CN101643576B - Zero halogen flame resistance alloy composite and preparation method thereof - Google Patents
Zero halogen flame resistance alloy composite and preparation method thereof Download PDFInfo
- Publication number
- CN101643576B CN101643576B CN 200910165324 CN200910165324A CN101643576B CN 101643576 B CN101643576 B CN 101643576B CN 200910165324 CN200910165324 CN 200910165324 CN 200910165324 A CN200910165324 A CN 200910165324A CN 101643576 B CN101643576 B CN 101643576B
- Authority
- CN
- China
- Prior art keywords
- mixing
- flame resistance
- fire retardant
- phosphoric acid
- acid ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 57
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 24
- 150000002367 halogens Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003063 flame retardant Substances 0.000 claims abstract description 98
- 239000004417 polycarbonate Substances 0.000 claims abstract description 61
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 60
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 20
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 20
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 13
- 229920001971 elastomer Polymers 0.000 claims abstract description 12
- 239000005060 rubber Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims description 99
- 239000007788 liquid Substances 0.000 claims description 44
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 39
- 239000010452 phosphate Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 13
- 230000002572 peristaltic effect Effects 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 125000006267 biphenyl group Chemical group 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 9
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 8
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 5
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 35
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 35
- 238000000034 method Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
- 239000002341 toxic gas Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 235000021317 phosphate Nutrition 0.000 abstract 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract 2
- 206010028980 Neoplasm Diseases 0.000 abstract 1
- 201000011510 cancer Diseases 0.000 abstract 1
- 239000000779 smoke Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 49
- 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 description 47
- 239000011678 thiamine pyrophosphate Substances 0.000 description 36
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 36
- 101000837308 Homo sapiens Testis-expressed protein 30 Proteins 0.000 description 32
- 229910000831 Steel Inorganic materials 0.000 description 32
- 102100028631 Testis-expressed protein 30 Human genes 0.000 description 32
- 238000001125 extrusion Methods 0.000 description 32
- 239000002994 raw material Substances 0.000 description 32
- 239000010959 steel Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 27
- 239000000463 material Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 17
- 238000005304 joining Methods 0.000 description 12
- 229920000388 Polyphosphate Polymers 0.000 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 description 11
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 11
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 11
- 239000001205 polyphosphate Substances 0.000 description 11
- 235000011176 polyphosphates Nutrition 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000012752 auxiliary agent Substances 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000013022 venting Methods 0.000 description 4
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 4
- 238000003889 chemical engineering Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- NUHSROFQTUXZQQ-UHFFFAOYSA-N isopentenyl diphosphate Chemical compound CC(=C)CCO[P@](O)(=O)OP(O)(O)=O NUHSROFQTUXZQQ-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920003987 resole Polymers 0.000 description 3
- 0 *=C1CCCCC1 Chemical compound *=C1CCCCC1 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000004646 arylidenes Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- KWQPWOQUXSQDNN-UHFFFAOYSA-N (2,3,4-trimethylphenyl) dihydrogen phosphate Chemical compound CC1=CC=C(OP(O)(O)=O)C(C)=C1C KWQPWOQUXSQDNN-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- WFFORRREWUAYIL-UHFFFAOYSA-N CCC(C)(CC)C1CCCC1 Chemical compound CCC(C)(CC)C1CCCC1 WFFORRREWUAYIL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UVAUHTUDFIJIDS-UHFFFAOYSA-N FC(C(C(C(F)(F)F)(F)F)(F)F)([K])F Chemical compound FC(C(C(C(F)(F)F)(F)F)(F)F)([K])F UVAUHTUDFIJIDS-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N O=P(Oc1ccccc1)(Oc1ccccc1)Oc1ccccc1 Chemical compound O=P(Oc1ccccc1)(Oc1ccccc1)Oc1ccccc1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 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
- 239000003054 catalyst Substances 0.000 description 1
- 230000034303 cell budding Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 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
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 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 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a zero halogen flame resistance alloy composite which mainly comprises 80-95 parts of resin mixture, 20-5 parts of phosphates fire retardant and 0.1-2 parts of polytetrafluoroethylene by weight, wherein the resin mixture comprises 40-90wt% of polycarbonate and 10-60wt% of rubber modified graft copolymer. The invention also discloses a preparation method of the zero halogen flame resistance alloy composite. In the method of the invention, a mixture of various phosphates is used as fire retardant so as to largely reduce the dosage of fire retardant and ensure that the polycarbonate alloy has not only has good flame resistance and high heat resistance, but also does not generate a large amount of toxic gases and smoke and strong cancer-causing substances which is different than the PC alloy with halogen fire retardant. The method of the invention has simple operation and environmental friendly composite product and realizes the combination of high flame resistance and high heat resistance.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of Zero halogen flame resistance alloy composite that mainly contains polycarbonate and rubber-modified graft copolymer with and preparation method thereof.
Background technology
Polycarbonate (PC) is high performance engineering plastics, and it has very good shock resistance and thermotolerance, is applied in the various fields more and more widely.Yet, the polycarbonate price is always very high, and its melt viscosity is larger, pure polycarbonate is relatively more difficult as extruding with injection molding with common plastic working means, very difficult when particularly producing the comparatively complicated product of thinner thickness or shape, be exactly polycarbonate easy cracking under stress in addition.In order to improve the performance of polycarbonate, industrial usually with polycarbonate and rubber-modified graft copolymer, such as acrylonitrile-butadiene-styrene copolymer (ABS) together blending and modifying, this can reduce the viscosity of polycarbonate on the one hand, improve its processibility and improve its stress cracking resistance, also can increase substantially on the other hand the thermotolerance of ABS, the PC alloy that obtains not only over-all properties is very outstanding, and cost performance is also very high, thereby its market scale increases very fastly, increasing whenever to be close on 30% speed on Chinese market in recent years.
