CN114907570B - Tear-resistant resin, preparation method thereof and rubber composition containing resin - Google Patents
Tear-resistant resin, preparation method thereof and rubber composition containing resin Download PDFInfo
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- CN114907570B CN114907570B CN202110174203.2A CN202110174203A CN114907570B CN 114907570 B CN114907570 B CN 114907570B CN 202110174203 A CN202110174203 A CN 202110174203A CN 114907570 B CN114907570 B CN 114907570B
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- acid
- resin
- rosin
- stirring
- tear
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- 229920005989 resin Polymers 0.000 title claims abstract description 112
- 239000011347 resin Substances 0.000 title claims abstract description 112
- 229920001971 elastomer Polymers 0.000 title claims description 34
- 239000005060 rubber Substances 0.000 title claims description 34
- 239000000203 mixture Substances 0.000 title claims description 22
- 238000002360 preparation method Methods 0.000 title abstract description 9
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 82
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 81
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000003208 petroleum Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 23
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 3
- RJWBTWIBUIGANW-UHFFFAOYSA-N 4-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C=C1 RJWBTWIBUIGANW-UHFFFAOYSA-N 0.000 claims description 3
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 3
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- 229920003051 synthetic elastomer Polymers 0.000 claims description 3
- 239000005061 synthetic rubber Substances 0.000 claims description 3
- 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 1
- 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 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 238000004821 distillation Methods 0.000 abstract description 10
- 238000002844 melting Methods 0.000 abstract description 9
- 230000008018 melting Effects 0.000 abstract description 9
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 15
- 229910052740 iodine Inorganic materials 0.000 description 15
- 239000011630 iodine Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003784 tall oil Substances 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 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 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- MXYATHGRPJZBNA-KRFUXDQASA-N isopimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@](C=C)(C)CC2=CC1 MXYATHGRPJZBNA-KRFUXDQASA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 1
- YPGLTKHJEQHKSS-ASZLNGMRSA-N (1r,4ar,4bs,7r,8as,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,7,8,8a,9,10,10a-dodecahydrophenanthrene-1-carboxylic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@H](C(C)C)C[C@@H]2CC1 YPGLTKHJEQHKSS-ASZLNGMRSA-N 0.000 description 1
- UZZYXZWSOWQPIS-UHFFFAOYSA-N 3-fluoro-5-(trifluoromethyl)benzaldehyde Chemical compound FC1=CC(C=O)=CC(C(F)(F)F)=C1 UZZYXZWSOWQPIS-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- MLBYBBUZURKHAW-UHFFFAOYSA-N 4-epi-Palustrinsaeure Natural products CC12CCCC(C)(C(O)=O)C1CCC1=C2CCC(C(C)C)=C1 MLBYBBUZURKHAW-UHFFFAOYSA-N 0.000 description 1
- MXYATHGRPJZBNA-UHFFFAOYSA-N 4-epi-isopimaric acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)CC1=CC2 MXYATHGRPJZBNA-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 1
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- RWWVEQKPFPXLGL-ONCXSQPRSA-N L-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC=C(C(C)C)C=C2CC1 RWWVEQKPFPXLGL-ONCXSQPRSA-N 0.000 description 1
- RWWVEQKPFPXLGL-UHFFFAOYSA-N Levopimaric acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CC=C(C(C)C)C=C1CC2 RWWVEQKPFPXLGL-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-UHFFFAOYSA-N Me ester-3, 22-Dihydroxy-29-hopanoic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(=C(C)C)C=C1CC2 KGMSWPSAVZAMKR-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 description 1
- MLBYBBUZURKHAW-MISYRCLQSA-N Palustric acid Chemical compound C([C@@]12C)CC[C@@](C)(C(O)=O)[C@@H]1CCC1=C2CCC(C(C)C)=C1 MLBYBBUZURKHAW-MISYRCLQSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 description 1
- 229940118781 dehydroabietic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a tear-resistant resin and a preparation method thereof, wherein the preparation method comprises the following steps: heating and melting rosin or derivatives thereof, and controlling the reaction temperature at 100-140 ℃; 2) After rosin or derivatives thereof are completely melted, adding a catalyst and a modifier, stirring, controlling the reaction temperature to be 100-180 ℃, and stirring and mixing for 0.3-3 hours; 3) Adding an antioxidant, controlling the temperature to be 100-150 ℃, adding petroleum resin, controlling the reaction temperature to be 120-180 ℃ after the petroleum resin is completely melted, stirring and mixing for 0.2-4 h, and neutralizing; 4) After the completion of the reaction, distillation was carried out under reduced pressure. The resin has the advantages of simple synthesis process, low cost, no wastewater generation and easy industrial utilization.
