CN114773501A - Cross-linked modified diene rubber, preparation method thereof and rubber material - Google Patents
Cross-linked modified diene rubber, preparation method thereof and rubber material Download PDFInfo
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- CN114773501A CN114773501A CN202210479088.4A CN202210479088A CN114773501A CN 114773501 A CN114773501 A CN 114773501A CN 202210479088 A CN202210479088 A CN 202210479088A CN 114773501 A CN114773501 A CN 114773501A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 118
- 239000005060 rubber Substances 0.000 title claims abstract description 118
- 229920003244 diene elastomer Polymers 0.000 title claims abstract description 110
- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 129
- 239000002184 metal Substances 0.000 claims abstract description 129
- 239000003446 ligand Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 21
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 25
- 238000004132 cross linking Methods 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 24
- 150000003384 small molecules Chemical class 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 18
- 229920003049 isoprene rubber Polymers 0.000 claims description 16
- 238000004073 vulcanization Methods 0.000 claims description 16
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
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- NCJXHPIYRWIILF-UHFFFAOYSA-N 1h-triazole-4,5-dione Chemical compound OC1=NN=NC1=O NCJXHPIYRWIILF-UHFFFAOYSA-N 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 12
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 12
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- 125000005594 diketone group Chemical group 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- -1 1-ethyl- (3-dimethylaminopropyl) Chemical group 0.000 claims description 8
- HJXSWOLXAUFWKK-UHFFFAOYSA-N 2-[4-(4-sulfanyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,2-dioxaborolane-4-thiol Chemical compound C1(=CC=C(C=C1)B1OCC(O1)S)B1OCC(O1)S HJXSWOLXAUFWKK-UHFFFAOYSA-N 0.000 claims description 8
- 238000005189 flocculation Methods 0.000 claims description 8
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- 239000003292 glue Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
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- 230000002441 reversible effect Effects 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 3
- IAJLTMBBAVVMQO-UHFFFAOYSA-N 1h-benzimidazol-2-ylmethanol Chemical compound C1=CC=C2NC(CO)=NC2=C1 IAJLTMBBAVVMQO-UHFFFAOYSA-N 0.000 claims description 3
- MEOBATHMTGFVOA-UHFFFAOYSA-N 2,6-bis(1-methylbenzimidazol-2-yl)-1h-pyridin-4-one Chemical compound C1=CC=C2N(C)C(C=3C=C(O)C=C(N=3)C=3N(C4=CC=CC=C4N=3)C)=NC2=C1 MEOBATHMTGFVOA-UHFFFAOYSA-N 0.000 claims description 3
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 3
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 3
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001430 chromium ion Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 150000002466 imines Chemical class 0.000 claims description 3
- 238000010952 in-situ formation Methods 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 abstract description 16
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- DZAUWHJDUNRCTF-UHFFFAOYSA-N 3-(3,4-dihydroxyphenyl)propanoic acid Chemical compound OC(=O)CCC1=CC=C(O)C(O)=C1 DZAUWHJDUNRCTF-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 12
- ZEMKCDHZMTZUKJ-UHFFFAOYSA-N 2-imidazol-1-ylpropan-1-ol Chemical compound OCC(C)N1C=CN=C1 ZEMKCDHZMTZUKJ-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
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- 238000011084 recovery Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 150000002009 diols Chemical class 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/08—Epoxidation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2315/00—Characterised by the use of rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
Abstract
The invention discloses a cross-linked modified diene rubber, a preparation method thereof and a rubber material, and belongs to the field of diene rubbers. The method comprises the steps of taking diene rubber as a matrix, taking micromolecules containing metal coordination bond ligands as grafts, taking borate micromolecules containing dimercapto as a cross-linking agent, and introducing metal coordination bonds and borate exchangeable bonds into molecular chains of the diene rubber to obtain the cross-linked modified diene rubber. The invention is applied to the aspect of rubber materials, solves the problems of low strength and creep deformation in service of the existing borate ester bond crosslinked diene rubber, has the characteristics of no influence on the repeated processing performance of the material while enhancing and toughening the rubber and improving the creep resistance of the rubber, strong environmental stability, small room temperature lag, and high adjustability and controllability of mechanical property and dynamic property.
Description
Technical Field
The invention belongs to the field of diene rubber, and particularly relates to a crosslinked modified diene rubber, a preparation method thereof and a rubber material.
Background
Rubber is a strategic material with high elasticity, and has an indispensable effect in the fields of civil use, national defense and the like. Covalent bond crosslinking is a premise for obtaining excellent performances of high elasticity, dimensional stability and the like of rubber. The diene rubbers used in the largest industrial quantities are generally crosslinked using sulfur or peroxides, however, the crosslinks formed in this manner are not reversible, which makes recycling of the waste rubbers difficult. China is the country with the most waste rubber, only one waste tire reaches 1500 ten thousand tons in 2018, and the huge waste rubber generation amount causes the problems of environmental pollution and resource waste. Most of the existing modes for treating the waste rubber belong to degradation recovery, and have the problems of time consumption, energy consumption, secondary pollution and the like. Therefore, how to design and prepare the cross-linked rubber material with both thermoplastic material plasticity and thermosetting material excellent performance is one of the hot spots and difficulties of the current rubber field research, and has important scientific value and practical significance.
The incorporation of dynamic covalent bonds into the polymer cross-linked network allows the preparation of moldable thermoset polymers. The dynamic covalent bond is based on a series of reversible equilibrium chemical reactions, can generate reversible 'fracture' and 'recombination' under external stimulation (light, heat, pH value, catalyst and the like), and realizes the network topological structure rearrangement of the polymer through the thermodynamic equilibrium reaction among molecules, thereby endowing the covalent bond crosslinked polymer with the capabilities of healing, reshaping and reprocessing. In 2011, Leibler et al introduced thermally activated associative exchangeable bonds (β -hydroxy ester bonds) into a system of polybasic fatty acids and bisphenol a diglycidyl ether to prepare a plastic thermosetting epoxy resin and proposed the notion of Vitrimer, translated by zushi into a "glass-like polymer".
