CN115785522B - Azeotroping agent generating system and thermoplastic vulcanized rubber - Google Patents
Azeotroping agent generating system and thermoplastic vulcanized rubber Download PDFInfo
- Publication number
- CN115785522B CN115785522B CN202211500970.9A CN202211500970A CN115785522B CN 115785522 B CN115785522 B CN 115785522B CN 202211500970 A CN202211500970 A CN 202211500970A CN 115785522 B CN115785522 B CN 115785522B
- Authority
- CN
- China
- Prior art keywords
- area
- entrainer
- tert
- rubber
- vulcanizing agent
- 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.)
- Active
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 41
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 12
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 12
- 239000004636 vulcanized rubber Substances 0.000 title claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 28
- 239000004743 Polypropylene Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- 229920001155 polypropylene Polymers 0.000 claims abstract description 23
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 17
- -1 polypropylene Polymers 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 14
- 239000004014 plasticizer Substances 0.000 claims abstract description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 31
- 229920006342 thermoplastic vulcanizate Polymers 0.000 claims description 29
- 229920001971 elastomer Polymers 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 18
- 239000005060 rubber Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000004073 vulcanization Methods 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 239000010456 wollastonite Substances 0.000 claims description 6
- 229910052882 wollastonite Inorganic materials 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 5
- LIXPMKNZESBUKY-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(O)(C(CO)(CO)CO)C1=CC(=C(C(=C1)C(C)(C)C)C)C(C)(C)C)C(C)(C)C)C Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(O)(C(CO)(CO)CO)C1=CC(=C(C(=C1)C(C)(C)C)C)C(C)(C)C)C(C)(C)C)C LIXPMKNZESBUKY-UHFFFAOYSA-N 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 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 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000002656 Distearyl thiodipropionate Substances 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 4
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019305 distearyl thiodipropionate Nutrition 0.000 claims description 4
- 125000002917 halogen containing inorganic group Chemical group 0.000 claims description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims description 3
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 3
- 239000005662 Paraffin oil Substances 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 2
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 2
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 229960003742 phenol Drugs 0.000 claims 2
- BSKJUAKMZZKMKC-UHFFFAOYSA-N 1,2-ditert-butyl-3,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)(C)C)C(C(C)(C)C)=C1C(C)C BSKJUAKMZZKMKC-UHFFFAOYSA-N 0.000 claims 1
- KJEKRODBOPOEGG-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n-[3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoylamino]propyl]propanamide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 KJEKRODBOPOEGG-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 150000008301 phosphite esters Chemical class 0.000 claims 1
- 229920005606 polypropylene copolymer Polymers 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 229920005604 random copolymer Polymers 0.000 claims 1
- 229920006027 ternary co-polymer Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 34
- 229920002725 thermoplastic elastomer Polymers 0.000 abstract description 18
- 230000008901 benefit Effects 0.000 abstract description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000012855 volatile organic compound Substances 0.000 description 38
- 238000000034 method Methods 0.000 description 24
- 239000000126 substance Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000009835 boiling Methods 0.000 description 10
- 239000000806 elastomer Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 5
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical group CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000010690 paraffinic oil Substances 0.000 description 3
- 239000011265 semifinished product Substances 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 150000005323 carbonate salts Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 description 1
- KPIUMNFVTXCIAJ-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)-n-[3-[2-(3,5-ditert-butyl-4-hydroxyphenyl)propanoylamino]propyl]propanamide Chemical compound C=1C(C(C)(C)C)=C(O)C(C(C)(C)C)=CC=1C(C)C(=O)NCCCNC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 KPIUMNFVTXCIAJ-UHFFFAOYSA-N 0.000 description 1
- ZPMCCZKDFLIVHD-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylpropane;1,2-di(propan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C.CC(C)C1=CC=CC=C1C(C)C ZPMCCZKDFLIVHD-UHFFFAOYSA-N 0.000 description 1
- 235000003332 Ilex aquifolium Nutrition 0.000 description 1
- 235000002296 Ilex sandwicensis Nutrition 0.000 description 1
- 235000002294 Ilex volkensiana Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an entrainer generating system and thermoplastic vulcanized rubber, wherein the entrainer generating system comprises carbonate and weak acid, and the acidity of the weak acid is greater than that of carbonic acid; the thermoplastic vulcanized rubber comprises a component A and an entrainer generating system, wherein the component A comprises EPDM rubber, polypropylene, a filler, a plasticizer, a lubricant, an antioxidant and a vulcanizing agent; the entrainer generating system accounts for 1-10% of the component A by mass. The thermoplastic vulcanized rubber obtained by the invention has the performance reaching the international similar product level, and compared with the most advanced technology in the industry, the odor advantage exceeds 0.5 level, the VOC data is in the dominant position as a whole, and the advantages of the odor and the VOC lead the thermoplastic vulcanized rubber to be uniformly approved and well-appreciated in the whole automobile material industry, thereby greatly improving the use space of the thermoplastic elastomer and expanding the application amount of the market.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an entrainer generation system and thermoplastic vulcanized rubber.
Background
Along with the enhancement of environmental awareness, the process of replacing traditional rubber with thermoplastic elastomer is continuously accelerated, and besides the basic performance requirement of the thermoplastic elastomer for vehicles, the thermoplastic elastomer for vehicles is required to meet the environmental protection and green problem, and the problems of smell, VOC and the like of the thermoplastic elastomer are solved, so that the thermoplastic elastomer can be dominant in the market.
The existing methods for reducing odor and VOC comprise a shielding method, a chemical deodorant deodorizing method, a physical adsorption method, a devolatilization baking method, a gas method or an azeotropic method, and the like, and the azeotropic method is the only effective method for removing deep low molecular substances on the premise that the azeotropic agent can fully play a role in a plurality of common methods for reducing odor and VOC, and is limited by the prior art, so that the effect of the azeotropic agent is low and is far from expectations.
