CN102010563A - Nano clay compounded flame-retardant ABS resin - Google Patents
Nano clay compounded flame-retardant ABS resin Download PDFInfo
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- CN102010563A CN102010563A CN 201010551592 CN201010551592A CN102010563A CN 102010563 A CN102010563 A CN 102010563A CN 201010551592 CN201010551592 CN 201010551592 CN 201010551592 A CN201010551592 A CN 201010551592A CN 102010563 A CN102010563 A CN 102010563A
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Abstract
The invention discloses nano clay compounded flame-retardant ABS resin, which is prepared by blending the following components in part by weight: 40 to 60 parts of acrylonitrile butadiene-styrene (ABS), 20 to 30 parts of compound flame retardant, 1 to 5 parts of nano clay, 3 to 10 parts of compatilizer, 10 to 30 parts of toughening agent and 0.1 to 2 parts of antioxidant. A preparation method comprises the following steps of: weighing the raw materials according to a ratio in the formula, premixing the ABS and the nano clay in a medium speed mixer for 2 to 5 minutes, adding other raw materials, and mixing for 5 to 10 minutes; and putting the mixed raw materials into a double screw extrusion machine, performing melt extrusion and granulation to obtain the nano clay compounded flame-retardant ABS resin. The resin can reach UL94-V0 class, has stable machinability and mechanical properties, ensures that the micromolecular flame retardant does not seep in the using process, is environment-friendly and can be widely applied in the fields such as electronics, electrical equipment and automobile industry.
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 chemical stability, 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, behind fire, still burn away, 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 Poly Brominated Diphenyl Ethers etc., though have very high flame retardant effect and lower price as the compound flame retardant of mentioning among CN1962751, CN1412238A, the CN1765985, but the objectionable impurities for clearly forbidding in European Union's announced " about ban use of some objectionable impurities instruction in electronic electric equipment " (abbreviation " RoHS instruction ") to use such as Poly Brominated Diphenyl Ethers, this just makes ABS resin of using this based flame retardant be subjected to very big impact on using.
In addition, also there is the inorganic combustion inhibitor of use to prepare ABS resin, main inorganic combustion inhibitor is magnesium hydroxide and aluminium hydroxide 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, as disclosing ABS resin forming process temperature among CN1616545A, the US64621125 more than 200 ℃, so phosphorus flame retardant uses in high-temperature molding and is very restricted.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 solution used in the present invention 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 antimonous oxide 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 height of fire retardant is 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 to ABS base material physicals, make material simultaneously by taper calorimetric experiment and traditional flame retardant test, have good flame retardancy;
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 limiting the scope of the 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 see Table 1.
Table 5 embodiment 1-4 prepares the correlated performance of sample
Claims (6)
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:
40～60 parts of acrylonitrile-butadiene-styrene (ABS)s
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.
2. nano clay compositional flame-retardant ABS resin according to claim 1, it is characterized in that: described compound flame retardant is that the brominated epoxy resin oligopolymer of 10～20 weight parts, the antimonous oxide 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.
3. nano clay compositional flame-retardant ABS resin according to claim 1 is characterized in that: described nano clay is for being the organic montmorillonoid of intercalator with two octadecyl dimethyl brometo de amonios.
4. nano clay compositional flame-retardant ABS resin according to claim 1 is characterized in that: described compatilizer is maleic anhydride graft styrene-ethylene butadiene-styrene block copoly merization elastomerics or maleic anhydride graft acrylonitrile butadiene-styrene copolymer.
5. nano clay compositional flame-retardant ABS resin according to claim 1 is characterized in that: described toughner is ABS high glue powder or ethylene-octene copolymer.
6. 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 |
Publications (2)
| Publication Number | Publication Date |
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| CN102010563A true CN102010563A (en) | 2011-04-13 |
| CN102010563B CN102010563B (en) | 2012-04-25 |
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| Application Number | Title | Priority Date | Filing Date |
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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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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107974026A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of delustring anti-flaming 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 |
| CN111690197A (en) * | 2020-07-02 | 2020-09-22 | 南京工程学院 | Melamine-containing direct intercalation g-C3N4Flame-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 |
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| CN1148605A (en) * | 1995-08-25 | 1997-04-30 | 东都化成株式会社 | Fire-retardant compound, process for producing said fire-retardant compound and fire-retarding thermoplastic resin composition including said fire-retardant compound |
| WO2004104098A2 (en) * | 2003-05-14 | 2004-12-02 | Albemarle Corporation | Stabilized flame retardant additives and their use |
| JP2005068407A (en) * | 2003-08-06 | 2005-03-17 | Techno Polymer Co Ltd | Flame retardant thermoplastic resin composition |
| CN101061177A (en) * | 2005-12-19 | 2007-10-24 | Lg化学株式会社 | Acrylonitrile-butadiene-styrene resin composition having good weatherability and thermostability |
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2010
- 2010-11-12 CN CN2010105515928A patent/CN102010563B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1148605A (en) * | 1995-08-25 | 1997-04-30 | 东都化成株式会社 | Fire-retardant compound, process for producing said fire-retardant compound and fire-retarding thermoplastic resin composition including said fire-retardant compound |
| WO2004104098A2 (en) * | 2003-05-14 | 2004-12-02 | Albemarle Corporation | Stabilized flame retardant additives and their use |
| JP2005068407A (en) * | 2003-08-06 | 2005-03-17 | Techno Polymer Co Ltd | Flame retardant thermoplastic resin composition |
| CN101061177A (en) * | 2005-12-19 | 2007-10-24 | Lg化学株式会社 | Acrylonitrile-butadiene-styrene resin composition having good weatherability and thermostability |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107974026A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of delustring anti-flaming ABS material 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 |
| CN111690197A (en) * | 2020-07-02 | 2020-09-22 | 南京工程学院 | Melamine-containing direct intercalation g-C3N4Flame-retardant cable 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102010563B (en) | 2012-04-25 |
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Granted publication date: 20120425 Termination date: 20131112 |