Description
Technical Field
The invention belongs to the field of composition additives, and particularly relates to a tear-resistant resin, a preparation method thereof and a rubber composition containing the resin.
Background
The tire can be damaged to different degrees in the use process, especially the tire is more easily scratched by the impact of sharp objects under the condition of relatively poor road surface condition, the service life of the tire is greatly shortened, the excellent service performance can be given to the tire by good tearing resistance and puncture resistance, the durability of the tire is improved, and the service life of the tire is prolonged.
Patent CN20131068381 discloses a tear-resistant resin with highly rigid DCPD and phenol as main chains, which has good compatibility with rubber, and the resin improves tear resistance and also effectively improves processability of rubber materials, and has good application effect.
The patent CN105254854A adds rosin or a derivative structure thereof on the basis of CN20131068381, and utilizes the hydroxyl of the resin and the carboxyl of the rosin to carry out esterification reaction, so that the prepared resin has good compatibility with rubber, the Mooney viscosity is reduced, and the physical properties of the obtained rubber composition are improved. The rosin modified C9 petroleum resin is prepared by high-temperature high-pressure polymerization reaction in the patent CN106967201A, and can improve the tear resistance of the tire table surface, but the reaction needs to be carried out at high temperature and high pressure, the reaction condition is harsh, and the production cost is high.
On the basis, the application provides the modified resin with the tear resistance, which has the advantages of simple synthesis process, low cost, no wastewater generation and easy industrial utilization.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the modified resin with the tear resistance, the preparation method and the application thereof, the resin has simple synthesis process, no waste water is generated, the added modifier is not generated by extra liquid or gas waste, the environment is protected, the cost is low, and the industrial utilization is easy; the rubber composition additive prepared from the resin has good compatibility with rubber, after the rubber additive is added in a sizing formula, the tear resistance is obviously improved, the product stability is good, the tear resistance after aging is kept good, the scorching time can be prolonged, the processing safety is improved, and the vulcanization reduction resistance is obviously improved.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a tear resistant resin made from a feedstock comprising rosin or a derivative thereof and a petroleum resin; the tear resistant resin has an iodine value of 20 to 190.
Preferably, the rosin or derivative thereof comprises any one or a combination of at least two of rosin, tall oil rosin, maleic rosin, rosin glycerol ester, polymerized rosin, hydrogenated rosin. Preferably, the petroleum resin is selected from any one or a combination of at least two of C9 petroleum resin, C5/C9 copolymerized petroleum resin, DCPD petroleum resin.
Preferably, the polymer has the structure of formula I, said formula I polymer comprising 10-70wt.% of said tear resistant resin.
Wherein, in the formula I,
r1 is one of a H, C1-C12 linear or branched alkyl group;
r2 is one of C1-C4 branched or straight-chain alkyl;
r3 is one of C1-C4 straight chain or branched alkyl;
r5 is a single bond, - (CH) 2 ) m -one of linear or branched alkyl groups; m is selected from integers of 0-10, n is selected from integers of 4-10;
r6 is a single bond, -CH 2 -、-(CH 2 ) 2 、-CH(CH 3 ) -, or-C (CH) 3 ) 2 -one of the following.
In another aspect, the present invention provides a method for preparing a modified resin having tear resistance as described above, the method comprising:
the invention provides a preparation method of tear-resistant resin, which comprises the following steps:
(1) Rosin or derivatives thereof are added into a reaction bottle according to a proportion, heated and melted, stirring is started, and the reaction temperature is controlled to be about 100-140 ℃;
(2) After rosin or derivatives thereof are completely melted, adding a catalyst, adding a modifier, stirring, controlling the reaction temperature to be 100-180 ℃, and stirring and mixing for 0.3-3 hours;
(3) Adding an antioxidant, adding petroleum resin at a temperature of between 100 and 150 ℃, controlling the reaction temperature to be between 120 and 180 ℃ after the petroleum resin is completely melted, stirring and mixing for 0.2 to 4 hours, and neutralizing with alkali;
(4) After the reaction is completed, reduced pressure distillation is started, and small molecular oligomers can be distilled out.
