CN101817934B - Process for stress-induced desulfurization reaction of waste tire rubber - Google Patents
Process for stress-induced desulfurization reaction of waste tire rubber Download PDFInfo
- Publication number
- CN101817934B CN101817934B CN2010101572014A CN201010157201A CN101817934B CN 101817934 B CN101817934 B CN 101817934B CN 2010101572014 A CN2010101572014 A CN 2010101572014A CN 201010157201 A CN201010157201 A CN 201010157201A CN 101817934 B CN101817934 B CN 101817934B
- Authority
- CN
- China
- Prior art keywords
- rubber
- desulfurization
- reaction
- butyl
- product
- 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
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 93
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 76
- 230000023556 desulfurization Effects 0.000 title claims abstract description 74
- 229920001971 elastomer Polymers 0.000 title claims abstract description 66
- 239000005060 rubber Substances 0.000 title claims abstract description 66
- 239000010920 waste tyre Substances 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title abstract description 34
- 230000008569 process Effects 0.000 title abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 36
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 28
- 238000001125 extrusion Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 8
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000003490 calendering Methods 0.000 claims abstract description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 48
- -1 alcohols compound Chemical class 0.000 claims description 23
- 238000005516 engineering process Methods 0.000 claims description 13
- 239000002699 waste material Substances 0.000 claims description 13
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical group CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 11
- 229960002447 thiram Drugs 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000002530 phenolic antioxidant Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 239000000344 soap Substances 0.000 claims description 6
- 239000003017 thermal stabilizer Substances 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229920003052 natural elastomer Polymers 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 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
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 claims description 2
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 claims description 2
- BEKZTYVULLHLHB-UHFFFAOYSA-N 4,4-ditert-butyl-3-methylcyclohexa-1,5-dien-1-ol Chemical compound C(C)(C)(C)C1(C(C=C(C=C1)O)C)C(C)(C)C BEKZTYVULLHLHB-UHFFFAOYSA-N 0.000 claims description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 2
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 claims description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 claims 2
- FANGQVKSFHFPBY-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FANGQVKSFHFPBY-UHFFFAOYSA-N 0.000 claims 1
- 229920001400 block copolymer Polymers 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003723 Smelting Methods 0.000 abstract 1
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000565 sealant Substances 0.000 description 25
- 239000002174 Styrene-butadiene Substances 0.000 description 17
- 230000008859 change Effects 0.000 description 15
- 239000004743 Polypropylene Substances 0.000 description 13
- 239000003292 glue Substances 0.000 description 13
- 229920001155 polypropylene Polymers 0.000 description 13
- 238000005987 sulfurization reaction Methods 0.000 description 12
- 239000004636 vulcanized rubber Substances 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000012190 activator Substances 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- VUBOQPNQIMKEKI-UHFFFAOYSA-N 3,8-dithiatricyclo[5.1.0.02,4]oct-5-en-4-ol Chemical compound C12SC2C=CC2(O)C1S2 VUBOQPNQIMKEKI-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000012675 alcoholic extract Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007863 gel particle Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000010353 tongjiang Substances 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 1
- TXLINXBIWJYFNR-UHFFFAOYSA-N 4-phenylpyridine-2-carbonitrile Chemical compound C1=NC(C#N)=CC(C=2C=CC=CC=2)=C1 TXLINXBIWJYFNR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper 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
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000000813 microbial effect Effects 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/57—Screws provided with kneading disc-like elements, e.g. with oval-shaped elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention relates to a process for waste tire rubber stress induced desulfurization reaction, which comprises the steps of mixing a linear high molecular substance, waste tire rubber powder, a stabilizing auxiliary agent and a desulfurization promoter; and adding the mixture into a high-rotating-speed and high-shear co-rotating double-screw extruder, carrying out melt extrusion desulfurization reaction, and carrying out water cooling, grain cutting, drying or roller calendering, cooling and flaking on reaction products to obtain the desulfurization modified reclaimed rubber product. The invention integrates the desulphurization reaction and the processes of rough smelting, refining and rubber filtering of reaction products, has high desulphurization process efficiency, high yield, low energy consumption, easy large-scale and large-scale production, and easy control of the desulphurization reaction process; the desulfurization promoter can accelerate the desulfurization reaction and protect the molecular main chain and double bonds of the desulfurization product, thereby improving the probability of selective breakage of S-S bonds in the tire rubber cross-linked network. The reaction process has little pollution to the environment, and the mechanical property of the resulfurized material prepared by blending the desulfurization product with the styrene butadiene rubber is good.
Description
Technical field:
The present invention relates to a kind of technology of improved waste and old tyre rubber stress induced desulphurization reaction, belong to the modification field of polymer materials.
Background technology:
According to statistics, the output of present global annual doughnut is between 1,500,000,000 to 2,000,000,000, and is suitable with the junked tire quantity of scrapping every year.Because the developing rapidly of automotive industry, the production and consumption of China's tire presents a rapidly rising trend in recent years.China's tire ultimate production was about 4.33 hundred million in 2006, increased by 15% on a year-on-year basis; 2007 5.57 hundred million, increase by 23% on a year-on-year basis.After import and export offseted, the domestic needs amount had reached 300,000,000 at the most.Calculate by average turnover rate 70%, the quantum of output of junked tire has promptly reached more than 200,000,000, has occupied the second in the world.
The production of tire need consume a large amount of natural rubbers and synthetic rubber resource.According to the data report, in order to satisfy the demand of Chinese tire builder industry, the hylaeion hypotropicum of south east asia has suffered from felling without restraint, is seriously threatening the existence of rare animals such as elephant; And the bulk deposition of junked tire or unsuitable processing have caused very grave disaster to environment.Therefore under the situation that current oil spike, shortage of resources and environment quicken to worsen, quicken to explore effective comprehensive Utilization Ways of waste and old tyre rubber, alleviate environmental pressure, recycle waste rubber resources expeditiously, realize the green circulation of the basic raw material utilization of resources, be significant.
