CN114907570A - 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
- Publication number
- CN114907570A CN114907570A CN202110174203.2A CN202110174203A CN114907570A CN 114907570 A CN114907570 A CN 114907570A CN 202110174203 A CN202110174203 A CN 202110174203A CN 114907570 A CN114907570 A CN 114907570A
- Authority
- CN
- China
- Prior art keywords
- rosin
- petroleum resin
- resin
- tear
- acid
- 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.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 136
- 239000011347 resin Substances 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920001971 elastomer Polymers 0.000 title description 34
- 239000005060 rubber Substances 0.000 title description 34
- 239000000203 mixture Substances 0.000 title description 19
- 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 103
- 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 102
- 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 102
- 239000003208 petroleum Substances 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 238000004821 distillation Methods 0.000 claims abstract description 12
- 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 9
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 16
- 229910052740 iodine Inorganic materials 0.000 claims description 16
- 239000011630 iodine Substances 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 11
- 239000003784 tall oil Substances 0.000 claims description 11
- 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
- 239000000463 material Substances 0.000 claims description 10
- -1 pentaerythritol ester Chemical class 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 6
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 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
- HBKBEZURJSNABK-MWJPAGEPSA-N 2,3-dihydroxypropyl (1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(=O)OCC(O)CO HBKBEZURJSNABK-MWJPAGEPSA-N 0.000 claims description 3
- 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
- 239000007983 Tris buffer Substances 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
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 3
- 235000010985 glycerol esters of wood rosin Nutrition 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 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 1
- 150000008301 phosphite esters Chemical class 0.000 claims 1
- 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
- 239000002253 acid Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 238000004073 vulcanization Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000000052 comparative effect Effects 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
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 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
- 238000012545 processing Methods 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
- 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
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 125000001931 aliphatic group Chemical group 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
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 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
- 241000557752 Khaya 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
- 238000003889 chemical engineering Methods 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
- 238000001514 detection method Methods 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
- 238000009472 formulation Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 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
- 238000004806 packaging method and process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229960003742 phenol Drugs 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
- 239000007858 starting material 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
- 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 to be 100-140 ℃; 2) after the rosin or the 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 reaction was completed, distillation was performed under reduced pressure. The resin has simple synthesis process and low cost, does not produce waste water, and is easy for 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 in different degrees in the using process, and is particularly easy to be struck and torn by sharp objects under the condition of poor road conditions, so that the service life of the tire is greatly shortened, the excellent service performance of the tire can be endowed by good tear 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 DCPD and phenol as main chains with high rigidity, which has good compatibility with rubber, and the resin improves tear-resistant performance, and also effectively improves processability of rubber, and has good application effect.
In patent CN105254854A, rosin or a derivative structure thereof is added on the basis of CN20131068381, and the esterification reaction is carried out by utilizing the hydroxyl of resin and the carboxyl of the rosin, so that the prepared resin has good compatibility with rubber, the Mooney viscosity is reduced, and the mechanical property of the obtained rubber composition is improved. The patent CN106967201A prepares rosin modified C9 petroleum resin through high-temperature high-pressure polymerization, the resin can improve the tear resistance of the tire table, but the reaction needs to be carried out at high temperature and high pressure, the reaction conditions are harsh, and the production cost is high.
On the basis, the modified resin with the tear resistance is provided, and is simple in synthesis process, low in cost, free of wastewater and easy to industrially utilize.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the modified resin with the tear resistance and the preparation method and the application thereof, the resin has simple synthesis process, no waste water is generated, no extra liquid or gas waste is generated in the added modifier, the resin is environment-friendly, the cost is low, and the resin is easy to be industrially utilized; the rubber composition additive prepared from the resin has good compatibility with rubber, the tear resistance is obviously improved after the rubber additive is added into a rubber material formula, 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.
In order 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 iodine value of the tear-resistant resin is 20-190.
