CN114957898B - 一种可逆应力响应材料及其制备方法和应用 - Google Patents
一种可逆应力响应材料及其制备方法和应用 Download PDFInfo
- Publication number
- CN114957898B CN114957898B CN202210669588.4A CN202210669588A CN114957898B CN 114957898 B CN114957898 B CN 114957898B CN 202210669588 A CN202210669588 A CN 202210669588A CN 114957898 B CN114957898 B CN 114957898B
- Authority
- CN
- China
- Prior art keywords
- molar ratio
- linear polymer
- reversible
- npi
- tad
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000002441 reversible effect Effects 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000003938 response to stress Effects 0.000 title abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims description 71
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 38
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 101000595534 Homo sapiens Transforming growth factor beta regulator 1 Proteins 0.000 claims description 25
- 102100036078 Transforming growth factor beta regulator 1 Human genes 0.000 claims description 25
- 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 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 20
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 19
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 19
- 125000001041 indolyl group Chemical group 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- KLLLJCACIRKBDT-UHFFFAOYSA-N 2-phenyl-1H-indole Chemical compound N1C2=CC=CC=C2C=C1C1=CC=CC=C1 KLLLJCACIRKBDT-UHFFFAOYSA-N 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VYSYZMNJHYOXGN-UHFFFAOYSA-N ethyl n-aminocarbamate Chemical compound CCOC(=O)NN VYSYZMNJHYOXGN-UHFFFAOYSA-N 0.000 claims description 3
- -1 methylene diphenyl Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 15
- 239000002861 polymer material Substances 0.000 abstract description 12
- 229920006037 cross link polymer Polymers 0.000 abstract description 10