The tough matrix material of height that junked tire is made up of high-quality rubber, carbon black, organic fibre and steel wire etc. has huge internal economy and is worth.It as the heat energy material use, is easily produced a large amount of obnoxious flavour contaminate environment, and recycling economy is worth very low.Be used to prepare fuel oil, then the rubber sources waste greatly.Be prepared into trickle rubber powder as the blending material, the economic worth that it utilized is not high, can not give full play of the latent value of regeneration that it should possess.The consumption that original shape utilizes is then limited, can not in time digest the scrap rubber resource of this enormous amount.Have only high efficiency contrary vulcanization reaction---desulfurization regeneration, continue its rubber equivalent material as rubber items such as preparation tires is recycled waste rubber resources, be only really solution route effectively.
Yet waste and old tyre rubber has the molecular structure of three-dimensional network shape, does not melt, do not dissolve, and is difficult to reuse.Since vulcanization of rubber technological invention, develop a kind of contrary effectively sulfuration (being desulfurization) reaction technology, make the one-dimensional linear structure before its molecule returns to sulfuration, and, be the target that the various countries chemists lay siege to always simultaneously with good revulcanization activity.And develop for this reason and a series of desulfurization regeneration method and technology.Wherein the method for outbalance and technology have: early stage water/oil method, oil process, High Temperature High Pressure dynamic desulfurization, the mixing sulfur removal technology of DE-LINK low temperature etc.Recently the more method of report has: radiation and desulfuration method (microwave method), heat-mechanical force and chemical doctor treatment (twin-roll mixing or screw rod are extruded doctor treatment) and ultrasonic wave doctor treatment etc.But because these method ubiquity reaction process are incomplete, product gel content height, generally up to about 60%, can not fused gel particles size big, and often cause the minimizing of calculation in fracture of too much molecular backbone chain and the crosslinking activity, so gained reclaimed rubber quality product is relatively poor, the mechanical property of revulcanization material often can only reach about 1/3rd of former rubber vulcanizing material mechanical strength, do not have really to reach the purpose that to reuse separately, can not the blending of more ground among rubber, be used to prepare the tire use.
The pure power chemical desulfurization of relevant in addition solid-state powder method, microbial technique doctor treatment, supercritical CO
2Swelling doctor treatment etc. sees that also report is arranged, but still be in research at present, the exploitation among.
Generally speaking, in melt extruding in processing or the blend process of polymer materials, the shearing action of mechanical force is except having intensive blend effect, also can bring out the chain-breaking reaction of polymer materials melt, cause to produce macromolecular radical, the degraded that causes polymer materials, grafting, block or side reaction such as crosslinked, cause the physics of polymer materials and the change of chemical property.But general extruding under the processing conditions since the screw speed of forcing machine lower (≤200r/min), the effect of this kind reaction is not fairly obvious, is not usually paid attention to by people.Yet, in recent years along with twin screw extruder tool improvement of Manufacturing Technology, the driving screw rotating speed occurs up to high rotating speed, the high-shear type co-rotating twin screw extruder tool of 1200～3000r/min (be general twin screw extruder screw speed 5～10 times).Polymkeric substance and intermingling material thereof under so high shear stress field action condition, the degraded of its free radical type, grafting, block or to separate force-chemical reaction such as crosslinked very fierce, and caused the remarkable change of polymkeric substance and intermingling material performance thereof thus.This Chinese patent CN101168600A (application number 200710132935.5) proposed to melt extrude at tire glue powder add the linear polymeric material in the process as swelling agent and carrying fluid, and adopt the high shear stress induced method that improves the twin screw extruder screw speed, induce the chain rupture of waste-tyre rubber-powder, degraded to conciliate crosslinking reaction.According to this kind of report sulfur method the gel content of waste-tyre rubber-powder is dropped to about 20%, the molten gel particle size does not drop to below the 1.0 μ m; In this reclaimed rubber 30% blending and the styrene-butadiene rubber(SBR), the tensile strength of its revulcanization material can reach about 90% of former rubber vulcanizing material tensile strength, and elongation reaches about 120% of former rubber vulcanizing material.This method provides new approach for effective desulphurization reaction of waste-tyre rubber-powder.Yet under higher screw speed or higher extrusion temperature condition, this kind sulfur method also existence can cause and the problem of too much molecular backbone chain fracture and the decline of revulcanization tensile strength of material influenced the further raising of reclaimed rubber material property.The discharge of obnoxious flavoures such as more hydrogen sulfide and sulfurous gas is arranged in this kind method sweetening process on the other hand, influenced operating environment, and equipment is caused corrosion.
Similar with the effect of impact polymers such as light, heat and high-energy radiation, when the stress that acts on polymer molecular chain surpasses its threshold value, promptly can bring out the chain-breaking reaction of polymer molecular chain, produce macromolecular radical, cause the change of polymer degradation or chemical conduct such as crosslinked, cause the new chemical reaction of its macromolecular chain.Stress has directivity in addition, can cause in the crosslinked polymer network chain break perpendicular to stress direction, and it is constant to keep the chain length that is parallel to stress direction; Can quicken the relative movement between the macromolecular chain, suppress the crosslinking side reaction between the macromolecular chain, and not influence the reaction between macromolecular chain and the small molecules.In addition the bond energy of S-S (270kJ/mol), S-C (310kJ/mol) in the tire sealant cross-linked network and C-C (370kJ/mol) key relatively, the bond energy of S-S key is obviously lower.Therefore under higher shear stress field action condition, can realize reaction in theory to the preferential fracture of S-S key in the cross-linked network.Induce promotor to the provide protection of the attacking role of S-S key and stablizer when being aided with simultaneously as further, be expected to improve the probability of the selectivity fracture of S-S key, realize effectively separating crosslinking reaction backbone molecule.
