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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- CN104530634A CN104530634A CN201410838663.0A CN201410838663A CN104530634A CN 104530634 A CN104530634 A CN 104530634A CN 201410838663 A CN201410838663 A CN 201410838663A CN 104530634 A CN104530634 A CN 104530634A
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- 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 63
- 239000003063 flame retardant Substances 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 16
- -1 tri-bromophenyl Chemical group 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 238000004891 communication Methods 0.000 claims abstract description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012745 toughening agent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000007983 Tris buffer Substances 0.000 claims description 6
- 239000001177 diphosphate Substances 0.000 claims description 6
- 235000011180 diphosphates Nutrition 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-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
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 claims description 3
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- YASRHLDAFCMIPB-UHFFFAOYSA-N (1-oxo-2,6,7-trioxa-1$l^{5}-phosphabicyclo[2.2.2]octan-4-yl)methanol Chemical compound C1OP2(=O)OCC1(CO)CO2 YASRHLDAFCMIPB-UHFFFAOYSA-N 0.000 claims description 2
- OAGSJMRKTNUIFI-UHFFFAOYSA-N (2-tert-butylphenyl) phenyl hydrogen phosphate Chemical compound CC(C)(C)C1=CC=CC=C1OP(O)(=O)OC1=CC=CC=C1 OAGSJMRKTNUIFI-UHFFFAOYSA-N 0.000 claims description 2
- AENLCTMTBNXDPC-UHFFFAOYSA-N 1,2-dimethyl-3,4-diphenylbenzene phosphoric acid Chemical compound P(=O)(O)(O)O.C1(=CC=CC=C1)C=1C(=C(C(=CC1)C)C)C1=CC=CC=C1 AENLCTMTBNXDPC-UHFFFAOYSA-N 0.000 claims description 2
- RYUJRXVZSJCHDZ-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC(C)C)OC1=CC=CC=C1 RYUJRXVZSJCHDZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- AIGAEIONZZWHGH-UHFFFAOYSA-N [3-bis(2,3-dimethylphenoxy)phosphoryloxyphenyl] bis(2,3-dimethylphenyl) phosphate Chemical compound P(=O)(OC1=CC(=CC=C1)OP(=O)(OC1=C(C(=CC=C1)C)C)OC1=C(C(=CC=C1)C)C)(OC1=C(C(=CC=C1)C)C)OC1=C(C(=CC=C1)C)C AIGAEIONZZWHGH-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 2
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- YDICVVYPXSZSFA-UHFFFAOYSA-N diphenyl propan-2-yl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OC(C)C)OC1=CC=CC=C1 YDICVVYPXSZSFA-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000010433 feldspar Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000391 magnesium silicate Substances 0.000 claims description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 2
- 235000019792 magnesium silicate Nutrition 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- VXZJUYUVOQZBNU-UHFFFAOYSA-N phosphoric acid 1,2-xylene Chemical compound P(=O)(O)(O)O.CC1=C(C=CC=C1)C.CC1=C(C=CC=C1)C.CC1=C(C=CC=C1)C VXZJUYUVOQZBNU-UHFFFAOYSA-N 0.000 claims description 2
- KLLINNYXPAAVLS-UHFFFAOYSA-N phosphoric acid;toluene Chemical compound OP(O)(O)=O.CC1=CC=CC=C1.CC1=CC=CC=C1.CC1=CC=CC=C1 KLLINNYXPAAVLS-UHFFFAOYSA-N 0.000 claims description 2
- 238000010008 shearing Methods 0.000 claims description 2
- 125000000123 silicon containing inorganic group Chemical group 0.000 claims description 2
- 239000000429 sodium aluminium silicate Substances 0.000 claims description 2
- 235000012217 sodium aluminium silicate Nutrition 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 claims description 2
- FSLSJTZWDATVTK-UHFFFAOYSA-N tris(6-methylheptyl) phosphate Chemical compound CC(C)CCCCCOP(=O)(OCCCCCC(C)C)OCCCCCC(C)C FSLSJTZWDATVTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 abstract description 60
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 230000000979 retarding effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 230000006872 improvement Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 206010051246 Photodermatosis Diseases 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000008845 photoaging Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- BPILDHPJSYVNAF-UHFFFAOYSA-M sodium;diiodomethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(I)I BPILDHPJSYVNAF-UHFFFAOYSA-M 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
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 invention relates to the technical field of modified ABS, in particular to an environment-friendly high-proportion regenerated ABS (r-ABS) flame-retardant modified composition, and a preparation method and application of the composition.