Preferably, the rosin or derivative thereof comprises any one or a combination of at least two of rosin, tall oil rosin, maleic rosin, rosin glycerol ester, polymerized rosin, hydrogenated rosin.
Preferably, the rosin or derivative thereof comprises rosin, tall oil rosin, and maleic rosin.
Preferably, the catalyst comprises an acid catalyst.
Preferably, the acid catalyst comprises any one or a combination of at least two of oxalic acid, formic acid, acetic acid, benzenesulfonic acid, p-toluenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 4-chlorobenzenesulfonic acid and dodecylbenzenesulfonic acid.
Preferably, the modifier comprises any one or a combination of at least two of styrene, alpha-methyl styrene, maleic anhydride and bismaleimide.
Preferably, the antioxidant comprises any one or a combination of at least two of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-Ding Jiben-yl) phosphite, bis (2, 4-di-tert-Ding Jiben-yl) pentaerythritol diphosphite.
Preferably, the petroleum resin comprises any one or a combination of at least two of C9 petroleum resin, C5/C9 copolymerized petroleum resin, DCPD petroleum resin.
Preferably, the petroleum resin is used in an amount of 10 to 90% by weight; the dosage of the rosin or the derivative thereof is 5-70%; the modifier is used in an amount of 0-30%.
Preferably, the petroleum resin is used in an amount of 20-80%, the rosin or the derivative thereof is used in an amount of 10-70%, and the modifier is used in an amount of 2-20%.
Preferably, the petroleum resin is used in an amount of 30-75%, the rosin or the derivative thereof is used in an amount of 20-70%, and the modifier is used in an amount of 2-15%.
Preferably, the petroleum resin is used in an amount of 30-70%, the rosin or the derivative thereof is used in an amount of 30-60%, and the modifier is used in an amount of 2-10%.
In another aspect, the invention also provides a tear resistant resin prepared by any one of the preparation methods.
Preferably, the softening point of the prepared tear-resistant resin is 70-130 ℃, the acid value is 5-300 mg KOH/g, and the iodine value is 20-190.
In another aspect, the present invention provides a rubber composition comprising a tear resistant resin as described in any one of the preceding.
Preferably, the rubber composition further comprises any one of natural rubber, synthetic rubber, or a combination of at least two.
The invention has the following beneficial effects:
(1) The production process is simple, the solvent is not needed in the reaction process, high pressure is not needed, no waste water is generated in the reaction process, and the environmental pollution is reduced.
(2) The rubber composition has good compatibility with rubber, after the rubber additive is added in a rubber material formula, the tear resistance is obviously improved, the product stability is good, the mechanical properties such as the tear resistance after aging are kept good, the t5 scorch time can be prolonged, the processing safety is improved, the t35-t5 is shortened, the vulcanization efficiency of the rubber composition is improved, and the vulcanization reduction resistance is obviously improved.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The invention will be described in further detail with reference to the following examples, which are given by way of illustration only and are not intended to be limiting.
The present invention provides a tear-resistant resin prepared from raw materials including rosin or a derivative thereof and petroleum resin; the tear resistant resin has an iodine value of 20 to 190.
Preferably, the rosin or derivative thereof comprises any one or a combination of at least two of rosin, tall oil rosin, maleic rosin, rosin glycerol ester, polymerized rosin, hydrogenated rosin.
Preferably, the petroleum resin is selected from any one or a combination of at least two of C9 petroleum resin, C5/C9 copolymerized petroleum resin, DCPD petroleum resin. Preferably, the polymer has the structure of formula I, said formula I polymer comprising 10-70wt.% of said tear resistant resin.
Wherein, in the formula I,
r1 is one of a H, C1-C12 linear or branched alkyl group;
r2 is one of C1-C4 branched or straight-chain alkyl;
r3 is one of C1-C4 straight chain or branched alkyl;
r5 is a single bond, - (CH) 2 ) n -one of linear or branched alkyl groups; the method comprises the steps of carrying out a first treatment on the surface of the m is an integer of 0 to 10, and n is an integer of 4 to 10.