U.S. Pat 6548560B1 and Chinese patent CN1517391A (application number 200410001214.7) reported respectively in 2003 and 2004 in addition, under high temperature, high pressure and organic alcohol compound existence condition, swelling and desulphurization reaction can take place in sulfurized rubber powder micelle surface.But this desulphurization reaction is to carry out in having the pressure pan of stirring, and technological process exists desulphurization reaction not exclusively to separate the problem of organic alcohol solvent with needs.
Summary of the invention:
Purpose of the present invention promptly is for improving the problem that existing sulfur method existence can cause that too much molecular backbone chain fracture and revulcanization tensile strength of material descend, influenced the further raising of reclaimed rubber material property, the discharge of obnoxious flavoures such as more hydrogen sulfide and sulfurous gas is arranged in the sweetening process, influenced operating environment, and equipment caused deficiencies such as corrosion and proposed a kind of technology of improved waste and old tyre rubber stress induced desulphurization reaction.
The technical solution adopted in the present invention is: a kind of technology of waste and old tyre rubber stress induced desulphurization reaction, its concrete steps are: A. will account for reactant gross weight percentage composition 5%-42% the linear polymeric material, to account for waste-tyre rubber-powder that the reaction-ure mixture percentage composition is 49%-85%, account for reactant gross weight percentage composition be that the stabilizing additive of 0.01%-2% is that the desulfurization promotor of 1%-8% is mixed mutually with accounting for reactant gross weight percentage composition; Wherein desulfurization promotor is the mixture of organic alcohols compound or organic alcohols compound and sulfide;
B. above-mentioned mixture is added in the co-rotating twin screw extruder of high rotating speed, high shear force in the lump, melt extrude desulphurization reaction;
C. reaction product through water-cooled, drying or through roller calendering cooling, in flakes, promptly obtain the reclaimed rubber product of desulfurization modification.
Wherein said linear polymeric material is polyethylene (PE), polypropylene (PP), Ethylene-Propylene Block Copolymer (copolymerization PP), ethylene-propylene random copolymer (EPR), ethylene-butene copolymer (LLDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-octene copolymer (POE), ethylene-propylene-dienes terpolymer (EPDM), hydrogenated styrene-butadiene-styrene block copolymers (SEBS), unvulcanized styrene-butadiene rubber(SBR) (SBR), in the rubber unvulcanizate of unvulcanized cis-1,4-polybutadiene rubber (BR) or unvulcanized natural rubber (NR) any one.
Wherein said waste-tyre rubber-powder is any one in 8 order to 80 purpose automobile radial rubber powders, automobile Bias tyre rubber powder, bicycle tyre rubber powder, sulfurized rubber plate or the sulfurized travelling belt rubber powder.
Its described stabilizing additive is the mixture of phenolic antioxidant and metal soap thermal stabilizers; The mass ratio of phenolic antioxidant and metal soap thermal stabilizers is 1: 1～1: 5.
Wherein said stabilizing additive is at least phenolic antioxidant, four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecanol ester of propionic acid (antioxidant 1076), 4,4 '-thiobis (2-methyl-6-tert butyl phenol) (oxidation inhibitor 736) or 1,3,5-three (3,5-di-t-butyl-4-hydroxyl Bian Ji) guanamine, 4,6-(1H, 3H, 5H)-a kind of in the triketone (antioxidant 3114); Described metal soap thermal stabilizers is at least a kind of in the mixture of calcium stearate, barium stearate or Zinic stearas.
Wherein said organic alcohols compound is at least a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol or the 4-methyl-2-amylalcohol.
Wherein said sulfide is a kind of in tetramethyl-thiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD) or the tetrabutylthiuram disulfide (TMTT); Perhaps be 2,2-curing two (6-tertiary butyl Pyrogentisinic Acid) (activator 420), 2,2-curing two (4,4-di-t-butyl-3-methylphenol) (activator 463) or 2, a kind of in the 2-curing two (single, two or three (α, alpha-alpha-dimethyl Bian Ji) phenol) (activators 901).The mass ratio of its organic alcohols compound and sulfide is 1: 5 to 5: 1.
The above-mentioned extrusion temperature that melt extrudes desulphurization reaction is 150-320 ℃; The screw speed of the co-rotating twin screw extruder of described high rotating speed, high-shear type is the co-rotating twin screw extruder of the second order of 400r/min-1600r/min to quadravalence, screw slenderness ratio is 24-60, forms by carrying screwing element, kneading screwing element, compression screwing element and left-hand thread element to mix.
Beneficial effect:
1. do not use small molecules desulfurization tenderizer, add linear macromolecule modified material and adopt, utilize the material modified infiltration of linear polymeric, swelling waste and old tyre rubber powder particles, desulphurization reaction is effective, and not existing organic molecule to influence product property or volatilize influences problem of environment.
2. desulphurization reaction is easy to control, and the desulphurization reaction degree can be adjusted according to screw speed, screw slenderness ratio, screw thread array configuration and temperature of reaction.
3. in sweetening process, be aided with the effect of organic alcohols compound desulfurization promotor, can make the SH, the SO that are produced in organic alcoholic extract hydroxyl group and the desulphurization reaction process
2Or～the SH effect, form mercaptan, sulfuric ester or thioether, desulphurization reaction is carried out to positive dirction, and reduced discharge of harmful gases in the sweetening process simultaneously.
4. formed dehydrogenation free radical of organic pure molecule and alpha-substitution base free radical can quicken the carrying out of desulphurization reaction and desulfurization product molecular backbone chain and two key thereof are played a protective role, and improve the probability of S-S key selectivity fracture in the tire sealant cross-linked network.
5. by changing the kind that linear polymeric adds material, utilize grafting or block reaction in the sweetening process, the consistency character that can modification desulfurization tire sealant or the molecular mass of expansion desulfurization tire sealant are to make things convenient for the different application of desulfurization tire sealant.