Despite a series of advances in molecular mechanism of action, design preparation and application, the glass-like polymers still have the following difficulties and disadvantages: the contradiction between catalyst and material life; the contradiction between dynamic property and dimensional stability; the contradiction between reinforcement and repeated processing. In fact, the above-mentioned contradiction is particularly prominent in the diene rubber based glass polymer. As shown in FIG. 1, borate esters are formed by condensation of boric acid with a diol at room temperature (FIG. 1a), which, in addition to hydrolysis (FIG. 1a), can undergo an associative exchange reaction with a diol (FIG. 1b) or another molecule of borate (FIG. 1 c). Although the borate ester bond-based glass-like polymer has excellent healing and repeated processing capabilities without the participation of a catalyst, the borate ester bond can generate exchange reaction at room temperature, the network structure of the polymer is changed, the material is subjected to creep deformation, and the application of the material in many fields is limited.
Disclosure of Invention
Aiming at the problems of low strength and creep during service of the existing borate ester bond crosslinked diene rubber, the invention provides a crosslinked modified diene rubber which has the advantages of rubber reinforcement and toughening, rubber creep resistance improvement, no influence on the repeated processing performance of the material, strong environmental stability, small room temperature lag, high mechanical property and dynamic property controllability, a preparation method thereof and a rubber material.
In order to solve the technical problem, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of cross-linked modified diene rubber, which comprises the steps of taking diene rubber as a substrate, taking micromolecules containing metal coordination bond ligands as grafts, taking borate micromolecules containing dimercapto as a cross-linking agent, and introducing metal coordination bonds and borate exchangeable bonds into molecular chains of the diene rubber to obtain the cross-linked modified diene rubber;
the diene rubber comprises epoxidized diene rubber, vinyl-containing diene rubber or diene rubber with a main chain containing double bonds;
the micromolecule of the ligand containing the metal coordination bond comprises a ligand containing the metal coordination bond, and the terminal group is provided with a group which can directly or indirectly react with the epoxy group, the vinyl group and the main chain double bond of the diene rubber;
the terminal group of the micromolecule containing the metal coordination bond ligand comprises carboxyl, hydroxyl and triazoline diketone.
Preferably, the metal coordinate bond is obtained by coordinating a ligand grafted to the rubber with a metal ion in a metal salt, wherein the metal salt comprises a metal ion and a counter anion, the metal ion is selected from any one of iron, zinc, copper, cobalt, nickel and chromium ions, and the counter anion is selected from Cl-、NO3 -、SO4 2+、CH3COO-、NTf2 -、AcAc-Any one of them.
Preferably, the diene rubber is any one selected from isoprene rubber, styrene-butadiene rubber, epoxidized natural rubber, butadiene rubber, nitrile rubber and butadiene-isoprene rubber; the micromolecule containing the metal coordination bond ligand is selected from any one of 3-amino-1, 2, 4-triazole, 2-hydroxymethylbenzimidazole, 2, 6-bis (1' -methylbenzimidazolyl) -4-hydroxypyridine and maleic anhydride.
Preferably, when the terminal group of the small molecule containing a ligand with a metal coordination bond is a carboxyl group, the preparation process comprises: uniformly mixing micromolecules containing metal coordination bond ligands of carboxyl end groups, metal salt, a catalyst and diene rubber containing epoxy groups in an internal mixer, carrying out hot vulcanization on the uniformly mixed rubber, and synchronously realizing grafting of the rubber, formation of metal coordination bonds and dynamic covalent bond crosslinking of the rubber in the hot vulcanization process to obtain the crosslinked modified diene rubber;
when the terminal group of the micromolecule containing the metal coordination bond ligand is hydroxyl or triazoline diketone, the preparation process comprises the following steps: firstly, carrying out solution grafting modification on diene rubber, then uniformly mixing the graft modified rubber with metal salt and a crosslinking agent 2,2' - (1, 4-phenylene) -bis [ 4-mercapto-1, 3, 2-dioxaborolan ] (BDB), then vulcanizing, and realizing the formation of metal coordination bonds and the dynamic covalent bond crosslinking of the rubber in the vulcanizing process to obtain the crosslinked modified diene rubber.
Preferably, when the terminal group of the small molecule containing a ligand with metal coordination bond is carboxyl, the preparation process specifically comprises:
1-10 parts by mass of the micromolecule containing the metal coordination bond ligand, 1, 2-dimethyl imidazole with the molar content of 25% of the micromolecule containing the metal coordination bond ligand, 1.5 parts by mass of 2,2'- (1, 4-phenylene) -bis [ 4-sulfydryl-1, 3, 2-dioxaborolan ], 26% of 4-dimethylamino pyridine with the molar content of 2,2' - (1, 4-phenylene) -bis [ 4-sulfydryl-1, 3, 2-dioxaborolan ], a metal salt with the molar content of 1/3 of the micromolecule containing the metal coordination bond ligand and the diene rubber are directly mixed in an internal mixer, the rubber is vulcanized on a flat-plate vulcanizing machine, and grafting of the rubber is synchronously completed in the vulcanizing process, The in-situ formation of metal coordination bonds and the dynamic covalent crosslinking of the rubber.
