CN105462157A - High-fluidity, scratch-resistant and low-temperature-resistant brominated flame-retardant ABS (acrylonitrile-butadiene-styrene)/TPU (thermoplastic polyurethane) alloy material as well as preparation method and application thereof - Google Patents
High-fluidity, scratch-resistant and low-temperature-resistant brominated flame-retardant ABS (acrylonitrile-butadiene-styrene)/TPU (thermoplastic polyurethane) alloy material as well as preparation method and application thereof Download PDFInfo
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- CN105462157A CN105462157A CN201511000226.2A CN201511000226A CN105462157A CN 105462157 A CN105462157 A CN 105462157A CN 201511000226 A CN201511000226 A CN 201511000226A CN 105462157 A CN105462157 A CN 105462157A
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 76
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 76
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 70
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 title claims abstract description 48
- 239000000956 alloy Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 title 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 class 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 abstract description 19
- 230000003678 scratch resistant effect Effects 0.000 title abstract 2
- 239000003063 flame retardant Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000004891 communication Methods 0.000 claims abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 20
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052794 bromium Inorganic materials 0.000 claims description 20
- 238000012360 testing method Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052787 antimony Inorganic materials 0.000 claims description 11
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 11
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 150000003918 triazines Chemical class 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 claims description 6
- 238000001746 injection moulding Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- -1 photostabilizer Substances 0.000 claims description 6
- 229920001897 terpolymer Polymers 0.000 claims description 6
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 4
- UIDCKBLSASIYHR-UHFFFAOYSA-N [Sb].P(O)(O)O Chemical compound [Sb].P(O)(O)O UIDCKBLSASIYHR-UHFFFAOYSA-N 0.000 claims description 4
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 235000006708 antioxidants Nutrition 0.000 claims description 4
- 238000005453 pelletization Methods 0.000 claims description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical class CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 3
- MRZRZQWTALHURL-UHFFFAOYSA-N furan-2,5-dione;1-phenylpyrrole-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1.O=C1C=CC(=O)N1C1=CC=CC=C1 MRZRZQWTALHURL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 2
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 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
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract description 3
- 238000005469 granulation Methods 0.000 abstract description 2
- 230000003179 granulation Effects 0.000 abstract description 2
- 150000001463 antimony compounds Chemical class 0.000 abstract 1
- 230000007123 defense Effects 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000012545 processing Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 3
- BIEHXHIWQHAVFZ-UHFFFAOYSA-M bromoantimony Chemical compound [Sb]Br BIEHXHIWQHAVFZ-UHFFFAOYSA-M 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 241000271569 Rhea Species 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-fluidity, scratch-resistant and low-temperature-resistant brominated flame-retardant ABS (acrylonitrile-butadiene-styrene)/TPU (thermoplastic polyurethane) alloy material. The ABS/TPU alloy material mainly comprises the following components in parts by weight: 45-70 parts of ABS resin, 10-30 parts of thermoplastic polyurethane (TPU), 10-15 parts of a brominated flame retardant and 2-5 parts of an antimony compound. The flame-retardant ABS/TPU alloy material prepared by the invention has the advantages of both ABS and TPU, has good wear resistance, good low temperature resistance, excellent flame-retardant effect and wonderful processability; in a preparation method of the alloy material, blending, extrusion and granulation are conducted at one time by a twin-screw extruder, so the process is simple, convenient to operate and suitable for industrial production; and a final product has application values in the fields of electronic electric appliances, communications and transportation, military and national defense and the like.
Description
Technical field
The present invention relates to a kind of ABS modified composite material, particularly relate to a kind of high flowing, damage resistant, low temperature resistant bromine system flame-proof ABS/TPU alloy material and preparation method thereof and application, belong to polymeric material field.
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.But the oxygen index of ABS resin only has 18, belongs to inflammable material, therefore when for electronic and electrical equipment, mostly need to carry out flame-retardant modified, to reach fire safety service requirements.Flame-retardant modified mainly the passing through of current ABS resin adds the bromide fire retardant more than 15% mass fraction and antimonous oxide compound system, the bromide fire retardant that wherein ABS resin is the most frequently used is as TDE, brominated epoxy, brominated triazine and tetrabromo-bisphenol etc., but because ABS resin is a kind of triblock copolymer, belong to typical sea-island structure.The membership that adds of so many bromo-antimony compound flame retardant significantly worsens ABS resin physicochemical property inherently, as TDE flame-retardant system significantly can worsen mobility, the shock strength of ABS matrix resin; Brominated epoxy flame-retardant system significantly can worsen the shock strength of system; Brominated triazine and tetrabromo-bisphenol flame-retardant system also can produce larger impact to the low-temperature flexibility of system.Meanwhile, the wear resistance of ABS resin is not good, and low temperature resistant toughness is general.Mobility and low-temperature impact and elongation at break often conflicting, the ABS of high rubber content has good impact property, but mobility is not good; And the ABS of high workability often impact property is unsatisfactory.