6. but adopt the primary device of the high-level efficiency twin screw extruder tool of serialization, automatization as desulphurization reaction; technological processs such as kneading, filter glue, refining are become one, can realize the desulfurization production of high-level efficiency, less energy-consumption, serialization, automatization and mass-producing.
7. in the relevant screw thread combined segment of twin screw extruder, be easy to install vacuum devolatilization device, realize the removing of small amount of exhaust gas, absorption and waste water circular treatment.
Description of drawings:
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is one of primary device of the present invention φ-35 twin screw extruder screw combinations figure; A-second venting port wherein, B-first venting port, C-charging opening.
Embodiment:
Below by embodiment the present invention is specifically described, it is important to point out that following examples only are used for the present invention is further detailed, can not be interpreted as limiting the scope of the invention.The person skilled in the art of this area can carry out some nonessential improvement and adjustment according to the invention described above content.
Embodiment 1 (adopting tire glue powder desulphurization reaction and the blending SBR rubber performance of sec-butyl alcohol) as promotor, tire glue powder (GTR) 20 orders, Tongjiang, Jiangsu plastic cement company limited provides, get through thermogravimetic analysis (TGA): rubber content is 42.9%, content of carbon black is 33.2%, the ash content of coal is 18.3%, and volatile content is 5.6%.
Above-mentioned tire glue powder 800 grams are mixed mutually with 200 gram EPDM (NDR4770 Dupont-Tao Shi company product), sec-butyl alcohol 50 grams, 2 gram antioxidant 1010s and 1.5 gram calcium stearates; It is 35mm that mixture adds screw diameter in the lump, and length-to-diameter ratio is (inferior mechanical means company limited of Nanjing section produces, and expressing technique and extrusion device screw combinations figure are referring to accompanying drawing 1 and accompanying drawing 2) in 45 the three rank co-rotating twin screw extruders; Control extrusion reaction temperature is 240 ℃, and the control screw speed is 1000r/min; In extrusion reaction, start water-ring vacuum pump, the volatile gases that produces during the vacuum removal desulphurization reaction; Extruding product promptly obtains desulfurization tire sealant product or claims desulfur blend thing (DGTR/EPDM) through water-cooled, drying.
Desulfurization tire sealant product through 150 order copper mesh wrap up, to get product gel content be 40.7% in the dimethylbenzene extracting; The colloidal sol that is dissolved in dimethylbenzene in the extractive process through acetone precipitating, drying, weighing obtains desulfurization tire sealant product colloidal sol.
With 30 parts of above-mentioned desulfurization tire sealant products, 70 parts in styrene-butadiene rubber(SBR) (1502 Jilin Chemical Industry Company product) and carbon black (N330, the meticulous carbon black plant of Wuxi City Su Xin product) 35 parts add co-blended in the double roll mill in the lump, add 2 parts in 2 parts in sulphur, 1.3 parts of promotor, 5 parts in zinc oxide, 2 parts of stearic acid and anti-aging agent simultaneously, mix and slice.The mixed sheet of gained was placed after 24 hours, and with 160 ℃ of vulcanizing press compressing tablets, curing time is 6 minutes, obtains the vulcanized rubber sheet; The vulcanized rubber sheet is placed after 24 hours and is measured mechanical property.
With reference to the tensile strength of this vulcanized rubber sheet of respective country standard test is that 19.3MPa, elongation at break are 567.3%, tear strength is that 89.5kN/m, Shao Shi A type hardness tester are 67.
The correlation data that can get embodiment 1 under the different screw condition by fixation reaction temperature change screw speed is as shown in table 1:
Table 1 screw speed is to the * that influences of DGTR/EPDM performance and SBR/ (DGTR/EPDM) sulfuration blend mechanical property
* desulfurization reaction temperature is 240 ℃, and desulfurization promotor is sec-butyl alcohol
The correlation data that can get embodiment 1 under the different extrusion reaction temperature condition by standing screw rotating speed change temperature of reaction is as shown in table 2:
Table 2 extrusion temperature is to the * that influences of DGTR/EPDM performance and SBR/ (DGTR/EPDM) sulfuration blend mechanical property
* the desulphurization reaction screw speed is 1000r/min, and desulfurization promotor is sec-butyl alcohol.
By data in table 1 and the table 2 as can be known, be under the condition of desulfurization promotor selecting sec-butyl alcohol for use, screw speed is 1000r/min and extrusion reaction temperature when being 240 ℃, desulphurization reaction effect and gained revulcanization material mechanical performance are optimum.
Comparative example 1 (sulfuration styrene-butadiene rubber(SBR) mechanical property): with 100 parts in styrene-butadiene rubber(SBR) (1502 Jilin Chemical Industry Company product) and carbon black (N330, the meticulous carbon black plant of Wuxi City Su Xin product) 40 parts (the control content of carbon black is close with embodiment 1) adds co-blended in the double roll mill in the lump, add 2 parts in 2 parts in sulphur, 1.3 parts of promotor, 5 parts in zinc oxide, 2 parts of stearic acid and anti-aging agent simultaneously, mix and slice.The mixed sheet of gained was placed after 24 hours, and with 160 ℃ of vulcanizing press compressing tablets, curing time is 6 minutes, obtains the vulcanized rubber sheet.The vulcanized rubber sheet is placed after 24 hours and is measured mechanical property, records tensile strength and be 22.0MPa, elongation at break and be 391%, tear strength is that 37.1kN/m, Shao Shi A type hardness tester are 63.
Above comparative example data show, when adopting 30 parts of desulfurization tire sealant products of the present invention to substitute styrene-butadiene rubber(SBR), the tensile strength of its gained vulcanized rubber material, elongation at break and tear strength reach 87.7%, 145% and 241% of former styrene-butadiene rubber(SBR) vulcanizing material respectively.