Preferably, when the terminal group of the small molecule containing a metal coordination bond ligand is a hydroxyl group, the preparation process specifically comprises:
grafting mercaptopropionic acid to a vinyl-containing diene rubber molecular chain;
dissolving mercaptopropionic acid graft-modified vinyl-containing diene rubber in toluene, adding hydroxyl-terminated micromolecules containing metal coordination bond ligands, 1-ethyl- (3-dimethylaminopropyl) carbodiimide and 4-dimethylaminopyridine into a glue solution for reaction, pouring the glue solution into excessive absolute ethyl alcohol for flocculation and purification after the reaction is finished, and drying the rubber in vacuum to obtain the hydroxyl-terminated vinyl-containing diene rubber grafted by the hydroxyl-terminated micromolecules containing metal coordination bond ligands.
Preferably, when the terminal group of the small molecule containing a metal coordination bond ligand is a triazolinedione, the preparation process specifically comprises:
adding 1-6 parts by mass of triazoline diketone into a diene rubber solution, reacting at room temperature, pouring the rubber solution into excessive absolute ethyl alcohol for flocculation and purification, and drying rubber in vacuum to obtain triazoline diketone grafted diene rubber.
Alternatively, the borate exchangeable bond may be replaced with any one of a β -hydroxy ester exchangeable bond, a disulfide exchangeable bond, an acetal exchangeable bond, a silyl ether exchangeable bond, and an imine exchangeable bond.
The invention also provides a cross-linked modified diene rubber prepared by the preparation method of the cross-linked modified diene rubber in any technical scheme.
Preferably, the molecular chain of the cross-linked modified diene rubber contains metal coordination bonds and borate exchangeable bonds; at a lower temperature, the metal coordination bonds are used as physical crosslinking points to limit the movement of molecular chains and increase the volume content of limited chain segments in a network, when the material is stretched under stress, the material is reinforced and toughened through reversible fracture and reconstruction, and the exchange reaction of boric acid ester bonds is inhibited through reducing the movement capacity of the molecular chains, so that the creep deformation of the rubber material is inhibited; at high temperatures, the metal coordination bonds dissociate.
The invention also provides a rubber material which comprises the crosslinking modified diene rubber in any technical scheme.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a crosslinking modified diene rubber, the adopted diene rubbers are all commercial products in the rubber industry, the rubber modification method is simple and operable, the processing equipment is all universal rubber processing equipment, the preparation process is simple and feasible, large-scale industrial production can be realized, and the market popularization is facilitated; the molecular chain of the cross-linked modified diene rubber prepared by the method contains metal coordination bonds and borate exchangeable bonds, so that the cross-linked modified diene rubber has the characteristics of no influence on the repeated processing performance of materials while enhancing and toughening rubber and improving the creep resistance of rubber, strong environmental stability, small room temperature hysteresis, and high controllability of mechanical property and dynamic property; the invention also provides a rubber material, which has wider application field.
Drawings
FIG. 1 is a schematic diagram of a reaction process that may occur for a boronic ester;
FIG. 2 is a process flow diagram of a process for preparing a cross-linked modified diene rubber according to an embodiment of the present invention;
FIG. 3 is a creep curve of the sample obtained in example 1 at 100 ℃ under a constant stress of 0.1 MPa;
FIG. 4 is a creep curve of the sample obtained in example 2 at 110 ℃ under a constant stress of 0.15 MPa.
Detailed Description
The technical solutions in the embodiments of the present invention will be fully described in detail below with reference to the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the general principles of the invention, and are not intended to limit the invention to the precise embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the general idea of the invention, fall within the scope of protection of the invention.
As shown in FIG. 2, one aspect of the present invention provides a method for preparing a cross-linked modified diene rubber, wherein a diene rubber is used as a matrix, a small molecule containing a ligand with a metal coordinate bond is used as a graft, and a small molecule containing a dimercapto borate is used as a cross-linking agent (preferably 2,2' - (1, 4-phenylene) -bis [ 4-mercapto-1, 3, 2-dioxaborolan)](BDB)), introducing a metal coordinate bond and a borate exchangeable bond into a molecular chain of the diene rubber, thereby obtaining the crosslinked modified diene rubber. Optionally, the metal coordination bond is obtained by coordinating a ligand grafted on a rubber molecular chain with a metal cation in a metal salt, wherein the metal salt comprises a metal ion and a counter anion, the metal ion is selected from any one of iron, zinc, copper, cobalt, nickel and chromium ions, and further, the counter anion is selected from Cl-、NO3 -、SO4 2+、CH3COO-、NTf2 -、AcAc-Any one of them.
Sacrificial bonds are widely found in nature and include hydrogen bonds, metal coordination bonds, pi-pi interactions, and the like. The sacrificial bond as a weak bond can be broken in preference to a covalent bond, so that energy is dissipated, the integrity of a rubber network is preserved, and the strength and the toughness of the material are remarkably improved on the premise of not sacrificing the elongation at break. In addition, the sacrificial bond has a dissociation temperature (Td), and when T < Td, the sacrificial bond is in an associated state; when T > Td, the sacrificial bond starts to dissociate. Compared with other types of sacrificial bonds, the metal coordination bond has the remarkable advantages that the metal coordination bond is not easily influenced by moisture, the bond energy is highly adjustable, the dissociation temperature is higher, and compared with a hydrogen bond, the advantages of the metal coordination bond are represented as follows: (1) the metal coordination bond is not sensitive to moisture and has higher environmental stability; (2) the bond energy of the metal coordination bond is high, and the relaxation rate is slow, so that the room temperature lag of the rubber material containing the metal coordination bond is small; (3) the thermodynamics and kinetics properties of the metal coordination bond have flexible adjustability in a large range, and the relaxation time of the metal coordination bond can be systematically changed by changing the types of the ligand and the metal ion, so that the controllability of the physical and mechanical properties and the dynamic properties of the material is improved.