Preferably, the rosin or the derivative thereof comprises any one of rosin, tall oil rosin, maleic rosin, rosin glycerol ester, polymerized rosin, hydrogenated rosin or a combination of at least two of the rosin, the tall oil rosin, the maleic rosin, the rosin glycerol ester, the polymerized rosin and the hydrogenated rosin. Preferably, the petroleum resin is selected from any one of C9 petroleum resin, C5 petroleum resin, C5/C9 copolymerized petroleum resin and DCPD petroleum resin or the combination of at least two of the above resins.
Preferably the polymer has the structure according to formula I, said formula I polymer comprising 10-70 wt.% of the tear resistant resin.
Wherein, in the formula I,
r1 is one of H, C1-C12 straight chain or branched chain alkyl;
r2 is one of C1-C4 branched chain or straight chain alkyl;
r3 is one of C1-C4 straight chain or branched chain alkyl;
r5 is a single bond, - (CH) 2 ) m -one of a linear or branched alkyl group; m is an integer from 0 to 10, and n is an integer from 4 to 10;
r6 is a single bond, -CH 2 -、-(CH 2 ) 2 、-CH(CH 3 ) -, or-C (CH) 3 ) 2 -one of the above.
In another aspect, the present invention provides a method for preparing a modified resin with tear resistance as described above, the method comprising:
the invention provides a preparation method of tear-resistant resin, which comprises the following steps:
(1) adding rosin or derivatives thereof into a reaction bottle in proportion, heating for melting, starting stirring, and controlling the reaction temperature to be about 100-140 ℃;
(2) after the rosin or the derivative thereof is 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 with alkali;
(4) after the reaction is finished, reduced pressure distillation is started, and the small molecular oligomer can be distilled out.
Preferably, the rosin or its derivative includes any one of rosin, tall oil rosin, maleated rosin, glycerol ester of rosin, polymerized rosin, hydrogenated rosin, or a combination of at least two of them.
Preferably, the rosin or derivative thereof comprises rosin, tall oil rosin, maleated rosin.
Preferably, the catalyst comprises an acid catalyst.
Preferably, the acid catalyst comprises any one of oxalic acid, formic acid, acetic acid, benzenesulfonic acid, p-toluenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 4-chlorobenzenesulfonic acid, dodecylbenzenesulfonic acid or a combination of at least two thereof.
Preferably, the modifier comprises any one of styrene, alpha-methyl styrene, maleic anhydride and bismaleimide or the combination of at least two of the styrene, the alpha-methyl styrene, the maleic anhydride and the bismaleimide.
Preferably, the antioxidant comprises any one of or a combination of at least two of tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, tris (2, 4-di-tert-butylyl) phosphite, bis (2, 4-di-tert-butylyl) pentaerythritol diphosphite.
Preferably, the petroleum resin comprises any one of C9 petroleum resin, C5 petroleum resin, C5/C9 copolymerized petroleum resin, DCPD petroleum resin or a combination of at least two of the same.
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 dosage of the modifier is 0-30%.
Preferably, the amount of the petroleum resin is 20-80%, the amount of the rosin or the derivative thereof is 10-70%, and the amount of the modifier is 2-20%.
Preferably, the dosage of the petroleum resin is 30-75%, the dosage of the rosin or the derivative thereof is 20-70%, and the dosage of the modifier is 2-15%.
Preferably, the dosage of the petroleum resin is 30-70%, the dosage of the rosin or the derivative thereof is 30-60%, and the dosage of the modifier is 2-10%.
On the other hand, the invention also provides the tear-resistant resin prepared by the preparation method.
Preferably, the prepared tear-resistant resin has a softening point of 70-130 ℃, an acid value of 5-300 mg KOH/g and an iodine value of 20-190.
In another aspect, the invention provides a rubber composition comprising a tear resistant resin as described in any of the preceding.
Preferably, the rubber composition further includes any one of natural rubber, synthetic rubber, or a combination of at least two thereof.
The invention has the following beneficial effects:
(1) the production process is simple, no solvent or high pressure is needed in the reaction process, no wastewater 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 into a rubber material formula, the tear resistance is obviously improved, the product stability is good, the mechanical properties such as tear resistance after aging and the like are kept good, the t5 scorching time can be prolonged, the processing safety is improved, meanwhile, 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 present invention is further described in detail with reference to the following examples, which are intended to be illustrative of the invention only and are not intended to be limiting.