Thermoplastic polyurethane TPU is linear block copolymers, along with rising or the reduction of temperature, lightly crosslinked between the crosslinked or macromole of intermolecular hydrogen bonding have reversibility, and therefore TPU not only has the elasticity of rubber, excellent processing characteristics, has more excellent wear resistance, low temperature folding endurance.
Point out that TPU and ABS has good consistency in " ABS/TPU alloy property and microtexture " " modern plastics processed and applied " and " thermoplastic polyurethane is studied the blending and modifying of ABS " " synthetic resins and plastics ", TPU adds toughness and the mobility that can improve ABS simultaneously, but how to prepare and there is balanced intensity, good wear resistance and lower temperature resistance, the flame retardant effect of excellence and the flame-proof ABS/TPU alloy material of fabulous processibility, but have no report at present.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, the invention provides a kind of high flowing, damage resistant, low temperature resistant bromine system flame-proof ABS/TPU alloy material and preparation method thereof and application, the alloy material being prepared gained by the method has good wear resistance, low temperature resistant folding endurance, flame retardant effect and fabulous processibility.
The present invention is achieved by the following technical solutions:
A kind of high flowing, damage resistant, low temperature resistant bromine system flame-proof ABS/TPU alloy material, comprise following each component by weight: 45-70 part ABS resin, 10-30 part thermoplastic polyurethane TPU, 10-15 part bromide fire retardant and 2-5 part antimony based compound; Shao A hardness of wherein said thermoplastic polyurethane TPU is 70-95HA by ASTMD2240-2005 standard testing value; Described bromide fire retardant is at least one in tetrabromo-bisphenol, brominated epoxy, brominated triazine and TDE; Described antimony based compound is at least one in antimonous oxide, colloidal antimony pentoxide, sodium antimonate, phosphorous acid antimony, butter of antimony, antimony pentachloride, phosphorous acid antimony, polyphosphoric acid antimony and complexing antimony, and described ABS resin is acrylonitrile-butadiene-styrene terpolymer.
Its further technical scheme is:
Described alloy material also comprises maleic anhydride modified Its Compatibilizing Technology 1-5 part by weight.
Described maleic anhydride modified Its Compatibilizing Technology is at least one in vinylbenzene-N-phenylmaleimide-maleic anhydride terpolymer AS-MS-NB, styrene-maleic anhydride copolymer SMA and maleic anhydride-g-SBS, preferred maleic anhydride modified Its Compatibilizing Technology be vinylbenzene-N-phenylmaleimide-maleic anhydride terpolymer AS-MS-NB and its consumption is 2-4% time every mechanical property of the finished product and processing characteristics reach optimum balance.
Described alloy material also comprises toughner 0-10 part by weight, oxidation inhibitor 0-1 part, photostabilizer 0-1 part and processing aid 0-5 part.
Described toughner is at least one in terpolymer EP rubber, chlorinatedpolyethylene and high glue powder.
Described oxidation inhibitor is the compound of Hinered phenols primary antioxidant and phosphorous acid esters auxiliary anti-oxidant composition, is preferably the compound of Irganox1010 and Irganox168 composition.
Described photostabilizer is benzophenone, benzotriazole category, triazines, poly-at least one in the fine class of propylene, Oxamides and hindered amines.
Described processing aid is at least one in stearylamide series lubricant agent, silicone oil and white mineral oil, wherein the preferred EBS of stearylamide series lubricant agent.