Based on the above characteristics of metal coordinate bond, if Td can be obtained appropriately by designing the structure of metal coordinate bond reasonably so that Td is higher than the service temperature and lower than the repeated working temperature, the toughness and creep resistance of the material can be improved without affecting the repeated working performance of the material. The preparation method provided by the technical scheme of the invention takes diene rubber as a matrix, and introduces metal coordination bonds and borate exchangeable bonds in a rubber molecular chain. At a lower temperature, the movement of a molecular chain can be limited by taking a metal coordination bond as a physical cross-linking point, the volume content of a limited chain segment in a network is increased by introducing the metal coordination bond, so that the material can be reinforced and toughened through reversible fracture and reconstruction when the material is stressed and stretched, and the exchange reaction of a boric acid ester bond can be inhibited by reducing the movement capability of the molecular chain, so that the creep deformation of the rubber material is inhibited; at high temperature, the metal coordination bond is dissociated, the rearrangement of the network structure is not hindered, and the material is endowed with good repeated processing performance. Thereby realizing the reinforcement and toughening of the material and inhibiting the creep thereof on the premise of not influencing the repeated processing performance of the material. In addition, the diene rubber adopted by the method is a commercialized product in the rubber industry, the rubber modification method is simple and operable, the processing equipment is universal rubber processing equipment, the preparation process is simple and feasible, and the method can be used for large-scale industrial production and is beneficial to market popularization.
The technical scheme of the application provides a preparation method of the crosslinking modified diene rubber with Td higher than the service temperature and lower than the repeated processing temperature by limiting raw materials and a preparation process, and specifically, the diene rubber comprises epoxidized diene rubber, vinyl-containing diene rubber or diene rubber with a main chain containing double bonds; optionally, the diene rubber is any one selected from isoprene rubber, styrene-butadiene rubber, epoxidized natural rubber, butadiene rubber, nitrile rubber and butadiene-isoprene rubber. The micromolecule of the ligand containing the metal coordination bond comprises a ligand containing the metal coordination bond, and the terminal group is provided with a group which can directly or indirectly react with the epoxy group, the vinyl group and the main chain double bond of the diene rubber; the end group of the micromolecule containing the metal coordination bond ligand comprises carboxyl, hydroxyl and triazoline diketone; optionally, the small molecule containing the metal coordination bond ligand is selected from any one of 3-amino-1, 2, 4-triazole, 2-hydroxymethylbenzimidazole, 2, 6-bis (1' -methylbenzimidazolyl) -4-hydroxypyridine and maleic anhydride.
Wherein, when the terminal group of the small molecule containing the metal coordination bond ligand is carboxyl, the preparation process comprises the following steps: uniformly mixing micromolecules containing metal coordination bond ligands of terminal carboxyl groups, metal salt, catalysts and diene rubber containing epoxy groups in an internal mixer, carrying out hot vulcanization on the uniformly mixed rubber, and synchronously realizing grafting of the rubber, formation of metal coordination bonds and dynamic covalent bond crosslinking of the rubber in the hot vulcanization process to obtain the crosslinked modified diene rubber; specifically, for the ligand graft micromolecule containing a terminal carboxyl group, the graft micromolecule, a cross-linking agent (preferably 2,2' - (1, 4-phenylene) -bis [ 4-mercapto-1, 3, 2-dioxaborolan ], BDB for short), a catalyst for a cross-linking reaction, an additional metal salt and diene rubber containing an epoxy group are mixed uniformly in a rubber internal mixer, then a sample is subjected to heat vulcanization, grafting of the ligand micromolecule to the rubber is synchronously completed in the heat vulcanization process, and a metal coordination bond and a covalent bond of a dynamic borate bond to the rubber are formed in situ by a grafted ligand group and metal ions in the metal salt. When the end group of the small molecule containing the metal coordination bond ligand is hydroxyl or triazoline diketone, the preparation process comprises the following steps: firstly, carrying out solution grafting modification on diene rubber, then uniformly mixing the graft modified rubber, metal salt and a cross-linking agent BDB, then carrying out vulcanization, and realizing the formation of metal coordination bonds and the dynamic covalent bond cross-linking of the rubber in the vulcanization process to obtain the cross-linked modified diene rubber; specifically, when the end group of the small molecule containing the metal coordination bond ligand is a hydroxyl group, mercaptopropionic acid can be grafted to a rubber molecule chain on a diene rubber molecule chain through mercapto-ene 'click' chemistry, then the ligand graft small molecule containing the end hydroxyl group is grafted to the diene rubber molecule chain through an esterification reaction between the grafted carboxyl group and the hydroxyl group in the ligand graft small molecule containing the end hydroxyl group, then the modified rubber, a cross-linking agent (BDB) and an additional metal salt are uniformly mixed in a rubber internal mixer, then a sample is subjected to heat vulcanization, the grafted ligand group and the metal ion in the metal salt form a metal coordination bond in situ in the heat vulcanization process, and the covalent bond crosslinking of the dynamic borate bond to the rubber is realized; when the end group of the micromolecule containing the metal coordination bond ligand is triazolinedione, the process is similar to the condition of the micromolecule containing the metal coordination bond ligand of which the end group is hydroxyl, namely, rubber is firstly grafted and modified (can be completed in one step), the small molecules of the graft containing the triazolinedione ligand are grafted to the molecular chain of the diene rubber through solution grafting and click reaction, then the modified rubber, a cross-linking agent (BDB) and additional metal salt are uniformly mixed in a rubber internal mixer, then a sample is thermally vulcanized, the metal coordination bond is formed in situ by the grafted ligand group and metal ions in the metal salt in the thermal vulcanization process, and the covalent bond crosslinking of the dynamic borate bond to the rubber is realized.