The patent CN 108997703A aims at solving the problems that the existing liquid entrainer is not easy to fuse with paste in a molten state to reduce odor and VOC (volatile organic compound) and has low efficiency, the stripping agent in solid or paste form is used for premixing with raw materials, ethanol in the stripping agent and the paste in the molten state of the thermoplastic elastomer are uniformly mixed during melt extrusion, the ethanol escapes from the paste in the form of bubbles, small molecular organic matters contained in the paste are dissolved in the bubbles during the process, the paste is discharged along with the bubbles, the VOC content in the paste is reduced, and a low-VOC product is obtained after extrusion and cooling. However, the disadvantage is that in the actual production process, the low boiling point organic matter is quickly gasified at the moment of adding into the screw, and is usually lost from the exhaust port in the cylinder before the material and the high boiling point organic matter form a homogeneous system, even if the exhaust port is not provided, the gas floats on the surface of the material and is difficult to enter the interior to combine with the high boiling point organic matter, so that the action efficiency of the low boiling point matter is very low, and the effects of effectively removing VOC and reducing odor are very limited.
The patent CN105367987A solves the problems in the process, and the particles after the granulation in the manufacturing process are volatilized through a high-vacuum and high-hot air circulation system to prepare the thermoplastic elastomer material with low emission and low odor, but the limitation is that only micromolecule substances formed by the material can be volatilized, the micromolecule substances which cannot be volatilized in the material can not be thoroughly solved, and the high-hot air circulation process has longer time consumption, lower efficiency and larger energy consumption, so that the odor and VOC (volatile organic compound) can not be reduced to an ideal state.
Whether rubber materials or plastic materials, including the current novel materials thermoplastic elastomer materials, have odor and VOC problems, and the main sources are as follows:
Firstly, the material itself contains low molecular substances, and has certain odor and VOC;
Secondly, under the actions of heat, shearing and the like, the material can generate odor substances and VOC again;
Thirdly, the material has complex formula, a large number of chemical reaction processes, high probability of generating low-molecular odor substances and VOC, and difficulty in avoiding, and the odor and VOC of the material can not meet the existing requirements along with the gradual improvement of the requirements of various automobile factories and other factories.
Therefore, in order to meet the market demand, to solve the problems of low efficiency of reducing odor and VOC, low efficiency of acting an entrainer and oxidative degradation odor of materials in the process of preparing and improving an elastomer in the prior art, it is necessary to provide an entrainer capable of deeply and efficiently treating odor and VOC so as to obtain a thermoplastic vulcanizate with low odor and low VOC.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention provides an entrainer generation system and thermoplastic vulcanizate, the entrainer generation system comprising a carbonate salt and a weak acid, the acidity of the weak acid being greater than that of carbonic acid; thermoplastic vulcanizates (TPV) comprising component a and an entrainer generating system, component a comprising EPDM rubber, polypropylene, filler, plasticizer, lubricant, antioxidant, vulcanizing agent; the entrainer generating system accounts for 1-10% of the component A by mass. The thermoplastic vulcanized rubber obtained by the invention has the performance reaching the international similar product level, and compared with the most advanced technology in the industry, the odor advantage exceeds 0.5 level, the VOC data is in the dominant position as a whole, and the advantages of the odor and the VOC lead the thermoplastic vulcanized rubber to be uniformly approved and well-appreciated in the whole automobile material industry, thereby greatly improving the use space of the thermoplastic elastomer and expanding the application amount of the market.
The technical scheme of the invention is as follows:
an entrainer generation system comprising a carbonate salt and a weak acid having an acidity greater than that of carbonic acid; the molar ratio of carbonate to weak acid is 1:0.2-2.
Preferably, the weak acid is one or two combination including but not limited to acetic acid and citric acid.
Preferably, the carbonate is one or more of sodium carbonate, calcium carbonate and ammonium carbonate.
A thermoplastic vulcanizate (TPV) comprises a component A and an entrainer generating system, wherein the component A comprises the following raw materials in parts by weight:
15-50 parts of polypropylene, 1-45 parts of filler, 5-40 parts of plasticizer, 0.01-0.08 part of lubricant, 0.015-0.08 part of antioxidant, 0.5-5 parts of vulcanizing agent, 0.01-0.18 part of accelerator and 0.01-0.5 part of auxiliary vulcanizing agent based on EPDM rubber;
The entrainer generating system accounts for 1-10% of the component A by mass.
Preferably, the entrainer generation system accounts for 3-5% of the mass of the component A.
Preferably, the EPDM includes, but is not limited to, one or more of the shanghai petrochemical 3092PM, the united states dow 3720P, the united states dow 4770R, korean brocade lake KFP330, korean brocade lake 4640E (containing 75phr of paraffinic oil), exkesen mobil 3666 (containing 75phr of paraffinic oil), aroneoceae 5467C (containing 75phr of paraffinic oil), sha Bike 626; the EPDM elastomer is an EPDM elastomer with the third monomer mole content less than or equal to 10 percent.
Preferably, the polypropylene (PP) is one or a combination of a plurality of homo-polypropylene, block co-propylene, random co-polypropylene and ternary co-polypropylene.
Preferably, the polypropylene (PP) includes, but is not limited to, one or more combinations of petrifaction K7726H, petrifaction K7100, petrifaction 5606, bassell HP500D, bassell HP400H, petrifaction 4220, shanghai petrifaction 8003, and table plastic B1101.
Preferably, the filler includes, but is not limited to, one or more combinations of talc, calcium carbonate, wollastonite, kaolin, mica powder, montmorillonite, barium sulfate.
Preferably, the plasticizer is one or more of paraffin oil and naphthenic oil.
