction.Again because hydroxyl not in the ABS resin owing to there is the existence of phosphonium flame retardant to form the charing film hardly, causes fire retardation not obvious when burning.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, provide a kind of flame retardant properties good, do not use objectionable impurities, and can keep the nano clay compositional flame-retardant ABS resin of ABS good mechanical performance and processing characteristics.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of nano clay compositional flame-retardant ABS resin, this resin are that each the component blend by following weight part forms:
40～60 parts of acrylonitrile-butadiene-styrene copolymers (ABS)
20～30 parts of compound flame retardants
1～5 part of nano clay
3～10 parts of compatilizers
10～30 parts of toughner
0.1～2 part in oxidation inhibitor
The above-mentioned compound flame retardant of the present invention is that (BEO, molecular formula is (C for the brominated epoxy resin oligopolymer of 10～20 weight parts
18H
16O
3Br
4)
n), the Antimony Trioxide: 99.5Min of 2～6 weight parts and the trimeric cyanamide of 3～8 weight parts mix, and the consumption summation of above-mentioned three kinds of materials is 20～30 parts.
The above-mentioned nano clay of the present invention is with two octadecyl dimethyl-brometo de amonios (CAS number: 3700-67-2) be the organic montmorillonoid of intercalator.
Said compatilizer is maleic anhydride graft styrene-ethylene-butadiene-styrene block copoly merization elastomerics (SEBS-g-MAH) or maleic anhydride graft acrylonitrile-butadiene-styrene terpolymer (ABS-g-MAH).
Said toughner is ABS high glue powder or ethylene-octene copolymer (POE).
Said oxidation inhibitor is polyphenol antioxidant 1010.
Nano clay compositional flame-retardant ABS resin preparation method of the present invention is: take by weighing each raw material by formula rate; Earlier with ABS and nano clay premix 2～5 minutes in moderate-speed mixers; Add compatilizer, compound flame retardant, toughner, oxidation inhibitor premix 5～10 minutes in moderate-speed mixers then; Again raw materials mixed is placed dual-screw-stem machine, through melt extruding granulation (being routine techniques in the industry).
Nano clay compositional flame-retardant ABS resin of the present invention has following beneficial effect:
1. to adopt high-molecular weight brominated epoxy resin oligopolymer be main flame retardant in the present invention; Brominated epoxy resin has higher flame retarding efficiency; Good thermostability and light stability; And can give by ignition resistant substrate good mechanical performance, therefore, its use has solved because the high caused small molecules fire retardant evaporable problem of ABS processing temperature; Simultaneously, because the molecular weight of fire retardant is high, less to the mechanical property influence of ABS;
2. the present invention has successfully used low-cost nano clay; Reaching under other prerequisite of expection flame retardant grade; Can reduce the consumption of fire retardant; Reduce the detrimentally affect of fire retardant, make material, have good flame retardancy simultaneously through taper calorimetric experiment and traditional flame retardant test to ABS base material physicals;
3. to adopt trimeric cyanamide be to assist fire retardant in the present invention, and trimeric cyanamide not only has the good flame effect, and brominated epoxy resin is had crosslinked action, thereby has reduced the detrimentally affect of fire retardant to the ABS resin mechanical property.
Embodiment
Provide embodiment below and further specify nano clay compositional flame-retardant ABS resin of the present invention.It is important to point out that following examples only are used for further specifying of the present invention; Can not be interpreted as the restriction to protection domain of the present invention, content still belongs to protection scope of the present invention to some nonessential improvement and the adjustment that the present invention makes to the person skilled in the art in this field according to the present invention.
Each raw material that following examples of the present invention are used is not done specified otherwise and is the commercially available prod.
Embodiment 1
Table 1 embodiment 1 each proportioning raw materials
With A component premix 3 minutes in moderate-speed mixers, and then add the B component and mixed 10 minutes; Compound is placed dual-screw-stem machine; Through melt extruding, granulation gets final product under 120～260 ℃ of temperature (120 ℃ of twin screw extruder one district's temperature, 180 ℃ of two district's temperature, 200 ℃ of three district's temperature, 240 ℃ of four district's temperature, 240 ℃ of five district's temperature, 240 ℃ of six district's temperature).
Embodiment 2
Table 2 embodiment 2 each proportioning raw materials
Used step is with embodiment 1.
Embodiment 3
Table 3 embodiment 3 each proportioning raw materials
Used step is with embodiment 1.
Embodiment 4
Table 4 embodiment 4 each proportioning raw materials
Used step is with embodiment 1.