In a preferred embodiment, when the terminal group of the small molecule containing the ligand with metallic coordination bond is carboxyl, the preparation process specifically comprises:
1 to 10 parts of micromolecule containing metal coordination bond ligand, 1, 2-dimethyl imidazole with the molar content of 25 percent of micromolecule containing metal coordination bond ligand, 1.5 parts of 2,2'- (1, 4-phenylene) -bis [ 4-sulfydryl-1, 3, 2-dioxaborolan ] and 2,2' - (1, 4-phenylene) -bis [ 4-sulfydryl-1, 3, 2-dioxaborolan ] with the molar content of 26 percent of 4-dimethylamino pyridine, and metal salt with the molar content of 1/3 percent of micromolecule containing metal coordination bond ligand are directly mixed with the diene rubber in an internal mixer, the rubber is vulcanized on a flat-plate vulcanizing machine, and grafting of the rubber is synchronously completed in the vulcanizing process, The in situ formation of metal coordination bonds and the dynamic covalent crosslinking of the rubber. Wherein, the reaction related to the grafting modification is an esterification reaction between carboxyl and epoxy group, 1, 2-dimethyl imidazole is a catalyst of the esterification reaction, 4-dimethylamino pyridine is a catalyst of 2,2' - (1, 4-phenylene) -bis [ 4-mercapto-1, 3, 2-dioxaborane ] cross-linking epoxidized diene rubber, and metal ions in the added metal salt directly form a metal coordinate bond with the grafted ligand in situ in the rubber matrix.
In a preferred embodiment, when the terminal group of the small molecule containing a ligand with a coordination bond of metal is a hydroxyl group, the preparation process specifically comprises:
firstly, mercaptopropionic acid is grafted on a vinyl-containing diene rubber molecular chain, and the method specifically comprises the following steps of: dissolving rubber in toluene (1g/10mL) at room temperature, adding mercaptopropionic acid (1-5% of vinyl molar content) and azobisisobutyronitrile (AIBN for short, which is an initiator and accounts for 0.14% of vinyl molar content) into a rubber solution under the atmosphere of nitrogen, heating the rubber solution to 80 ℃, reacting for 2 hours, pouring the rubber solution into excessive absolute ethyl alcohol for flocculation and purification, and vacuum-drying the rubber; then, preferably at room temperature, dissolving the mercaptopropionic acid graft-modified vinyl-containing diene rubber in toluene (preferably 1g/10mL), adding a small molecule (preferably in an amount equal to the molar amount of the grafted mercaptopropionic acid) containing a metal coordination bond ligand having a terminal hydroxyl group, 1-ethyl- (3-dimethylaminopropyl) carbodiimide (preferably in an amount 1.3 times the molar amount of the grafted mercaptopropionic acid) and 4-dimethylaminopyridine (preferably in an amount 0.6 times the molar amount of the grafted mercaptopropionic acid) to the gum solution, reacting (preferably at 30 ℃ for 24 hours), pouring the gum solution into excess anhydrous ethanol for flocculation purification after the reaction is finished, and drying the rubber in vacuum to obtain the small molecule grafted vinyl-containing diene rubber containing a metal coordination bond ligand having a terminal hydroxyl group. The first step of the preparation process is 'click' chemical reaction of mercapto group and vinyl group, and the second step is esterification reaction between the carboxyl group grafted in the first step and hydroxyl group in the hydroxyl-terminated ligand micromolecule.
In a preferred embodiment, when the terminal group of the small molecule containing a ligand with a metal coordination bond is triazolinedione, the preparation process specifically comprises:
adding 1-6 parts by mass of triazoline dione (TAD for short) into a diene rubber solution (the preferable concentration is 1g/10mL, and the solvent is tetrahydrofuran), reacting at room temperature (the preferable reaction time is 24h), pouring the rubber solution into excessive absolute ethyl alcohol for flocculation and purification, and drying the rubber in vacuum to obtain the triazoline dione grafted diene rubber. The chemistry involved in this preparation is a "click" chemical reaction of the triazolinedione with the double bond in the diene rubber. It should be noted that Triazolinedione (TAD) can also serve as a graft small molecule containing an amide bond to provide a "hydrogen bond", because TAD is not only a hydrogen bond donor receptor, but also can serve as a ligand to form a metal coordination bond in situ with a metal ion in an added metal salt in a rubber matrix, and construction of different chemical bonds can be achieved only by changing experimental conditions.
Optionally, the borate exchangeable bond may be replaced with any one of a β -hydroxy ester exchangeable bond, a disulfide exchangeable bond, an acetal exchangeable bond, a silyl ether exchangeable bond, and an imine exchangeable bond.
The invention also provides a cross-linked modified diene rubber prepared by the preparation method of the cross-linked modified diene rubber in any technical scheme. The dissociation temperature Td of the crosslinking modified diene rubber is higher than the service temperature and lower than the repeated processing temperature, the toughness and creep resistance of the material can be improved while the repeated processing performance of the material is not influenced, and the crosslinking modified diene rubber has the characteristics of strong environmental stability, small room temperature lag, and high controllability of mechanical performance and dynamic performance. Optionally, the molecular chain of the cross-linked modified diene rubber contains a metal coordination bond and a borate exchangeable bond; at a lower temperature, the metal coordination bonds are used as physical crosslinking points to limit the movement of molecular chains and increase the volume content of limited chain segments in a network, when the material is stretched under stress, the material is reinforced and toughened through reversible fracture and reconstruction, and the exchange reaction of boric acid ester bonds is inhibited through reducing the movement capacity of the molecular chains, so that the creep deformation of the rubber material is inhibited; at high temperatures, the metal coordination bonds dissociate.