R6 is a single bond, -CH 2 -、-(CH 2 ) 2 、-CH(CH 3 ) -, or-C (CH) 3 ) 2 -one of the following.
The invention also provides a preparation method of the tear-resistant resin, which comprises the following steps:
(1) Rosin or derivatives thereof are added into a reaction bottle according to a proportion, heated and melted, stirring is started, and the reaction temperature is controlled to be about 100-140 ℃;
(2) After rosin or derivatives thereof are completely melted, adding a catalyst, adding a modifier, stirring, controlling the reaction temperature to be 100-180 ℃, and stirring and mixing for 0.3-3 hours;
(3) Adding an antioxidant, adding petroleum resin at a temperature of between 100 and 150 ℃, controlling the reaction temperature to be between 120 and 180 ℃ after the petroleum resin is completely melted, stirring and mixing for 0.2 to 4 hours, and neutralizing with alkali;
(4) After the reaction is completed, vacuum distillation is started to distill out small molecular oligomers;
(5) Discharging, granulating and packaging.
Preferably, the rosin or derivative thereof comprises any one or a combination of at least two of rosin, tall oil rosin, maleic rosin, rosin glycerol ester, polymerized rosin, hydrogenated rosin.
Preferably, the rosin or the derivative thereof comprises rosin, tall oil rosin, and maleated rosin.
Wherein the rosin comprises one or more of abietic acid, levopimaric acid, dehydroabietic acid, neoabietic acid, palustric acid, tetrahydroabietic acid, pimaric acid, isopimaric acid and dihydroabietic acid, the softening point is 70-100 ℃, and the acid value is 164-166 mgKOH/g;
wherein the maleic anhydride adduct content of the maleic rosin resin is 5-50%, the softening point is 80-110 ℃, and the structural formula is
Wherein the softening point of the tall oil rosin resin is 65-100 ℃.
Preferably, the catalyst is an acid catalyst.
Preferably, the acid catalyst is selected from any one or a combination of at least two of oxalic acid, formic acid, acetic acid and sulfonic acid R-SO3 organic acids. Wherein, the sulfonic acid R-SO3 organic acid comprises benzenesulfonic acid, p-toluenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 4-chlorobenzenesulfonic acid and dodecylbenzenesulfonic acid.
Preferably, the modifier is selected from any one or a combination of at least two of styrene, alpha-methyl styrene, maleic anhydride and bismaleimide;
preferably, the antioxidant is selected from any one or a combination of at least two of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-Ding Jiben-yl) phosphite and bis (2, 4-di-tert-Ding Jiben-yl) pentaerythritol diphosphite.
Preferably, the petroleum resin is selected from any one or a combination of at least two of C9 petroleum resin, C5/C9 copolymerized petroleum resin, DCPD petroleum resin.
Wherein the softening point of the C9 petroleum resin is 80-130 ℃, and the structural formula is
Wherein n is an integer of 4 to 10;
r1 is one of a H, C1-C12 linear or branched alkyl group;
r2 is one of C1-C3 aliphatic hydrocarbon radical or C1-C4 branched or straight-chain alkyl radical; r3 is one of C1-C4 straight chain or branched alkyl;
wherein the softening point of the C5 petroleum resin is 70-120 ℃, and the structural formula is that
Wherein n is an integer of 3 to 7;
wherein the softening point of the C5/C9 copolymerized petroleum resin is 80-130 ℃, and the structural formula is that
Wherein n is an integer of 2 to 10;
r4 is one of C1-C3 aliphatic hydrocarbon radical or C1-C4 branched or straight-chain alkyl radical; wherein the softening point of the DCPD resin is 80-145 ℃, and the structural formula is
Preferably, the tear resistant resin in the present invention is preferably prepared by reacting the following components in weight percent:
10-90% of petroleum resin; 5-70% of rosin or derivatives thereof; 0-30% of modifier;
preferably, the petroleum resin is 20-80%, the rosin or the derivative thereof is 10-70%, and the modifier is 2-20%;
preferably, the petroleum resin is used in an amount of 30-75%, the rosin or the derivative thereof is used in an amount of 20-70%, and the modifier is used in an amount of 2-15%;
preferably, the petroleum resin is used in an amount of 30-70%, the rosin or the derivative thereof is used in an amount of 30-60%, and the modifier is used in an amount of 2-10%.