The invention also discloses the preparation method of a kind of above-mentioned high flowing, damage resistant, low temperature resistant bromine system flame-proof ABS/TPU alloy material, the method comprises the steps:
(a) by ABS resin before blended at 85 DEG C dry 2-4 hour, thermoplastic polyurethane TPU before blended at 100 DEG C dry 2-4 hour;
B () fully mixes 2-10 minute by the ABS resin of the bromide fire retardant of formula consumption, antimony based compound, maleic anhydride modified Its Compatibilizing Technology, toughner, oxidation inhibitor, photostabilizer, processing aid, the dry gained of warp (a) with through the thermoplastic polyurethane TPU of (a) dry gained in mixing machine, obtain mixture;
C the mixture of gained in (b) is transported in twin screw extruder through the pay-off of delicate metering by (), each section of extruder temperature of forcing machine controls between 160-220 DEG C, the length-to-diameter ratio of twin screw extruder is 25-40, screw speed is 200-800 rev/min, screw rod shearing, mixing and conveying under, material is able to abundant fusing, compound, then obtains flame-proof ABS/TPU alloy plastic particles through extruding pelletization, drying;
D the ABS/TPU alloy plastic particles of gained in (c) joins in injection moulding machine and is processed into required batten by (), injecting condition is: barrel temperature 170-210 DEG C, die temperature 60-70 DEG C, injection pressure 6-10MPa.
Thermoplastic polyurethane TPU in the present invention is linear block copolymers, along with rising or the reduction of temperature, lightly crosslinked between the crosslinked or macromole of intermolecular hydrogen bonding have reversibility, and therefore TPU not only has the elasticity of rubber, excellent processing characteristics, has more excellent wear resistance, low temperature folding endurance.-NHCOO-unit on linear block copolymers TPU main chain and the acrylonitrile unit-CH in ABS resin in addition
2cH (CN)-, the two forms hydrogen bond by blended; The simultaneously polyester of acrylonitrile unit and TPU or the stronger in addition dipole-dipole effect of polyester soft segment, so have good consistency therebetween.Therefore flame-proof ABS/TPU alloy material is prepared by ABS, TPU and bromo-antimony compounding flame retardant, wear resistance and the low temperature folding endurance of ABS resin can be significantly improved on the one hand, on the other hand the processing characteristics of ABS resin is significantly improved, make final flame-proof ABS/TPU alloy have balanced intensity, good wear resistance and lower temperature resistance, excellent flame retardant effect and fabulous processibility.
In addition the invention also discloses above-mentioned high flowing, damage resistant, the application of low temperature resistant bromine system flame-proof ABS/TPU alloy material in electronic apparatus, communications and transportation and military project national defence.
Advantageous Effects of the present invention is: preparation method of the present invention adopts the granulation of twin screw extruder blending extrusion once to complete, technique is simple, easy to operate, be suitable for suitability for industrialized production, flame-proof ABS/TPU the alloy material of gained processed has good wear resistance, low temperature resistant folding endurance, excellent flame retardant effect and fabulous processibility, has using value in fields such as electronic apparatus, communications and transportation, military project national defence.
Embodiment
Further illustrate the present invention below by specific embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
Now following explanation is done to embodiment and comparative example starting material used, but be not limited to these materials: ABS resin selects the ABSAG15A1 of Taiwan; The TPU-KF90A that thermoplastic polyurethane TPU selects Taiwan rainbow to overflow; Tetrabromo-bisphenol selects the FR-1524 of Dead Sea bromine company of Israel; The CXB-714C that brominated epoxy selects Korea S's space to enter; TDE selects 4010 of Ya Bao company of the U.S.; Brominated triazine selects the FR-245 of Dead Sea bromine company of Israel; Sb system fire retardant selects Hua Changti industry company S-05N; Compatilizer selects the AS-MS-NB of NEC chemistry; High glue powder selects the HR181 of Korea S's brocade lake chemical industry; Milan, Nanjing chemical industry photostabilizer HS-770 selected by photostabilizer; Oxidation inhibitor selects pentaerythritol ester 1010 and the phosphorous acid ester 168 of Ciba; Processing aid selects white mineral oil No. 70 white oils of Liaoning AoKe Chemical Co., Ltd; Calcium stearate BS-3818 is commercially available prod.
The plant and instrument that the present invention is prepared used by composition has: twin screw extruder is the SHJ-30 produced by Rhea superpolymer Equipment Limited, Nanjing; The injection moulding machine that test bars preparation adopts is the B-920 type produced by Zhejiang Hai Tian injection moulding machine company limited; The instrument of test melt flow rate (MFR) is the ZR21452 Melt Flow Rate Measurer that Mei Site industrial system (China) company limited produces; The T92 type of TiniusOlsenis company of the impact experiment Ji Shi U.S. production of test shock strength; The universal testing machine of test tensile strength is the H10K-S that Hounsfield company produces; The UL-94 vertical combustion Yi Shi U.S. ATLASHVUL-2 that test UL94 uses; The Shore durometer of test shore hardness is the HR-150A that Olympic Competition special company in Shenzhen produces; The friction wear tester of test friction wear is the TRB of the CSM instrument company of Switzerland.