Comparative example 2 (not adding the tire glue powder desulphurization reaction and the blending SBR rubber performance of desulfurization promotor): do not use sec-butyl alcohol as desulphurization reaction promotor, other is identical with embodiment 1.Gained desulfurization tire sealant product gel content is 40.7%, and the tensile strength of vulcanized rubber sheet is that 17.0MPa, elongation at break are 501%, tear strength is that 37.1kN/m, Shao Shi A type hardness tester are 66.
The correlation data that can get comparative example 2 under the differential responses temperature condition by standing screw rotating speed change extrusion reaction temperature is as shown in table 3:
Table 3 extrusion temperature is to the * that influences of DGTR/EPDM performance and SBR/ (DGTR/EPDM) sulfuration blend mechanical property
* the desulphurization reaction screw speed is 1000r/min, does not add desulfurization promotor
The correlation data that can get comparative example 2 under the different screw condition by fixation reaction temperature change screw speed is as shown in table 4:
Table 4 screw speed is to the * that influences of DGTR/EPDM performance and SBR/ (DGTR/EPDM) sulfuration blend mechanical property
* desulfurization reaction temperature is 180 ℃, does not add desulfurization promotor
Data presentation in above comparative example 2 series (table 3, table 4): desulfurization tire sealant product gel content and revulcanization material mechanical performance all are worse than pairing data in embodiment 1 series (table 1, table 2), the gel content of desulfurization tire sealant product is 44.2% under the wherein optimum desulfurization condition, the tensile strength of revulcanization material, elongation at break and tear strength are respectively 18.1MPa, 510% and 32.3kN/m, be worse than the data (gel content 40.7%, tensile strength 19.3MPa and elongation at break 567% and 89.5kN/m) of embodiment 1 material correspondence.Illustrate that desulfurization promotor sec-butyl alcohol helps the carrying out of desulphurization reaction and to the provide protection of product molecular backbone chain, improves the probability of S-S key selectivity fracture in the tire sealant cross-linked network.
Embodiment 2 (selecting car tires tyre surface rubber powder for use): tire glue powder is changed into the 10 order car tires tyre surface rubber powders (GTR) that provide by the green ring waste old recovery of Yangzhou company limited also with the tire glue powder desulphurization reaction and the blending SBR rubber performance of sec-butyl alcohol as desulfurization promotor, get through thermogravimetic analysis (TGA): rubber content is 46.8%, content of carbon black is 33.8%, the ash content of coal is 12.1%, and volatile content is 7.3%.Other is same as embodiment 1.The gel content of gained desulfurization tire sealant product is 29.3%, and the tensile strength of vulcanized rubber sheet is that 18.5MPa, elongation at break are 887.6%, tear strength is that 94.8kN/m, Shao Shi A type hardness tester are 62.
Embodiment 2 product gel content are 29.3% to be starkly lower than the gel content 40.7% of embodiment 1 product, the cross-linking density of the cross-linking density of car tires tyre surface rubber powder less than the truck tyre rubber powder is described, so the gel content of products therefrom is obviously lower under the same desulfurization condition.
The correlation data that can get embodiment 2 under the different screw condition by fixing extrusion reaction temperature change screw speed is as shown in table 5:
Table 5 screw speed is to the * that influences of DGTR/EPDM performance and SBR/ (DGTR/EPDM) sulfuration blend mechanical property
* desulfurization reaction temperature is 240 ℃, and desulfurization promotor is sec-butyl alcohol
Embodiment 3 (select car tires tyre surface rubber powder for use and adopt tire glue powder desulphurization reaction and the blending SBR rubber performance of the trimethyl carbinol as desulfurization promotor): change desulphurization reaction promotor into the trimethyl carbinol by sec-butyl alcohol, other is same as embodiment 2.Gained desulfurization tire sealant product gel content is 32.6%, and the tensile strength of vulcanized rubber sheet is that 16.1MPa, elongation at break are 864.5%, tear strength is that 86.7kN/m, Shao Shi A type hardness tester are 60.
The correlation data that can get embodiment 3 under the different screw condition by fixing extrusion reaction temperature change screw speed is as shown in table 6:
Table 6 screw speed is to the influence of DGTR/EPDM performance and SBR/ (DGTR/EPDM) sulfuration blend mechanical property
* desulfurization reaction temperature is 240 ℃, and desulfurization promotor is the trimethyl carbinol
Embodiment 4 (selecting car tires tyre surface rubber powder for use also with tire glue powder desulphurization reaction and the blending SBR rubber performance of propyl carbinol as desulfurization promotor): change desulphurization reaction promotor into propyl carbinol by sec-butyl alcohol, other is same as embodiment 2.The gel content of gained desulfurization tire sealant product is 33.7%, and the tensile strength of vulcanized rubber sheet is that 16.4MPa, elongation at break are 878.7%, tear strength is that 81.7kN/m, Shao Shi A type hardness tester are 64.
The correlation data that can get embodiment 3 under the different screw condition by fixing extrusion reaction temperature change screw speed is as shown in table 7:
Table 7 screw speed is to the * that influences of DGTR/EPDM performance and SBR/ (DGTR/EPDM) sulfuration blend mechanical property
* desulfurization reaction temperature is 240 ℃, and desulfurization promotor is propyl carbinol
Data comparative descriptions in table 5, table 6 and the table 7, when screw speed is 1000r/min and under 240 ℃ the condition, the gel content of gained desulfurization tire sealant product is lower when being desulfurizing assistant agent with the sec-butyl alcohol, and tensile strength, elongation at break and the tear strength of blending material in styrene-butadiene rubber(SBR) are all higher.
Embodiment 5 (select for use car tires tyre surface rubber powder and with sec-butyl alcohol and tetramethyl-thiuram disulfide (TMTD) reaction and blending SBR rubber performance): change sec-butyl alcohol 50 grams of desulphurization reaction promotor into 30 and restrain as composite desulfate promotor, tetramethyl-thiuram disulfide (TMTD) 20 grams, other is same as embodiment 2.Gained desulfurization tire sealant product gel content is 35.9%, and the tensile strength of vulcanized rubber sheet is that 19.3MPa, elongation at break are 1503%, tear strength is that 44.5kN/m, Shao Shi A type hardness tester are 65.