Preferably, the softening point of the tearing-resistant resin prepared by the method is 70-130 ℃, the acid value is 5-300 mg KOH/g, and the iodine value is 20-190.
Softening point test: according to GB/T2294-1997, a softening point test is carried out by using a SYD-2806H full-automatic asphalt softening point tester;
acid value test: titration tests were performed according to GB/T264-1983-acid value determination of petroleum products.
Iodine value test: tested according to GB/T9104-2008 industrial stearic acid test method.
Wherein the raw materials used in the following examples: antioxidant 1010 (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), kaija chemical; c9 or C5 petroleum resins, department of petrochemicals limited in the public market; maleated rosin, guangxi brand, chemical industry Co., ltd; rosin and derivatives, styrene, formic acid, sodium hydroxide, and the like are commercially available.
Example 1
In a 500ml flask equipped with a stirring device and a thermometer, a petroleum resin according to C9: gum rosin: styrene mass ratio 50:30:20 proportion, firstly adding 105g of gum rosin, heating and melting, controlling the reaction temperature to be about 110 ℃, after the gum rosin is completely melted, adding 1.75g of formic acid and 70g of styrene, controlling the reaction temperature to be 150 ℃, stirring and mixing for 1h, adding 0.88g of antioxidant 1010, adding 175g of C9 petroleum resin, controlling the reaction temperature to be 150 ℃, stirring for 0.5h, neutralizing by NaOH, starting reduced pressure distillation, controlling the vacuum degree to be-0.1 MPa to-0.04 MPa, completely evaporating the oligomer, controlling the cone-plate viscosity to be about 30-60P (140 ℃ 5# rotor), weighing and discharging to obtain the tear-resistant resin, wherein the tested softening point is 101 ℃, the acid value is 50mgKOH/g, the iodine value is 170, the ash content is 0.01%, and the detected product contains about 69% of the following structures:
wherein, in the formula I,
r1 is one of a H, C1-C12 linear or branched alkyl group;
r2 is one of C1-C4 branched or straight-chain alkyl;
r3 is one of C1-C4 straight chain or branched alkyl;
n=an integer of 4 to 10.
Example 2
The raw materials are prepared from C5 petroleum resin: maleic rosin resin: adding 175g of maleic rosin into the mixture at the mass ratio of 30:50:20, heating and melting the mixture, controlling the reaction temperature to be about 110 ℃, adding 1.75g of formic acid and 70g of alpha-methylstyrene after the maleic rosin is completely melted, controlling the reaction temperature to be 140 ℃, stirring and mixing for 1h, adding 0.5g of antioxidant 1010, adding 105g of C5 petroleum resin, controlling the reaction temperature to be 150 ℃, stirring for 0.5h, neutralizing, starting reduced pressure distillation, controlling the vacuum degree to be-0.1 MPa to-0.04 MPa, discharging the mixture after the oligomer is completely distilled out, and obtaining the anti-tearing resin, wherein the softening point is 99 ℃ through test, the acid value is 51mgKOH/g, and the iodine value is 90.
Example 3
The raw material mass ratio is that according to the example 1, 105g of maleic rosin is firstly added for heating and melting, the reaction temperature is controlled to be 100 ℃, after the maleic rosin is completely melted, 1.75g of formic acid and 70g of styrene are added, the reaction temperature is controlled to be 140 ℃, stirring and mixing are carried out for 1h, 0.88g of antioxidant 1010 is added, 175g of C9 petroleum resin is added, the reaction temperature is controlled to be 160 ℃, stirring is carried out for 0.5h, neutralization and reduced pressure distillation are started, the vacuum degree is controlled to be-0.1 MPa to-0.04 MPa, after all the oligomer is distilled out, the material is discharged, and the tear-resistant resin is obtained, wherein the softening point is 80 ℃ through test, the acid value is 100mgKOH/g, and the iodine value is 150.