Preferably, the lubricant is erucamide, oleamide, polyethylene wax, or silicone
Preferably, the antioxidant is a mixture of phosphite secondary antioxidant and at least one of hindered amine or hindered phenol primary antioxidants.
Preferably, the hindered amine antioxidant is at least one of N, N' -1, 3-propylene-bis [3, 5-di-tert-butyl-4-hydroxy-phenyl-propionamide ] (1019), N-phenyl-aniline and 2, 4-trimethylpentene (5075), poly (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) ester (622);
The hindered phenol antioxidant is at least one of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine (1024) and 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (3114);
The phosphite auxiliary antioxidant is at least one of bis (2, 6-di-tert-butyl-4-tolyl) pentaerythritol diphosphite (636), distearyl thiodipropionate (DSTP), bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (626), tris (2, 4-di-tert-butylphenyl) phosphite (168) and bis (2, 6-di-tert-butyl-4-tolyl) pentaerythritol diphosphite (636);
Preferably, the vulcanizing agent includes, but is not limited to, a phenolic resin vulcanizing agent or a peroxide vulcanizing agent.
Preferably, the phenolic resin vulcanizing agent is a holly's vulcanizing resin SP1045; the peroxide vulcanizing agent is one or more of di-tert-butyl peroxide diisopropylbenzene (BPIB), 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane (di-penta) and di-tert-butyl peroxide (DTBP).
Preferably, when phenolic resin curing agents are employed, the accelerator is a halogen-containing inorganic salt; when peroxide curing agents are employed, the co-curing agent is one or more of N, N' -m-phenylene bismaleimide (HVA-2), trimethylol alkane trimetrayl acrylate (TMPTMA), trimethylol propane triacrylate (TMPTA), triallyl isocyanurate (TAIC), triallyl cyanurate (TAC).
Preferably, the halogen-containing inorganic salt is stannous chloride or ferrous chloride.
Preferably, the thermoplastic vulcanizate (TPV) is prepared by:
(1) Preparing an entrainer generation system: carbonate was reacted with a slightly stronger acid than carbonic acid according to 3:2, blending the mixture in a molar ratio of 2;
(2) Crushing EPDM rubber into particles, weighing EPDM rubber particles, polypropylene (PP), an antioxidant, a lubricant, a plasticizer and a filler according to parts by weight, mixing in an internal mixer until the plasticizer is fully absorbed by the rubber, fully melting the PP, discharging to obtain a blended rubber block, and crushing the blended rubber block into particles with the size of less than 8mm by a crusher after the blended rubber block is cooled to obtain rubber-plastic blend particles;
(3) Uniformly mixing the rubber and plastic blend particles obtained in the step (2) with a vulcanizing agent, an accelerator and a vulcanizing aid in a high-speed stirrer, adding the mixture into a double-screw extruder with the length-diameter ratio of more than 56:1 according to a set yield through a weightless scale, and setting the screw rotating speed of the double-screw extruder to 300-800rpm;
A side feeding extruder is arranged at the fourth-eighth section of barrel of the double-screw extruder, an entrainer generating system is uniformly fed into the side feeding extruder according to a set formula proportion by a weightlessness scale, the entrainer generating system is fed into the double-screw extruder by the side feeding extruder, and finally extrusion granulation is carried out by a die head, so that the low-odor and low-VOC thermoplastic vulcanized rubber TPV is obtained.
Preferably, in the step (3), the temperature of each zone of the screw of the twin-screw extruder is the temperature of each zone during dynamic vulcanization of the twin screw: one zone 100 ℃, two zones 140 ℃, three zones 150 ℃, four zones 160 ℃, five zones 160 ℃, six zones 160 ℃, seven zones 160 ℃, eight zones 190 ℃, nine zones 190 ℃, ten zones 200 ℃, eleven zones 200 ℃, twelve zones 200 ℃ (vacuum zone), thirteen zones 200 ℃, fourteen zones 200 ℃, and die 180 ℃.
In the step (3), an entrainer generating system is added at the fourth-eighth section of cylinder of the double-screw extruder in a lateral feeding mode, the tenth section of cylinder of the double-screw extruder starts to be a reaction section of the entrainer generating system through temperature control, ZME (tooth-shaped element) is adopted for a screw element of the tenth section, materials are subjected to rapid multiple diversion-mixing alternation, entrainer (water and carbon dioxide) generated by the entrainer generating system reaction is rapidly dispersed, the entrainer is rapidly and uniformly distributed in TPV melt, and simultaneously, the reflux loss can be effectively avoided; meanwhile, under the action of the screw rod original, the odor gas generated in the TPV dynamic vulcanization process and the entrainer are fully and uniformly mixed, so that the entrainer can carry the volatile organic gas to the greatest extent when escaping, and the removal efficiency of the volatile organic gas is improved. And then, adopting a combination of deep groove large-lead threads to small-lead threads at the twelfth section of vacuum port, adopting a combination of stronger compression at the downstream of the vacuum port, establishing a large pressure, improving the solubility of the entrainer in the TPV melt, simultaneously adopting a combination mainly comprising a conveying element (thread), realizing low shear heat generation, effectively reducing degradation in the material processing process, simultaneously connecting the twelfth section of cylinder vacuum port with a water ring vacuum pump, enabling a byproduct with higher boiling point generated in the preparation process of the entrainer and the TPV to act with the entrainer to generate an azeotropic mixture with the entrainer, and fully removing the azeotropic mixture with the entrainer under the negative pressure of the vacuum pump to prepare the low-odor and low-VOC thermoplastic vulcanizate TPV.
