CN101845205B - Halogen-free fire-resistant engineering plastics using waste PET bottle chips as raw material and preparation method thereof - Google Patents
Halogen-free fire-resistant engineering plastics using waste PET bottle chips as raw material and preparation method thereof Download PDFInfo
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- CN101845205B CN101845205B CN2010101967095A CN201010196709A CN101845205B CN 101845205 B CN101845205 B CN 101845205B CN 2010101967095 A CN2010101967095 A CN 2010101967095A CN 201010196709 A CN201010196709 A CN 201010196709A CN 101845205 B CN101845205 B CN 101845205B
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- pet bottle
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- 239000002699 waste material Substances 0.000 title claims abstract description 70
- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 36
- 230000009970 fire resistant effect Effects 0.000 title claims abstract description 35
- 239000002994 raw material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003063 flame retardant Substances 0.000 claims abstract description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- 239000012745 toughening agent Substances 0.000 claims abstract description 14
- 229920003023 plastic Polymers 0.000 claims abstract description 11
- 239000004033 plastic Substances 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 6
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 6
- 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 description 45
- -1 aryl phosphate ester Chemical class 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 30
- 239000011521 glass Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- 239000011574 phosphorus Substances 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 239000003365 glass fiber Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000012802 nanoclay Substances 0.000 claims description 12
- 238000006068 polycondensation reaction Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 238000005453 pelletization Methods 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 8
- 229920001038 ethylene copolymer Polymers 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011324 bead Substances 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 150000007974 melamines Chemical class 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 150000008301 phosphite esters Chemical class 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 3
- 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 3
- 229920001923 acrylonitrile-ethylene-styrene Polymers 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- PNWJXICONNROSM-UHFFFAOYSA-N ethene;prop-2-enenitrile;styrene Chemical compound C=C.C=CC#N.C=CC1=CC=CC=C1 PNWJXICONNROSM-UHFFFAOYSA-N 0.000 claims description 3
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 claims description 3
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 3
- 239000001205 polyphosphate Substances 0.000 claims description 3
- 235000011176 polyphosphates Nutrition 0.000 claims description 3
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 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 3
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 3
- 235000010234 sodium benzoate Nutrition 0.000 claims description 3
- 239000004299 sodium benzoate Substances 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- GDCRSXZBSIRSFR-UHFFFAOYSA-N ethyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCOC(=O)C=C GDCRSXZBSIRSFR-UHFFFAOYSA-N 0.000 claims description 2
- 229920006228 ethylene acrylate copolymer Polymers 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical group NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 239000004927 clay Substances 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 1
- 239000002667 nucleating agent Substances 0.000 abstract 1
- 239000012744 reinforcing agent Substances 0.000 abstract 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 68
- 239000005020 polyethylene terephthalate Substances 0.000 description 68
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- BJJQDHSYPNZEEU-UHFFFAOYSA-N ethene;oxiran-2-ylmethyl prop-2-enoate Chemical group C=C.C=CC(=O)OCC1CO1 BJJQDHSYPNZEEU-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000006057 Non-nutritive feed additive Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 206010013781 dry mouth Diseases 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- DYAHQFWOVKZOOW-UHFFFAOYSA-N Sarin Chemical compound CC(C)OP(C)(F)=O DYAHQFWOVKZOOW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000021443 coca cola Nutrition 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 235000021444 pepsi cola Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 1
Classifications
-
- B29C47/92—
Abstract
The invention discloses halogen-free fire-resistant engineering plastics using waste PET bottle chips as a raw material, a preparation method thereof and application thereof. The plastics consists of the following components in percentage by weight: 36 to 65 percent of waste PET bottle chips, 15 to 40 percent of reinforcing agent, 3 to 8 percent of toughening agent, 5 to 8 percent of phosphorous fire retardant, 2 to 8 percent of nitrogen fire retardant, 0 to 4 percent of nanometer clay, 0 to 0.5 percent of nucleating agent and 0 to 0.5 percent of antioxidant. The halogen-free fire-resistant engineering plastics are prepared by using the waste PET bottle chips as the raw materials, thereby contributing to environmental protection, reducing pollution of waste bottles and making recycled materials have high performance; in addition, because the phosphorous-nitrogen fire-resistant system and the nanometer clay are combined, the compound material is halogen free and fire resistant and simultaneously the fire-resistant material has a higher CTI value; and thus, the engineering plastics are applied in a field of electric products.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly a kind of is the halogen-free fire-resistant engineering plastics and the preparation method of raw material with waste PET (polyethylene terephthalate) bottle sheet.