Example 4
According to the mass ratio of the raw materials in example 1, 105g of maleic rosin is firstly added for heating and melting, the reaction temperature is controlled to be about 120 ℃, after the maleic rosin is completely melted, 1.75g of formic acid and 70g of styrene are added, the reaction temperature is controlled to be 160 ℃, after stirring and mixing for 1h, 0.88g of antioxidant is added, 175g of C9 petroleum resin is added, the reaction temperature is controlled to be 180 ℃, stirring is carried out for 0.5h, neutralization is carried out, reduced pressure distillation is started, the vacuum degree is controlled to be-0.1 MPa to-0.04 MPa, after all the oligomer is distilled out, the materials are discharged, and the tear-resistant resin is obtained, wherein the softening point is 90 ℃ through testing, the acid value is 90mgKOH/g, and the iodine value is 100.
Example 5
The raw material mass ratio is that according to the example 2, 175g of maleic rosin is firstly added for heating and melting, the reaction temperature is controlled to be 100 ℃, after the maleic rosin is completely melted, 1.75g of formic acid and 70g of alpha-methylstyrene are added, the reaction temperature is controlled to be 120 ℃, after stirring and mixing for 1h, 0.5g of antioxidant is added, 105g of C5 petroleum resin is added, the reaction temperature is controlled to be 140 ℃, after stirring for 1h, neutralization and reduced pressure distillation are started, the vacuum degree is controlled to be-0.1 MPa to-0.04 MPa, after all the oligomer is distilled out, the material is discharged, and the tear-resistant resin is obtained, and the softening point is 89 ℃ through test, the acid value is 60mgKOH/g, and the iodine value is 130.
Example 6
In a 500ml flask equipped with a stirring device and a thermometer, a petroleum resin according to C9: rosin: styrene, maleic anhydride mass ratio 50:30:10:10, firstly adding 105g of maleic rosin, heating and melting, controlling the reaction temperature to be about 110 ℃, adding 1.75g of formic acid, 35g of styrene and 35g of maleic anhydride after the maleic rosin is completely melted, controlling the reaction temperature to be 150 ℃, stirring and mixing for 1h, adding 0.88g of antioxidant, adding 175g of C9 petroleum resin, controlling the reaction temperature to be 150 ℃, stirring for 0.5h, neutralizing, starting reduced pressure distillation, controlling the vacuum degree to be-0.1 MPa to-0.04 MPa, completely distilling off the oligomer, and discharging to obtain the tear-resistant resin, wherein the softening point is 110 ℃ through test, the acid value is 40mgKOH/g, and the iodine value is 20.
Example 7
In a 1000mL flask equipped with a stirring device and a thermometer, a petroleum resin according to C9: rosin: the mass ratio of the alpha-methyl styrene is 50:40:10, 240g of rosin is firstly added for heating and melting, the reaction temperature is controlled to be 110 ℃, 3g of oxalic acid and 60g of alpha-methyl styrene are added after the rosin is completely melted, the reaction temperature is controlled to be 150 ℃, stirring and mixing are carried out for 2 hours, 1.5g of antioxidant is added, 300g of C9 petroleum resin is added, the reaction temperature is controlled to be 160 ℃, stirring is carried out for 1 hour, neutralization is carried out, reduced pressure distillation is started, the vacuum degree is controlled to be-0.1 MPa to-0.04 MPa, and after all micromolecular substances are distilled out, the material is discharged, so that the tear-resistant resin is obtained, the measured softening point is 115 ℃, the acid value is 100mgKOH/g, and the iodine value is 60.
Comparative example 1
In a 500mL flask equipped with a stirring device and a thermometer, the ratio was 6%:44%:20%:30% by weight, 18g of C9 petroleum resin, 132g of hydrogenated C9 resin, 60g of maleic rosin resin and 90g of styrene resin are added, after heating and melting, stirring is started, the reaction temperature is controlled to 160+/-10 ℃, stirring and mixing are carried out for 1.5 hours, reduced pressure distillation is started, the vacuum degree is controlled to-0.06 MPa to-0.08 MPa for 0.5 hour, and the materials are discharged, so that the tear-resistant resin is obtained, and the softening point is 100 ℃ after testing, the acid value is 50mgKOH/g, and the iodine value is 10.
The tear-resistant resin can be prepared in all of examples 1 to 7, and the tear-resistant resin prepared in comparative example 1 is prepared by a one-pot method, namely, no catalyst is added, no modifier is added, and all the substances are simply stirred and mixed uniformly at high temperature.