The TPV provided by the invention can be applied to a plurality of fields such as automobile interior trim parts, instrument panels, skins, automobile sealing strips, household electrical appliances, bathroom products, medical products and the like, can solve the requirements of industries such as automobiles, household electrical appliances and the like on low-emission materials, comprehensively realizes a solution of high-quality low-emission materials, creates higher benefits for enterprises, and increases market competitiveness. Through the research of the project, the industrialization of the product is realized, the produced low-emission thermoplastic elastomer material is mainly applied to automobile sealing strips and automobile interior trim products, and the yield of 6300 tons is realized at present. From the analysis result of the product cost, the project reduces the subsequent separation procedure, reduces the cost by 323.5 yuan/ton, and has great price advantage.
Compared with the prior art, the invention has the beneficial effects that:
1. in the invention, the entrainer generating system prepared by carbonate and weak acid is adopted, the chemical temperature is higher than the melting temperature of the raw materials of the TPV, when the entrainer generating system is applied to the preparation of the thermoplastic elastomer (TPV), after all the raw materials are melted, the entrainer generating system is subjected to chemical reaction to generate low-boiling entrainer (namely water and carbon dioxide), the low-boiling entrainer is mixed with high-boiling volatile organic matters in the raw materials of the TPV to form a mixture with boiling point lower than that of the high-boiling volatile matters, and then the mixture is gasified and removed by vacuum negative pressure in a double-screw extruder, so that the entrainer generating system has the advantage of high removal efficiency.
2. According to the invention, the azeotropic agent generating system is rapidly dispersed through the screw combination of rapid diversion and mixing, and the azeotropic agent solubility is improved through the double screw combination technology of high build pressure, so that the action efficiency of the azeotropic agent is greatly improved in the blending extrusion process of a double screw extruder, and the odor and low molecular substances in the raw material melting reaction process are effectively removed; meanwhile, degradation in the raw material processing process is effectively reduced through the combination of the high-dispersion low-shear heat-generating screw, and the low-odor low-VOC plastic elastomer material is developed.
3. By selecting low-emissivity raw materials, the problem of mutual influence caused by blending, crosslinking and the like is solved.
4. The method is characterized in that an entrainer generating system is prepared by compounding carbonate and weak acid with acidity larger than that of carbonic acid according to a certain proportion, when the material temperature of an elastomer rises to be higher than the reaction temperature of two substances, the entrainer generating system is subjected to chemical reaction to generate low-boiling-point substances, so that the entrainer generating system generates low-boiling-point substances after the elastomer is melted, and the generated low-boiling-point substances are wrapped by a melt, so that the volatility loss is greatly reduced.
5. According to the invention, an independently developed controllable entrainer generation system is used, and a screw combination of high-speed shunt mixing and azeotropic agent solubility improvement is combined, so that the action efficiency of the entrainer is greatly improved, and odorous substances and VOC substances are greatly removed; the various schemes for inhibiting degradation are summarized through control optimization of temperature of the temperature screw, screening of the antioxidant and control of the processing times.
6. The thermoplastic elastomer (TPV) provided by the invention has the performance reaching the international similar product level, and compared with the most advanced technology in the industry, the odor advantage exceeds 0.5 level, the VOC data is in the dominant position as a whole, and the advantages of the odor and the VOC lead the thermoplastic elastomer to be uniformly approved and favored in the whole automobile material industry, so that the use space of the thermoplastic elastomer is greatly improved, and the application amount of the market is expanded.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 shows the ZME structure of the screw elements in the tenth barrel.
FIG. 2 shows the entrainer generation section and downstream screw combination.
Fig. 3 is a combination 1 deep groove large delivery thread element.
Fig. 4 is a combination 2 common large delivery thread element.
Detailed Description
In order to better understand the technical solutions of the present invention, the following description will clearly and completely describe the technical solutions of the embodiments of the present invention in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
Step one: preparing an entrainer generation system, and blending sodium carbonate and citric acid according to a molar ratio of 1:0.5;
Step two: crushing EPDM 3092PM rubber into particles, weighing 45 parts of rubber particles, 4220 parts of PP 428 parts, 0.02 part of antioxidant 1019, 636.02 parts of antioxidant, 0.015 part of lubricant erucamide and 20 parts of filler nano talcum powder according to parts by weight, and adding into a high-speed stirrer to mix raw materials;
Step three: adding the mixed raw materials obtained in the step two into a double-screw extruder for granulating, after the mixed raw materials are melted, adding plasticizer paraffin oil into the double-screw extruder through an oil pump or a metering scale, and mixing with the melted mixed raw materials to obtain semi-finished product master batches; the temperature of each zone of the screw is the temperature of each zone during dynamic vulcanization of the double screws: 180 ℃ in the first area, 190 ℃ in the second area, 190 ℃ in the third area, 190 ℃ in the fourth area, 190 ℃ in the fifth area, 200 ℃ in the sixth area, 200 ℃ in the seventh area, 200 ℃ in the eighth area, 200 ℃ in the ninth area, 200 ℃ in the tenth area, 200 ℃ in the eleventh area, 200 ℃ in the twelve areas, 200 ℃ in the thirteenth area, 200 ℃ in the fourteenth area, 180 ℃ in the head, and 400 revolutions per minute of the twin-screw extruder;
Step four: adding a vulcanizing agent, an accelerator and a vulcanizing aid into the mixture obtained in the step three to obtain a mixture, adding the mixture into a high-speed stirrer, then adding the mixture into a double-screw extruder to carry out dynamic vulcanization for extrusion granulation, adding an entrainer base material into a fifth section of cylinder of the double-screw extruder by lateral feeding, and rapidly dispersing and blending the entrainer by a screw combination (large-lead screw block SK type threads+downstream banburying rotor kneading type) of rapid diversion mixing, wherein a ZME (tooth-shaped element) (figure 1) is adopted in an entrainer generation section, rapidly dispersing the entrainer for multiple times by a combination of rapidly compressed materials through screw lead reduction at the downstream (figure 2), adopting a deep groove large-lead screw to small-lead screw arrangement combination at the vacuum position and adopting a stronger compression combination at the downstream (figure 3), so as to improve the solubility of the entrainer, realize high dispersion and low shear heat generation, and effectively reduce degradation in the material processing process, thereby obtaining the green low-odor low-VOC thermoplastic elastomer. The temperature of each zone of the screw is the temperature of each zone during dynamic vulcanization of the double screws: the rotation speed of the twin-screw extruder is 400 revolutions per minute, namely 100 ℃ in the first area, 140 ℃ in the second area, 150 ℃ in the third area, 160 ℃ in the fourth area, 160 ℃ in the fifth area, 160 ℃ in the sixth area, 160 ℃ in the seventh area, 190 ℃ in the eighth area, 190 ℃ in the ninth area, 200 ℃ in the tenth area, 200 ℃ in the eleventh area, 200 ℃ in the twelve areas (vacuum segment), 200 ℃ in the thirteenth area, 200 ℃ in the fourteenth area, 180 ℃ in the head and the twin-screw extruder.