Background technology
Usually mineral water bottle is made with PVC or PET, and carbonated drink bottle such as coke coca cola, pepsi cola, Sprite etc. are made with PET.Flourish along with beverage industries, China's PET bottle accounts for the whole world more than 50%, about 1,500,000 tons of year consumption; Huge consumption makes the annual waste PET that produces of China up to 1,000,000 tons; Become the main source of waste plastic, not only cause the huge waste of resource, destroy ecotope; And not meeting the view of science of sustainable development, the regenerated using waste PET becomes the problem that domestic and international scientific and technological circle and industry member are paid close attention to.
Waste PET is directly comparatively ripe as fiber or direct utilization technology, but the added value that waste PET utilizes is not high.A technology that receives the great attention of domestic and international scientific and technological circle and industry member at present is to utilize waste PET regeneration to prepare the high performance engineering materials; Prepared high performance engineering materials can be widely used in field of electronics, especially is fit to make various rly.s, patch switch, electrical component, transformer framework etc.
Less relatively about the research of waste PET Halogen through engineering approaches, Chinese patent 200810037742.6 discloses a kind of " enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance and preparation method thereof " that are used for electronic apparatus, automotive field.Chinese patent 200810227352.5 discloses a kind of " halogen-free flameproof polyethylene terephthalate engineering plastic composite material and preparation method thereof ".
More than the main raw material of two kinds of methods be brand-new PET resin; See from other formula constituents: (1) Chinese patent 200810037742.6; The flame-retardant system of this product is the red phosphorus flame-retardant system; Water absorbability is strong, toning property is poor, and the acid attack property material that discharges in the processing can cause damage to mould.(2) Chinese patent 200810227352.5, and the flame-retardant system of this product is inorganic melamine pyrophosphate salt, organic ammonium polyphosphate, weisspiessglanz compositional flame-retardant.It is comparatively loaded down with trivial details that this method prepares process, needs earlier different component pre-treatment and make master batch and carry out secondary processing again.Simultaneously, the weisspiessglanz that contains in the system can cause the thermal destruction of PET resin, is not suitable for the recycling in the electric equipment products.
Chinese patent 200510080229.1 discloses a kind of " is the green fireproof reinforced composite material of matrix to reclaim the PET resin ".This material component is various and relate to multiple low molecule processing aid; The thermostability of low molecule processing aid is lower; The affiliation that adds of multiple low molecule processing aid has influence on the thermostability of matrix material; The processing aid component too much can make matrix material localized phase separation in hot procedure, occur, influences the thermotolerance of material; Processing aid generally has polar functional group more, not only can have influence on the electrical property [CTI] of matrix material, and the degree that in hot procedure, presents sour environment is higher, makes the possible performance of waste PET resin degraded bigger.Be not mentioned to the thermal property and the electrical property of material in this patent yet.Yet the thermotolerance of material and CTI (relative discharge tracking index) value is one of important indicator in the field of electronics.
Summary of the invention
It is the halogen-free fire-resistant engineering plastics of raw material with the waste PET bottle chips that primary and foremost purpose of the present invention is to provide a kind of, is characterized in utilizing waste PET to be raw material, overcome as waste PET since viscosity low (molecular weight is little; Due to the degraded); Repeatedly very easily degrading in the hot procedure, making material forfeiture mechanical property, be difficult to defective as the engineering plastics regenerated using; Make its regenerating high-performanceization, demonstrate outstanding cost performance and environmental friendly regenerated advantage; Another characteristics of the present invention are to have overcome the low shortcoming of waste PET mechanical strength, and prepared halogen-free flame-retardant composite material not only satisfies actual request for utilization on fire-retardant, electric, thermal property, on mechanical strength, also satisfy the demand of through engineering approaches.
It is the preparation method of the halogen-free fire-resistant engineering plastics of raw material with the waste PET bottle chips that another purpose of the present invention is to provide above-mentioned.
It is the application of the halogen-free fire-resistant engineering plastics of raw material with the waste PET bottle chips that a purpose more of the present invention is to provide above-mentioned.
The object of the invention is realized through following technical proposals:
A kind of is the halogen-free fire-resistant engineering plastics of raw material with the waste PET bottle chips, is made up of following component by weight percentage:
Waste PET bottle chips 36～65%
Toughener 15～40%
Toughner 3～8%
Phosphorus flame retardant 5～8%
Nitrogen flame retardant 2～8%
Nanoclay 0～4%
Nucleator 0～0.5%
Oxidation inhibitor 0～0.5%.
Said waste PET bottle chips limiting viscosity is 0.4～0.6dl/g.Said waste PET bottle chips is the PET bottle of recovery, makes through separation (removing bottle cap, label etc.), cleaning, drying, fragmentation.
Said toughener is short glass fiber, thomel, glass microballon, ceramic fine bead, talcum powder (order number below 1500 orders and the big 10-40% of addition), mica or the alkali-free long glass fibres through the siloxanes coupling agent treatment; Wherein, Preferably pass through the alkali-free long glass fibres of siloxanes coupling agent treatment; This processing generally is that the siloxanes coupling agent is applied on the glass, its objective is the boundary strength that increases glass and organic resin, thereby improves the reinforced effects of glass to organic resin.The modification that is used for that general glass manufacturer produces all is through the finished product after the coupling processing with glass.
Said toughner is at least a in maleic anhydride graft polyolefin elastomer, propenoate-glycidyl ester-ethylene copolymer, methacrylic ester-styrene-butadiene rubber(SBR)-styrol copolymer, ethylene-acrylate copolymer, ethylene vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile ethylene styrene copolymer and the segmented copolymer (like TPEE Hai Cui) that contains hard section of polyester and polyester soft segment; Wherein, Propenoate-glycidyl ester-the ethylene copolymer that preferably has epoxy-functional; This multipolymer is when realization is toughness reinforcing, and the epoxy-functional of self has the chain extension effect to PET.
Said phosphorus flame retardant is at least a in triphenylphosphate, Tritolyl Phosphate, tolyl diphenyl phosphoester and the polycondensation aryl phosphate ester, and wherein, said polycondensation aryl phosphate ester is Resorcinol polycondensation aryl phosphate ester or polycondensation phenyl-phosphate.
Said nitrogen flame retardant is at least a in trimeric cyanamide, melamine salt and the ammonium polyphosphate, and wherein, said melamine salt is melamine cyanurate salt, SULPHOSUCCINIC ACID ESTER melamine salt or poly phosphate melamine salt.
The particle diameter of said nanoclay is 50～100nm, and composition is an organo montmorillonite.
Said nucleator is at least a in talcum powder (the order number is more than 4000 orders reach, and addition＜1%), zinc powder, zinc oxide, Sodium Benzoate, polyethyleneglycol diglycidylether, glycidyl ester Sipacril 2739OF, tetrafluoroethylene and the ethylene-acrylic acid copolymer sodium salt (the sarin resin of Du Pont).
Said oxidation inhibitor is at least a in phenolic antioxidant, phosphite ester kind antioxidant and the metal passivator; Wherein, The preferred β of said phenol antioxidant-(4-hydroxyl-3,5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid (Irganox 1076), four (3,5-di-t-butyl-4-4 phenylor) (Irganox 1010), N; N '-hexylidene-1; 6-two [3-(3,5-di-t-butyl-4-4 phenylor) propionic acid amide] (Irganox 1098) or three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid esters (Irganox 3114); Preferred three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (Irganox 168) of said phosphite ester kind antioxidant; The preferred MD102 of said metal passivator.
With the waste PET bottle chips is the preparation method of the halogen-free fire-resistant engineering plastics of raw material, comprises following operation steps:
(1) with waste PET bottle chips in 100～140 ℃ of forced air dryings 3～6 hours;
(2) drying is good waste PET bottle chips, toughner, phosphorus flame retardant, nitrogen flame retardant, nanoclay, nucleator and oxidation inhibitor add in the stirrer successively, under 300～500 rev/mins rotating speed, mix 3～5 minutes, obtain mixture;
(3) step (2) gained mixture is added in the twin screw extruder; Again dried toughener is introduced the forcing machine from the glass mouth; Through melt extruding granulation, extruded material is after cooling, air-dry, pelletizing, drying, and obtaining with the waste PET bottle chips is the halogen-free fire-resistant engineering plastics finished product of raw material;
The fabrication process condition of said twin screw extruder is following:
Temperature is: 170～200 ℃ in a district; 180～200 ℃ in two districts; 180～200 ℃ in three districts; 190～210 ℃ in four districts; 180～200 ℃ in five districts; 190～210 ℃ in six districts; 200～240 ℃ of heads;
20～40 ℃ of tank temperature;
Pressure is 11～17MPa;
Screw speed is 250～400rpm;
The dicing machine rotating speed is 600～1000rpm.
The said drying of step (3) is that the alkali-free long glass fibres of siloxanes coupling agent treatment is 120～180 ℃ through temperature is that the glass moisture eliminator of 0.5～3m carries out drying with tube length; Or with short glass fiber, thomel, glass microballon, ceramic fine bead, talcum powder or mica at 110～170 ℃ of drying 2～4h.
The above-mentioned waste PET bottle chips that uses can be applicable to prepare switch connector, transformer framework, electric switch, adapter skeleton, conducting strip, junctor, electromagnetic oven baking oven accessory or blower accessory as the halogen-free fire-resistant engineering plastics of feedstock production.
Handy waste PET bottle chips be the halogen-free fire-resistant engineering plastics ISO examination criteria of feedstock production, performance is following:
Density: 1.50-1.69g/cm
3
Elongation at break: 8-15%
Tensile strength: 80-120MPa
Flexural strength: 100-160MPa
Modulus in flexure: 4500-9000MPa
Socle girder notched Izod impact strength: 4-9KJ/m
2
Melting index: 15-45g/10min (265 ℃, 2.16Kg)
160 ℃-245 ℃ of heat-drawn wires (0.45MPa)
Flame retardant resistance (UL94): V-0,0.8mm
Relative discharge tracking index CTI (V) 600.
Fire retardant mechanism about phosphorus nitrogen flame-retardant system; It is generally acknowledged non-flammable gases such as nitrogen flame retardant burnt ammonia, nitrogen, degree of depth oxynitride, water vapor; Greatly reduce the polymer surfaces temperature; Play the fire-retardant effect of gas phase, but because a large amount of gases of nitrogen flame retardant because of producing can not be used for filling reinforced plastics separately.In the phosphorus flame retardant combustion processes, the polyphosphoric acid of generation can impel the plastics carbonization, makes frosting form carburization zone, plays the fire-retardant effect of solid phase.The present invention plays the fire-retardant effect of synergistic through nitrogen flame retardant and phosphorus flame retardant are composite, and on the one hand, the nitrogen flame retardant can promote the carbonization of phosphorus flame retardant, can form the layer of even foam layer, plays iris action, and can prevent drippage; On the other hand, phosphorus nitrogen compositional flame-retardant system can improve the thermostability of phosphorus flame retardant, help simultaneously improving material electrical property (CTI) [fire retardant is to the influence of CTI, CTI from high to low: nitrogen system＞phosphorus system＞halogen, antimony compounds].The synergistic effect of two kinds of flame-retardant systems can reduce the fire retardant consumption, helps improving the over-all properties of matrix material.
The present invention compared with prior art has following advantage and beneficial effect:
(1) the present invention is feedstock production halogen-free flameproof engineering materials with the waste PET bottle chips; Not only help environmental protection, reduce discarded bottle pollution; And make the twice-laid stuff high performance; Realize turning waste into wealth, energy-conserving and environment-protective, make the twice-laid stuff high performance in, make product have more outstanding cost performance;
(2) adopt phosphorus nitrogen flame-retardant system and nanoclay composite, when realizing the matrix material halogen-free flameproof, guaranteed the CTI value that fire retardant material is higher, thereby be applicable to field of electronics;
(3) material prepn of the present invention convenient, need not mould temperature forming process.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but embodiment of the present invention is not limited thereto, the processing parameter for not indicating especially can carry out with reference to routine techniques.
Wherein, the used waste PET bottle sheet stock of the present invention all is that the PET bottle numerous from the Pearl River Delta reclaims the direct purchase of enterprise.
Embodiment 1
(1) with waste PET bottle chips in 115 ℃ of forced air dryings 4 hours;
(2) waste PET bottle chips (limiting viscosity is 0.5dl/g) 48g, toughening agent maleic anhydride grafting polyolefin elastomer 5g, phosphorus flame retardant Resorcinol polycondensation aryl phosphate ester 8g, nitrogen flame retardant trimeric cyanamide 6g that drying is good, (particle diameter is 100nm to nanoclay; Select Nanocor company for use I.28E) 2.5g, nucleator Sodium Benzoate 0.3g and oxidation inhibitor β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) the positive octadecyl ester 0.2g of propionic acid adds in the stirrer successively; Under 400 rev/mins rotating speed, mixed 3 minutes, and obtained mixture;
(3) step (2) gained mixture is added in the twin screw extruder; Alkali-free long glass fibres 30g with toughener siloxanes coupling agent treatment passes through glass moisture eliminator (160 ℃ of drying temperatures again; Dry tube length 1.5m) introduce the forcing machine from the glass mouth dry back; Through melt extruding granulation, extruded material is after cooling, air-dry, pelletizing, drying, and obtaining with the waste PET bottle chips is the halogen-free fire-resistant engineering plastics finished product of raw material;
The fabrication process condition of said twin screw extruder is following:
Temperature is: 170 ℃ in a district; 180 ℃ in two districts; 190 ℃ in three districts; 200 ℃ in four districts; 190 ℃ in five districts; 205 ℃ in six districts; 230 ℃ of heads;
40 ℃ of tank temperature;
Pressure is 16MPa;
Screw speed is 300rpm;
The dicing machine rotating speed is 800rpm.
The waste PET bottle chips that is able to is that the halogen-free fire-resistant engineering plastics finished product of raw material is following through detecting performance:
Density: 1.60g/cm
3
Elongation at break: 11%
Tensile strength: 110MPa
Flexural strength: 152MPa
Modulus in flexure: 8100MPa
Socle girder notched Izod impact strength: 7KJ/m
2
Melting index: 33g/10min (265 ℃, 2.16Kg)
243 ℃ of heat-drawn wires (0.45MPa)
Flame retardant resistance (UL94): V-0,0.8mm
Relative discharge tracking index CTI (V): 600.
Embodiment 2
(1) with waste PET bottle chips in 115 ℃ of forced air dryings 4 hours;
(2) waste PET bottle chips (limiting viscosity is 0.4dl/g) 36g that drying is good, propenoate-glycidyl ester-ethylene copolymer 8g, phosphorus flame retardant triphenylphosphate 8g, nitrogen flame retardant ammonium polyphosphate 6g that toughner has epoxy-functional, (particle diameter is 50nm to nanoclay; Select Nanocor company for use I.28E) 1.5g, nucleator talcum powder 0.3g and oxidation inhibitor four (3; 5-di-t-butyl-4-4 phenylor) 0.2g adds in the stirrer successively; Under 400 rev/mins rotating speed, mixed 3 minutes, and obtained mixture;
(3) step (2) gained mixture is added in the twin screw extruder; Alkali-free long glass fibres 40g with toughener siloxanes coupling agent treatment passes through glass moisture eliminator (180 ℃ of drying temperatures again; Dry tube length 0.5m) introduce the forcing machine from the glass mouth dry back; Through melt extruding granulation, extruded material is after cooling, air-dry, pelletizing, drying, and obtaining with the waste PET bottle chips is the halogen-free fire-resistant engineering plastics finished product of raw material;
The fabrication process condition of said twin screw extruder is following:
Temperature is: 170 ℃ in a district; 180 ℃ in two districts; 190 ℃ in three districts; 200 ℃ in four districts; 190 ℃ in five districts; 200 ℃ in six districts; 235 ℃ of heads;
30 ℃ of tank temperature;
Pressure is 17MPa;
Screw speed is 300rpm;
The dicing machine rotating speed is 600rpm.
The waste PET bottle chips that is able to is that the halogen-free fire-resistant engineering plastics finished product of raw material is following through detecting performance:
Density: 1.65g/cm
3
Elongation at break: 9%
Tensile strength: 115MPa
Flexural strength: 158MPa
Modulus in flexure: 9000MPa
Socle girder notched Izod impact strength: 6.5KJ/m
2
Melting index: 40g/10min (265 ℃, 2.16Kg)
245 ℃ of heat-drawn wires (0.45MPa)
Flame retardant resistance (UL94): V-0,0.8mm
Relative discharge tracking index CTI (V): 600.
Embodiment 3
(1) with waste PET bottle chips in 100 ℃ of forced air dryings 6 hours;
(2) waste PET bottle chips (limiting viscosity is 0.6dl/g) 62g that drying is good, propenoate-glycidyl ester-ethylene copolymer 3g, phosphorus flame retardant Tritolyl Phosphate 5g, nitrogen flame retardant melamine cyanurate salt 8g that toughner has epoxy-functional, (particle diameter is 80nm to nanoclay; Select Nanocor company for use I.28E) 1.5g, nucleator zinc oxide 0.3g and oxidation inhibitor three (2; The 4-di-tert-butyl-phenyl) phosphorous acid ester 0.2g adds in the stirrer successively; Under 400 rev/mins rotating speed, mixed 3 minutes, and obtained mixture;
(3) step (2) gained mixture is added in the twin screw extruder; Toughener short glass fiber 20g with (150 ℃ condition under dry 2h) after the drying introduces the forcing machine from the glass mouth again; Through melt extruding granulation; Extruded material is after cooling, air-dry, pelletizing, drying, and obtaining with the waste PET bottle chips is the halogen-free fire-resistant engineering plastics finished product of raw material;
The fabrication process condition of said twin screw extruder is following:
Temperature is: 180 ℃ in a district; 190 ℃ in two districts; 200 ℃ in three districts; 210 ℃ in four districts; 200 ℃ in five districts; 210 ℃ in six districts; 240 ℃ of heads;
35 ℃ of tank temperature;
Pressure is 11MPa;
Screw speed is 300rpm;
The dicing machine rotating speed is 1000rpm.
The waste PET bottle chips that is able to is that the halogen-free fire-resistant engineering plastics finished product of raw material is following through detecting performance:
Density: 1.56g/cm
3
Elongation at break: 10%
Tensile strength: 105MPa
Flexural strength: 135MPa
Modulus in flexure: 7100MPa
Socle girder notched Izod impact strength: 7KJ/m
2
Melting index: 22g/10min (265 ℃, 2.16Kg)
200 ℃ of heat-drawn wires (0.45MPa)
Flame retardant resistance (UL94): V-0,0.8mm
Relative discharge tracking index CTI (V): 600.
Embodiment 4
(1) with waste PET bottle chips in 140 ℃ of forced air dryings 3 hours;
(2) waste PET bottle chips (limiting viscosity is 0.55dl/g) 65g that drying is good, propenoate-glycidyl ester-ethylene copolymer 6g, phosphorus flame retardant tolyl diphenyl phosphoester 7g, nitrogen flame retardant SULPHOSUCCINIC ACID ESTER melamine salt 6g, nucleator tetrafluoroethylene 0.5g and the oxidation inhibitor N that toughner has epoxy-functional; N '-hexylidene-1; [3-(3 for 6-two; 5-di-t-butyl-4-4 phenylor) propionic acid amide] 0.5g adds in the stirrer successively; Under 400 rev/mins rotating speed, mixed 3 minutes, and obtained mixture;
(3) step (2) gained mixture is added in the twin screw extruder; Toughener thomel (toray T300) 15g with (110 ℃ condition under dry 4h) after the drying introduces the forcing machine from the glass mouth again; Through melt extruding granulation; Extruded material is after cooling, air-dry, pelletizing, drying, and obtaining with the waste PET bottle chips is the halogen-free fire-resistant engineering plastics finished product of raw material;
The fabrication process condition of said twin screw extruder is following:
Temperature is: 180 ℃ in a district; 185 ℃ in two districts; 185 ℃ in three districts; 200 ℃ in four districts; 200 ℃ in five districts; 210 ℃ in six districts; 225 ℃ of heads;
25 ℃ of tank temperature;
Pressure is 15MPa;
Screw speed is 350rpm;
The dicing machine rotating speed is 700rpm.
The waste PET bottle chips that is able to is that the halogen-free fire-resistant engineering plastics finished product of raw material is following through detecting performance:
Density: 1.55g/cm
3
Elongation at break: 8%
Tensile strength: 100MPa
Flexural strength: 130MPa
Modulus in flexure: 6500MPa
Socle girder notched Izod impact strength: 5.5KJ/m
2
Melting index: 20g/10min (265 ℃, 2.16Kg)
180 ℃ of heat-drawn wires (0.45MPa)
Flame retardant resistance (UL94): V-0,0.8mm
Relative discharge tracking index CTI (V): 600.
Embodiment 5
(1) with waste PET bottle chips in 120 ℃ of forced air dryings 4 hours;
(2) waste PET bottle chips (limiting viscosity is 0.45dl/g) 44g that drying is good, propenoate-glycidyl ester-ethylene copolymer 8g, phosphorus flame retardant tolyl diphenyl phosphoester 8g, the nitrogen flame retardant melamine cyanurate salt 2g that toughner has epoxy-functional; (particle diameter is 70nm to nanoclay; Select Nanocor company for use I.28E) 3g; In the inferior adding stirrer, under 500 rev/mins rotating speed, mixed 3 minutes, obtain mixture;
(3) step (2) gained mixture is added in the twin screw extruder; Toughener ceramic fine bead 35g with (170 ℃ condition under dry 2h) after the drying introduces the forcing machine from the glass mouth again; Through melt extruding granulation; Extruded material is after cooling, air-dry, pelletizing, drying, and obtaining with the waste PET bottle chips is the halogen-free fire-resistant engineering plastics finished product of raw material;
The fabrication process condition of said twin screw extruder is following:
Temperature is: 200 ℃ in a district; 200 ℃ in two districts; 200 ℃ in three districts; 190 ℃ in four districts; 180 ℃ in five districts; 190 ℃ in six districts; 200 ℃ of heads;
20 ℃ of tank temperature;
Pressure is 17MPa;
Screw speed is 300rpm;
The dicing machine rotating speed is 800rpm.
The waste PET bottle chips that is able to is that the halogen-free fire-resistant engineering plastics finished product of raw material is following through detecting performance:
Density: 1.68g/cm
3
Elongation at break: 9%
Tensile strength: 95MPa
Flexural strength: 128MPa
Modulus in flexure: 5800MPa
Socle girder notched Izod impact strength: 5KJ/m
2
Melting index: 28g/10min (265 ℃, 2.16Kg)
165 ℃ of heat-drawn wires (0.45MPa)
Flame retardant resistance (UL94): V-0,0.8mm
Relative discharge tracking index CTI (V): 600.
Embodiment 6
(1) with waste PET bottle chips in 110 ℃ of forced air dryings 5 hours;
(2) waste PET bottle chips (limiting viscosity is 0.6dl/g) 50g, toughner (having the propenoate-glycidyl ester-ethylene copolymer 3g of epoxy-functional and the mixture of ethylene vinyl acetate copolymer 3g) 6g, phosphorus flame retardant polycondensation phenyl-phosphate 8g, nitrogen flame retardant poly phosphate melamine salt 6.5g that drying is good, (particle diameter is 80nm to nanoclay; Selecting Nanocor company for use I.28E) 1g, nucleator ethylene-acrylic acid copolymer sodium salt 0.3g and oxidation inhibitor metal passivator MD102 (production of vapour Bagong department) 0.2g add in the stirrer successively; Under 300 rev/mins rotating speed, mixed 3 minutes, and obtained mixture;
(3) step (2) gained mixture is added in the twin screw extruder; Again the toughener mica 28g glass mouth of (160 ℃ condition under dry 2.5h) after the drying is introduced in the forcing machine; Through melt extruding granulation; Extruded material is after cooling, air-dry, pelletizing, drying, and obtaining with the waste PET bottle chips is the halogen-free fire-resistant engineering plastics finished product of raw material;
The fabrication process condition of said twin screw extruder is following:
Temperature is: 170 ℃ in a district; 180 ℃ in two districts; 190 ℃ in three districts; 205 ℃ in four districts; 190 ℃ in five districts; 200 ℃ in six districts; 240 ℃ of heads;
30 ℃ of tank temperature;
Pressure is 15MPa;
Screw speed is 250rpm;
The dicing machine rotating speed is 800rpm.
The waste PET bottle chips that is able to is that the halogen-free fire-resistant engineering plastics finished product of raw material is following through detecting performance:
Density: 1.64g/cm
3
Elongation at break: 12%
Tensile strength: 105MPa
Flexural strength: 125MPa
Modulus in flexure: 7600MPa
Socle girder notched Izod impact strength: 4KJ/m
2
Melting index: 20g/10min (265 ℃, 2.16Kg)
170 ℃ of heat-drawn wires (0.45MPa)
Flame retardant resistance (UL94): V-0,0.8mm
Relative discharge tracking index CTI (V): 600.
Embodiment 7
The difference of present embodiment and embodiment 1 is,
(2) waste PET bottle chips 55g, toughner acrylonitrile ethylene styrene copolymer 5g, phosphorus flame retardant Resorcinol polycondensation aryl phosphate ester 8g, nitrogen flame retardant trimeric cyanamide 2.5g that drying is good, (particle diameter is 100nm to nanoclay; Selecting Nanocor company for use I.28E) 4g and nucleator polyethyleneglycol diglycidylether 0.5g add in the stirrer successively; Under 400 rev/mins rotating speed, mixed 3 minutes, and obtained mixture; (3) step (2) gained mixture is added in the twin screw extruder; Again dried toughener short glass fiber 25g is introduced the forcing machine from the glass mouth; Through melt extruding granulation; Extruded material is after cooling, air-dry, pelletizing, drying, and obtaining with the waste PET bottle chips is the halogen-free fire-resistant engineering plastics finished product of raw material.
The waste PET bottle chips that is able to is that the halogen-free fire-resistant engineering plastics finished product of raw material is following through detecting performance:
Density: 1.62g/cm
3
Elongation at break: 12%
Tensile strength: 100MPa
Flexural strength: 126MPa
Modulus in flexure: 6800MPa
Socle girder notched Izod impact strength: 5KJ/m
2
Melting index: 32g/10min (265 ℃, 2.16Kg)
160 ℃ of heat-drawn wires (0.45MPa)
Flame retardant resistance (UL94): V-0,0.8mm
Relative discharge tracking index CTI (V): 600
Embodiment 8
Material transformer framework of the present invention
It is that the connector that the halogen-free fire-resistant engineering plastics of raw material is used for field of electronics is made that 1 of embodiment is able to waste PET bottle chips, and manufacture craft is following:
(1) will be halogen-free fire-resistant engineering plastics dry 4h under 130 ℃ of raw material with the waste PET bottle chips;
(2) Shooting Technique is following:
Injection temperature: 1 section 265 ℃, 2 sections 260 ℃, 3 sections 255 ℃;
Injection moulding speed: 1 section 20%, 2 section 20%, 3 section 20%;
Injection pressure: 1 section 500bar, 2 sections 500bar, 3 sections 500bar;
Dwell pressure: 1 section 500bar, 2 sections 500bar, 3 sections 500bar;
The injection time: 10s;
Cooling time: 10s;
Dwell time: 13s;
Mould temperature: 80 degree.
(3) directly injection moulding.
The connector test performance of above-mentioned preparation is following:
1. shrinking percentage 0.5-0.8%, product size is qualified;
2. the outward appearance judgement is qualified;
3. environmental protection tests:
Cd:0 (ppm); Cr:0 (ppm); Pb:10.1 (ppm); Cl:566 (ppm); Hg:0 (ppm); Br:0 (ppm), it is qualified that environmental protection is judged.
4. heat-resisting test: 140 ℃ of baking 4h, no variable color.
5. scolding tin test (420 ℃ ± 10 ℃): the slight melting loss of body, judgement is passed through.
6. strength test: 2.5-3.4kg, it is qualified to judge.
7. (3sec): test is passed through for 3.5KV, 5mA in Hi-pot test.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. be the halogen-free fire-resistant engineering plastics of raw material with the waste PET bottle chips, form by following component by weight percentage:
2. plastics according to claim 1 is characterized in that:
Said phosphorus flame retardant is at least a in triphenylphosphate, Tritolyl Phosphate, tolyl diphenyl phosphoester and the polycondensation aryl phosphate ester;
Said nitrogen flame retardant is at least a in trimeric cyanamide, melamine salt and the ammonium polyphosphate;
The particle diameter of said nanoclay is 50～100nm.
3. plastics according to claim 2 is characterized in that:
Said polycondensation aryl phosphate ester is Resorcinol polycondensation aryl phosphate ester or polycondensation phenyl-phosphate;
Said melamine salt is melamine cyanurate salt, SULPHOSUCCINIC ACID ESTER melamine salt or poly phosphate melamine salt.
4. plastics according to claim 1 is characterized in that:
Said toughener is short glass fiber, thomel, glass microballon, ceramic fine bead, talcum powder, mica or the alkali-free long glass fibres that passes through the siloxanes coupling agent treatment;
Said toughner is the maleic anhydride graft polyolefin elastomer, it is at least a to have in the propenoate-glycidyl ester of epoxy-functional-ethylene copolymer, methacrylic ester-styrene-butadiene rubber(SBR)-styrol copolymer, ethylene-acrylate copolymer, ethylene vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer and the acrylonitrile ethylene styrene copolymer;
Said nucleator is at least a in talcum powder, zinc powder, zinc oxide, Sodium Benzoate, polyethyleneglycol diglycidylether, glycidyl ester Sipacril 2739OF, tetrafluoroethylene and the ethylene-acrylic acid copolymer sodium salt.
5. plastics according to claim 1 is characterized in that: said oxidation inhibitor is at least a in phenolic antioxidant, phosphite ester kind antioxidant and the metal passivator.
6. plastics according to claim 5 is characterized in that:
Said phenol antioxidant is β-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid, four (3; 5-di-t-butyl-4-4 phenylor), N, N '-hexylidene-1, [3-(3 for 6-two; 5-di-t-butyl-4-4 phenylor) propionic acid amide] and three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester at least a;
Said phosphite ester kind antioxidant is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester;
Said metal passivator is MD102.
7. plastics according to claim 1 is characterized in that: said waste PET bottle chips limiting viscosity is 0.4～0.6dl/g.
8. claim 1 is described is the preparation method of the halogen-free fire-resistant engineering plastics of raw material with the waste PET bottle chips, it is characterized in that, may further comprise the steps:
(1) with waste PET bottle chips in 100～140 ℃, forced air drying 3～6 hours;
(2) with stirring in the dry good waste PET bottle chips of step (1), toughner, phosphorus flame retardant, nitrogen flame retardant, nanoclay, nucleator and the oxidation inhibitor adding stirrer, obtain mixture;
(3) step (2) gained mixture is added in the twin screw extruder; Again dried toughener is introduced the forcing machine from the glass mouth; Through melt extruding granulation, extruded material is after cooling, air-dry, pelletizing, drying, and obtaining with the waste PET bottle chips is the halogen-free fire-resistant engineering plastics finished product of raw material.
9. preparation method according to claim 8 is characterized in that:
The said agitation condition of step (2) is: 300～500 rev/mins of rotating speeds, churning time 3～5 minutes;
The said drying of step (3) is that the alkali-free long glass fibres of siloxanes coupling agent treatment is 120～180 ℃ through temperature is that the glass moisture eliminator of 0.5～3m carries out drying with tube length; Or with short glass fiber, thomel, glass microballon, ceramic fine bead, talcum powder or mica at 110～170 ℃ of drying 2～4h;
The fabrication process condition of the said twin screw extruder of step (3) is following:
Temperature is: 170～200 ℃ in a district; 180～200 ℃ in two districts; 180～200 ℃ in three districts; 190～210 ℃ in four districts; 180～200 ℃ in five districts; 190～210 ℃ in six districts; 200～240 ℃ of heads;
20～40 ℃ of tank temperature;
Pressure is 11～17MPa;
Screw speed is 250～400rpm;
The dicing machine rotating speed is 600～1000rpm.
10. the application of the said plastics of claim 1 is characterized in that, said plastics are used to prepare transformer framework, switch connector, adapter skeleton, conducting strip, junctor, electromagnetic oven baking oven accessory, circuit breaker shell or blower accessory.
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| CN101974211A (en) * | 2010-10-14 | 2011-02-16 | 苏州市科创聚合物有限公司 | Inflaming retarding slot material prepared by recycling and modifying waste polyester bottle |
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| CN100425652C (en) * | 2005-12-13 | 2008-10-15 | 苏州市凯米克新材料有限公司 | High-performance reinforced fire-retardant polyster engineering plastic |
| CN101570629A (en) * | 2009-04-16 | 2009-11-04 | 从化市聚赛龙工程塑料有限公司 | Halogen-free flame retardant PC/PET composite material and preparation method thereof |
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