CN104530634A - Environment-friendly high-proportion r-ABS (Recycled ABS) flame-retardant modified composition and preparation method and application thereof - Google Patents
Environment-friendly high-proportion r-ABS (Recycled ABS) flame-retardant modified composition and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an environment-friendly high-proportion r-ABS (Recycled ABS) flame-retardant modified composition and a preparation method and application thereof. The r-ABS flame-retardant modified composition adopts the formula as follows: 70 parts of r-ABS, 30 parts of high-rigidity ABS resin, 10-25 parts of an environment-friendly brominated flame retardant, 0-1 part of an antimonic flame-retardant synergist, 1-5 parts of a phosphorus-based flame-retardant synergist, 5-15 parts of a flexibilizer, 1-3 parts of a compatilizer and 1-5 parts of inorganic powder, wherein the environment-friendly brominated flame retardant is tri(tri-bromophenyl) cyanurate. The invention further provides a preparation method and preparation of the r-ABS flame-retardant modified composition. The r-ABS flame-retardant modified composition provided by the invention can still keep relatively high mechanical property and flame-retardant property after flame-retardant modification, and meanwhile is extremely low in cost. The r-ABS flame-retardant modified composition is suitable to be popularized and applied in various fields needing flame retarding, such as the fields of household appliances, transportation and communication.
Description
Technical field
The present invention relates to modified ABS technical field, be specially the flame-proof modified composition that a kind of environment-friendly type regenerates ABS (Recycled ABS, be called for short r-ABS) at high proportion, and the preparation method of this composition and application.
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 the plating performance of excellent processing characteristics, resistance to low temperature, electrical insulation capability, resistance to chemical corrosion and high gloss and excellence, there is the excellent characteristics such as creep resistant is good, dimensional stability is high, molding shrinkage is little simultaneously, in field application such as military project, automobile, electronic apparatuss widely.
ABS is in the extensive application of above-mentioned every field, the a large amount of electronic products such as (TV, washing machine, refrigerator, air-conditioning, computer) particularly applying ABS resin production over nearly 5 years are in a replacement and obsoleteness peak period, the regeneration ABS producing flood tide thus enjoys the concern of material manufacturer, the core of concern to be want the cost by utilizing the ABS of regeneration to reduce product.But the plastic material used due to electric series products is except ABS resin, also the plastics such as PP, PC, PE and improved composition thereof may be had, so also some inorganic powders, metallic impurity and some other non-chief constituent may be contained, in addition, reclaim in ABS resin process and need rinsing, it also may introduce some element in rinse cycle, as Cl element etc.The composition of above-mentioned non-ABS resin may be all the important factor worsening regeneration ABS resin performance, on the other hand, due to the structural performance of ABS resin itself, the photoaging effect that ABS goods are in use subject to, the double bond of rubber phase is wherein saturated, and then form the crosslinked of segment, rubber phase is reduced, because this reducing the shock resistance of ABS resin.The effect of photoaging simultaneously makes the segment of ABS resin rupture, the molecular weight and molecular weight of polymkeric substance, and cause the Young's modulus of material and tensile strength to reduce, heat-drawn wire reduces.Further, the photochemical reaction of ABS creates a large amount of novel substances, and as aldehyde, ketone and superoxide, and the appearance of carbonyl structure result in the xanthochromia of ABS, superoxide is to ultraviolet-sensitive, and its existence exacerbates the photoaging of ABS resin and the deterioration of performance further.The common results of above-mentioned two factor effects causes the performance of ABS resin significantly to worsen, and the modification follow-up for it adds difficulty.
Therefore, a large amount of deep research has been carried out in the raising of scientific worker to the performance of regeneration ABS resin, if the people such as Wang Jikui are at article " performance study of ABS reclaimed materials " (" Shanghai Plastic ", 2005, Vol.9, No.3:16-19) in propose in r-ABS, add the shock resistance that special toughner can improve r-ABS.Publication number is in the patent documentation of CN1646280, disclose the method recovering the physicals of r-ABS by adding ABS resin, this method can only be that component loops make use of r-ABS, performance for r-ABS itself does not play any change, the performance of only sacrificing ABS resin realizes, and the ratio of the lifting of its performance and the ABS resin of interpolation is closely bound up.The people such as Zhang Hongmei " reclaim the performance boost of ABS resin " (" polymer material science and engineering " at article, 2011, Vol.27, No.3:62-66) the composite modified scheme of high glue powder/inorganic nano-particle is proposed in, add the high glue powder of 5%-8% and the inorganic nano-particle of 2%-3%, significantly can promote the toughness reclaiming ABS resin, take into account the rigidity of material, intensity and resistance toheat simultaneously.In the patent documentation of grant number CN103254561B, improved the toughness reclaiming ABS by the method that high glue powder is toughness reinforcing, this method is just realized in the application to the less demanding field of materials'use by toughness reinforcing single performance.