In actual life, show that through years of researches using the flame retardant resistance macromolecular material is to prevent and reduce one of effective measures of fire.Fire retardant material is compared with fire retardant material not, the former fires than difficult point, and the rate of flame propagation during burning is little, and mass loss rate and heat release rate are all lower, sometimes propagation of flame is understood automatic distinguishing to certain distance, so fire retardant material can prevent little fire and develop into tragic fire, and fire was eliminated in its budding stage, reduces fire hazard, even flame is failed from putting out, fire retardant material also can delay the generation of big fire, provides the more time to evacuating personnel, reduces fire losses.The most important Application Areas of PC alloy is electric, in order to guarantee the safety in utilization of these electronic and electrical equipments, generally all requires used PC alloy to have high flame retardant resistance (self-extinguishing).Pure polycarbonate is owing to the aromatic ring rigid structure of its molecular chain itself, and oxygen index is the polymkeric substance that can certainly put out up to 26.But, rubber-modified graft copolymer, owing to its a large amount of rubber constituent and alkane composition, oxygen index is about 16 such as ABS, is easy to burning.The PC alloy that the direct blend of PC and rubber-modified graft copolymer obtains is generally not fire retardant material, and its flame retardant resistance is lower, does not have from putting out characteristic.
Giving the general method of macromolecular material flame retardant resistance is to introduce fire retardant in its preparation or modifying process, up to the present consumption is very large, flame retardant resistance higher and to the Effect on Mechanical Properties of macromolecular material less be halogenated flame retardant, the fire retardant that comprises chlorine system and bromine system, but the material that halogenated flame retardant is fire-retardant, in combustion processes, can discharge than the not more toxic gas volume of fire retardant material and cigarette amount, this not only can cause more dead disaster, also can produce secondary pollution and environmental pollution, more seriously, show after deliberation, halogenated flame retardant especially can produce dioxin after the halogenated diphenyl ether burning, be many halogenated diphenyls Bing diox and many halogenated diphenyls and furans, this material has strong carinogenicity, and this has limited its application, and people have carried out many researchs in the hope of substituting halogen fire retardant with halogen-free flame retardants.The halogen-free flame retardants of consumption maximum is metal hydroxides on the market now, comprises aluminium hydroxide and magnesium hydroxide, but owing to can discharge water outlet under their born alkalescence and the high temperature, thereby therefore the degraded of catalyst, polyester can not be used for PC and alloy thereof.The patent CN1617905 of General Electric discloses perfluoro butyl potassium sulfonate (PPFBS) fire retardation PC, and the PPFBS that adds minute quantity in PC can reach the UL94V-0 flame retardant rating, but PPFBS only to pure PC fire-retardant effectively, the PC alloy is not had flame retardant effect substantially.The patent CN1412246A of Asahi Chemical Industry discloses with organopolysiloxane and inorganic alkaline metal salt or alkaline earth salt composite flame-proof PC alloy, but it can not realize high flame retardant rating.Nitrogenated flame retardant such as melamine cyanurate (MC) etc. also are widely used as halogen-free flame retardants, but a large amount of nitrogenated flame retardants that studies show that does not have fire retardation substantially to PC and PC alloy.The halogen-free flame retardants that now is used in a large number the PC alloy substantially all is the fire retardant of phosphoric acid ester system, but these phosphoric acid ester are small molecules mostly, it is the lower solid of liquid or fusing point under the normal temperature, the introducing of these phosphoric acid ester can reduce mechanical property and the thermal characteristics of PC alloy to a great extent, especially for the slightly low PC alloy of PC content, need to add a large amount of phosphoric acid ester obtaining high flame retardant resistance, but greatly reduced thermotolerance (heat-drawn wire) and the mechanical property of material.In order to obtain high thermotolerance, the method of adding filler (mica or talcum powder) in the PC alloy that Japan Supreme Being people's patent CN1514856A discloses at organic phosphate flame-retardant, although mica or talcous adding have improved the thermotolerance of PC flame-retardant alloy, largely reduced the shock strength of material; The patent CN1388816A of Korea S LG chemical company comes the fire retardation PC alloy with phosphoric acid ester and resol, and the synergy of using resol and phosphoric acid ester has reduced the amount of the phosphoric acid ester of required interpolation, but the introducing of resol has reduced the shock strength of PC alloy.
Summary of the invention
The objective of the invention is to be to address the above problem, the halogen-free, flame-retardant composition of high flame retardant resistance, mechanical property and resistance toheat of a kind of PC of giving alloy is provided.
Another object of the present invention is to provide the preparation method of above-mentioned composition.
In order to solve the problem of mentioning in the background technology, we have carried out a large amount of research, found that for having good flame retardant synergistic effect between the different phosphoric acid ester of PC alloy, the mixture that mixes with the different phosphate acid esters of certain proportioning carries out fire-retardant to the PC alloy, especially for the PC alloy that hangs down the PC component, consumption that can the decrease phosphoric acid ester, the flame resistance alloy composite that obtains not only flame retardant resistance are high, and mechanical property and thermotolerance are all very high.
Purpose of the present invention can reach by following measures:
A kind of Zero halogen flame resistance alloy composite, said composition mainly by
(A) resin compound of 80-95 weight part, resin compound is comprised of the polycarbonate of 40-90wt% and the rubber-modified graft copolymer of 10-60wt%;
(B) the phosphoric acid ester fire retardant of 20-5 weight part and
(C) tetrafluoroethylene of 0.1-2 weight part forms.
Also can add therein other auxiliary agents, also can be formed by above-mentioned three components separately.