Correlated performance for the nano clay compositional flame-retardant ABS resin of investigating the present invention preparation; The present invention with embodiment gained sample according to GB/T 1040.2-2006 test tensile strength; According to GB/T1843-2008 test socle girder notched Izod impact strength; According to GB/T2408-2008 test vertical combustion rank, according to ISO11358-1997 test heat decomposition temperature.Wherein burning time and peak heat rate of release adopt FTT taper calorimeter, and testing standard is ISO5660, irradiation power 35kW/m
2All test results are seen table 1.
Table 5 embodiment 1-4 prepares the correlated performance of sample
Claims (2)
1. nano clay compositional flame-retardant ABS resin is characterized in that: this resin is that each the component blend by following weight part forms:
Described compound flame retardant is that the brominated epoxy resin oligopolymer of 10～20 weight parts, the Antimony Trioxide: 99.5Min of 2～6 weight parts and the trimeric cyanamide of 3～8 weight parts mix, and the consumption summation of above-mentioned three kinds of materials is 20～30 parts;
Described nano clay is for being the organic montmorillonoid of intercalator with two octadecyl dimethyl-brometo de amonios;
Described compatilizer is maleic anhydride graft styrene-ethylene-butadiene-styrene block copoly merization elastomerics or maleic anhydride graft acrylonitrile-butadiene-styrene terpolymer;
Described toughner is ABS high glue powder or ethylene-octene copolymer.
2. nano clay compositional flame-retardant ABS resin according to claim 1 is characterized in that: described oxidation inhibitor is polyphenol antioxidant 1010.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105515928A CN102010563B (en) | 2010-11-12 | 2010-11-12 | Nano clay compounded flame-retardant ABS resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105515928A CN102010563B (en) | 2010-11-12 | 2010-11-12 | Nano clay compounded flame-retardant ABS resin |
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| Publication Number | Publication Date |
|---|---|
| CN102010563A CN102010563A (en) | 2011-04-13 |
| CN102010563B true CN102010563B (en) | 2012-04-25 |
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| CN2010105515928A Expired - Fee Related CN102010563B (en) | 2010-11-12 | 2010-11-12 | Nano clay compounded flame-retardant ABS resin |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102367322A (en) * | 2011-10-17 | 2012-03-07 | 常熟市星源金属涂层厂 | ABS (acrylonitrile butadiene styrene) halogen-free flame-retardant composite material and preparation method thereof |
| CN103992612A (en) * | 2014-05-19 | 2014-08-20 | 宁波泛塑新材料科技有限公司 | High-polymer bromine flame retardant/nano clay compound flame-retardant ABS (acrylonitrile-butadiene-styrene) resin and preparation method thereof |
| CN107974026B (en) * | 2016-10-21 | 2020-07-24 | 中国石油化工股份有限公司 | Extinction flame-retardant ABS material and preparation method thereof |
| CN109796722A (en) * | 2019-01-04 | 2019-05-24 | 新沂天晟新材料有限公司 | A kind of ABS modified material and preparation method thereof |
| CN111690197B (en) * | 2020-07-02 | 2022-09-13 | 南京工程学院 | Melamine-containing direct intercalation g-C 3 N 4 Flame-retardant cable material and preparation method thereof |
| CN113277785A (en) * | 2021-05-26 | 2021-08-20 | 胡朝阳 | Flame-retardant high-temperature-resistant concrete and preparation method thereof |
| CN113771466A (en) * | 2021-08-31 | 2021-12-10 | 昆山永宝顺复合面料有限公司 | Flame-retardant TPU composite fabric and preparation method thereof |
| CN116178879B (en) * | 2023-02-27 | 2025-06-10 | 金发科技股份有限公司 | Weather-resistant flame-retardant ABS material, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TW383326B (en) * | 1995-08-25 | 2000-03-01 | Toto Kasei Co Ltd | A fire-retardant compound and a fire-retarded thermoplastic resin composition including said fire retardant compound |
| US20040229982A1 (en) * | 2003-05-14 | 2004-11-18 | Goossens Danielle F. | Stabilized flame retardant additives and their use |
| JP2005068407A (en) * | 2003-08-06 | 2005-03-17 | Techno Polymer Co Ltd | Flame retardant thermoplastic resin composition |
| KR100787772B1 (en) * | 2005-12-19 | 2007-12-24 | 주식회사 엘지화학 | Flame retardant resin composition excellent in weatherability and thermal stability |
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| CN102010563A (en) | 2011-04-13 |
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