Above-mentioned document just proposes some modified methods for the deficiency of r-ABS performance in a certain respect, as modifications such as toughness reinforcing, enhancings, or by reaching with the composite of ABS resin the performance promoting regeneration ABS resin, or reduce the object recycled that service requirements realizes regenerating ABS.Above-mentioned improving countermeasure is the improved performance based on r-ABS resin itself, and not in modified ABS resin field, how to utilize r-ABS resin particularly in flame-proof ABS modification field, major cause is that the structural changes etc. caused in the impact of the impurity of its basic reason do not reduced for r-ABS performance-namely and use procedure proposes ameliorative way targetedly.
Summary of the invention
Primary and foremost purpose of the present invention is to provide a kind of environment-friendly type r-ABS flame-proof modified composition at high proportion, and this r-ABS flame-proof modified composition has excellent in mechanical performance, fire-retardant stable and extremely low cost.
Another object of the present invention is to preparation method and application thereof that above-mentioned r-ABS flame-proof modified composition is provided.
For achieving the above object, the present invention adopts following technical scheme:
Environment-friendly type regenerates ABS flame-proof modified composition at high proportion, is made up of the raw material of following weight parts:
Wherein,
Described environmental protection bromide fire retardant is three (three-bromophenyl) cyanurate.
Described antimony system fire retarding synergist is at least one in following material: antimonous oxide, colloidal antimony pentoxide, butter of antimony, antimony pentachloride.
Described phosphorous flame-retardant synergist can be at least one in following material: metaphenylene tetraphenyl diphosphate, dihydroxyphenyl propane two (diphenyl phosphoester), metaphenylene four (xylyl) biphosphonate, metaphenylene four (xylyl) biphosphonate oligopolymer, triphenylphosphate, phosphoric acid hexichol (dimethylbenzene) ester, phosphoric acid hexichol isopropyl benzene ester, diphenyl 2 ethylhexyl phosphate, phosphate diphenyl isodecyl ester, tricresyl phosphate (toluene) ester, tricresyl phosphate (dimethylbenzene) ester, phosphoric acid phenyl trimethylphenylmethane base ester, alkane phenyl biphosphonate, containing the bis phosphoric acid acid esters of cycloalkyl, two (phenylbenzene) phosphoric acid ester of biphenyl, triethyl phosphate, tributyl phosphate, triisooctyl phosphate, tricresyl phosphate (2-fourth oxygen ethyl) ester, 1-oxo-4-methylol-2,6,7-trioxa-1-phosphabicyclo (2,2,2) octane, three (1-oxo-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane-methylene radical-4) phosphoric acid ester, 2，2-dimethyl-1，3-propanediol-two (neopentyl glycol) biphosphonate.
Described toughner can be the mixture of one or more in styrenic toughner, chlorinatedpolyethylene class toughner and ABS high glue powder.
Described compatilizer is one or more in SBS, SEBS, ABS-G-MAH, SMA700 and PP-G-MAH.
To be that one or more in the siliceous class mineral compound such as sodium aluminium silicate, polynite, kaolin, Feldspar Powder, wollastonite, mica powder, Magnesium Silicate q-agent and Calucium Silicate powder are composite form described inorganic powder.
Above-mentioned environment-friendly type regenerates the preparation method of ABS flame-proof modified composition at high proportion, comprises the steps:
A, in proportion described regeneration ABS, described high rigidity ABS, described environmental protection bromide fire retardant, described antimony system fire retarding synergist, described phosphorous flame-retardant synergist, described toughner, described compatilizer, described inorganic powder are added mixing machine and be mixed to get mixture; Wherein, described environmental protection bromide fire retardant is three (three-bromophenyl) cyanurate;
B, said mixture is joined in twin screw extruder, under the shearing, mixing and conveying of screw rod, through melting, extrude, granulation, drying, environment-friendly type regenerates ABS flame-proof modified composition at high proportion; Wherein, each section of extruder temperature of described forcing machine controls between 180-230 DEG C, and the length-to-diameter ratio of twin screw extruder is 25-40, and screw speed is 200-800 rev/min.
Environment-friendly type of the present invention regenerates ABS flame-proof modified composition at high proportion and can be widely used in household electrical appliance, communications and transportation, communication etc. each needs fire-retardant field.