Resin compound is comprised of 40-90wt% polycarbonate and 10-60wt% rubber-modified graft copolymer.Consider that for the thermotolerance that improves composition and flame retardant resistance aspect polycarbonate is selected aromatic copolycarbonate, is preferably bisphenol A polycarbonate.Rubber-modified graft copolymer comprises rigid phase and rubber phase, and rubber phase is dispersed in the rigid phase, wherein at least a portion rigid phase by chemical graft to rubber phase.Rubber phase is in order to improve the shock resistance of material, and suitable rubber polymer is polydiolefin, comprises a kind of polybutadiene polymers or poly-(styrene butadiene) multipolymer.In order to improve the flowability of material, generally select polystyrene (containing the vinylbenzene or derivatives thereof as monomer) polymkeric substance to be used as rigid phase, and in order to improve the consistency of its solvent resistance and itself and PC, introducing vinyl cyanide or its derivative monomer in polymkeric substance.In preferred embodiments, rubber-modified graft copolymer uses acrylonitrile-butadiene-styrene copolymer (ABS), its rigid phase is acrylonitritrile-styrene resin (AS), and rubber phase is polyhutadiene (PBD), wherein is grafted with AS on the surface of polyhutadiene.The preparation method of ABS generally can be divided into two kinds, a kind of is the polymerization of carrying out AS in the presence of disperse phase (PBD), another kind is exactly the AS grafting polyhutadiene (being commonly called as high glue powder) that synthesizes respectively AS and high rubber phase (PBD) content, is exactly ABS with AS and high glue powder mixing again.
Consider the over-all properties of prepared Zero halogen flame resistance alloy composite, the balance of flame retardant resistance, thermotolerance and shock resistance particularly, the content of polyhutadiene is preferably between 5-25wt% among the ABS, as be lower than the then shock resistance deficiency of composition of 5wt%, as be higher than flame retardant resistance and the thermotolerance that 25wt% then is meeting decrease composition.The content of vinyl cyanide preferably between 20-30wt%, between 24-28wt%, can greatly improve the consistency of PC and ABS like this among the rigid phase AS, thereby obtains the alloy composite of high comprehensive performance.
The used phosphoric acid ester fire retardant of the present invention is for containing the phosplate of (B1) 0-70wt% and (B2) mixture of the polyphosphate of 30-100wt%, and wherein the structural formula of phosplate is suc as formula shown in (1):
Wherein R1, R2 or R3 respectively be the alkyl of the C1-C10 that do not replace or replace independently or do not replace or the aryl of the C6-C10 of replacement.
Consider the thermostability of phosplate, R1, R2 and R3 are general preferred from aromatic yl group, such as trimethylphenyl phosphoric acid ester (TCP), cumyl phenyl phosphate ester (IPPP) and triphenyl (TPP), consider from the flame retardant resistance aspect, the higher TPP of phosphorus content particularly preferably, its molecular formula is suc as formula shown in (3):
The structural formula of described polyphosphate is suc as formula shown in (2):
Wherein R4, R5, R6 or R7 are respectively the aryl of the C6-C10 of not replacement or replacement independently, and n is the integer of 1-5, and X is the arylidene that does not replace or replace.Wherein " aryl " described in aryl and the arylidene for be generally replace or non-substituted benzene, biphenyl, terphenyl, many benzene for fat hydrocarbon, naphthalene, anthracene or luxuriant and rich with fragrance etc.The described substituting group of each group can be the alkyl of C1-C4, amino, hydroxyl etc. in formula (1) and the formula (2).
From cost consideration, preferably select biphosphonate cheap and easy to get (n=1), especially aryl condensation polyphosphate, Resorcinol two (diphenyl phosphoester) (RDP) and dihydroxyphenyl propane two (diphenyl phosphoester) (BDP), its chemical molecular formula of RDP and BDP is respectively suc as formula shown in (4) and the formula (5).And consider the mixture that is then particularly preferably formed by RDP and BDP from the flame retardant resistance aspect.
In order to obtain high flame retardant resistance, mechanical property and stable on heating combination, flame-retardant mixture is mixed by 0-70wt% phosplate and 30-100wt% polyphosphate and forms, and when (B1) phosplate was 0wt%, the phosphoric acid ester fire retardant was (B2) polyphosphate mixture that contains two or more.The phosphoric acid ester fire retardant is preferably the phosplate that contains (B1) 20-70wt% and (B2) mixture of the polyphosphate of 30-80wt%, the polyphosphate that wherein contains two or more in the phosphoric acid ester fire retardant, polyphosphate are preferably the mixture of 30-70wt%RDP and 70-30wt%BDP composition.Fire retardant of the present invention particularly preferably is, the mixture that is comprised of 20-70wt% triphenyl, 15-40wt% Resorcinol two (diphenyl phosphoester) and 15-40wt% dihydroxyphenyl propane pair (diphenyl phosphoester).
Also contain the tetrafluoroethylene of 0.1-2wt% in the Zero halogen flame resistance alloy composite of the present invention as Antidrip agent.
Other auxiliary agent comprises oxidation inhibitor, UV light stabilizing agent, lubricant, releasing agent etc., it is functional that the use of these auxiliary agents can improve some of composition, but its basic flame retardant properties and mechanics mechanical property there is not any impact substantially, can select general these commercially available auxiliary agents, they are not necessary for the present invention.The consumption of other auxiliary agents can be according to routinely consumption interpolation of the purpose of adding auxiliary agent.