The invention provides a tear-resistant resin, which is prepared from raw materials comprising rosin or derivatives thereof and petroleum resin; the iodine value of the tear-resistant resin is 20-190.
Preferably, the rosin or its derivative comprises any one of rosin, tall oil rosin, maleated rosin, rosin glyceride, polymerized rosin, hydrogenated rosin, or a combination of at least two of them.
Preferably, the petroleum resin is selected from any one of C9 petroleum resin, C5 petroleum resin, C5/C9 copolymerized petroleum resin and DCPD petroleum resin or the combination of at least two of the above resins. Preferably, the polymer has the structure according to formula I, said formula I polymer comprising 10-70 wt.% of the tear resistant resin.
Wherein, in the formula I,
r1 is one of H, C1-C12 straight chain or branched chain alkyl;
r2 is one of C1-C4 branched chain or straight chain alkyl;
r3 is one of C1-C4 straight chain or branched chain alkyl;
r5 is a single bond, - (CH) 2 ) n -one of a linear or branched alkyl group; (ii) a 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 above.
The invention also provides a preparation method of the tear-resistant resin, which comprises the following steps:
(1) adding rosin or derivatives thereof into a reaction bottle in proportion, heating and melting, starting stirring, and controlling the reaction temperature to be about 100-140 ℃;
(2) after the rosin or the derivative thereof is 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 with alkali;
(4) after the reaction is finished, starting reduced pressure distillation to evaporate small molecular oligomers;
(5) discharging, granulating and packaging.
Preferably, the rosin or the derivative thereof comprises any one of rosin, tall oil rosin, maleic rosin, rosin glycerol ester, polymerized rosin, hydrogenated rosin or a combination of at least two of the rosin, the tall oil rosin, the maleic rosin, the rosin glycerol ester, the polymerized rosin and the hydrogenated rosin.
Preferably, the rosin or derivative thereof comprises rosin, tall oil rosin, 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 of the maleic rosin resin has a content of 5-50%, a softening point of 80-110 ℃, and a structural formula of
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 of oxalic acid, formic acid, acetic acid, sulfonic acid type R-SO3 organic acid or the combination of at least two of the same. Wherein, the sulfonic acid R-SO3 organic acid comprises benzene sulfonic acid, p-toluenesulfonic acid, 2-naphthalene sulfonic acid, 4-hydroxybenzene sulfonic acid, 4-chlorobenzene sulfonic acid and dodecyl benzene sulfonic acid.
Preferably, the modifier is selected from any one of styrene, alpha-methyl styrene, maleic anhydride and bismaleimide or the combination of at least two of the styrene, the alpha-methyl styrene, the maleic anhydride and the bismaleimide;
preferably, the antioxidant is selected from any one of or a combination of at least two of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylyl) phosphite, bis (2, 4-di-tert-butylyl) pentaerythritol diphosphite.
Preferably, the petroleum resin is selected from any one of C9 petroleum resin, C5 petroleum resin, C5/C9 copolymerized petroleum resin and DCPD petroleum resin or the combination of at least two of the above resins.