The correlation data that can get embodiment 5 under the different screw condition by fixing extrusion reaction temperature change screw speed is as shown in table 8:
Table 8 screw speed is to the * that influences of DGTR/EPDM performance and SBR/ (DGTR/EPDM) sulfuration blend mechanical property
* desulfurization reaction temperature is 240 ℃, and desulfurization promotor is sec-butyl alcohol 3%, tetramethyl-thiuram disulfide (TMTD) 2%
Embodiment 6 (select for use car tires tyre surface rubber powder and with sec-butyl alcohol and polyalkylbenzene phenol disulphide (activator 420) reaction and blending SBR rubber performance): change sec-butyl alcohol 50 grams of desulphurization reaction promotor into 30 and restrain as composite desulfate promotor, polyalkylbenzene phenol disulphide (activator 420) 20 grams, other is same as embodiment 2.Gained desulfurization tire sealant product gel content is 35.7%, and the tensile strength of vulcanized rubber sheet is that 20.5MPa, elongation at break are 830%, tear strength is that 42.0kN/m, Shao Shi A type hardness tester are 69.
Changing the extrusion reaction temperature by fixing extruder screw rotating speed, can to get the correlation data of embodiment 6 under the condition of different temperatures as shown in table 9:
Table 9 extrusion temperature is to the * that influences of DGTR/EPDM performance and SBR/ (DGTR/EPDM) sulfuration blend mechanical property
* the desulphurization reaction screw speed is 1000r/min, and desulfurization promotor is sec-butyl alcohol 3%, polyalkylbenzene phenol disulphide (activator 420) 2%
Data declaration in above embodiment 5 and embodiment 6 and table 8 and the table 9, adopt sec-butyl alcohol and tetramethyl-thiuram disulfide (TMTD), or when adopting sec-butyl alcohol and polyalkylbenzene phenol disulphide (activator 420) as compound accelerant, though the gel content of desulfurization product is a little more than embodiment 2, the tensile strength of its blend styrene-butadiene rubber(SBR) revulcanization material and elongation at break all are better than the corresponding numerical value in embodiment 2 series.Show the chain transfer reaction that is beneficial to free radical in the reaction system that has of polythio aminocompound or polyalkylbenzene phenol disulphide, help provide protection, improve the probability of S-S key selectivity fracture in the tire sealant cross-linked network the desulfurization product molecular backbone chain.
Embodiment 7:(car tires tyre surface rubber powder blend POE thermoplastic elastomer desulphurization reaction and preparation PP dynamic crosslinking thermoplastic elastomer performance) tire glue powder (10 orders, the green ring waste old of Yangzhou reclaims company limited and provides) 700 grams are mixed mutually with 300 gram POE (Dupont-the Dow Chemical Company's product), 2 gram antioxidant 1076s and 3 gram barium stearates; Sec-butyl alcohol 20 grams, 2,2-curing two (6-tertiary butyl Pyrogentisinic Acid) (activator 420) 20 grams mix mutually; It is 35mm that mixture adds screw diameter in the lump, and length-to-diameter ratio is (inferior mechanical means company limited of Nanjing section produces, and expressing technique and extrusion device screw combinations figure are referring to accompanying drawing 1 and accompanying drawing 2) in 45 the three rank co-rotating twin screw extruders; Control extrusion reaction temperature is 240 ℃, and the control screw speed is 1000r/min; In extrusion reaction, start water-ring vacuum pump, the volatile gases that produces during the vacuum removal desulphurization reaction; Extruding product promptly obtains desulfurization tire sealant product or claims the desulfur blend thing through water-cooled, drying.The gel content of gained desulfurization product is 34.0% after measured.
With above-mentioned desulfurization tire sealant product 600 grams, polypropylene (PP F401, raising sub-petro-chemical corporation produces) 400 grams add co-blended in 170 ℃ the double roll mill in the lump, add initiator DCP 20 gram, sulphur 5 grams, zinc oxide 40 grams, stearic acid 5 grams, altax 10 grams, CZ 5 grams and antioxidant 4010 5 grams simultaneously, mix, dynamic vulcanization and slice.The dynamic vulcanization film of gained was placed after 24 hours, and preheating is 10 minutes on 170 ℃ of vulcanizing presses, pressurize 10 minutes, and mold pressing is in blocks.Obtain DGTR/POE/PP (48/12/40) dynamic crosslinking thermoplastic elastic material.
Above-mentioned dynamic crosslinking thermoplastic elastomer gets tensile strength 11.2MPa by the relevant criterion test, elongation at break 123%, and tear strength is 53.5kN/m, Shao Shi A type hardness tester 94.3.
Embodiment 8 (tire glue powder blend POE thermoplastic elastomer desulphurization reaction and Toughened PP material mechanical performance): tire glue powder (20 orders, Tongjiang, Jiangsu plastic cement company limited provides) 800 grams are mixed mutually with 200 gram POE (Dupont-the Dow Chemical Company's product), 40 gram sec-butyl alcohols, 0.15 gram antioxidant 1010 and 0.3 gram calcium stearate; It is 35mm that mixture adds screw diameter in the lump, and length-to-diameter ratio is (expressing technique and extrusion device screw combinations figure is referring to accompanying drawing 1 and accompanying drawing 2) in 45 the three rank co-rotating twin screw extruders; Control extrusion reaction temperature is 240 ℃, and the control screw speed is 1000r/min; In extrusion reaction, start water-ring vacuum pump, the volatile gases that produces when vacuum is deviate from desulphurization reaction; Extrude product and promptly obtain desulfurization tire sealant product (DGTR/POE) through water-cooled, pelletizing, drying.Gained desulfurization tire sealant product gel content is 43.4% after measured.