Example 2
Unlike example 1, the filler was wollastonite in an amount of 20 parts.
Example 3
In the third step, PP was K7726H, unlike example 2.
Example 4
The difference from example 2 is that in step two, the antioxidant is 1010.02 parts and the antioxidant 168.02 parts.
Example 5
Step one was to blend sodium carbonate and citric acid at a 1:0.8 molar ratio, unlike example 1.
Example 6
In a fourth step, the entrainer generating system was added with side feed at the sixth barrel of the twin screw extruder, unlike in example 1.
Example 7
Unlike example 1, the tenth shell section entrainer generation section did not use ZME (tooth element), and the downstream did not disperse the entrainer multiple times rapidly by a combination of a thread lead (fig. 2) narrowing the rapidly compressed material.
Example 8
The vacuum position and downstream position are different from example 1 using the combination 2 common large feed screw original combination of fig. 4.
Comparative example 1 differs from example 2 in that the plasticizer is a naphthenic oil.
Comparative example 2 differs from example 2 in that in step three PP is HP500D.
Comparative example 3 differs from example 1 in that step one, sodium carbonate was blended with acetic acid in a 1:0.8 molar ratio;
Comparative example 4 differs from example 1 in that no entrainer generating system was used, and a common entrainer was used, as follows:
Step one: crushing EPDM 3092PM rubber into particles, weighing 45 parts of rubber particles, 4220 parts of PP, 0.1 part of antioxidant 1019, 636.1 parts of antioxidant, 0.1 part of lubricant erucamide and 20 parts of filler wollastonite according to parts by weight, and adding the mixture into a high-speed stirrer to mix raw materials.
Step two: and (3) adding the mixture obtained in the step (A) into a double-screw extruder for granulating, and simultaneously adding the plasticizer into the double-screw extruder through an oil pump or a metering scale to be mixed with the melted materials, so as to obtain the semi-finished product master batch. The temperature of each zone of the screw is the temperature of each zone during dynamic vulcanization of the double screws: 180 ℃ in the first area, 190 ℃ in the second area, 190 ℃ in the third area, 190 ℃ in the fourth area, 190 ℃ in the fifth area, 200 ℃ in the sixth area, 200 ℃ in the seventh area, 200 ℃ in the eighth area, 200 ℃ in the ninth area, 200 ℃ in the tenth area, 180 ℃ in the head and 400 revolutions per minute of the double-screw extruder.
Step three: and (3) adding the mixture obtained in the step (II) into a vulcanizing agent, an accelerator, a vulcanizing aid and an entrainer, adding the mixture into a high-speed stirrer to obtain a mixture, adding the mixture into a double-screw extruder, carrying out dynamic vulcanization, and carrying out extrusion granulation, wherein the screw combination is the same as that of the example 1. The temperature of each zone of the screw is the temperature of each zone during dynamic vulcanization of the double screws: the rotation speed of the twin-screw extruder is 400 revolutions per minute, namely 100 ℃ in the first area, 140 ℃ in the second area, 150 ℃ in the third area, 160 ℃ in the fourth area, 160 ℃ in the fifth area, 160 ℃ in the sixth area, 160 ℃ in the seventh area, 190 ℃ in the eighth area, 190 ℃ in the ninth area, 200 ℃ in the tenth area, 200 ℃ in the eleventh area, 200 ℃ in the twelve areas (vacuum segment), 200 ℃ in the thirteenth area, 200 ℃ in the fourteenth area, 180 ℃ in the head and the twin-screw extruder.
Comparative example 5 differs from example 1 in that the entrainer generation system was not used and a porous calcium silicate/graphene composite was used.
Step one: crushing EPDM 3092PM rubber into particles, weighing 45 parts of rubber particles, 4220 parts of PP, 0.1 part of antioxidant 1019, 636.1 parts of antioxidant, 0.1 part of lubricant erucamide and 20 parts of filler wollastonite according to parts by weight, and adding the mixture into a high-speed stirrer to mix raw materials.
Step two: and (3) adding the mixture obtained in the step (A) into a double-screw extruder for granulating, and simultaneously adding the plasticizer into the double-screw extruder through an oil pump or a metering scale to be mixed with the melted materials, so as to obtain the semi-finished product master batch. The temperature of each zone of the screw is the temperature of each zone during dynamic vulcanization of the double screws: 180 ℃ in the first area, 190 ℃ in the second area, 190 ℃ in the third area, 190 ℃ in the fourth area, 190 ℃ in the fifth area, 200 ℃ in the sixth area, 200 ℃ in the seventh area, 200 ℃ in the eighth area, 200 ℃ in the ninth area, 200 ℃ in the tenth area, 180 ℃ in the head and 400 revolutions per minute of the double-screw extruder.