The invention also provides a rubber material which comprises the crosslinking modified diene rubber in any technical scheme. The rubber material improves the strength, toughness and creep resistance of the material by introducing a metal coordination bond into the borate crosslinked diene rubber, simultaneously retains the repeated processing performance of the material, and has wider application field.
In order to more clearly and specifically describe the crosslinked modified diene rubber, the preparation method thereof, and the rubber material provided in the examples of the present invention, the following description will be given with reference to specific examples.
Example 1
A preparation method of isoprene rubber with high obdurability, creep resistance and repeatable processing comprises the following steps:
(1) firstly, the double bond on the isoprene rubber molecular chain is partially oxidized into epoxy group, and the epoxidation degree is (1% -4%, and the percentage is the mol percentage of the double bond on the main chain being oxidized into the epoxy group). The specific reaction process is as follows: 5g of Isoprene Rubber (IR) was dissolved in cyclohexane, a certain amount of m-chloroperoxybenzoic acid was dissolved in 25mL of THF, and the resulting solution was added dropwise to the IR solution via a dropping funnel within 30min, followed by reaction at room temperature for 1 hour for oxidative modification. Pouring the reacted glue solution into excessive absolute ethyl alcohol for flocculation and purification to obtain IR (modified rubber 1-4) with different epoxidation degrees. The amounts of the drugs used during grafting are shown in table 1.
TABLE 1 dosage of drugs
| |
|
Modified rubber 3 | Modified rubber 4 | |
| |
5 | 5 | 5 | 5 |
| Meta-chloroperoxybenzoic acid | 0.13 | 0.26 | 0.39 | 0.52 |
The units for the materials listed in table 1 are grams.
(2) Modified rubber 1-4, 3- (3, 4-dihydroxyphenyl) propionic acid, ferric acetylacetonate, 1, 2-Dimethylimidazole (DMI), 4-Dimethylaminopyridine (DMAP), 2' - (1, 4-phenylene) -bis [ 4-mercapto-1, 3, 2-dioxaborane ] (BDB) are added into an internal mixer at 90 ℃ according to the formula listed in the samples 1-4 in the table 2 for mixing for 10min, and the obtained mixed rubber is vulcanized at 160 ℃ according to the positive vulcanization time to obtain isoprene rubber with high toughness, creep resistance and repeatable processing, which respectively correspond to the samples 1-4. Wherein, in the vulcanization process, carboxyl in the 3- (3, 4-dihydroxyphenyl) propionic acid reacts with epoxy groups on the modified rubber 1-4 to complete the grafting of the 3- (3, 4-dihydroxyphenyl) propionic acid on the modified rubber 1-4; and (3) enabling sulfydryl in the BDB to react with residual epoxy groups on molecular chains of 1-4 modified rubber to realize crosslinking of the rubber. The hydroxyl group in the grafted 3- (3, 4-dihydroxyphenyl) propionic acid can form a metal coordination bond with the iron ion in the iron acetylacetonate.
TABLE 2 sample formulation
| |
|
Sample 3 | Sample No. 4 | |
|
| IR | - | - | - | - | 100 |
| |
100 | - | - | - | - |
| Modified rubber 2 | - | 100 | - | - | |
| Modified rubber 3 | - | - | 100 | - | - |
| Modified rubber 4 | - | - | - | 100 | - |
| BDB | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| 3- (3, 4-dihydroxyphenyl) propionic acid | 1.33 | 2.66 | 3.99 | 5.32 | - |
| DMI | 0.41 | 0.82 | 1.23 | 1.64 | - |
| DMAP | 0.203 | 0.203 | 0.203 | 0.203 | 0.203 |
| Iron acetylacetonate | 0.86 | 1.72 | 2.58 | 3.44 | - |
The units for the materials listed in table 2 are in grams; modified rubber 1-4: BDB ═ 100:1.5 (mass ratio) in all formulations, 3- (3, 4-dihydroxyphenyl) propionic acid: DMI 100:25 (molar ratio), BDB: DMAP 100:26 (molar ratio), 3- (3, 4-dihydroxyphenyl) propionic acid: iron acetylacetonate is 3:1 (molar ratio).
Properties of the samples listed in Table 2 As shown in Table 3, the tensile strength and energy to break of the 3- (3, 4-dihydroxyphenyl) propionic acid grafted samples (samples 1 to 4) were higher than those of the sample (comparative sample 1) in which 3- (3, 4-dihydroxyphenyl) propionic acid was not grafted, and the tensile strength and energy to break of the material tended to increase with the increase in the grafting amount (i.e., the content of metal coordinate bonds) of the 3- (3, 4-dihydroxyphenyl) propionic acid. For example, when the grafting amount of the 3- (3, 4-dihydroxyphenyl) propionic acid graft is 4% of the IR main chain double bond, the tensile strength and the energy to break of the material are respectively improved by 7.6 and 5.9 times, while the elongation to break remains almost unchanged. And crushing the crosslinked sample, and then carrying out hot pressing again to obtain a repeatedly processed sample, wherein the tensile strength of the repeatedly processed sample is almost consistent with that of the original sample.
TABLE 3 Performance test results
| Sample No. 1 | |
Sample 3 | Sample No. 4 | |
|
| Tensile Strength (MPa) | 9.8 | 14.8 | 17.9 | 29.0 | 3.8 |
| Elongation at Break (%) | 411 | 405 | 398 | 401 | 399 |
| Energy to break (MJ/m)3) | 16.8 | 22.5 | 32.0 | 44.6 | 7.5 |
| Drawing of reworked samplesTensile Strength recovery (%) | 98 | 97 | 96 | 95 | 96 |
The creep curves of samples 1-4 and comparative sample 1 at 100 ℃ are shown in fig. 3, and it can be seen that the creep rate of comparative sample 1 is the fastest, and the creep amount is the largest, and as the content of the metal coordination bond in the samples gradually increases, the creep rate of the material gradually decreases, and the creep amount also gradually decreases. It is shown that the introduction of the metal coordinate bond significantly suppresses the creep of the material.