The effective components of the anti-tearing resin prepared in the examples 1-7 are about 10-70%, and the iodine value is 89-190; the effective active ingredients of the tear-resistant resin prepared in the comparative example are about 20%, and the iodine value is 10-30.
It is still another object of the present invention to provide a rubber composition comprising the above tear resistant resin and one or more selected from the group consisting of natural rubber, synthetic rubber and mixtures thereof. The rubber composition comprises one or more tire portions including a tire tread, carcass reinforcement, sidewalls, or a combination thereof.
In order to test the application performance of the resin in the rubber compound, the tear-resistant resin prepared in example 1 was selected for the application performance test, and the rubber composition formula is shown in table 1.
Table 1 rubber composition formulation
phr: the parts (parts per hundreds of rubber) added per 100 parts by mass of rubber are shown.
300% stretching stress, 100% stretching stress, tensile strength and elongation at break are measured according to a GB/T528-2009 method, tear strength is measured according to a GB/T529-2008 method, tear resistance is measured according to a GB/T3512-2014 method, mooney viscosity ML (1+4) is measured according to a GB/T1232.1-2016 method at 100 ℃, scorch time is measured according to a GB/T1233-2008 method, hardness is measured according to a GB/T6031-2017 method, and vulcanization characteristics of rubber compounds are measured according to a GB/T9869-2014 method.
Table 2 vulcanization characteristics 151 ℃ for 90min
Test item | Blank space | Example 1 | Comparative example 1 |
ML/dNm | 4.60 | 4.58 | 4.7 |
MH/dNm | 21.22 | 21.00 | 22.01 |
Ts2/min | 3.12 | 4.09 | 3.10 |
T10/min | 4.07 | 5.12 | 3.98 |
T90/min | 7.8 | 7.59 | 7.72 |
REV 97/min | 51.56 | 84.07 | 41.05 |
TABLE 3 Mooney viscosity and Mooney scorch
TABLE 4 physical Properties
As can be seen from the application test data in tables 2, 3 and 4, the application performance of the rubber compound prepared in the embodiment 1 can be effectively improved by adding 3phr of the rubber compound, and compared with the rubber compound prepared in the embodiment 1 without adding the anti-tearing resin or with the rubber compound prepared in the comparative embodiment 1, the mechanical properties such as tearing performance, tensile performance and the like of the rubber compound prepared in the embodiment 1 are obviously improved, and the mechanical properties such as tearing performance and the like after aging are kept good; the addition of the tear-resistant resin does not affect other properties, and the physical properties of the sizing material are kept good; meanwhile, the addition of the tear-resistant resin prolongs the scorching time to a certain extent, the vulcanization time is not increased, the processing safety is improved, the reversion resistance is greatly improved, the rubber material is not easy to reversion, the vulcanization flattening period is long enough, and the stability of the crosslinked structure is ensured.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and variations could be made by those skilled in the art without departing from the principles of the present invention, and such modifications and variations should also be considered as being within the scope of the present invention.
Claims (5)
1. A tear resistant resin, prepared by the process of:
heating gum rosin to completely melt, adding a catalyst and a modifier, stirring, controlling the reaction temperature to be 100-180 ℃, and stirring and mixing for 0.3-3 hours;
adding an antioxidant, controlling the temperature to be 100-150 ℃, adding C9 petroleum resin, controlling the reaction temperature to be 120-180 ℃ after the petroleum resin is completely melted, stirring and mixing for 0.2-4 h, neutralizing with alkali, and distilling under reduced pressure to obtain the modified petroleum resin;
wherein the modifier is styrene;
the C9 petroleum resin: gum rosin: the mass ratio of the styrene is 50:30:20, a step of;
the catalyst comprises any one or a combination of at least two of oxalic acid, formic acid, acetic acid, benzenesulfonic acid, p-toluenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 4-chlorobenzenesulfonic acid and dodecylbenzenesulfonic acid.
2. The tear resistant resin of claim 1 wherein,
the antioxidant comprises any one or a combination of at least two of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tri (2, 4-di-tert-butylphenyl) phosphite and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
3. Use of the tear resistant resin of any one of claims 1-2 in a rubber composition.
4. A rubber composition comprising the tear resistant resin of any one of claims 1-2.
5. The tear resistant resin rubber composition of claim 4 further comprising any one or a combination of at least two of natural rubber, synthetic rubber.
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