Step three: adding the mixture obtained in the step two into a vulcanizing agent, an accelerator, a vulcanizing aid and a porous calcium silicate/graphene composite material, adding the mixture into a high-speed stirrer to obtain a mixture, adding the mixture into a double-screw extruder for dynamic vulcanization, extruding and granulating, and combining screws in the same way as in the example 1. The temperature of each zone of the screw is the temperature of each zone during dynamic vulcanization of the double screws: the rotation speed of the twin-screw extruder is 400 revolutions per minute, namely 100 ℃ in the first area, 140 ℃ in the second area, 150 ℃ in the third area, 160 ℃ in the fourth area, 160 ℃ in the fifth area, 160 ℃ in the sixth area, 160 ℃ in the seventh area, 190 ℃ in the eighth area, 190 ℃ in the ninth area, 200 ℃ in the tenth area, 200 ℃ in the eleventh area, 200 ℃ in the twelve areas (vacuum segment), 200 ℃ in the thirteenth area, 200 ℃ in the fourteenth area, 180 ℃ in the head and the twin-screw extruder.
Comparative example 6 differs from example 1 in that in step three the entrainer generating system was added with a side feed at the fourth barrel of the twin screw extruder.
Comparative example 7 differs from example 7 in that the azeotroping agent generating section employs a combination of ZME (tooth element), a downstream fast compressed material without thread lead reduction, to disperse the azeotroping agent a plurality of times.
Comparative example 8 differs from example 8 in that the vacuum position does not employ a combination of large lead threads to small lead threads and a stronger compression downstream.
The difference between comparative example 9 and example 1 is that the temperature of each temperature zone of the processing engineering in the fourth step is 150 ℃ in the first zone, 160 ℃ in the second zone, 180 ℃ in the third zone, 180 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the seventh zone, 190 ℃ in the eighth zone, 190 ℃ in the ninth zone, 200 ℃ in the tenth zone, 200 ℃ in the eleventh zone, 200 ℃ in the twelve zones (vacuum zone), 200 ℃ in the thirteenth zone, 200 ℃ in the fourteen zones, 180 ℃ in the head and 400 revolutions per minute of the twin-screw extruder.
Experimental example result analysis
The samples completed in the experimental examples were subjected to the following performance evaluation methods and implementation criteria:
1. Odor assessment was carried out according to Q/JLY J7110538D-2018, with the assessment criteria as shown in Table 1:
2. the VOC test standard was evaluated on the basis of Q/JLY J7110274C-2016 and the results are shown in Table 2.
Table 1 odor evaluation criteria
Table 2 the VOC test results for the examples and comparative examples are as follows
From table 2, it is possible to: by comparing example 1, example 2, example 3 and example 4, it can be summarized that the selection of raw materials such as filler, PP, antioxidant and the like has obvious influence on smell and VOC oil of the thermoplastic elastomer, for example, example 1 and example 2, the smell and VOC of the filler selected from nano talcum powder can be better than wollastonite, and the nano talcum powder has large specific surface area and micropores, so that the generated micromolecular substances are easy to separate out from the surface of the talcum powder in the blending process of the twin-screw extruder.
The effect of the entrainer in-situ generating agent on reducing odor and VOC is better than that of an ordinary directly added entrainer through comparative examples 5, 4 and 5, and is better than that of a porous calcium carbonate/graphene composite material, and the types and weight ratios of the acids in comparative examples 1,5 and 3 also play a certain role in influencing odor and VOC, and the carbonate and the citric acid are used in the following steps: blending at a ratio of 0.8 parts by weight gives the best results.
The positions and the downstream screw combinations of the feeding barrel of the entrainer in-situ generating agent, the reaction section and the downstream combination of the entrainer in-situ generating agent, the vacuum section and the downstream screw combination and the processing temperature are indispensable by using the lateral feeding to add the entrainer substrate at the fifth barrel of the double-screw extruder, the SK-type high-lead screw thread is adopted, the conveying and the shearing are accelerated, the temperature is set to be only slightly higher than the melting temperature (such as about 160 ℃) of the elastomer, the entrainer autogenous generation system is inhibited, and the entrainer generation system and the thermoplastic elastomer are firstly blended and dispersed, but the entrainer is not generated by the reaction.
Generally, after an entrainer generating system is added into an elastomer melt and then subjected to 8D-12D kneading (namely a 4D cylinder body in a 2-3 zone), the temperature of a screw is set to be higher than the chemical reaction temperature of the entrainer generating system, the entrainer generating system generates chemical reaction to generate water and carbon dioxide entrainer, ZME is adopted in a generating section for distributed mixing, ZME is used for carrying out rapid multiple diversion-rebubbling on materials, and the entrainer, volatile organic compounds and the melt are rapidly and uniformly mixed to form an isotropic system. After the entrainer, the volatile organic compound, the entrainer and the elastomer melt are uniformly mixed, the compression combination from large lead to small lead is adopted, so that the solubility of the entrainer in the elastomer melt is improved, the entrainer is dissolved in the melt and cannot return to a co-generator adding port or a natural exhaust port to volatilize and lose, and the entrainer can further form an azeotropic system with low molecular substances produced in the later stage;
The vacuum port adopts deep groove large lead threads as shown in figure 3, the material fullness is low, the pressure is suddenly reduced, the volatile organic compounds and the entrainer in the melt form a homogeneous system which is rapidly gasified and fully separated from the elastomer melt; the residual volatile matters which are separated from the melt are difficult to enter the material body again and return to the vacuum port to be continuously removed, so that the odor and VOC are further reduced.
The invention provides a set of brand new technical route and sets the process conditions in the technical route, effectively improves the action efficiency of the entrainer, fully exerts the performance of the entrainer, achieves the effect of efficiently reducing VOC and odor in TPV, and simultaneously can furthest reduce aldehydes and other low molecular organic matters generated by oxidative degradation by optimizing the screw combination (shown in figures 1-4) and the process.