Background
The ABS resin is a terpolymer consisting of styrene, butadiene and acrylonitrile, integrates the high fluidity of the styrene, the rubber toughness of the butadiene and the chemical resistance of the acrylonitrile, has excellent processability, low temperature resistance, electric insulation performance, chemical corrosion resistance, high gloss and excellent electroplating performance, has the excellent characteristics of good creep resistance, high dimensional stability, small molding shrinkage and the like, and is widely applied to the fields of war industry, automobiles, electronic and electric appliances and the like.
The great application of ABS in the above-mentioned fields, especially the great number of electronic products such as (tv, washing machine, refrigerator, air conditioner, computer) produced by using ABS resin in the last five years is in a peak of updating and eliminating, and thus the huge amount of regenerated ABS is receiving attention from material manufacturers, and the core of attention is to reduce the cost of the product by using regenerated ABS. However, the plastic material used in the electrical and electronic products may contain some inorganic powder, metal impurities and other unknown components, besides ABS resin, also may contain some elements, such as Cl element, etc. during the rinsing process. The above components of the non-ABS resin may be an important factor to deteriorate the performance of the regenerated ABS resin, and on the other hand, due to the structural characteristics of the ABS resin, the double bonds of the rubber phase in the ABS product are saturated by the photo-aging effect during use, thereby forming the cross-linking of the segments and reducing the rubber phase, thus reducing the impact resistance of the ABS resin. Meanwhile, due to the photo-aging effect, the chain segment of the ABS resin is broken, the molecular weight of the polymer is reduced, the elastic modulus and the tensile strength of the material are reduced, and the thermal deformation temperature is reduced. Further, the photochemical reaction of ABS produces a large amount of new substances such as aldehydes, ketones and peroxides, and the occurrence of carbonyl structure leads to yellowing of ABS, and the presence of peroxide is sensitive to uv light, which further aggravates photoaging and deterioration of properties of ABS resin. The combination of the above two factors results in a great deterioration in the performance of the ABS resin, which makes its subsequent modification difficult.
Therefore, scientists have made extensive and intensive studies on the improvement of the properties of recycled ABS resins, for example, Wangjiquai et al have proposed that the impact resistance of r-ABS can be improved by adding a special toughening agent to r-ABS in the article "Property study of ABS recycled Material" ("Shanghai plastics", 2005, Vol.9, No. 3: 16-19). Patent document CN1646280 discloses a method for recovering the physical properties of r-ABS by adding ABS resin, which only partially recycles r-ABS and does not change the properties of r-ABS itself but only sacrifices the properties of ABS resin, and the improvement of the properties is related to the proportion of added ABS resin. Zhang Hongmei et al put forward a high rubber powder/inorganic nano particle composite modification scheme in the article "Performance improvement of recovered ABS resin" ("high polymer Material science and engineering", 2011, Vol.27, No. 3: 62-66), and 5% -8% of high rubber powder and 2% -3% of inorganic nano particles are added, so that the toughness of the recovered ABS resin can be greatly improved, and meanwhile, the rigidity, strength and heat resistance of the material are considered. In the patent document of No. CN103254561B, the toughness of recovered ABS is improved by a method of toughening with high rubber powder, and this method is only applied in the field with low requirement for material use by single performance of toughening.
The above documents only propose some modification means aiming at the performance deficiency of one aspect of r-ABS, such as toughening, strengthening and other modifications, or achieve the purpose of improving the performance of the regenerated ABS resin by compounding with ABS resin, or reduce the use requirement to realize the recycling of the regenerated ABS. The improvement scheme is based on the performance improvement of the r-ABS resin, and how to utilize the r-ABS resin in the field of modified ABS resin, particularly in the field of flame-retardant ABS modification is not provided, and the main reason is that a targeted improvement method is not provided for the root cause of the performance reduction of the r-ABS, namely the influence of impurities, structural change caused in the using process and the like.
Disclosure of Invention
The invention aims to provide an environment-friendly high-proportion r-ABS flame-retardant modified composition which has excellent mechanical property, stable flame retardance and extremely low cost.
The invention also aims to provide a preparation method and application of the r-ABS flame-retardant modified composition.
In order to achieve the purpose, the invention adopts the following technical scheme:
the environment-friendly high-proportion regenerated ABS flame-retardant modified composition is composed of the following raw materials in parts by weight:
wherein,
the environment-friendly brominated flame retardant is tris (tri-bromophenyl) cyanurate.
The antimony flame-retardant synergist is at least one of the following substances: antimony trioxide, colloidal antimony pentoxide, antimony trichloride, antimony pentachloride.
The phosphorus-based flame retardant synergist can be at least one of the following substances: m-phenylene tetraphenyl diphosphate, bisphenol A bis (diphenyl phosphate), m-phenylene tetraxylyl diphosphate oligomer, triphenyl phosphate, diphenyl (xylene) phosphate, diphenyl isopropyl phenyl phosphate, diphenyl isooctyl phosphate, diphenyl isodecyl phosphate, tri (toluene) phosphate, tri (xylene) phosphate, phenyl tert-butylphenyl phosphate, alkylphenyl diphosphate, cycloalkyl-containing diphosphate, diphenyl bis (diphenyl) phosphate, triethyl phosphate, tributyl phosphate, triisooctyl phosphate, tris (2-butoxyethyl) phosphate, 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo (2, 2, 2) octane, tris (1-oxo-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-methylene-4) phosphate, 2-dimethyl-1, 3-propanediol-bis (neopentyl glycol) diphosphate.
The toughening agent can be one or a mixture of more of a styrene toughening agent, a chlorinated polyethylene toughening agent and ABS high rubber powder.
The compatilizer is one or more of SBS, SEBS, ABS-G-MAH, SMA700 and PP-G-MAH.
The inorganic powder is formed by compounding one or more of silicon-containing inorganic compounds such as sodium aluminosilicate, montmorillonite, kaolin, feldspar powder, wollastonite, mica powder, magnesium silicate, calcium silicate and the like.
The preparation method of the environment-friendly high-proportion regenerated ABS flame-retardant modified composition comprises the following steps:
a. proportionally adding the regenerated ABS, the high-rigidity ABS, the environment-friendly brominated flame retardant, the antimony flame retardant synergist, the phosphorus flame retardant synergist, the toughening agent, the compatilizer and the inorganic powder into a mixer to be mixed to obtain a mixture; wherein the environment-friendly brominated flame retardant is tris (tri-bromophenyl) cyanurate;
b. adding the mixture into a double-screw extruder, and carrying out melting, extrusion, granulation and drying under the shearing, mixing and conveying of screws to obtain an environment-friendly high-proportion regenerated ABS flame-retardant modified composition; wherein, the temperature of each section of screw of the extruder is controlled between 180 ℃ and 230 ℃, the length-diameter ratio of the double-screw extruder is 25-40, and the rotating speed of the screw is 200 ℃ and 800 r/min.
The environment-friendly high-proportion regenerated ABS flame-retardant modified composition can be widely applied to various fields needing flame retardance, such as household appliances, transportation, communication and the like.
The invention has the following beneficial effects:
1) the flame retardant grade of the environment-friendly high-proportion regenerated ABS flame retardant modified composition can reach UL94V-2-V-01.5mm-3.0mm, and the impact strength is kept at 15kJ/m2The melting index is above 40g/10min, and the heat resistance is excellent under the condition of better mechanical properties.
2) The environment-friendly high-proportion regenerated ABS flame-retardant modified composition has the advantages of simple and easy preparation method, easy processing and low cost, and is very suitable for various fields needing flame retardance, such as household appliances, transportation, communication and the like.
Detailed Description
The environment-friendly high-proportion recycled ABS flame-retardant modified composition, the preparation method and the application thereof are further described in the following with reference to some specific embodiments. The specific examples are intended to illustrate the present invention in further detail, and are not intended to limit the scope of the present invention.
The environment-friendly high-proportion recycled ABS flame-retardant modified composition provided by the invention is subjected to the performance tests listed in the following table 1 according to standard prepared sample bars.
TABLE 1 Performance test and standards thereof
In all the embodiments provided by the invention, the provided raw materials can be purchased from the market. Wherein,
the r-ABS resin is regenerated ABS from Japanese tussah refrigerator plates;
the high-rigidity ABS resin is ABS AG15A1 from Taiwan Chinesemedicine
The brominated triazine is FR-245 of Israel dead sea bromine company;
the toughening agent is HR181 of Korea brocade lake company;
the antimony flame-retardant synergist is S-05N of Yunnan Murilieantimony industry Co Ltd;
the phosphorus flame retardant synergist-1 is bisphenol A bis (diphenyl phosphate) WSFR-BDP-N2 from Wansheng company of Zhejiang;
the phosphorus flame retardant synergist-2 is selected from m-phenylene tetraphenyl diphosphate WSFR-RDP of Wansheng company of Zhejiang;
the compatilizer is selected from PP-G-MAH of Nanjing Taotai
The inorganic powder is NYAD MD400 from NYCO
Examples 1 to 4 and comparative examples 1 to 4
Adding the components into a high-speed mixer according to the weight parts listed in the table 2 for uniform mixing, and then feeding the mixture into a double-screw extruder for mixing, extruding, drawing into strips, cooling by water and granulating; wherein the length-diameter ratio of the double-screw extruder is 25-40; the barrel temperature is set as follows: the temperature of a first area is 180 ℃, the temperature of a second area is 190 ℃, the temperature of a third area is 200 ℃, the temperature of a fourth area is 210 ℃, the temperature of a fifth area is 220 ℃, the temperature of a sixth area is 220 ℃, the temperature of a seventh area is 220 ℃, the temperature of an eighth area is 220 ℃, the temperature of a ninth area is 220 ℃, the temperature of a tenth area is 220 ℃ and the temperature of a machine head is 230 ℃; the screw rotation speed is 200-800 rpm.
The environment-friendly high-proportion recycled ABS flame-retardant modified composition prepared by the method is subjected to various performance tests listed in Table 1 according to standard preparation sample bars, and the data is recorded in Table 2.
TABLE 2
As shown in Table 2 above, when examples 1 to 4 are compared with comparative examples 1 to 4, it can be seen that the mechanical properties of r-ABS of comparative example 1 are significantly reduced as compared with ABS AG15A1 of comparative example 2, and if the same flame retardant modification method is used as shown in comparative examples 3 and 4, the flame retardant ABS prepared in comparative example 4 has excellent properties, but the flame retardant ABS prepared in comparative example 3 has further deteriorated properties, especially impact properties as low as 4kJ/m2Such low impact properties are of little use value for flame retardant ABS compositions. However, the formulation design of the environment-friendly high-proportion recycled ABS flame-retardant modified composition described in examples 1-4 can still prepare a flame-retardant composition with excellent flame-retardant property, balanced mechanical properties, excellent flow property and extremely low cost under the condition that the r-ABS addition proportion is up to 70 parts. According to different requirements on flame retardant property, a proper formula is selected, and the prepared corresponding environment-friendly high-proportion regenerated ABS flame retardant modified composition can be applied to various fields needing flame retardance, such as household appliances, transportation, communication and the like.
Claims (9)
1. The environment-friendly high-proportion regenerated ABS flame-retardant modified composition is characterized in that: the composite material consists of the following raw materials in parts by weight:
2. the environment-friendly high-proportion recycled ABS flame-retardant modified composition according to claim 1, characterized in that: the environment-friendly brominated flame retardant is tris (tri-bromophenyl) cyanurate.
3. The environment-friendly high-proportion recycled ABS flame-retardant modified composition according to claim 1, characterized in that: the antimony flame-retardant synergist is at least one of the following substances: antimony trioxide, colloidal antimony pentoxide, antimony trichloride, antimony pentachloride.
4. The environment-friendly high-proportion recycled ABS flame-retardant modified composition according to claim 1, characterized in that: the phosphorus-based flame retardant synergist can be at least one of the following substances: m-phenylene tetraphenyl diphosphate, bisphenol A bis (diphenyl phosphate), m-phenylene tetraxylyl diphosphate oligomer, triphenyl phosphate, diphenyl (xylene) phosphate, diphenyl isopropyl phenyl phosphate, diphenyl isooctyl phosphate, diphenyl isodecyl phosphate, tri (toluene) phosphate, tri (xylene) phosphate, phenyl tert-butylphenyl phosphate, alkylphenyl diphosphate, cycloalkyl-containing diphosphate, diphenyl bis (diphenyl) phosphate, triethyl phosphate, tributyl phosphate, triisooctyl phosphate, tris (2-butoxyethyl) phosphate, 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo (2, 2, 2) octane, tris (1-oxo-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-methylene-4) phosphate, 2-dimethyl-1, 3-propanediol-bis (neopentyl glycol) diphosphate.
5. The environment-friendly high-proportion recycled ABS flame-retardant modified composition according to claim 1, characterized in that: the toughening agent can be one or a mixture of more of a styrene toughening agent, a chlorinated polyethylene toughening agent and ABS high rubber powder.
6. The environment-friendly high-proportion recycled ABS flame-retardant modified composition according to claim 1, characterized in that: the compatilizer is one or more of SBS, SEBS, ABS-G-MAH, SMA700 and PP-G-MAH.
7. The environment-friendly high-proportion recycled ABS flame-retardant modified composition according to claim 1, characterized in that: the inorganic powder is formed by compounding one or more of silicon-containing inorganic compounds such as sodium aluminosilicate, montmorillonite, kaolin, feldspar powder, wollastonite, mica powder, magnesium silicate, calcium silicate and the like.
8. The preparation method of the environment-friendly high-proportion recycled ABS flame-retardant modified composition as claimed in any one of claims 1 to 7, characterized in that: the method comprises the following steps:
a. proportionally adding the regenerated ABS, the high-rigidity ABS, the environment-friendly brominated flame retardant, the antimony flame retardant synergist, the phosphorus flame retardant synergist, the toughening agent, the compatilizer and the inorganic powder into a mixer to be mixed to obtain a mixture; wherein the environment-friendly brominated flame retardant is tris (tri-bromophenyl) cyanurate;
b. adding the mixture into a double-screw extruder, and carrying out melting, extrusion, granulation and drying under the shearing, mixing and conveying of screws to obtain an environment-friendly high-proportion regenerated ABS flame-retardant modified composition; wherein, the temperature of each section of screw of the extruder is controlled between 180 ℃ and 230 ℃, the length-diameter ratio of the double-screw extruder is 25-40, and the rotating speed of the screw is 200 ℃ and 800 r/min.
9. The environment-friendly high-proportion recycled ABS flame-retardant modified composition as recited in any of claims 1 to 7, characterized in that: the method is applied to the fields of household appliances, transportation and communication.
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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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