Wherein the softening point of the C9 petroleum resin is 80-130 ℃, and the structural formula is
Wherein n is an integer of 4-10;
r1 is one of H, C1-C12 straight chain or branched chain alkyl;
r2 is one of C1-C3 aliphatic hydrocarbon group or C1-C4 branched or straight chain alkyl; r3 is one of C1-C4 straight chain or branched chain alkyl;
wherein the softening point of the C5 petroleum resin is 70-120 ℃, and the structural formula is
Wherein n is an integer of 3-7;
wherein the softening point of the C5/C9 copolymerized petroleum resin is 80-130 ℃, and the structural formula is
Wherein n is an integer of 2-10;
r4 is one of C1-C3 aliphatic hydrocarbon group or C1-C4 branched or straight chain alkyl; wherein the softening point of the DCPD resin is 80-145 ℃, and the structural formula is shown in the specification
Preferably, the tear-resistant resin in the invention is prepared by reacting the following components in percentage by weight:
10-90% of petroleum resin; 5-70% of rosin or derivatives thereof; 0-30% of a modifier;
preferably, the using amount of the petroleum resin is 20-80%, the using amount of the rosin or the derivative thereof is 10-70%, and the using amount of the modifier is 2-20%;
preferably, the using amount of the petroleum resin is 30-75%, the using amount of the rosin or the derivative thereof is 20-70%, and the using amount of the modifier is 2-15%;
preferably, the dosage of the petroleum resin is 30-70%, the dosage of the rosin or the derivative thereof is 30-60%, and the dosage of the modifier is 2-10%.
Preferably, the anti-tear resin prepared by the method has a softening point of 70-130 ℃, an acid value of 5-300 mg KOH/g and an iodine value of 20-190.
Softening point test: according to GB/T2294-1997, a SYD-2806H full-automatic asphalt softening point tester is used for softening point test;
acid value test: titration tests were carried out according to GB/T264-1983-Petroleum products acid number determination.
And (3) iodine value test: tested according to GB/T9104-2008 industrial stearic acid test method.
Wherein the following examples used the starting materials: antioxidant 1010 (pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], chemical engineering, Khaya Shanghai; c9 or C5 petroleum resin, Puyang, a commercial science petro-chemical company, Inc.; maleated rosin, guangxi chemical company, leap-chemical company; rosin and its derivatives, styrene, formic acid, sodium hydroxide, etc. are all commercially available.
Example 1
In a 500ml flask equipped with a stirrer and a thermometer, the mass ratio of petroleum resin according to C9: gum rosin: styrene mass ratio 50: 30: adding 105g of gum rosin, heating and melting, controlling the reaction temperature to be about 110 ℃, adding 1.75g of formic acid and 70g of styrene after the gum rosin is completely melted, 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 with NaOH, starting reduced pressure distillation, controlling the vacuum degree to be-0.1 MPa to-0.04 MPa, weighing and discharging after oligomers are completely evaporated, wherein the cone plate viscosity is about 30-60P (140 ℃ 5# rotor), and obtaining 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%, the volatile content is 0.02%, and the product contains about 69% of the following structure by detection:
wherein, in the formula I,
r1 is one of H, C1-C12 straight chain or branched chain alkyl;
r2 is one of C1-C4 branched chain or straight chain alkyl;
r3 is one of C1-C4 straight chain or branched chain alkyl;
n is an integer of 4 to 10.
Example 2
The raw materials are mixed according to the proportion of C5 petroleum resin: maleic rosin resin: feeding alpha-methyl styrene according to the mass ratio of 30:50:20, firstly adding 175g of maleated rosin, heating and melting, controlling the reaction temperature to be about 110 ℃, adding 1.75g of formic acid and 70g of alpha-methyl styrene after the maleated 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 after all oligomers are steamed out, obtaining the tear-resistant resin, testing that the softening point is 99 ℃, the acid value is 51mgKOH/g, and the iodine value is 90.
Example 3
The raw materials are fed according to the mass ratio of the raw materials in the embodiment 1, 105g of maleated rosin is added and heated to be melted, the reaction temperature is controlled to be about 100 ℃, after the maleated rosin is completely melted, 1.75g of formic acid and 70g of styrene are added, the reaction temperature is controlled to be 140 ℃, after 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 ℃, after 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-0.04 MPa, after all oligomers are steamed out, discharging is carried out, the tear-resistant resin is obtained, the softening point is tested to be 80 ℃, the acid value is 100mgKOH/g, and the iodine value is 150.