The preparation of high flowing, damage resistant, low temperature resistant bromine system flame-proof ABS/TPU alloy material: first by the drying 2 hours at 85 DEG C before blended of the ABS resin in each comparative example and embodiment (as table 1-3), by thermoplastic polyurethane TPU drying 2 hours under 100 DEG C of conditions before blended; Then the ABS resin of bromide fire retardant, antimony based compound, maleic anhydride modified Its Compatibilizing Technology, toughner, oxidation inhibitor, photostabilizer, processing aid, dry gained and the thermoplastic polyurethane TPU of dry gained are fully mixed 2-10 minute in mixing machine, obtain mixture; Then by said mixture through the pay-off of delicate metering be transported in twin screw extruder carry out mixing, extrude, tie rod, water-cooled and pelletizing, wherein, the length-to-diameter ratio of twin screw extruder is 25-40; Barrel temperature is set as: district's temperature 80 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 220 DEG C; Screw speed is 200-800 rev/min.Screw rod shearing, mixing and conveying under, material is able to abundant fusing, compound, then obtains flame-proof ABS/TPU alloy plastic particles through extruding pelletization, drying; The ABS/TPU alloy plastic particles of above-mentioned gained is joined the standard batten becoming test in injection moulding machine by standard size injection molding, injecting condition is: barrel temperature 170-210 DEG C, die temperature 60-70 DEG C, injection pressure 6-10MPa, and carry out each performance test by testing standard; The performance test data of each routine sample is in Table 1-3.
The performance test standard of each material in table 1 embodiment 1-20 and comparative example 1-6
The concrete proportioning (wt%) respectively formed in table 2 embodiment 1-2 and comparative example 1-6 and test performance result thereof
Its test performance result of concrete proportioning (wt%) of each composition in table 3 embodiment 3 ~ 11
Its test performance result of concrete proportioning (wt%) of each composition in table 4 embodiment 12 ~ 20
From table 2-4, flame-proof ABS/TPU alloy material is prepared by ABS, TPU and bromo-antimony compounding flame retardant blending extrusion, the anti-flaming ABS material prepared with identical flame-retardant system is compared, every mechanical property of material all improves, especially the low temperature of system tough and and the mobility of system improve more very, and flame-proof ABS/TPU alloy system every mechanical property and processibility when AS-MS-NB content is about 3% reach optimum balance.Simultaneously along with the increase of TPU content, the mobility of system continues to increase, and abrasion loss reduces, and fold resistance and low-temperature flexibility are obviously improved.The toughness of the sustainable raising system of the introducing of toughner HR181 in addition, but fold resistance and low-temperature flexibility and abrasion loss are had no significant effect.In sum, the bromine system flame-proof ABS/TPU alloy material of preparation has good wear resistance and fold resistance and low-temperature flexibility, excellent flame retardant effect and fabulous processibility.
Claims (10)
1. high flowing, damage resistant, low temperature resistant bromine system flame-proof ABS/TPU alloy material, is characterized in that: comprise following each component by weight: 45-70 part ABS resin, 10-30 part thermoplastic polyurethane TPU, 10-15 part bromide fire retardant and 2-5 part antimony based compound;
Shao A hardness of wherein said thermoplastic polyurethane TPU is 70-95HA by ASTMD2240-2005 standard testing value; Described bromide fire retardant is at least one in tetrabromo-bisphenol, brominated epoxy, brominated triazine and TDE; Described antimony based compound is at least one in antimonous oxide, colloidal antimony pentoxide, sodium antimonate, phosphorous acid antimony, butter of antimony, antimony pentachloride, phosphorous acid antimony, polyphosphoric acid antimony and complexing antimony.
2. high flowing according to claim 1, damage resistant, low temperature resistant bromine system flame-proof ABS/TPU alloy material, is characterized in that: described alloy material also comprises maleic anhydride modified Its Compatibilizing Technology 1-5 part by weight.
3. high flowing according to claim 2, damage resistant, low temperature resistant bromine system flame-proof ABS/TPU alloy material, is characterized in that: described maleic anhydride modified Its Compatibilizing Technology is at least one in vinylbenzene-N-phenylmaleimide-maleic anhydride terpolymer AS-MS-NB, styrene-maleic anhydride copolymer SMA and maleic anhydride-g-SBS.