Although the present invention has been described in detail by way of reference to preferred embodiments, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. A thermoplastic vulcanizate, characterized in that: the composition comprises a component A and an entrainer generation system, wherein the component A comprises the following raw materials in parts by weight:
15-50 parts of polypropylene, 1-45 parts of filler, 5-40 parts of plasticizer, 0.01-0.08 part of lubricant, 0.015-0.08 part of antioxidant, 0.5-5 parts of vulcanizing agent, 0.01-0.18 part of accelerator and 0.01-0.5 part of auxiliary vulcanizing agent based on EPDM rubber;
the entrainer generation system comprises carbonate and weak acid, wherein the weak acid is one or two of acetic acid and citric acid;
the entrainer generating system accounts for 3-5% of the component A by mass percent;
the preparation method of the thermoplastic vulcanized rubber comprises the following steps:
(1) Preparing an entrainer generation system: carbonate and weak acid according to 3:2, blending the mixture in a molar ratio of 2;
(2) Crushing EPDM rubber into particles, weighing EPDM rubber particles, polypropylene, an antioxidant, a lubricant, a plasticizer and a filler according to parts by weight, mixing in an internal mixer until the plasticizer is fully absorbed by the rubber, fully melting PP, discharging to obtain a blended rubber block, cooling the blended rubber block, and crushing the cooled blended rubber block into particles with the size of less than 8mm by adopting a crusher to obtain rubber-plastic blend particles;
(3) Uniformly mixing the rubber and plastic blend particles obtained in the step (2) with a vulcanizing agent, an accelerator and a vulcanizing aid in a high-speed stirrer, adding the mixture into a double-screw extruder with the length-diameter ratio of more than 56:1 according to a set yield through a weightless scale, and setting the screw rotating speed of the double-screw extruder to 300-800rpm;
A side feeding extruder is arranged at the fourth-eighth section of barrel of the double-screw extruder, an entrainer generating system is uniformly fed into the side feeding extruder according to a set formula proportion by a weightlessness scale, the entrainer generating system is fed into the double-screw extruder by the side feeding extruder, and finally extrusion granulation is carried out by a die head, so that the low-odor and low-VOC thermoplastic vulcanized rubber TPV is obtained.
2. A thermoplastic vulcanizate according to claim 1, wherein: the carbonate is one or a combination of more of sodium carbonate, calcium carbonate and ammonium carbonate.
3. The thermoplastic vulcanizate of claim 1, wherein: the EPDM rubber is EPDM rubber with the mole content of the third monomer less than or equal to 10 percent; the EPDM rubber is one or more of Shanghai petrochemical 3092PM, american Dow 3720P, american Dow 4770R, korean Jinhu KFP330, korean Jinhu 4640E, ekkimei 3666, allangneate 5467C and Sha Bike 626;
The polypropylene is one or a combination of a plurality of homo-polypropylene, block propylene, random copolymer polypropylene and ternary copolymer polypropylene;
The filler is one or a combination of more of talcum powder, calcium carbonate, wollastonite, kaolin, mica powder, montmorillonite and barium sulfate;
the plasticizer is one or a combination of more of paraffin oil and naphthenic oil;
The antioxidant is a mixture of phosphite ester auxiliary antioxidants and at least one of hindered amine or hindered phenol main antioxidants; the vulcanizing agent is phenolic resin vulcanizing agent or peroxide vulcanizing agent.
4. The thermoplastic vulcanizate of claim 3, wherein the polypropylene is one or more of a combination of a yankee K7726H, a yankee K7100, a yankee 5606, a bassell HP500D, a bassell HP400H, a yankee 4220, a Shanghai petrochemical 8003, a table plastic B1101; the hindered amine antioxidant is at least one of N, N' -1, 3-propylene bis [3, 5-di-tert-butyl-4-hydroxy-benzene propionamide ], N-phenylaniline, 2, 4-trimethylpentene and poly (4-hydroxy-2, 6-tetramethyl-1-piperidylethanol) ester;
the hindered phenol antioxidant is at least one of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxy phenyl) propionic acid ] pentaerythritol ester, N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxy phenyl) propionyl ] hydrazine and 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxy benzyl) isocyanuric acid;
The phosphite auxiliary antioxidant is at least one of bis (2, 6-di-tert-butyl-4-tolyl) pentaerythritol diphosphite, distearyl thiodipropionate (DSTP), bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite and bis (2, 6-di-tert-butyl-4-tolyl) pentaerythritol diphosphite;
the phenolic resin vulcanizing agent is a vulcanizing resin SP 1045 of Santa Clay;
The peroxide vulcanizing agent is one or a combination of more of di-tert-butyl diisopropyl benzene peroxide, 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane and di-tert-butyl peroxide.
5. The thermoplastic vulcanizate of claim 4, wherein when phenolic resin curatives are employed, the accelerator is a halogen-containing inorganic salt; when peroxide vulcanizing agent is adopted, the auxiliary vulcanizing agent is one or a combination of more of N, N' -m-phenylene bismaleimide, trimethylol alkyl tri-tetrayl acrylate, trimethylol propane triacrylate, triallyl isocyanurate and triallyl cyanurate.
6. The thermoplastic vulcanizate of claim 5, wherein the halogen-containing inorganic salt is stannous chloride or ferrous chloride.