The present invention has following beneficial effect:
1) flame retardant rating that environment-friendly type of the present invention regenerates ABS flame-proof modified composition at high proportion can reach UL94V-2-V-0@1.5mm-3.0mm, and shock strength then remains on 15kJ/m
2above, melt index at more than 40g/10min, and under all other mechanical properties all preferably situation, has excellent resistance toheat simultaneously.
2) to regenerate ABS flame-proof modified composition preparation method at high proportion simple for environment-friendly type of the present invention, and handling ease, with low cost, each needs fire-retardant field to be highly suitable for household electrical appliance, communications and transportation, communication etc.
Embodiment
Regenerate ABS flame-proof modified composition, preparation method and application thereof below in conjunction with some embodiments at high proportion to environment-friendly type of the present invention to be described further.Specific embodiment is for further describing the present invention, non-limiting protection scope of the present invention.
Environment-friendly type of the present invention regenerates ABS flame-proof modified composition at high proportion and carries out performance test listed in following table 1 according to standard system for batten.
Table 1 performance test and standard thereof
In all embodiments provided by the invention, the starting material provided all can obtain from market buying.Wherein,
R-ABS resin selects PANASONIC refrigerator plate to regenerate ABS;
The ABS AG15A1 of Taiwan company selected by high rigidity ABS resin
Brominated triazine selects the FR-245 of Dead Sea bromine company of Israel;
The HR181 of Jin Hu company of Korea S selected by toughner;
Antimony system fire retarding synergist selects the S-05N of Yunnan Mu Liti industry company limited;
Phosphorous flame-retardant synergist-1 selects two (diphenyl phosphoester) WSFR-BDP-N2 of the dihydroxyphenyl propane of Zhejiang Wan Sheng company;
Phosphorous flame-retardant synergist-2 selects the metaphenylene tetraphenyl diphosphate WSFR-RDP of Zhejiang Wan Sheng company;
Compatilizer selects the PP-G-MAH of Nanjing Su Tai company
Inorganic powder selects the NYAD MD400 of Nyco SA of the U.S.
Embodiment 1-4, comparative example 1-4
According to weight part listed in table 2 each component added in high-speed mixer and carries out Homogeneous phase mixing, then said mixture is sent into mixing in twin screw extruder, extrude, tie rod, water-cooled, pelletizing; Wherein, the length-to-diameter ratio of twin screw extruder is 25-40; Barrel temperature is set as: district's temperature 180 DEG C, two district's temperature 190 DEG C, three district's temperature 200 DEG C, four district's temperature 210 DEG C, five district's temperature 220 DEG C, six district's temperature 220 DEG C, seven district's temperature 220 DEG C, eight district's temperature 220 DEG C, nine district's temperature 220 DEG C, ten district's temperature 220 DEG C, head temperature 230 DEG C; Screw speed is 200-800 rev/min.
The environment-friendly type that aforesaid method is obtained regenerate at high proportion ABS flame-proof modified composition carry out table 1 according to standard system for batten in listed each performance test record data in table 2.
Table 2
From in upper table 2, embodiment 1-4 and comparative example 1-4 compares, can find out, the r-ABS of comparative example 1 compares with the ABS AG15A1 in comparative example 2, every mechanical property all has one to reduce significantly, if adopt identical method for modifying flame as shown in comparative example 3 and comparative example 4, and flame-proof ABS excellent performance prepared by comparative example 4, but flame-proof ABS performance prepared by comparative example 3 further worsens again compared with the performance of r-ABS, and especially impact property is low to moderate 4kJ/m
2, so low impact property, for flame-retardant ABS composition, almost without any use value.But the environment-friendly type described in embodiment 1-4 regenerates the formulating of recipe of ABS flame-proof modified composition at high proportion, when r-ABS adding proportion is up to 70 parts, still can prepare excellent fireproof performance, every mechanical property is balanced, the flowing property of the excellence simultaneously had and extremely low cost.According to the difference required flame retardant properties, select suitable formula, the corresponding environment-friendly type of preparation regenerates ABS flame-proof modified composition at high proportion and can be applicable to household electrical appliance, communications and transportation, communication etc. each needs fire-retardant field.
Claims (9)
1. environment-friendly type regenerates ABS flame-proof modified composition at high proportion, it is characterized in that: be made up of the raw material of following weight parts:
2. environment-friendly type according to claim 1 regenerates ABS flame-proof modified composition at high proportion, it is characterized in that: described environmental protection bromide fire retardant is three (three-bromophenyl) cyanurate.
3. environment-friendly type according to claim 1 regenerates ABS flame-proof modified composition at high proportion, it is characterized in that: described antimony system fire retarding synergist is at least one in following material: antimonous oxide, colloidal antimony pentoxide, butter of antimony, antimony pentachloride.
4. environment-friendly type according to claim 1 regenerates ABS flame-proof modified composition at high proportion, it is characterized in that: described phosphorous flame-retardant synergist can be at least one in following material: metaphenylene tetraphenyl diphosphate, dihydroxyphenyl propane two (diphenyl phosphoester), metaphenylene four (xylyl) biphosphonate, metaphenylene four (xylyl) biphosphonate oligopolymer, triphenylphosphate, phosphoric acid hexichol (dimethylbenzene) ester, phosphoric acid hexichol isopropyl benzene ester, diphenyl 2 ethylhexyl phosphate, phosphate diphenyl isodecyl ester, tricresyl phosphate (toluene) ester, tricresyl phosphate (dimethylbenzene) ester, phosphoric acid phenyl trimethylphenylmethane base ester, alkane phenyl biphosphonate, containing the bis phosphoric acid acid esters of cycloalkyl, two (phenylbenzene) phosphoric acid ester of biphenyl, triethyl phosphate, tributyl phosphate, triisooctyl phosphate, tricresyl phosphate (2-fourth oxygen ethyl) ester, 1-oxo-4-methylol-2,6,7-trioxa-1-phosphabicyclo (2,2,2) octane, three (1-oxo-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane-methylene radical-4) phosphoric acid ester, 2，2-dimethyl-1，3-propanediol-two (neopentyl glycol) biphosphonate.
5. environment-friendly type according to claim 1 regenerates ABS flame-proof modified composition at high proportion, it is characterized in that: described toughner can for the mixture of one or more in styrenic toughner, chlorinatedpolyethylene class toughner and ABS high glue powder.
6. environment-friendly type according to claim 1 regenerates ABS flame-proof modified composition at high proportion, it is characterized in that: described compatilizer is one or more in SBS, SEBS, ABS-G-MAH, SMA700 and PP-G-MAH.
7. environment-friendly type according to claim 1 regenerates ABS flame-proof modified composition at high proportion, it is characterized in that: to be that one or more in the siliceous class mineral compound such as sodium aluminium silicate, polynite, kaolin, Feldspar Powder, wollastonite, mica powder, Magnesium Silicate q-agent and Calucium Silicate powder are composite form described inorganic powder.
8. one of any described environment-friendly type of claim 1-7 regenerates the preparation method of ABS flame-proof modified composition at high proportion, it is characterized in that: comprise the steps:
A, in proportion described regeneration ABS, described high rigidity ABS, described environmental protection bromide fire retardant, described antimony system fire retarding synergist, described phosphorous flame-retardant synergist, described toughner, described compatilizer, described inorganic powder are added mixing machine and be mixed to get mixture; Wherein, described environmental protection bromide fire retardant is three (three-bromophenyl) cyanurate;
B, said mixture is joined in twin screw extruder, under the shearing, mixing and conveying of screw rod, through melting, extrude, granulation, drying, environment-friendly type regenerates ABS flame-proof modified composition at high proportion; Wherein, each section of extruder temperature of described forcing machine controls between 180-230 DEG C, and the length-to-diameter ratio of twin screw extruder is 25-40, and screw speed is 200-800 rev/min.
9. one of any described environment-friendly type of claim 1-7 regenerates ABS flame-proof modified composition at high proportion, it is characterized in that: be applied to household electrical appliance, communications and transportation and communication field.
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Cited By (3)
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| CN105171854A (en) * | 2015-08-05 | 2015-12-23 | 南京林业大学 | Carbonized inflaming-retarding poplar composite board |
| CN106221104A (en) * | 2016-08-26 | 2016-12-14 | 青岛海尔新材料研发有限公司 | Flame retardant styrene resin compositions and preparation method thereof |
| CN106380770A (en) * | 2016-08-26 | 2017-02-08 | 青岛海尔新材料研发有限公司 | Flame-retardant styrene resin composition and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105171854A (en) * | 2015-08-05 | 2015-12-23 | 南京林业大学 | Carbonized inflaming-retarding poplar composite board |
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Effective date of registration: 20190523 Address after: 221300 Jiangsu, Xuzhou, Pizhou high tech Industrial Development Zone, the southern side of Chun Hing Road, the west side of Jian Qiu road. Co-patentee after: Shanghai Blonde Technology Development Co., Ltd. Patentee after: Jiangsu golden hair Environmental Protection Technology Co., Ltd. Co-patentee after: Tianjin Kingfa New Materials Co., Ltd. Address before: 201714 No. 88 Kangyuan Road, Zhujiajiao Industrial Park, Qingpu District, Shanghai Co-patentee before: Tianjin Kingfa New Materials Co., Ltd. Patentee before: Shanghai Kingfa Science and Technology Development Co., Ltd. |
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