30 parts of desulfurization products and PP (J340, raising sub-petro-chemical corporation produces) 70 parts mix, adding screw diameter in the lump is 20mm, length-to-diameter ratio is that melt blending closes in 32 the three rank co-rotating twin screw extruders, driving screw rotating speed 200r/min, extrude 200 ℃ of blending temperatures, extrudate promptly obtains elastic body toughening PP material (PP/DGTR/POE (70/24/6)) through water-cooled, pelletizing, drying.
This elastic body toughening PP material is measured material mechanical performance by relevant criterion and is got: socle girder notched impact strength 34.4kJ/m through 220 ℃ of injection moulding sample preparations
2, tensile strength 30.3MPa, elongation at break 506%, melt flow rate (MFR) (230 ℃, 2.16kg load) 2.52g/10min.
The correlation data that can get embodiment 8 under the different screw by the screw speed that changes desulphurization reaction is as follows:
Table 10 screw speed is to the * that influences of DGTR/POE performance and PP/DGTR/POE intermingling material mechanical property
* desulfurization reaction temperature is 240 ℃, and desulfurization promotor is sec-butyl alcohol 4%
The mechanism of this organic alcohols compound promoted desulphurization reaction is: the SH, the SO that are produced in (1) organic alcoholic extract hydroxyl group and the desulphurization reaction process
2Or～the SH effect, form mercaptan, sulfuric ester or thioether, desulphurization reaction is carried out to positive dirction, and reduced discharge of harmful gases in the sweetening process simultaneously.(2) because the influence of hydroxyl; in the alcohol molecule with carbon atom that hydroxyl is connected on α-hydrogen atom more active; form dehydrogenation free radical and alpha-substitution base free radical easily; the attacking role of S-S key can be quickened the carrying out of desulphurization reaction in the dehydrogenation radical pair cross-linked network, and the coupling of the macromolecular radical that produces when alpha-substitution base free radical and desulphurization reaction or chain transfer can play provide protection to desulfurization product molecular backbone chain and two key thereof.
Claims (3)
1. the technology of a waste and old tyre rubber stress induced desulphurization reaction, its concrete steps are:
A. will account for reactant gross weight percentage composition 5%-42% the linear polymeric material, to account for waste-tyre rubber-powder that the reaction-ure mixture percentage composition is 49%-85%, account for reactant gross weight percentage composition be that the stabilizing additive of 0.01%-2% is that the desulfurization promotor of 1%-8% is mixed mutually with accounting for reactant gross weight percentage composition; Wherein desulfurization promotor is the organic alcohols compound, or the mixture of organic alcohols compound and sulfide, wherein the mass ratio of organic alcohols compound and sulfide is 1: 5 to 5: 1 in the mixture of organic alcohols compound and sulfide, wherein the organic alcohols compound is at least methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, a kind of in amylalcohol or the 4-methyl-2-amylalcohol, sulfide is tetramethyl-thiuram disulfide, tetraethylthiuram disulfide or tetrabutylthiuram disulfide, 2,2-curing two (6-tertiary butyl Pyrogentisinic Acid), 2,2-curing two (4,4-di-t-butyl-3-methylphenol) or 2, the 2-curing is two (single, two or three (α, alpha-alpha-dimethyl Bian Ji) phenol) a kind of in; Wherein said linear polymeric material is any one in the rubber unvulcanizate of polyethylene, polypropylene, Ethylene-Propylene Block Copolymer, ethylene-propylene random copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-octene copolymer, ethylene-propylene-dienes terpolymer, hydrogenated styrene-butadiene-styrene block copolymers, unvulcanized styrene-butadiene rubber(SBR), unvulcanized cis-1,4-polybutadiene rubber or unvulcanized natural rubber; Described stabilizing additive is the mixture of phenolic antioxidant and metal soap thermal stabilizers; The mass ratio of phenolic antioxidant and metal soap thermal stabilizers is 1: 1～1: 5;
B. above-mentioned mixture is added in the lump in the co-rotating twin screw extruder of high rotating speed, high-shear type, melt extrude desulphurization reaction; The extrusion temperature that wherein melt extrudes desulphurization reaction is 150-320 ℃; The screw speed of the co-rotating twin screw extruder of described high rotating speed, high-shear type is the co-rotating twin screw extruder of the second order of 400r/min-1600r/min to quadravalence, screw slenderness ratio is 24-60, forms by carrying screwing element, kneading screwing element, compression screwing element and left-hand thread element to mix;
C. reaction product through water-cooled, drying or through roller calendering cooling, in flakes, promptly obtain the reclaimed rubber product of desulfurization modification.
2. technology according to claim 1 is characterized in that described waste-tyre rubber-powder is any one in 8～80 purpose automobile radial rubber powders, automobile Bias tyre rubber powder, bicycle tyre rubber powder, sulfurized rubber plate or the sulfurized travelling belt rubber powder.