7. The thermoplastic vulcanizate of claim 1, wherein in step (3), the temperature of each zone of the twin screw extruder is the temperature of each zone during twin screw dynamic vulcanization: 50-100 ℃ in the first area, 120-160 ℃ in the second area, 140-170 ℃ in the third area, 140-170 ℃ in the fourth area, 140-170 ℃ in the fifth area, 140-170 ℃ in the sixth area, 140-170 ℃ in the seventh area, 180-190 ℃ in the eighth area, 180-190 ℃ in the ninth area, 190-230 ℃ in the tenth area, 190-230 ℃ in the eleventh area, 190-230 ℃ in the twelve area, 190-230 ℃ in the thirteenth area, 190-230 ℃ in the fourteen area, 180-200 ℃ in the screen changer and 170-200 ℃ in the head.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211500970.9A CN115785522B (en) | 2022-11-28 | 2022-11-28 | Azeotroping agent generating system and thermoplastic vulcanized rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211500970.9A CN115785522B (en) | 2022-11-28 | 2022-11-28 | Azeotroping agent generating system and thermoplastic vulcanized rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115785522A CN115785522A (en) | 2023-03-14 |
| CN115785522B true CN115785522B (en) | 2024-06-25 |
Family
ID=85442167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211500970.9A Active CN115785522B (en) | 2022-11-28 | 2022-11-28 | Azeotroping agent generating system and thermoplastic vulcanized rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115785522B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164544A (en) * | 1996-03-04 | 1997-11-12 | 三井石油化学工业株式会社 | Foamable olefin thermoplastic elastomer compositions and foamed products thereof |
| KR20150049711A (en) * | 2013-10-30 | 2015-05-08 | 제일모직주식회사 | Thermoplastic resin composition for reducing volatile organic compound |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3976605A (en) * | 1974-03-28 | 1976-08-24 | Sumitomo Chemical Company, Limited | Foamed plastics of resin compositions comprising pullulan type resins and thermoplastic resins and process for producing the same |
| AUPM294993A0 (en) * | 1993-12-13 | 1994-01-13 | HADDON, Bruce Alexander | A deodorizer |
| AU2002303397A1 (en) * | 2002-04-19 | 2003-11-11 | Advanced Elastomer Systems, L.P. | Soft chemically foamed thermoplastic vulcanizate for sealing application by robotic extrusion |
| CN105504584A (en) * | 2015-12-31 | 2016-04-20 | 东莞市祺龙电业有限公司 | Tasteless PVC modified material and preparation method thereof |
| CN107828079A (en) * | 2017-11-03 | 2018-03-23 | 宜兴丹森科技有限公司 | Water-absorbing resins and its manufacture method |
| EP3858905A4 (en) * | 2018-09-28 | 2022-06-15 | Sekisui Chemical Co., Ltd. | Crosslinked polyolefin resin foam and multilayer body |
| CN110256770A (en) * | 2019-06-18 | 2019-09-20 | 广州华新科智造技术有限公司 | Thermoplastic dynamic perduren and preparation method thereof |
| CN111574797A (en) * | 2020-04-16 | 2020-08-25 | 道恩高材(北京)科技有限公司 | Oil-resistant high-temperature-resistant acrylate rubber/polypropylene thermoplastic vulcanized rubber and preparation method thereof |
-
2022
- 2022-11-28 CN CN202211500970.9A patent/CN115785522B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164544A (en) * | 1996-03-04 | 1997-11-12 | 三井石油化学工业株式会社 | Foamable olefin thermoplastic elastomer compositions and foamed products thereof |
| KR20150049711A (en) * | 2013-10-30 | 2015-05-08 | 제일모직주식회사 | Thermoplastic resin composition for reducing volatile organic compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115785522A (en) | 2023-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2002537432A (en) | Thermoplastic vulcanized rubber and method for producing the same | |
| EP0837098A4 (en) | Rubber composition and process for the production thereof | |
| CN1832992A (en) | Nucleated thermoplastic elastomer compositions and related methods | |
| EP1279702A1 (en) | Fully cured thermoplastic elastomer, process for its manufacture and applications thereof | |
| KR20060041217A (en) | Method of producing thermoplastic vulcanizates | |
| CN105566751A (en) | High-crystallinity polypropylene foaming master batch and preparation method thereof | |
| CN1944497A (en) | Method for preparing thermoplastic vulcanized rubber by peroxide vulcanizing system | |
| CN109608809B (en) | Low-odor polypropylene composite material and preparation method thereof | |
| EP2670797B1 (en) | Peroxide mixtures for the accelerated cure of ethylene-vinyl acetate | |
| CN102516655A (en) | Strengthening and toughening polypropylene composite and preparation method thereof | |
| CN110698771A (en) | TPV micro-foaming material and production process thereof | |
| CN114891356B (en) | Thermoplastic elastomer material and preparation method thereof | |
| CN115785522B (en) | Azeotroping agent generating system and thermoplastic vulcanized rubber | |
| DE60213261T2 (en) | MASTERBATCH CONTAINS RUBBER COMPONENTS, FILLERS, SOFTWARE AND NETWORKERS | |
| CN114933741A (en) | High-rigidity high-impact-resistance polypropylene composite additive and preparation method thereof | |
| CN1137933C (en) | High-rigidity high-toughness plastics and its preparing process | |
| CN104558808B (en) | Prolylene polymer composition and product prepared therefrom | |
| CN116120672B (en) | Ultrahigh-fluidity thermoplastic elastomer for automobile parts and preparation method thereof | |
| CN117659552A (en) | Polyethylene composition for film and preparation method thereof | |
| CN114031863A (en) | High-conductivity PS/HDPE composite material and preparation method thereof | |
| CN116023736B (en) | Styrene-butadiene rubber/polypropylene thermoplastic elastomer composition, vulcanized styrene-butadiene rubber/polypropylene thermoplastic elastomer, preparation method and application | |
| CN1009105B (en) | High-fluidity high-toughness polypropylene plastic and preparation thereof | |
| CN112778615A (en) | Composition for preparing ethylene-octene copolymer/polylactic acid thermoplastic elastomer foaming material, preparation method and application thereof | |
| CN108727677A (en) | A kind of preparation method of low-odor thermoplastic elastic composition | |
| CN104448536B (en) | High-rigidity TPV (thermoplastic vulcanizate) toughened polypropylene composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |