CN103740038B - High glaze halogen-free flame retardant ABS material and preparation method thereof - Google Patents
High glaze halogen-free flame retardant ABS material and preparation method thereof Download PDFInfo
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- CN103740038B CN103740038B CN201310684580.6A CN201310684580A CN103740038B CN 103740038 B CN103740038 B CN 103740038B CN 201310684580 A CN201310684580 A CN 201310684580A CN 103740038 B CN103740038 B CN 103740038B
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- abs
- flame retardant
- halogen
- fire retardant
- free flame
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Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 37
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 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 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000002421 finishing Substances 0.000 claims abstract description 15
- 239000012745 toughening agent Substances 0.000 claims abstract description 15
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 14
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical group C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000001993 wax Substances 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000410 antimony oxide Inorganic materials 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
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- LLGQASFNQPXBKT-UHFFFAOYSA-N 2,4,5,6-tetraphenylbenzene-1,3-diol Chemical compound C=1C=CC=CC=1C1=C(C=2C=CC=CC=2)C(O)=C(C=2C=CC=CC=2)C(O)=C1C1=CC=CC=C1 LLGQASFNQPXBKT-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229920002313 fluoropolymer Polymers 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 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
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical group COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 239000001205 polyphosphate Substances 0.000 claims 1
- 235000011176 polyphosphates Nutrition 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000008447 perception Effects 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 238000007493 shaping process Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 26
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 25
- 238000005259 measurement Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- -1 flame-retardant modified ABS Chemical class 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000004135 Bone phosphate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- GTDHYNXLIKNVTJ-UHFFFAOYSA-N n-(1-hydroxy-2-methylpropan-2-yl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC(C)(C)CO GTDHYNXLIKNVTJ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a kind of high glaze halogen-free flame retardant ABS material, which is mixed by ABS resin, SAN resins, toughener, fire retardant, antioxidant, finishing agent, optothermal stabilizer and processing aid, and the mass ratio of each component is 55~70：9~15:7~12:14~20:0.2~0.7:0.1~0.4:0.1~1:0.5~1.The high glaze halogen-free flame retardant ABS material of the present invention is while retaining the advantages that original ABS resin impact strength is high, chemical resistance is strong, machine-shaping is good, the surface brightness of material is significantly increased under synergistic effect between each component, perception is good, impart the higher flame retardant property of material, meet current safety environmental regulation requirement, improves the heat resistance and processing stability of material.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of high glaze halogen-free flame retardant ABS material and its system
Preparation Method.
Background technology
In recent years, with economic development and improvement of living standard, the population in various public places and the intensive journey of property
Benefit of subsisting increases, and large-scale liability accident especially fire incident happens occasionally, and public safety problem has increasingly becomed the public
Focus of attention.The reason of causing these fire disaster accidents is varied, the selection of material is improper be it is wherein critically important because
Element.Therefore the flame retardant property for being improved material using flame-retarded technology is reduced the probability that fire occurs, is the effective of abatement of fire hazard
One of means.
ABS (acrylonitrile-butadiene-styrene terpolymer) has good mechanical property, chemical resistance corrosion
Performance, and it is easy to process, it is widely used in the fields such as auto industry, electronic apparatus industry.But its limit oxygen index LOI is only
18.0%, inflammable and can release a large amount of toxic gases and black smoke in combustion, there is also melting drip phenomenons, have very
Big security risk.Therefore, flame-retardant modified ABS resin is of great practical significance.It is used for modified ABS anti-flammability at present
The fire retardant of energy is mainly halogenated flame retardant, especially bromide fire retardant（Such as polybrominated diphenyl ethers, polybrominated biphenyls）Have to ABS
Good flame retardant effect.However halogenated flame retardant its fire-retardant high molecular material can generate a large amount of cigarette in thermal cracking and burning
Dirt and corrosive gas cause prodigious harm to the mankind and environment.The ROSH promulgated according to European Union in 2002 and WEEE instructions
It is required that while reducing and preventing harmful effect of the halogen based flame retardant to environment and human health, exploitation halogen-free flame retardant ABS high score
Sub- material becomes a urgent project.The high molecular material of halogen-free flame-retardant is because have many advantages, such as low toxicity, environmental protection, it is with only
Special is environmentally friendly, harmless to human health and favored by society, has broad application prospects.
Currently, to be concentrated mainly on perception good for requirement of the people to plastic product, high glaze, it is light the features such as, however due to
Fire retardant has certain extinction, so on the one hand halogen-free flame retardants is added in ABS resin improves flame retardant property, while
The surface gloss of ABS resin is reduced, resin how is solved while there is flame retardant property and high gloss to become current research
Difficult point.Therefore, the environmental-protection flame-retardant ABS of research high glaze low smoke, zero halogen has practical significance.
Invention content
The object of the present invention is to provide a kind of high glaze halogen-free flame retardant ABS material, the material is to remain ABS resin original
On the basis of excellent performance, assigns its high flame retardant using Non-halogen Flame Retardant Technology and compound compatible technique and improve the light of product
Damp degree.
It is a further object of the present invention to provide a kind of preparation methods of high glaze halogen-free flame retardant ABS material.
The purpose of the present invention can be achieved by the following measures：
A kind of high glaze halogen-free flame retardant ABS material, the material is by ABS resin, SAN resins, toughener, fire retardant, antioxygen
Agent, finishing agent, optothermal stabilizer and processing aid mix, each component ABS resin, SAN resins, toughener, fire-retardant
Agent, antioxidant, finishing agent, optothermal stabilizer and processing aid mass ratio be 55~70：9~15:7~12:14~20:
0.2~0.7:0.1~0.4:0.1~1:0.5~1.
It is each component ABS resin in the high glaze halogen-free flame retardant ABS material of the present invention, SAN resins, toughener, fire retardant, anti-
Oxygen agent, finishing agent, optothermal stabilizer and processing aid preferred mass ratio be 60~70：10~13:8~10:14~18:
0.2~0.5:0.2~0.4:0.2~0.8:0.5~1.
The ABS resin is the blend of ABS (AC-800) resins and ABS (TE-10S) resin, ABS (AC-800) trees
The weight part ratio of fat and ABS (TE-10S) resin is 4~1.5：1, preferably 3~1.5：1, most preferably 7:3.ABS (AC-800) has
There are preferable mechanical performance, ABS (TE-10S) that there is higher glossiness and preferable heat resistance, the two compatibility is good, at it
He combines the lower mixing of cooperation and shares while remaining good mechanicalness and preferable glossiness.
The SAN resins melt the SAN for height flowing, it melts index more than 7g/10min, to improve under the conditions of 200 DEG C
The glossiness of the ABS resin.
The toughener is organic silicon toughener or ABS high glue powders, preferably ABS high glue powders.
The fire retardant is the composite flame-retardant agent of phosphorus system, antimony system, and phosphorus system and antimony system weight part ratio are 7:1~2:1, preferably
2~5：1.Wherein the Sb system fire retardant is one kind in antimony oxide or antimony pentoxide, preferably antimony oxide；Institute
The phosphorus flame retardant stated is trimethyl phosphate（TMP）, triethyl phosphate（TEP）, tetraphenyl resorcinol double focusing phosphate
（RDP）, tetraphenyl bisphenol A double focusing phosphates（BDP）Or tricresyl phosphate（TCP）One or more of mixture,
The antioxidant is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters（1010）Or
Three [2.4- di-tert-butyl-phenyls] phosphite esters（168）In one kind or two kinds.
The finishing agent is one kind in modified ethylene bis stearic acid amide (TAF) or EVA waxes, preferably EVA waxes.
The optothermal stabilizer is the silicic acid of inorganic acid lead salt, organic acid lead salt, organic tin heat stabilizer, alkali metal
One or more of the silicate of salt or alkaline earth metal, such as lead sulfate tribasic.
The processing aid is lubricant and Antidrip agent.Wherein lubricant is selected from PE waxes, stearic acid amide, methylene bis
One or more of stearmide or ethylene bis stearic acid amide (EBS), preferably ethylene bis stearic acid amide (EBS).It is antidrip
It is fluorinated polymer, preferably polytetrafluoroethylene to fall agent（PTFE）.Lubricant is 9~1 with Antidrip agent weight ratio:1, preferably 7
~1.5:1, more preferable 7:1.
The present invention provides a kind of preparation methods of above-mentioned high glaze halogen-free flame retardant ABS material：By ABS resin, SAN trees
Sb system fire retardant, antioxidant, finishing agent, optothermal stabilizer and processing aid in fat, toughener, fire retardant are sufficiently mixed
Afterwards, it puts into double screw extruder and carries out melting extrusion, is granulated, the phosphorus flame retardant in fire retardant is from liquid spout in the process
Double screw extruder is added.
The present invention provides the preparation methods of another above-mentioned high glaze halogen-free flame retardant ABS material, as follows into
Row：
（1）Weigh by weight ABS resin, SAN resins, toughener, Sb system fire retardant, antioxidant, finishing agent,
Optothermal stabilizer, processing aid are put into high-speed mixer and mix fully.
（2）By blends described above put into double screw extruder in, through melting extrusion, be granulated, in the process phosphorus flame retardant by
Metering pump control is added from liquid spout.
The double screw extruder draw ratio is 36~40, with accurate temperature controller device, liquid spout and is vacuumized
Device, at 160~230 DEG C, screw speed is controlled at 100~500 revs/min for extruder temperature control.
The present invention compared with the existing technology, has the following advantages that and advantageous effect：
1, high glaze halogen-free flame retardant ABS material of the invention, is prepared using twin screw extrusion process, simple with flow,
Continuously, the advantage that production efficiency height, product quality are stablized.
2, high glaze halogen-free flame retardant ABS material of the present invention retain original ABS resin impact strength is high, chemical resistance is strong,
While the advantages that machine-shaping is good, addition SAN resins, finishing agent, phosphorus flame retardant, antioxidant and optothermal stabilizer,
And the surface brightness of material is significantly increased under the synergistic effect between each component, perception is good, and it is higher to impart material
Flame retardant property, meet current safety environmental regulation requirement, improve the heat resistance and processing stability of material.
3, high glaze halogen-free flame retardant ABS material glossiness of the present invention is high, flame retardant property is good, while selecting halogen-free flameproof
Agent, be truly realized to class health and environment it is nuisanceless, greatly improve the application range of product, can be widely used for automobile,
In the fields such as household electrical appliances, building, office equipment, electronic apparatus.
Specific implementation mode
Below in conjunction with embodiment, the invention will be further described
Raw material：
The new lake ABS (AC-800)（Changzhou）Petrochemical industry Co., Ltd produces；
ABS (TS-10S) Japan Electric chemical industry Co., Ltd. produces；
SAN resins Ningbo Tai Hua Co., Ltds produce（200 DEG C melt index and are more than 7g/10min）；
Toughener（ABS high glue powders）Sinopec Shanghai Gaoqiao Petrochemical Company produces；
Fire retardant（RDP）Albemarle Corporation of the U.S. produces；
Fire retardant（Antimony oxide）Hunan Anhua Kui Xi Ti Ye Co., Ltds produce；
Antioxidant (1010) Ciba Specialty Chemicals produce；
The production of BASF joint-stock company of finishing agent (EVA) Germany；
Optothermal stabilizer (lead sulfate tribasic) Ciba Specialty Chemicals produce；
Processing aid（Lubricate EBS）Chengdu is produced with power auxiliary agent Co., Ltd；
Processing aid（Antidrip agent PTFE）Chengdu is produced with power auxiliary agent Co., Ltd；
Other unmentioned various raw materials and auxiliary agent are commercially available general commodity.