The preparation method of Zero halogen flame resistance alloy composite of the present invention, can select in following two kinds of methods any one:
1. with polycarbonate, rubber-modified graft copolymer, tetrafluoroethylene and solid phosphate ester (perhaps also comprising other auxiliary agent) by being transported to the forcing machine from main opening for feed after the proportioning pre-mixing, again the liquid phosphoric acid ester is mixed into liquid mixture by desired proportioning, then this liquid mixture is joined in the forcing machine with special-purpose liquid feeding device or peristaltic pump, under 200-270 ℃, carry out melt blending, make Zero halogen flame resistance alloy composite;
2. with polycarbonate, rubber-modified graft copolymer and tetrafluoroethylene (perhaps also comprising other auxiliary agent) by being transported to the forcing machine from main opening for feed after the proportioning pre-mixing, phosphoric acid ester (liquid phosphoric acid ester and solid phosphate ester) is mixed into liquid mixture by desired proportioning, then this liquid mixture is joined in the forcing machine with special-purpose liquid feeding device or peristaltic pump, under 200-270 ℃, carry out melt blending, make Zero halogen flame resistance alloy composite.
The solid phosphate ester of this place speech refers to that fusing point more than normal temperature (25 ℃), generally be the phosphoric acid ester that is in solid, and the liquid phosphoric acid ester refers to fusing point below normal temperature (25 ℃), generally is the phosphoric acid ester that is in liquid.The general fusing point of solid phosphate ester flame retardant is lower, and is directly reinforced with main hopper or side feeding, builds bridge easily and causes production not carry out continuously at charging opening.Our research finds that solid phosphate ester can be dissolved in the liquid phosphoric acid ester well, thereby solid phosphate ester can be dissolved in the liquid phosphoric acid ester in advance and form mixture, liquid feeding device or peristaltic pump by special use joins in the forcing machine together, thereby improved expressing technique.
Beneficial effect of the present invention:
Used in the present invention the mixture of multiple phosphoric acid ester as fire retardant, can significantly reduce the consumption of fire retardant, so that polycarbonate alloy not only has excellent flame retardancy and high heat resistance simultaneously, and different from the PC material that contains halogenated flame retardant, can in combustion processes, can not discharge a large amount of toxic gas volumes and cigarette amount, can not produce strong carinogenicity material yet.The inventive method is simple to operate, the composition environmental friendliness of preparation, and realized the combination of high flame retardant and high heat resistance.
Embodiment
The present invention is described in detail with reference to the following examples and Comparative Examples, but these examples do not limit the scope of the invention.
Embodiment and Comparative Examples have been used following component.
(A) resinous principle
(A1) polycarbonate
Polycarbonate: IR2500, Japanese Idemitsu Petrochemical Co., Ltd..
(A2) rubber-modified graft copolymer
Acrylonitritrile-styrene resin: 1200C, toray Co., Ltd..
Acrylonitrile-styrene-methylmethacrylate copolymer: 1920B, toray Co., Ltd..
Acrylonitrile-butadiene-styrene copolymer: HR2600P, toray Co., Ltd..
MBS: EXL-2691, ROHM AND HAAS.
By 1200C or 1920B, form rubber-modified graft copolymer with HR2600P or EXL-2691.
A1/A2 is the weight ratio of polycarbonate and rubber-modified graft copolymer.
(B) phosphate flame retardant
(B1) phosplate
TPP: triphenyl, Israel's chemical engineering industry, solid.
IPPP: cumyl phenyl phosphate ester, Tianjin Lianrui Chemical Co.,Ltd, liquid.
(B2) polyphosphate
RDP: Resorcinol two (diphenyl phosphoester), Israel's chemical engineering industry, liquid.
BDP: dihydroxyphenyl propane two (diphenyl phosphoester), Israel's chemical engineering industry, liquid.
PX200: aryl condensation polyphosphate, large eight KCCs of Japan, solid.
(C) tetrafluoroethylene
PTFE: anti-dripping agent polytetrafluoroethylene powder, 3M company.
In other the auxiliary agent oxidation inhibitor select four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, IR1010, vapour bar fine chemistry industry is produced, lubricant is selected the hard esteramides of ethylene, EBS.
Performance test methods:
Thermotolerance
HDT: come the thermotolerance of indicator gained alloy with heat-drawn wire, its test is carried out in the load of 1.80MPa by standard ISO 75.
Flame retardant resistance
Test by standard UL94 with the vertical combustion method.Concrete is, Bunsen burner is placed the batten lower end of vertical placement, and then igniting 10S removes burning things which may cause a fire disaster, the record sample flaming combustion time; Certainly put out in the 30S after removing flame such as sample, then again Bunsen burner is placed batten lower end igniting 10S, the record burning things which may cause a fire disaster is removed rear sample flaming combustion time and flameless combustion time, observe simultaneously and whether produce molten drop and molten drop and whether ignite and be put in the absorbent cotton of batten below, each sample is got 5 battens and is one group and tests, do not pass through such as first group of test, can get again one group and test.Its flame retardant resistance grade is divided into V-0, and V-1, and V-2 judge that by the listed index of table 1 wherein the flame retardant resistance of V-0 is best respectively, as all not in the listed indication range of table 1, then is judged to be NC (unclassified), and its flame retardant resistance is the poorest.
Table 1 UL94 burning grade is judged index
Embodiment and Comparative Examples
A1/A2＝50/50
Comparative Examples 1
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 2-1; use at normal temperatures the pre-mixing of high-speed mixing whipping appts even; compound joins TEX30 α parallel dual-screw extruding machine (Japan's steel processed) from main hopper and melt extrudes; 260 ℃ of extrusion temperatures; rotating speed 200rpm; tie rod after extruding is cut into the particle about length 3mm with dicing machine after tank cooling; this pellet is through 80 ℃ of vacuum-dryings after 8 hours; be injection molded into the standard batten with NEX1000 injection moulding machine (a Japan day smart company produces); carry out the mensuration of UL94 and HDT, it the results are shown in Table 2-1.
Comparative Examples 2
Take by weighing respectively resin raw material, TPP and PTFE in ratio shown in the table 2-1, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound joins TEX30 α parallel dual-screw extruding machine (Japan's steel processed) from main hopper and melt extrudes, 230 ℃ of extrusion temperatures, other identical with Comparative Examples 1.It the results are shown in Table 2-1.
Comparative Examples 3
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 2-1, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, RDP with peristaltic pump quantitatively the venting port before the forcing machine vacuum port join TEX30 α parallel dual-screw extruding machine (Japan's steel processed) and melt extrude, 240 ℃ of extrusion temperatures, other identical with Comparative Examples 1.It the results are shown in Table 2-1.
Comparative Examples 4
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 2-1, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, BDP quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with special-purpose liquid feeding device and melt extrudes, 240 ℃ of extrusion temperatures, other identical with Comparative Examples 1.It the results are shown in Table 2-1.
Comparative Examples 5
Take by weighing respectively resin raw material, PX200 and PTFE in ratio shown in the table 2-1, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, joining TEX30 α parallel dual-screw extruding machine (Japan's steel processed) from main hopper melt extrudes, 240 ℃ of extrusion temperatures, other identical with Comparative Examples 1.It the results are shown in Table 2-1.
Embodiment 1
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 2-2, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, liquid flame retardant RDP and BDP also take by weighing in proportion to stir and quantitatively join TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with special-purpose liquid feeding device and melt extrude afterwards, 230 ℃ of extrusion temperatures, other identical with Comparative Examples 1.It the results are shown in Table 2-2.
Embodiment 2
Take by weighing respectively resin raw material, PX200 and PTFE in ratio shown in the table 2-2, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, liquid flame retardant RDP and BDP also take by weighing in proportion to stir and quantitatively join TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with special-purpose liquid feeding device and melt extrude afterwards, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 2-2.
Embodiment 3
Take by weighing respectively resin raw material, TPP and PTFE in ratio shown in the table 2-2, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, liquid flame retardant RDP and BDP also take by weighing in proportion to stir and quantitatively join TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with special-purpose liquid feeding device and melt extrude afterwards, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 2-2.
Embodiment 4
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 2-2, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, after TPP dissolving with peristaltic pump quantitatively the venting port before the forcing machine vacuum port join TEX30 α parallel dual-screw extruding machine (Japan's steel processed) and melt extrude, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 2-2.
Embodiment 5
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 2-2, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, after TPP dissolving with peristaltic pump quantitatively the venting port before the forcing machine vacuum port join TEX30 α parallel dual-screw extruding machine (Japan's steel processed) and melt extrude, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 2-2.
Embodiment 6
Take by weighing respectively resin raw material, TPP and PTFE in ratio shown in the table 2-2, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant RDP and BDP also take by weighing in proportion and stir, with peristaltic pump quantitatively the venting port before the forcing machine vacuum port join TEX30 α parallel dual-screw extruding machine (Japan's steel processed) and melt extrude, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 2-2.
Proportioning and the performance thereof of table 2-1 Zero halogen flame resistance alloy composite
Proportioning and the performance thereof of table 2-2 Zero halogen flame resistance alloy composite
2-1 can find out that do not add the polycarbonate alloy of phosphoric acid ester, its heat-drawn wire (HDT) is very high from table, but after adding phosphoric acid ester owing to the plastification of phosphoric acid ester so that its HDT value decrease.Comparative Examples 2,3,4 and 5 can be found out, only adds merely a kind of phosphoric acid ester, for the polycarbonate alloy of high rubber graft copolymer content, need to add quite a large amount of phosphoric acid ester, but its incendivity also is difficult to reach V-0, and its HDT is very low, can not satisfy the requirement of use.Embodiment 1-6 uses the mixture of multiple different phosphate acid esters, and reaching the required phosphoric acid ester consumption of V-0 grade can significantly reduce, so that its HDT value is higher.Realized the combination of high flame retardant and high heat resistance.For embodiment 5 and embodiment 6, their composition and performance are just the same, difference is in embodiment 6, solid phosphate ester TPP joins the forcing machine from main hopper with other solid material, because the most fusing point of solid phosphate ester lower (be 50 ℃ such as the TPP fusing point), thereby can cause charging opening place material to build bridge, that extrudes is stable bad, and in embodiment 5, we find that TPP can be dissolved in the liquid phosphoric acid ester, so TPP is dissolved in first in the mixing solutions of RDP and BDP and mixes, one joins in the forcing machine by liquid feeding device again, such technique can not built bridge, and the stability of extruding is greatly improved.
A1/A2＝55/45
Comparative Examples 6
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 3; use at normal temperatures the pre-mixing of high-speed mixing whipping appts even; compound joins TEX30 α parallel dual-screw extruding machine (Japan's steel processed) from main hopper and melt extrudes; 260 ℃ of extrusion temperatures; rotating speed 200rpm; tie rod after extruding is cut into the particle about length 3mm with dicing machine after tank cooling; this pellet is through 80 ℃ of vacuum-dryings after 8 hours; be injection molded into the standard batten with NEX1000 injection moulding machine (a Japan day smart company produces); carry out the mensuration of UL94 and HDT, it the results are shown in Table 3.
Comparative Examples 7
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 3, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant RDP quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 3.
Embodiment 7
Take by weighing respectively resin raw material, TPP and PTFE in ratio shown in the table 3, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant BDP quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 3.
Embodiment 8
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 3, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, quantitatively joining TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with liquid feeding device after the TPP dissolving melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 3.
Embodiment 9
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 3, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, quantitatively joining TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with peristaltic pump after the TPP dissolving melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 3.
Embodiment 10
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 3, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, quantitatively joining TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with liquid feeding device after the TPP dissolving melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 3.
Embodiment 11
Take by weighing respectively resin raw material, PTFE and IR1010 in ratio shown in the table 3, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, quantitatively joining TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with liquid feeding device after the TPP dissolving melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 3.
The proportioning of table 3 Zero halogen flame resistance alloy composite and performance thereof
As can be seen from Table 3, only by the polycarbonate alloy of single organic phosphate flame-retardant, even add very a large amount of, the flame retardant resistance of alloy is also bad, and since the adding of a large amount of phosphoric acid ester so that the thermotolerance decrease of alloy, if and the mixture group of using multiple phosphoric acid ester to be mixed into is fire retardant, its addition can reduce greatly, has realized the combination of high flame retardant and high heat resistance.Can find out from embodiment 8 and embodiment 11, add oxidation inhibitor to flame retardant resistance and the not impact of HDT of composition.
A1/A2＝60/40
Comparative Examples 8
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 4; use at normal temperatures the pre-mixing of high-speed mixing whipping appts even; compound joins TEX30 α parallel dual-screw extruding machine (Japan's steel processed) from main hopper and melt extrudes; 260 ℃ of extrusion temperatures; rotating speed 200rpm; tie rod after extruding is cut into the particle about length 3mm with dicing machine after tank cooling; this pellet is through 80 ℃ of vacuum-dryings after 8 hours; be injection molded into the standard batten with NEX1000 injection moulding machine (a Japan day smart company produces); carry out the mensuration of UL94 and HDT, it the results are shown in Table 4.
Comparative Examples 9
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 4, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant BDP quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 4.
Embodiment 12
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 4, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, quantitatively joining TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with liquid feeding device after the TPP dissolving melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 4.
Embodiment 13
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 4, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, quantitatively joining TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with peristaltic pump after the TPP dissolving melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 4.
The proportioning of table 4 Zero halogen flame resistance alloy composite and performance thereof
Compare with Comparative Examples 9, embodiment 12 and 13 has used the mixture of multiple different phosphate acid esters, and the consumption of phosphoric acid ester greatly reduces, and flame retardant resistance and the thermotolerance of polycarbonate alloy all are greatly enhanced.
A1/A2＝70/30
Comparative Examples 10
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 5; use at normal temperatures the pre-mixing of high-speed mixing whipping appts even; compound joins TEX30 α parallel dual-screw extruding machine (Japan's steel processed) from main hopper and melt extrudes; 260 ℃ of extrusion temperatures; rotating speed 200rpm; tie rod after extruding is cut into the particle about length 3mm with dicing machine after tank cooling; this pellet is through 80 ℃ of vacuum-dryings after 8 hours; be injection molded into the standard batten with NEX1000 injection moulding machine (a Japan day smart company produces); carry out the mensuration of UL94 and HDT, it the results are shown in Table 5.
Comparative Examples 11
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 5, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant BDP quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 5.
Embodiment 14
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 5, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, quantitatively joining TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with liquid feeding device after the TPP dissolving melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 5.
Embodiment 15
Take by weighing respectively resin raw material, PTFE, IR1010 and EBS in ratio shown in the table 5, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, quantitatively joining TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with peristaltic pump after the TPP dissolving melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 5.
Embodiment 16
Take by weighing respectively resin raw material, PTFE, IR1010 and EBS in ratio shown in the table 5, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, quantitatively joining TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with peristaltic pump after the TPP dissolving melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 5.
Compare with Comparative Examples 11, embodiment 14 and 15 has used the mixture of multiple different phosphate acid esters, and the consumption of phosphoric acid ester greatly reduces, and flame retardant resistance and the thermotolerance of polycarbonate alloy all are greatly enhanced.The rubber-modified graft copolymer that embodiment 16 explanations are used other instead uses the mixture of different phosphate acid esters as fire retardant, also can obtain the polycarbonate alloy of excellent flame retardancy and thermotolerance combination.
The proportioning of table 5 Zero halogen flame resistance alloy composite and performance thereof
A1/A2＝80/20
Comparative Examples 12
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 6; use at normal temperatures the pre-mixing of high-speed mixing whipping appts even; compound joins TEX30 α parallel dual-screw extruding machine (Japan's steel processed) from main hopper and melt extrudes; 260 ℃ of extrusion temperatures; rotating speed 200rpm; tie rod after extruding is cut into the particle about length 3mm with dicing machine after tank cooling; this pellet is through 80 ℃ of vacuum-dryings after 8 hours; be injection molded into the standard batten with NEX1000 injection moulding machine (a Japan day smart company produces); carry out the mensuration of UL94 and HDT, it the results are shown in Table 6.
Comparative Examples 13
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 6, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant RDP quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 6.
Comparative Examples 14
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 6, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant RDP quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 6.
Embodiment 17
Take by weighing respectively resin raw material and PTFE in ratio shown in the table 6, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, quantitatively joining TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with liquid feeding device after the TPP dissolving melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 6.
Embodiment 18
Take by weighing respectively resin raw material, TPP and PTFE in ratio shown in the table 6, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, join the forcing machine from main hopper after mixing, fire retardant IPPP, RDP and BDP also take by weighing in proportion and stir, quantitatively joining TEX30 α parallel dual-screw extruding machine (Japan's steel processed) with liquid feeding device melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 6.
Compare with Comparative Examples 13, embodiment 17 has used the mixture of multiple different phosphate acid esters, and the consumption of phosphoric acid ester greatly reduces, and flame retardant resistance and the thermotolerance of polycarbonate alloy all are greatly enhanced.And compare with Comparative Examples 14, embodiment 18 has used mixture that two kinds of phosplates and two kinds of polyphosphates form as fire retardant, also can obtain all good polycarbonate alloys of flame retardant resistance and thermotolerance.
The proportioning of table 6 Zero halogen flame resistance alloy composite and performance thereof
Claims (3)
1. Zero halogen flame resistance alloy composite, it is characterized in that said composition mainly by
(A) resin compound of 80-95 weight part,
(B) the phosphoric acid ester fire retardant of 20-5 weight part and
(C) tetrafluoroethylene of 0.1-2 weight part forms,
Wherein said resin compound is comprised of the polycarbonate of 40-90wt% and the rubber-modified graft copolymer of 10-60wt%;
Described phosphoric acid ester fire retardant is for containing the mixture of 20-70wt% triphenyl, 15-40wt% Resorcinol two (diphenyl phosphoester) and 15-40wt% dihydroxyphenyl propane two (diphenyl phosphoester);
Described rubber-modified graft copolymer comprises rigid phase and rubber phase, and rigid phase is styrenic, and rubber phase is polydiene polymers.
2. the preparation method of a Zero halogen flame resistance alloy composite claimed in claim 1, it is characterized in that polycarbonate, rubber-modified graft copolymer, tetrafluoroethylene and solid phosphate ester, be transported to the forcing machine from main opening for feed after the pre-mixing, again the liquid phosphoric acid ester is mixed into liquid mixture, then this liquid mixture is joined in the forcing machine with liquid feeding device or peristaltic pump, under 200-270 ° of C, carry out melt blending, make Zero halogen flame resistance alloy composite.
3. the preparation method of a Zero halogen flame resistance alloy composite claimed in claim 1, it is characterized in that polycarbonate, rubber-modified graft copolymer and tetrafluoroethylene, be transported to the forcing machine from main opening for feed after the pre-mixing, phosphoric acid ester is joined in the forcing machine by liquid feeding device or peristaltic pump after mixing, under 200-270 ° of C, carry out melt blending, make Zero halogen flame resistance alloy composite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910165324 CN101643576B (en) | 2008-08-05 | 2009-07-31 | Zero halogen flame resistance alloy composite and preparation method thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810020878 | 2008-08-05 | ||
| CN200810020878.6 | 2008-08-05 | ||
| CN 200910165324 CN101643576B (en) | 2008-08-05 | 2009-07-31 | Zero halogen flame resistance alloy composite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101643576A CN101643576A (en) | 2010-02-10 |
| CN101643576B true CN101643576B (en) | 2013-04-10 |
Family
ID=41655645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910165324 Expired - Fee Related CN101643576B (en) | 2008-08-05 | 2009-07-31 | Zero halogen flame resistance alloy composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101643576B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982498A (en) * | 2010-09-30 | 2011-03-02 | 深圳市金缙业科技有限公司 | Halogen free antiflaming polycarbonate and rubber modified graft copolymer alloy and preparation method thereof |
| CN102464876A (en) * | 2010-11-15 | 2012-05-23 | 苏州汉扬精密电子有限公司 | PC/ABS defective material modified recovery formula |
| CN109161178A (en) * | 2018-07-19 | 2019-01-08 | 厦门聚信义塑胶有限公司 | A kind of flame retardant plastics and preparation method thereof |
| CN113603998B (en) * | 2021-08-30 | 2023-09-15 | 安庆会通新材料有限公司 | Low-odor flame-retardant antibacterial HIPS material for electric appliances and preparation method thereof |
| CN114230862A (en) * | 2021-11-24 | 2022-03-25 | 洛阳赛图新材料科技有限公司 | Micro-dispersed uniform liquid halogen-free high-performance synergistic flame retardant and preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4309142A1 (en) * | 1993-03-22 | 1994-09-29 | Bayer Ag | Flameproofed moulding compositions based on polycarbonates/graft polymer |
| EP0483628B1 (en) * | 1990-10-29 | 1996-05-29 | BASF Aktiengesellschaft | Flame-proof thermoplastic moulding compositions based on polycarbonates fee of chlorine or bromine, and copolymers of styrene and acrylonitrile |
| US5723526A (en) * | 1993-09-08 | 1998-03-03 | Teijin Chemicals Ltd | Resin composition and molded article |
| CN1232055A (en) * | 1998-02-13 | 1999-10-20 | 通用电气公司 | Flame-retardant carbonate polymer composition with improved hydrolytic stability |
| EP1022312A1 (en) * | 1997-07-23 | 2000-07-26 | Techno Polymer Co., Ltd. | Flame-retardant thermoplastic resin composition |
| EP1069156A1 (en) * | 1999-07-12 | 2001-01-17 | Cheil Industries Inc. | Flame retardant thermoplastic resin composition |
| JP2003041112A (en) * | 2001-07-31 | 2003-02-13 | Asahi Kasei Corp | Polycarbonate-based flame retardant resin composition and thin-walled molded product |
| CN1412247A (en) * | 2001-10-17 | 2003-04-23 | 旭电化工业株式会社 | Flame-retarded synthetic resin composition |
| CN1514856A (en) * | 2002-03-27 | 2004-07-21 | ������������ʽ���� | Flame-retardant aromatic polycarbonate resin composition |
| CN1813030A (en) * | 2003-06-26 | 2006-08-02 | 拜尔材料科学股份公司 | Polycarbonate moulding materials with improved melt flow and chemical resistance |
| CN101139459A (en) * | 2007-08-30 | 2008-03-12 | 上海金发科技发展有限公司 | Non-bittern flame-proof thermostable polycarbonate and acrylonitrile-butadiene-phenylethene grafted copolymer alloy resin and method for preparing same |
| CN101230188A (en) * | 2007-01-26 | 2008-07-30 | 佛山市顺德区汉达精密电子科技有限公司 | Polycarbonate/acrylonitrile-butadiene-phenylethene copolymer alloy |
-
2009
- 2009-07-31 CN CN 200910165324 patent/CN101643576B/en not_active Expired - Fee Related
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0483628B1 (en) * | 1990-10-29 | 1996-05-29 | BASF Aktiengesellschaft | Flame-proof thermoplastic moulding compositions based on polycarbonates fee of chlorine or bromine, and copolymers of styrene and acrylonitrile |
| DE4309142A1 (en) * | 1993-03-22 | 1994-09-29 | Bayer Ag | Flameproofed moulding compositions based on polycarbonates/graft polymer |
| US5723526A (en) * | 1993-09-08 | 1998-03-03 | Teijin Chemicals Ltd | Resin composition and molded article |
| EP1022312A1 (en) * | 1997-07-23 | 2000-07-26 | Techno Polymer Co., Ltd. | Flame-retardant thermoplastic resin composition |
| CN1232055A (en) * | 1998-02-13 | 1999-10-20 | 通用电气公司 | Flame-retardant carbonate polymer composition with improved hydrolytic stability |
| EP1069156A1 (en) * | 1999-07-12 | 2001-01-17 | Cheil Industries Inc. | Flame retardant thermoplastic resin composition |
| JP2003041112A (en) * | 2001-07-31 | 2003-02-13 | Asahi Kasei Corp | Polycarbonate-based flame retardant resin composition and thin-walled molded product |
| CN1412247A (en) * | 2001-10-17 | 2003-04-23 | 旭电化工业株式会社 | Flame-retarded synthetic resin composition |
| CN1514856A (en) * | 2002-03-27 | 2004-07-21 | ������������ʽ���� | Flame-retardant aromatic polycarbonate resin composition |
| CN1813030A (en) * | 2003-06-26 | 2006-08-02 | 拜尔材料科学股份公司 | Polycarbonate moulding materials with improved melt flow and chemical resistance |
| CN101230188A (en) * | 2007-01-26 | 2008-07-30 | 佛山市顺德区汉达精密电子科技有限公司 | Polycarbonate/acrylonitrile-butadiene-phenylethene copolymer alloy |
| CN101139459A (en) * | 2007-08-30 | 2008-03-12 | 上海金发科技发展有限公司 | Non-bittern flame-proof thermostable polycarbonate and acrylonitrile-butadiene-phenylethene grafted copolymer alloy resin and method for preparing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101643576A (en) | 2010-02-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5266618A (en) | Flame-retardant resin composition | |
| US8026303B2 (en) | Halogen-free flame retardant compositions, thermoplastic compositions comprising the same and methods of producing the compositions | |
| CN101875745B (en) | Flame-retardant styrene polymer compound containing smoke inhibitor and preparation method thereof | |
| CN101659779B (en) | Halogen-free flame-retardant ABS resin and preparation method thereof | |
| CN101857712B (en) | Halogen-free flame-retardant ABS/PET alloy and preparation method thereof | |
| CN102875982A (en) | In-situ modified halogen-free flame retardant thermoplastic resin composition and preparation method thereof | |
| CN104277443A (en) | Preparation method of heat-resistant halogen-free flame-retardant PC (polycarbonate)/ABS | |
| CN101643576B (en) | Zero halogen flame resistance alloy composite and preparation method thereof | |
| CN102516732A (en) | Polycarbonate (PC) resin/acrylonitrile-butadiene-styrene (ABS) alloy and preparation method thereof | |
| CN101341211A (en) | Flameretardant thermoplastic resin composition | |
| CN103374214A (en) | High-impact environment-friendly flame-retardant PC (Polycarbonate)/ABS (Acrylonitrile Butadiene Styrene) alloy material and preparation technology thereof | |
| KR20110043659A (en) | Flame Retardant Styrene-Containing Polymer Composition | |
| CN103289290A (en) | Phosphorus-based synergistic flame-retardant ABS (acrylonitrile-butadiene-styrene) composite material and preparation method thereof | |
| CN104334622A (en) | Antimony-free flame-retarded styrenic thermoplastic polymer composition, article containing same and method of making same | |
| CN102936402A (en) | Low-smoke heat-resistant halogen-free flame-retardant polycarbonate/acrylonitrile-butadiene-styrene resin composition and preparation method thereof | |
| CN102329488A (en) | Extrusion-grade low-smoke halogen-free flame-retardant PC (polycarbonate)/ABS (Acrylonitrile Butadiene Styrene) material and preparation method thereof | |
| CN103360739B (en) | A kind of phosphorus system synergistic fire retardation PC/ABS alloy material and preparation method thereof | |
| WO2015170130A1 (en) | Environmental friendly flame retardant moulding compositions based on thermoplastic impact modified styrenic polymers | |
| CN100400595C (en) | Self-extinguishing halogen-free flame-retardant PC/ABS alloy and its preparation process | |
| CN101724131B (en) | Flame retardant copolymer of polytetrafluoroethylene-styrene-acrylonitrile-butadiene styrene rubber, preparation method and application thereof | |
| JP2013518957A (en) | Refractory composition based on aromatic vinyl polymer containing antimony pentoxide | |
| CN101982498A (en) | Halogen free antiflaming polycarbonate and rubber modified graft copolymer alloy and preparation method thereof | |
| KR0150763B1 (en) | Thermoplastic resin composition having flame retardancy | |
| JP6092978B2 (en) | Thermoplastic resin composition and molded article produced therefrom | |
| CN104629320A (en) | Low-smoke nano flame retardant PC/ABS alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130410 Termination date: 20160731 |