Example 4
According to the mass ratio of the raw materials in the embodiment 1, firstly 105g of maleated rosin is added and heated to be melted, the reaction temperature is controlled to be about 120 ℃, after the maleated 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 are carried out for 1h, 0.88g of antioxidant is added, 175g of C9 petroleum resin is added, the reaction temperature is controlled to be 180 ℃, after 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 oligomers are steamed out, discharging is carried out, the tear-resistant resin is obtained, the tested softening point is 90 ℃, the acid value is 90mgKOH/g, and the iodine value is 100.
Example 5
The raw materials are fed according to the mass ratio of the embodiment 2, 175g of maleated rosin is added and heated to be melted, the reaction temperature is controlled to be about 100 ℃, after the maleated rosin is completely melted, 1.75g of formic acid and 70g of alpha-methyl styrene are added, the reaction temperature is controlled to be 120 ℃, after stirring and mixing are carried out 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 is carried out for 1h, 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 oligomers are steamed out, the materials are discharged, the tear-resistant resin is obtained, the tested softening point is 89 ℃, the acid value is 60mgKOH/g, and the iodine value is 130.
Example 6
In a 500ml flask equipped with a stirrer and a thermometer, the mass ratio of petroleum resin according to C9: rosin: the mass ratio of styrene to maleic anhydride is 50: 30: 10: adding 105g of maleated 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 maleated 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, discharging after all oligomers are steamed out to obtain the tear-resistant resin, testing the softening point to be 110 ℃, the acid value to be 40mgKOH/g and the iodine value to be 20.
Example 7
In a 1000mL flask equipped with a stirrer and a thermometer, the weight ratio of petroleum resin C9: rosin: the mass ratio of alpha-methyl styrene is 50:40:10, 240g of rosin is added for heating and melting, the reaction temperature is controlled to be 110 ℃, after the rosin is completely melted, 3g of oxalic acid and 60g of alpha-methyl styrene are added, the reaction temperature is controlled to be 150 ℃, stirring and mixing are carried out for 2h, 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 1h, neutralization is carried out, reduced pressure distillation is started, the vacuum degree is controlled to be-0.1 MPa to-0.04 MPa, after small molecular substances are completely evaporated, discharging is carried out, 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 is 6%: 44%: 20%: adding 18g of C9 petroleum resin, 132g of hydrogenated C9 resin, 60g of maleic rosin resin and 90g of styrene resin according to the proportion of 30 percent, heating and melting, starting stirring, controlling the reaction temperature to be 160 +/-10 ℃, stirring and mixing for 1.5h, starting reduced pressure distillation, controlling the vacuum degree to be-0.06 MPa to-0.08 MPa for 0.5h, discharging, and obtaining the tear-resistant resin, wherein the tested softening point is 100 ℃, the acid value is 50mgKOH/g, and the iodine value is 10.
The tear-resistant resins in examples 1 to 7 can be prepared, and the tear-resistant resin in comparative example 1 is prepared by a one-pot method, namely, the tear-resistant resin is prepared by simply stirring and mixing all the materials at high temperature without adding a catalyst or a modifier.
The tear-resistant resin prepared in the embodiments 1 to 7 has about 10 to 70 percent of effective components and an iodine value of 89 to 190; the effective active ingredient of the tear-resistant resin prepared by the comparative example is about 20 percent, and the iodine value is 10-30.
It is a further 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 components including a tire tread, carcass reinforcement, sidewall, or 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 formula of the rubber composition is shown in table 1.
TABLE 1 rubber composition formulation
phr: the number of parts (parts per each rubber of rubber) added per 100 parts (by mass) is shown.
The 300 percent stress at definite elongation, the 100 percent stress at definite elongation, the tensile strength and the elongation at break are measured according to the method GB/T528-2009, the tear strength is measured according to the method GB/T529-2008, the tear resistance is measured according to the method GB/T3512-2014, the Mooney viscosity ML (1+4) at 100 ℃ is measured according to the method GB/T1232.1-2016, the scorching time is measured according to the method GB/T1233-2008, the hardness is measured according to the method GB/T6031-2017, and the vulcanization characteristic of the rubber compound is measured according to the method GB/T9869-2014.