Example 2
Preparation method of styrene butadiene rubber with high strength and toughness, creep resistance and repeatable processing
The method comprises the following steps:
(1) firstly, mercapto propionic acid is grafted on styrene butadiene rubber containing vinyl through mercapto-alkene 'click' chemistry, wherein the grafting ratio is 1-4% (relative to the molar content of the vinyl), and the specific reaction process is as follows: and (2) dissolving styrene butadiene rubber in toluene (the concentration is 1g/10mL), heating the glue solution to 80 ℃, adding mercaptopropionic acid and azobisisobutyronitrile into the glue solution under the nitrogen atmosphere, stirring for 2 hours, pouring the glue solution into excessive absolute ethyl alcohol after the reaction is finished, flocculating and drying to obtain the carboxyl grafted styrene butadiene rubber.
(2) Grafting 2- (1H-imidazole-1-yl) propane-1-alcohol to the modified butadiene styrene rubber molecular chain obtained in the step (1) through esterification reaction. The specific reaction process is as follows: and (2) dissolving the rubber obtained in the step (1) in toluene (the concentration is 1g/10mL), adding 2- (1H-imidazole-1-yl) propane-1-ol, 1-ethyl- (3-dimethylaminopropyl), carbonyldiimine and 4-dimethylaminopyridine into the rubber solution under the nitrogen atmosphere, reacting for 24 hours at room temperature under the nitrogen atmosphere, slowly pouring the rubber solution into excessive absolute ethyl alcohol to flocculate and dry the rubber, and obtaining the 2- (1H-imidazole-1-yl) propane-1-ol grafted styrene butadiene rubber (5-8) of modified rubber. The atmosphere during the solution grafting was nitrogen, and the amounts of the chemicals used during the grafting are shown in table 4.
TABLE 4 dosage of drugs
The units for the materials listed in table 4 are grams; 2- (1H-imidazol-1-yl) propan-1-ol: mercaptopropionic acid 1:1 (molar ratio); 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine: mercaptopropionic acid 1.3:1 (molar ratio); 4-dimethylaminopyridine: mercaptopropionic acid ═ 0.6:1 (molar ratio)
(3) The modified styrene-butadiene rubbers 5 to 8 with different 2- (1H-imidazol-1-yl) propan-1-ol grafting ratios obtained in step (2) were mixed with BDB and a metal salt, respectively, in an internal mixer at 90 ℃ for 10 minutes according to the formulations of samples 5 to 8 and comparative sample 2 in Table 5, and the obtained rubber mixtures were vulcanized at 160 ℃ according to the normal vulcanization time to obtain samples 5 to 8 and comparative sample 2.
TABLE 5 sample formulation
| Sample No. 5 | Sample No. 6 | Sample 7 | Sample 8 | |
|
| SBR | - | - | - | - | 100 |
| |
100 | - | - | - | - |
| Modified rubber 6 | - | 100 | - | - | |
| Modified rubber 7 | - | - | 100 | - | - |
| Modified rubber 8 | - | - | - | 100 | - |
| BDB | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Iron acetylacetonate | 0.09 | 0.18 | 0.28 | 0.41 | - |
The units for the materials listed in table 5 are in grams; modified rubber 5-8 BDB ═ 100:1.5 (mass ratio), 2- (1H-imidazol-1-yl) propan-1-ol: iron acetylacetonate is 4:1 (molar ratio).
The properties of the samples prepared are shown in table 6. The tensile strength and the breaking energy of samples 5-8 prepared by grafting the styrene-butadiene rubber with the 2- (1H-imidazole-1-yl) propane-1-ol are higher than those of a comparative sample 2 prepared by non-grafted styrene-butadiene rubber with the 2- (1H-imidazole-1-yl) propane-1-ol, and the grafting rate of the 2- (1H-imidazole-1-yl) propane-1-ol is obviously improved along with the increase of the grafting rate of the 2- (1H-imidazole-1-yl) propane-1-ol. For example, the tensile strength and energy to break of sample 8 were improved by 9.3 times and 10.9 times, respectively, compared to comparative sample 2. While samples 5-8 have nearly unchanged the elongation at break and tensile strength recovery of the reprocessed samples compared to control 2.
TABLE 6 sample Performance test results
The creep curves at 110 ℃ for samples 5-8 and comparative sample 2 are shown in FIG. 4. As can be seen from fig. 4, comparative sample 2 has the fastest creep rate and the greatest amount of creep. As the content of the metal coordination bonds in the sample is gradually increased, the creep rate of the material is gradually reduced, and the creep amount is also gradually reduced. It is shown that the introduction of the metal coordinate bond significantly suppresses the creep of the material.
Claims (10)
1. A preparation method of cross-linked modified diene rubber is characterized in that diene rubber is used as a matrix, micromolecules containing metal coordination bond ligands are used as grafts, borate micromolecules containing dimercapto are used as cross-linking agents, and metal coordination bonds and borate exchangeable bonds are introduced into molecular chains of the diene rubber to obtain the cross-linked modified diene rubber;
the diene rubber comprises epoxidized diene rubber, vinyl-containing diene rubber or diene rubber with a main chain containing double bonds;
the micromolecule of the ligand containing the metal coordination bond comprises a ligand containing the metal coordination bond, and the terminal group is provided with a group which can directly or indirectly react with the epoxy group, the vinyl group and the main chain double bond of the diene rubber;
the end group of the micromolecule containing the metal coordination bond ligand comprises carboxyl, hydroxyl and triazoline diketone.