Mechanics and combustibility testing standard：
The measurement of impact strength is carried out according to GB/T1843-2008 plastics cantilever beam impact strength standards；
The measurement of tensile strength is carried out according to the bioassay standard of GB/T1040.1-2006 plastic tensile performances；
The measurement that note bending property is moulded according to GB/T9341-2008 carries out bending property measurement；
Vertical combustion survey is carried out according to the measurement Horizontal Bridgman Method and normal beam technique standard of GB/T2408-2008 Plastics Combustion performances
It is fixed.
Preparation method
First weigh ABS resin, SAN resins, toughener, Sb system fire retardant, antioxidant, finishing agent, optothermal stabilizer,
Processing aid, which is placed in high-speed mixer, to be mixed abundant, then blends described above is put into double screw extruder, through melting extrusion,
Tie rod, granulation, in the process phosphorus flame retardant by metering pump control from liquid spout be added.
The double screw extruder draw ratio is 40, carries liquid spout and vacuum extractor, and front-end temperature is
160~170 DEG C, stage casing temperature is 180~220 DEG C, and head temperature is 230 DEG C, and screw speed is controlled at 260 revs/min.
Particle obtained is put into vacuum drying oven dried 3~5 hours at 80~90 DEG C after with injection molding machine be molded into standard
Batten.Injection temperature is set as 200 DEG C of head, 210 DEG C of an area, 210 DEG C of 2nd area, 220 DEG C of 3rd area.Standard batten is carried out every
Performance test.
Examples 1 to 6
The recipe ingredient and weight percent of each example, as shown in table 1.
Table 1
Standard batten is respectively prepared in Examples 1 to 6 granule, carried out respectively by chinese national standard mechanical property and
Flame retardant property is tested, and the results are shown in Table 2.
Table 2
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Tensile strength | 41.8 | 41.2 | 40.9 | 43.0 | 42.5 | 42.1 |
| Elongation at break | 9 | 9 | 8 | 10 | 9 | 8 |
| Bending strength | 64.1 | 62.7 | 61.8 | 60.9 | 61.5 | 63.0 |
| Notch impact strength | 22.7 | 21.5 | 20.7 | 20.3 | 20.9 | 21.2 |
| Vertical combustion | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Surface gloss | Bloom | Bloom | Bloom | Bloom | Bloom | Bloom |
From table 2 it can be seen that this bright product is in the base with mechanical performances such as preferable tensile property, impact resistances
On plinth, halogen-free flame retardants and finishing agent is added and coordinates with other components, greatly improve product flame retardant property and
Surface brightness, product applications further expand, and can be widely applied to the industries such as automobile, electronics, building, household electrical appliance.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, therefore equivalent variations made by the scope of the claims of the present patent application, are included within the scope of the present invention.
Claims (7)
1. a kind of high glaze halogen-free flame retardant ABS material, it is characterised in that the material by ABS resins, SAN resins, toughener,
Fire retardant, antioxidant, finishing agent, optothermal stabilizer and processing aid mix, and the mass ratio of each component is 55~70：
9~15:7~12:14~20:0.2~0.7:0.1~0.4:0.1~1:0.5~1；The preparation method of the ABS materials is：
By Sb system fire retardant, antioxidant, finishing agent, the optothermal stabilizer in ABS resins, SAN resins, toughener, fire retardant
After being sufficiently mixed with processing aid, puts into double screw extruder and carry out melting extrusion, be granulated, in the process the phosphorus system in fire retardant
Double screw extruder is added from liquid spout in fire retardant；
Wherein：
The ABS resins are the blend of ABS (AC-800) resins and ABS (TE-10S) resin, and the weight ratio of the two is 4
~1.5：1；
The SAN resins its melt index under the conditions of 200 DEG C is more than 7g/10min；
The toughener is organic silicon toughener or ABS high glue powders；
The fire retardant is the mixing fire retardant of phosphorus flame retardant and Sb system fire retardant；
The antioxidant is selected from four [β-(3,5- di-t-butyl -4- hydroxy phenyls) propionic acid] pentaerythritol esters or three [2.4- bis-
Tert-butyl-phenyl] one kind in phosphite ester or two kinds；
The finishing agent is modified ethylene bis stearic acid amide or EVA waxes；
The optothermal stabilizer be selected from inorganic acid lead salt, organic acid lead salt, organic tin heat stabilizer, alkali metal silicate or
One or more of silicate of alkaline-earth metal；
The processing aid is lubricant and Antidrip agent, and lubricant is 9~1 with Antidrip agent weight part ratio:1；The lubrication
Agent is selected from one or more of PE waxes, stearic acid amide, methylene bis-stearamides or ethylene bis stearic acid amide；It is described antidrip
It is fluorinated polymer to fall agent.
2. according to the high glaze halogen-free flame retardant ABS material described in claim 1, it is characterised in that each component ABS trees in the material
Fat, SAN resins, toughener, fire retardant, antioxidant, finishing agent, optothermal stabilizer and processing aid mass ratio be 60~
70：10~13:8~10:14~18:0.2~0.5:0.2~0.4:0.2~0.8:0.5~1.
3. according to the high glaze halogen-free flame retardant ABS material described in claim 1, it is characterised in that the ABS resins are new lake
（Changzhou）The TE-10S types that the AC-800 types resin of petrochemical industry Co., Ltd production is produced with Japan Electric chemical industry Co., Ltd.
The weight ratio of the blend of resin, the two is 3~1.5：1.
4. according to the high glaze halogen-free flame retardant ABS material described in claim 1, it is characterised in that phosphorus flame retardant is hindered with antimony system
The weight ratio for firing agent is 2~7：1.
5. according to the high glaze halogen-free flame retardant ABS material described in claim 4, it is characterised in that the Sb system fire retardant is three
Aoxidize two antimony or antimony pentoxide；It is double that the phosphorus flame retardant is selected from trimethyl phosphate, triethyl phosphate, tetraphenyl resorcinol
One or more of polyphosphate, tetraphenyl bisphenol A double focusings phosphate or tricresyl phosphate；Phosphorous flame-retardant in fire retardant
The weight ratio of agent and Sb system fire retardant is 2~5：1.
6. high glaze halogen-free flame retardant ABS material according to claim 1, it is characterised in that lubricant and Antidrip agent weight
Part is than being 7~1.5:1.
7. according to the high glaze halogen-free flame retardant ABS material described in claim 1, it is characterised in that the twin-screw extrusion captain
Diameter ratio is 36~40, carries accurate temperature controller device, liquid spout and vacuum extractor, and wherein extruder temperature control exists
160~230 DEG C, screw speed is controlled at 100~500 revs/min.
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| CN105038096A (en) * | 2015-09-02 | 2015-11-11 | 连云港海水化工有限公司 | White high-brightness weather-proof material containing ABS resin and preparation method of white high-brightness weather-proof material |
| CN108623982A (en) * | 2017-03-26 | 2018-10-09 | 合肥杰事杰新材料股份有限公司 | A kind of glazed flame-retardant intelligence closet with flushing device PP Pipe Compound and preparation method thereof |
| CN107964209A (en) * | 2017-12-18 | 2018-04-27 | 温州瑞榕汽车零部件制造有限公司 | A kind of high fire-retardance ABS resin and its production technology |
| CN109705514A (en) * | 2018-12-17 | 2019-05-03 | 会通新材料股份有限公司 | A kind of automobile-used ABS material of high fondant-strength and preparation method thereof |
| CN110016199A (en) * | 2019-03-25 | 2019-07-16 | 合肥圆融新材料有限公司 | A kind of high-gloss metal texture exempts from spraying, environment friendly flame-proof ABS material and preparation method thereof |
| CN114987013A (en) * | 2022-05-30 | 2022-09-02 | 广东美的暖通设备有限公司 | Composite board for air conditioner shell, preparation method of composite board, air conditioner shell and air conditioner |
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