3. technology according to claim 1, it is characterized in that described phenolic antioxidant is at least four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, the β-positive octadecanol ester of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, 4,4 '-thiobis (2-methyl-6-tert butyl phenol) or 1,3,5-three (3,5-di-t-butyl-4-hydroxyl Bian Ji) guanamine, 4,6-(1H, 3H, 5H)-a kind of in the triketone; Metal soap thermal stabilizers is at least a kind of in calcium stearate, barium stearate or the Zinic stearas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101572014A CN101817934B (en) | 2010-04-26 | 2010-04-26 | Process for stress-induced desulfurization reaction of waste tire rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101572014A CN101817934B (en) | 2010-04-26 | 2010-04-26 | Process for stress-induced desulfurization reaction of waste tire rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101817934A CN101817934A (en) | 2010-09-01 |
| CN101817934B true CN101817934B (en) | 2011-08-31 |
Family
ID=42653220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101572014A Expired - Fee Related CN101817934B (en) | 2010-04-26 | 2010-04-26 | Process for stress-induced desulfurization reaction of waste tire rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101817934B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4098683A1 (en) * | 2017-05-28 | 2022-12-07 | Tyrec Ltd. | Method for producing recycled thermoplastic rubber masterbatch with improved green strength and tack |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073741B (en) * | 2012-12-26 | 2015-02-18 | 南京工业大学 | Method for inducing devulcanization reaction of vulcanized rubber powder by subcritical water extrusion method through stress |
| RS64817B1 (en) * | 2016-11-18 | 2023-12-29 | New Born Rubber License B V | Method for reclaiming rubber, and renewed rubber compositions obtainable thereby |
| CN107955205A (en) * | 2017-12-15 | 2018-04-24 | 马如其 | Devulcanization of rubber refines all-in-one machine |
| CN110746645A (en) * | 2019-09-23 | 2020-02-04 | 安徽省含山县锦华氧化锌厂 | Melting auxiliary agent for recycling rubber particles |
| EP4204198A4 (en) * | 2020-08-31 | 2024-09-04 | Ceat Ltd | A method for devulcanization of rubber |
| CN118256029A (en) * | 2024-04-02 | 2024-06-28 | 江苏海洋大学 | Preparation method of composite natural rubber of reclaimed rubber powder of waste tire with controllable molecular weight |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346840A (en) * | 1995-10-27 | 2002-05-01 | 埃克森研究工程公司 | Method of devulcanization of rubber |
| US6548560B1 (en) * | 2000-03-29 | 2003-04-15 | The Goodyear Tire & Rubber Company | Process for devulcanization of cured rubbers |
| CN1517391A (en) * | 2003-01-03 | 2004-08-04 | ��������̥��˾ | Desulfurization of sulfurized rubber |
| CN101168600A (en) * | 2007-09-20 | 2008-04-30 | 南京工业大学 | High shear stress induced desulfurization and modification method for waste tire rubber |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4046209B2 (en) * | 1998-07-24 | 2008-02-13 | 東洋ゴム工業株式会社 | Recycled vulcanized rubber |
-
2010
- 2010-04-26 CN CN2010101572014A patent/CN101817934B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346840A (en) * | 1995-10-27 | 2002-05-01 | 埃克森研究工程公司 | Method of devulcanization of rubber |
| US6548560B1 (en) * | 2000-03-29 | 2003-04-15 | The Goodyear Tire & Rubber Company | Process for devulcanization of cured rubbers |
| CN1517391A (en) * | 2003-01-03 | 2004-08-04 | ��������̥��˾ | Desulfurization of sulfurized rubber |
| CN101168600A (en) * | 2007-09-20 | 2008-04-30 | 南京工业大学 | High shear stress induced desulfurization and modification method for waste tire rubber |
Non-Patent Citations (3)
| Title |
|---|
| Debapriya De等."Reclaiming of ground rubber tire(GRT) by a novel reclaiming agent".《EUROPEAN POLYMER JOURNAL》.2005,第42卷(第4期),917-927. |
| JP特开200095895A 2000.04.04 |
| 沈季等."轮胎胶应力诱导脱硫及热塑性弹性体的制备".《高分子材料科学与工程》.2009,第25卷(第1期),118-121. |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4098683A1 (en) * | 2017-05-28 | 2022-12-07 | Tyrec Ltd. | Method for producing recycled thermoplastic rubber masterbatch with improved green strength and tack |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101817934A (en) | 2010-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101168600B (en) | High shear stress induced desulfurization and modification method for waste tire rubber | |
| CN101817934B (en) | Process for stress-induced desulfurization reaction of waste tire rubber | |
| KR100901561B1 (en) | Continuous process for devulcanization of reclaimed rubber in a extruder | |
| CN102977404B (en) | Method for continuous preparation of reclaimed rubber by using dual-band twin-screw extruder | |
| CN102911399B (en) | Method for regenerating waste rubber by different-screwing-direction double-screw extruder | |
| CN101508795B (en) | Method for desulfurization regeneration of vulcanized rubber by employing double-screw extruder | |
| CN103073741B (en) | Method for inducing devulcanization reaction of vulcanized rubber powder by subcritical water extrusion method through stress | |
| CN108219192B (en) | Method for producing environment-friendly reclaimed rubber through low-temperature desulfurization | |
| CN102816343B (en) | Method for preparing reclaimed rubber by continuous low-temperature high shear | |
| CN101418082A (en) | Green desulfurization technique of waste rubber | |
| CN114058097B (en) | High-performance uncrosslinked rubber asphalt and preparation method thereof | |
| CN105175976B (en) | Composite toughening modifier and its preparation method and application | |
| CN111961309A (en) | Modified ABS reclaimed material and preparation method thereof | |
| CN102020807A (en) | High-performance environment-friendly polypropylene blending material and preparation method thereof | |
| CN102501335B (en) | Novel process for reducing and regenerating waster rubber continuously | |
| WO2022152182A1 (en) | Modified cross-linked polyethylene and preparation method therefor, and recycled product and preparation method therefor | |
| CN115490939A (en) | High-strength wear-resistant regenerated rubber prepared from waste tires | |
| WO2001014464A1 (en) | Thermoplastic elastomer produced from waste rubber powder/plastic and the article made therefrom | |
| CN113150413B (en) | Liquid-containing reclaimed rubber conveyer belt cover rubber material and preparation method thereof | |
| CN1528815A (en) | In situ modified waste rubber powder composite material and preparing method thereof | |
| CN103834058A (en) | Method for inducing devulcanization reaction of vulcanized rubber powder by subcritical alcohol extrusion stress | |
| CN112724480A (en) | BR/SBR composite rubber, thermoplastic elastomer and ABS reinforced plastic | |
| CN103012895A (en) | Mixed regenerated rubber and preparation method thereof | |
| CN111718555A (en) | Sealing strip material based on partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer and preparation thereof | |
| WO2023138055A1 (en) | Light anti-cracking rubber sole and preparation method therefor |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110831 Termination date: 20130426 |