2. The process for preparing a crosslinked and modified diene rubber according to claim 1, wherein said metal coordination bond is obtained by coordinating a ligand grafted to the rubber to a metal ion in a metal salt, said metal salt comprising a metal ion selected from any one of iron, zinc, copper, cobalt, nickel and chromium ions and a counter anion selected from Cl-、NO3 -、SO4 2+、CH3COO-、NTf2 -、AcAc-Any one of them.
3. The process for producing a crosslinked modified diene rubber according to claim 1, wherein the diene rubber is any one selected from the group consisting of isoprene rubber, styrene-butadiene rubber, epoxidized natural rubber, butadiene rubber, nitrile rubber and butadiene-isoprene rubber; the micromolecule containing the metal coordination bond ligand is selected from any one of 3-amino-1, 2, 4-triazole, 2-hydroxymethylbenzimidazole, 2, 6-bis (1' -methylbenzimidazolyl) -4-hydroxypyridine and maleic anhydride.
4. The process for producing a crosslinked modified diene rubber according to claim 1, wherein,
when the terminal group of the small molecule containing the metal coordination bond ligand is a carboxyl group, the preparation process comprises the following steps: uniformly mixing micromolecules containing metal coordination bond ligands of carboxyl end groups, metal salt, a catalyst and diene rubber containing epoxy groups in an internal mixer, carrying out hot vulcanization on the uniformly mixed rubber, and synchronously realizing grafting of the rubber, formation of metal coordination bonds and dynamic covalent bond crosslinking of the rubber in the hot vulcanization process to obtain the crosslinked modified diene rubber;
when the end group of the small molecule containing the metal coordination bond ligand is hydroxyl or triazoline diketone, the preparation process comprises the following steps: firstly carrying out solution grafting modification on diene rubber, then uniformly mixing the graft modified rubber, metal salt and a crosslinking agent 2,2' - (1, 4-phenylene) -bis [ 4-sulfydryl-1, 3, 2-dioxaborane ], then vulcanizing, and realizing the formation of metal coordination bonds and the dynamic covalent bond crosslinking of the rubber in the vulcanizing process to obtain the crosslinked modified diene rubber.
5. The method of claim 4, wherein when the end group of the small molecule containing a ligand with a metal coordination bond is a carboxyl group, the method specifically comprises:
1-10 parts by mass of the micromolecule containing the metal coordination bond ligand, 1, 2-dimethyl imidazole with the molar content of 25% of the micromolecule containing the metal coordination bond ligand, 1.5 parts by mass of 2,2'- (1, 4-phenylene) -bis [ 4-sulfydryl-1, 3, 2-dioxaborolan ], 26% of 4-dimethylamino pyridine with the molar content of 2,2' - (1, 4-phenylene) -bis [ 4-sulfydryl-1, 3, 2-dioxaborolan ], a metal salt with the molar content of 1/3 of the micromolecule containing the metal coordination bond ligand and the diene rubber are directly mixed in an internal mixer, the rubber is vulcanized on a flat-plate vulcanizing machine, and grafting of the rubber is synchronously completed in the vulcanizing process, The in situ formation of metal coordination bonds and the dynamic covalent crosslinking of the rubber.
6. The method for preparing a cross-linked modified diene rubber according to claim 4, wherein when the terminal group of the small molecule containing the metal coordination bond ligand is a hydroxyl group, the preparation process specifically comprises:
grafting mercaptopropionic acid onto a vinyl-containing diene rubber molecular chain;
dissolving mercaptopropionic acid grafted and modified vinyl-containing diene rubber in toluene, adding a micromolecule containing a metal coordination bond ligand containing a terminal hydroxyl group, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine and 4-dimethylaminopyridine into a glue solution, reacting, pouring the glue solution into excessive absolute ethyl alcohol for flocculation and purification after the reaction is finished, and drying the rubber in vacuum to obtain the micromolecule grafted vinyl-containing diene rubber containing a metal coordination bond ligand containing a terminal hydroxyl group.
7. The method for preparing a cross-linked modified diene rubber according to claim 4, wherein when the terminal group of the small molecule containing a ligand having a metal coordinate bond is a triazolinedione, the preparation process specifically comprises:
adding 1-6 parts by mass of triazoline diketone into a diene rubber solution, reacting at room temperature, pouring the rubber solution into excessive absolute ethyl alcohol for flocculation and purification, and drying rubber in vacuum to obtain triazoline diketone grafted diene rubber.
8. The method for producing a crosslinked and modified diene rubber according to claim 1, wherein the borate exchangeable bond is replaceable with any one of a β -hydroxy ester exchangeable bond, a disulfide exchangeable bond, an acetal exchangeable bond, a silyl ether exchangeable bond, and an imine exchangeable bond.
9. A crosslinked modified diene rubber characterized by being obtained by the process for producing a crosslinked modified diene rubber according to any one of claims 1 to 8; the molecular chain of the cross-linked modified diene rubber contains a metal coordination bond and an exchangeable bond of boric acid ester; at a lower temperature, the metal coordination bonds are used as physical crosslinking points to limit the movement of molecular chains and increase the volume content of limited chain segments in a network, when the material is stretched under stress, the material is reinforced and toughened through reversible fracture and reconstruction, and the exchange reaction of boric acid ester bonds is inhibited through reducing the movement capacity of the molecular chains, so that the creep deformation of the rubber material is inhibited; at high temperatures, the metal coordination bonds dissociate.
10. A rubber material comprising the crosslinked modified diene rubber according to claim 9.
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