TABLE 2 vulcanization characteristics 151 ℃ 90min
| Test items | 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
Application test data in tables 2, 3 and 4 show that the rubber composition added with the tear-resistant resin prepared in the embodiment 1 can effectively improve the application performance of a rubber material by adding 3phr of the rubber composition, compared with the rubber composition not added with the tear-resistant resin or added with the rubber material of the comparative example 1, the tear performance, tensile property and other mechanical properties of the rubber material added with the tear-resistant resin prepared in the embodiment 1 are obviously improved, and the mechanical properties of the tear performance and the other mechanical properties after aging are kept good; the addition of the anti-tear resin does not affect other properties, and the physical properties of the rubber material are kept good; meanwhile, due to the addition of the anti-tear resin, the scorching time is prolonged to a certain extent, the vulcanization time is not increased, the processing safety is improved, the vulcanization reversion resistance is improved to a great extent, the rubber material is not easy to revert, the vulcanization flattening period is long enough, and the stability of a cross-linked structure is ensured.
The above is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of modifications and embellishments can be made without departing from the principle of the present invention, and these modifications and embellishments should also be regarded as the protection scope of the present invention.
Claims (10)
1. A tear resistant resin prepared from a material comprising rosin or a derivative thereof and a petroleum resin;
the iodine value of the tear-resistant resin is 20-190.
2. The tear resistant resin of claim 1 wherein the rosin or derivative thereof comprises any one of rosin, tall oil rosin, maleated rosin, glycerol ester of rosin, polymerized rosin, hydrogenated rosin, or a combination of at least two thereof.
3. The method according to claim 1, wherein the petroleum resin is selected from any one of C9 petroleum resin, C5 petroleum resin, C5/C9 copolymerized petroleum resin, DCPD petroleum resin or a combination of at least two thereof.
4. The tear resistant resin of claim 1 wherein the tear resistant resin comprises polymer I having the formula wherein polymer I comprises 10-70 wt.% of the tear resistant resin,
wherein, in the formula I, the compound has the structure shown in the specification,
r1 is one of H, C1-C12 straight chain or branched chain alkyl;
r2 is one of C1-C4 branched chain or straight chain alkyl;
r3 is one of C1-C4 straight chain or branched chain alkyl;
r5 is a single bond, - (CH) 2 ) m -one of a linear or branched alkyl group; 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 kind of (1).
5. A preparation method of tear-resistant resin is characterized by comprising the following steps:
1) heating and melting rosin or derivatives thereof, and controlling the reaction temperature to be 100-140 ℃;
2) after the rosin or the derivative thereof is completely melted, adding a catalyst and a modifier, stirring, controlling the reaction temperature at 100-180 ℃, and stirring and mixing for 0.3-3 h;
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 with alkali;
4) after the reaction was completed, distillation was performed under reduced pressure.
6. The method of claim 5, wherein the rosin or derivative thereof comprises any one of rosin, tall oil rosin, maleated rosin, glycerol ester of rosin, polymerized rosin, hydrogenated rosin, or a combination of at least two thereof.
7. The method of claim 5, wherein the catalyst comprises any one of oxalic acid, formic acid, acetic acid, benzene sulfonic acid, p-toluene sulfonic acid, 2-naphthalene sulfonic acid, 4-hydroxybenzene sulfonic acid, 4-chlorobenzene sulfonic acid, dodecyl benzene sulfonic acid, or a combination of at least two thereof.
8. The method of claim 5,
the modifier comprises any one of styrene, alpha-methyl styrene, maleic anhydride and bismaleimide or the combination of at least two of the styrene, the alpha-methyl styrene, the maleic anhydride and the bismaleimide.
9. The method of claim 5,
the antioxidant comprises any one of or a combination of at least two of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tris (2, 4-di-tert-butyl-based) phosphite ester and bis (2, 4-di-tert-butyl-based) pentaerythritol diphosphite ester.
10. The method according to claim 5, wherein the petroleum resin is selected from any one of C9 petroleum resin, C5 petroleum resin, C5/C9 copolymerized petroleum resin, DCPD petroleum resin or a combination of at least two thereof.
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