4. high flowing according to claim 1, damage resistant, low temperature resistant bromine system flame-proof ABS/TPU alloy material, is characterized in that: described alloy material also comprises toughner 0-10 part by weight, oxidation inhibitor 0-1 part, photostabilizer 0-1 part and processing aid 0-5 part.
5. high flowing according to claim 4, damage resistant, low temperature resistant bromine system flame-proof ABS/TPU alloy material, is characterized in that: described toughner is at least one in terpolymer EP rubber, chlorinatedpolyethylene and high glue powder.
6. high flowing according to claim 4, damage resistant, low temperature resistant bromine system flame-proof ABS/TPU alloy material, is characterized in that: described oxidation inhibitor is the compound of Hinered phenols primary antioxidant and phosphorous acid esters auxiliary anti-oxidant composition.
7. high flowing according to claim 4, damage resistant, low temperature resistant bromine system flame-proof ABS/TPU alloy material, is characterized in that: described photostabilizer is benzophenone, benzotriazole category, triazines, gather at least one in vinyl cyanide, Oxamides and hindered amines.
8. high flowing according to claim 4, damage resistant, low temperature resistant bromine system flame-proof ABS/TPU alloy material, is characterized in that: described processing aid is at least one in stearylamide series lubricant agent, silicone oil and white mineral oil.
9. a preparation method for the height flowing in claim 1 to 8 described in arbitrary claim, damage resistant, low temperature resistant bromine system flame-proof ABS/TPU alloy material, is characterized in that: comprise the steps:
(a) by ABS resin before blended at 85 DEG C dry 2-4 hour, thermoplastic polyurethane TPU before blended at 100 DEG C dry 2-4 hour;
B () fully mixes 2-10 minute by the ABS resin of the bromide fire retardant of formula consumption, antimony based compound, maleic anhydride modified Its Compatibilizing Technology, toughner, oxidation inhibitor, photostabilizer, processing aid, the dry gained of warp (a) with through the thermoplastic polyurethane TPU of (a) dry gained in mixing machine, obtain mixture;
C the mixture of gained in (b) is transported in twin screw extruder through the pay-off of delicate metering by (), each section of extruder temperature of forcing machine controls between 160-220 DEG C, the length-to-diameter ratio of twin screw extruder is 25-40, screw speed is 200-800 rev/min, screw rod shearing, mixing and conveying under, material is able to abundant fusing, compound, then obtains flame-proof ABS/TPU alloy plastic particles through extruding pelletization, drying;
D the ABS/TPU alloy plastic particles of gained in (c) joins in injection moulding machine and is processed into required batten by (), injecting condition is: barrel temperature 170-210 DEG C, die temperature 60-70 DEG C, injection pressure 6-10MPa.
10. the height flowing in claim 1 to 8 described in arbitrary claim, damage resistant, the application of low temperature resistant bromine system flame-proof ABS/TPU alloy material in electronic apparatus, communications and transportation and military project national defence.
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| CN105907021A (en) * | 2016-04-29 | 2016-08-31 | 江苏昇和新材料科技股份有限公司 | Cold-resistant modified ABS (acrylonitrile butadiene styrene) material and preparation method thereof |
| CN108070196A (en) * | 2016-11-18 | 2018-05-25 | 合肥市和裕达塑业有限公司 | A kind of anticorrosive, high-low temperature resistant ABS material and its preparation method and application |
| CN111004469A (en) * | 2018-10-08 | 2020-04-14 | 天津科技大学 | A kind of preparation method of high fluidity electroplating grade ABSTPU alloy material |
| CN111113774A (en) * | 2019-12-30 | 2020-05-08 | 河北盛邦兴泰新材料科技有限公司 | Preparation method of ABS-TPU (acrylonitrile butadiene styrene-thermoplastic polyurethane) assembled sports floor |
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| CN105907021A (en) * | 2016-04-29 | 2016-08-31 | 江苏昇和新材料科技股份有限公司 | Cold-resistant modified ABS (acrylonitrile butadiene styrene) material and preparation method thereof |
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| CN113024983A (en) * | 2021-02-26 | 2021-06-25 | 宁波坚锋新材料有限公司 | High-transparency high-impact flame-retardant MABS composite material and preparation method thereof |
| CN114262492A (en) * | 2021-12-30 | 2022-04-01 | 江苏松上科技有限公司 | Heat-resistant flame-retardant ABS material and production method thereof |
| CN115044164A (en) * | 2022-07-20 | 2022-09-13 | 江苏永成汽车零部件股份有限公司 | Self-cleaning anti-vibration plastic for automobile exterior parts and preparation method thereof |
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