- 239000007787 solid Substances 0.000 abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- ZMPYMKAWMBVPQE-UHFFFAOYSA-N 2-[(6-chloropyridin-3-yl)methyl-ethylamino]-2-methyliminoacetic acid Chemical compound CCN(CC1=CN=C(C=C1)Cl)C(=NC)C(=O)O ZMPYMKAWMBVPQE-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- IICQXOJPUDICND-UHFFFAOYSA-N 1,2,4-triazole-3,5-dione Chemical compound O=C1NC(=O)N=N1 IICQXOJPUDICND-UHFFFAOYSA-N 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 230000007017 scission Effects 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010505 homolytic fission reaction Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Images
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
- 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
- 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
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
- C08F267/06—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of esters
-
- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种可逆应力响应材料及其制备方法和应用。本发明所制备的可逆应力响应材料在室温下具有实时可逆力响应的特性,将其应用于交联塑料(高Tg)和橡胶(低Tg)聚合物材料,能够显著增强共价交联聚合物的机械强度和延展性。本发明使用具有力致可逆特性的三唑啉二酮‑吲哚点击化学构建力致可逆交联聚合物材料,这种力致可逆交联方法可以在固态下实现,而无需环境温度以外的任何外部刺激即可实现共价交联点在室温下的断裂和重构,这种室温力可逆C‑N共价交联可被视为设计高强韧聚合物材料的创新方法。
Description
技术领域
本发明属于特种材料技术领域,具体涉及一种可逆应力响应材料及其制备方法和应用。
背景技术
共价交联制备的高分子材料由于具有优异的机械强度和热稳定性,已广泛应用于日常生活的许多领域。大多数共价交联高分子材料是在室温环境下使用的,其中共价高分子网络的完整性直接影响高分子材料的性能和寿命。然而,在交联聚合物中,长期的外力扰动是不可避免的,通常会引起共价键的不可逆断裂,导致交联网络的化学破坏。这种现象严重削弱了共价交联高分子材料的力学性能和功能特性,缩短了其使用寿命,甚至给其应用带来安全风险。
一般来说,共价弱键会优先断裂,以耗散外力扰动的能量。目前,在共价聚合物网络中引入一系列弱力响应的共价键作为交联点,同时提高了聚合物材料的机械强度和延展性。虽然弱力响应的共价键可以通过外部刺激重新形成,如紫外线或可见光照射、加热或催化剂等,但是破坏的键不能在室温条件下实时重整,从而导致聚合物网络在长期应用过程中发生不可逆损伤。此外,均裂所形成的有机自由基显示出良好的解离和重构能力。然而,自由基容易与周围氧分子,水分子和周围其他分子发生不可逆反应,特别是长时间暴露在环境条件下时,自由基会失去其活性。
发明内容
针对上述现有技术中的缺陷,本发明提供一种可逆应力响应材料及其制备方法和应用。
为了达到上述目的,本发明所采用的技术方案是,提供一种可逆应力响应材料及其制备方法和应用。可逆应力响应材料的制备方法包括以下步骤:
S1:合成NPI和NIAM,取其中一种或两种作为吲哚基结构单元;
S2:将线性聚合物原料、吲哚基结构单元以及引发剂AIBN共溶于有机溶剂中,然后于保护气氛围中加热至70~80℃,并保温反应0.5~1h,得预聚物溶液;线性聚合物原料为聚丙烯酸甲酯、聚甲基丙烯酸甲酯、环氧树脂、聚氨酯、聚硅氧烷、聚芳醚酮、聚芳醚砜和聚酰亚胺中的至少一种;
S3:向预聚物溶液中加入ABVN,于50~60℃下反应20~25h,再将反应后的物质在110~130℃下加热2h,然后在75~85℃、0.05~0.1MPa下干燥12~15h,得含有吲哚侧基的线性聚合物;
S4:将含有吲哚侧基的线性聚合物溶解于有机溶剂中,并将溶液温度调节至15~20℃,然后在搅拌条件下加入MDI-TAD,然后将混合均匀的聚合物溶液浇注到玻璃板上,并于75~85℃的真空环境中蒸发10~15h,即得。
在上述技术方案的基础上,本发明还可以做如下改进。
进一步,NPI的合成包括以下步骤:
将2-苯基吲哚和N-羟甲基丙烯酰胺按1:1~1.5的摩尔比共溶于有机溶剂中,在搅拌条件下加入氯化铝,然后于冰浴下反应2h,再升温至室温,并在室温下继续反应45~50h,随后加入稀硫酸,并用DCM进行提取,收集有机相,再浓缩、纯化,即得;所加入的氯化铝与2-苯基吲哚的摩尔比为1:10;所加入的硫酸与氯化铝的摩尔比为3:2。
进一步,NIAM的合成包括以下步骤:
将吲哚和N-羟甲基丙烯酰胺按5:5~10的摩尔比共溶于有机溶剂中,在搅拌条件下加入氯化铝,然后于25~30℃下反应2~3天;随后加入稀硫酸,再抽滤、纯化,即得;所加入的氯化铝与吲哚的摩尔比为3:5;所加入的硫酸与氯化铝的摩尔比为3:2。
进一步,线性聚合物原料与吲哚基结构单元的摩尔比为20:0.5~2;含有吲哚侧基的线性聚合物与MDI-TAD的摩尔比为0.5~2:0.1~1。
进一步,线性聚合物原料为MA,吲哚基结构单元为NPI,MA与NPI的摩尔比为20:1,含有吲哚侧基的线性聚合物与MDI-TAD的摩尔比为1:0.5;或者是,线性聚合物原料为MA,吲哚基结构单元为NIAM,MA与NIAM的摩尔比为20:1,含有吲哚侧基的线性聚合物与MDI-TAD的摩尔比为1:0.5;或者是,线性聚合物原料为MA,吲哚基结构单元为NPI和NIAM,MA与NPI和NIAM的摩尔比为20:0.5:0.5,含有吲哚侧基的线性聚合物与MDI-TAD的摩尔比为0.5:0.5;或者是,线性聚合物原料为MMA,吲哚基结构单元为NPI,MMA与NPI的摩尔比为20:1,含有吲哚侧基的线性聚合物与MDI-TAD的摩尔比为1:0.5。
进一步,AIBN占线性聚合物原料和吲哚基结构单元总质量的0.01%~0.02%;ABVN的加入量占线性聚合物原料和吲哚基结构单元总质量的0.05%~0.2%。
进一步,S2中有机溶剂为N,N-二甲基甲酰胺;S4中有机溶剂为1,4-二氧六环或N,N-二甲基甲酰胺。
进一步,MDI-TAD经过以下步骤制得:
S1:分别将肼基甲酸乙酯和4,4'-亚甲基双(苯基异氰酸酯)溶解于有机溶剂中,再在保护气氛围中将两种溶液混合,混合后先在室温下搅拌反应1~3h,再升温至85~95℃,继续搅拌反应1~3h,随后过滤、洗涤,得双官能度氨基脲;
S2:将双官能度氨基脲溶解于碱液中,在90~120℃下回流1~3h,然后酸化、过滤,得双官能度脲唑;
S3:将双官能度脲唑和DABCO-Br共溶于有机溶剂中,室温下搅拌反应1~3h,随后过滤、真空浓缩,即得;
DABCO-Br的制备方法为:分别将三乙烯二胺和Br2溶解于有机溶剂中,再在保护气氛围中将两种溶液混合,混合后室温搅拌反应1~3h,然后过滤、洗涤、干燥,即得。
本发明还公开了可逆应力响应材料在制备高强韧聚合物的应用。
本发明的有益效果是:本发明所制备的可逆应力响应材料在室温下具有实时可逆力响应的特性,将其应用于交联塑料(高Tg)和橡胶(低Tg)聚合物材料,能够显著增强共价交联聚合物的机械强度和延展性。本发明使用具有力致可逆特性的三唑啉二酮-吲哚点击化学构建高强韧交联聚合物材料,这种力致可逆交联方法可以在固态下实现,而无需室温以外的任何外部刺激即可实现共价交联点在室温下的断裂和重构,这种室温力致可逆C-N共价交联可被视为设计高强韧聚合物材料的创新方法。
附图说明
图1为可逆应力响应材料的合成流程图;
图2为CPMA的核磁共振氢谱图,其中图2a为CPMA在DMSO-
d 6中的谱图,图2b为在7.8-6.8ppm范围内的局部放大图;
图3为CPMMA的核磁共振氢谱图,其中图3a为CPMMA在DMSO-
d 6中的谱图,图3b为在7.8-6.8ppm范围内的局部放大图;
图4为LPMMA、CPMMA、LPMA和CPMA薄膜的差示扫描量热分析;
图5为材料力致可逆C-N键的断裂进行核磁氢谱表征;
图6为不同交联密度材料的应力应变曲线;
图7和图8为材料的原位松弛-荧光和紫外吸收光谱;
图9为材料的原位拉伸-荧光光谱;
图10为材料在不同拉伸应变下C-N键的断裂和重构行为;
图11为力致可逆C-N交联聚合物材料的反复松弛测试结果。
具体实施方式
下面结合实施例对本发明的具体实施方式做详细的说明。
本发明中可逆应力响应材料的制备路径如图1所示。
实施例1
一种可逆应力响应材料,其经过以下步骤制得:
(1)合成N-(1H-2-苯基-吲哚-3-甲基)丙烯酰胺(NPI)
NPI的合成路线如式(1-1)所示。具体方法如下:
将2-苯基吲哚(19.32g,0.1mol)和N-羟甲基丙烯酰胺(12.13g,0.12mol)共溶于二氯甲烷(200mL)中,同时将无水氯化铝(1.34g,10mmol)溶于二氯甲烷(20mL)中形成悬浮液;然后在冰浴及搅拌条件下将含有氯化铝的悬浮液加入到2-苯基吲哚和N-羟甲基丙烯酰胺的混合溶液中,在冰浴中搅拌2小时后,将混合物逐渐升温至室温,并在室温下继续搅拌反应48小时;再向反应混合物加入冰稀硫酸溶液(硫酸与氯化铝的摩尔比为3:2),随后用二氯甲烷(DCM)进行多次提取,收集有机相并用去离子水洗涤,再用Na2SO4干燥、真空浓缩,得到粗产物。通过硅胶柱色谱法纯化粗产物,使用石油醚/乙酸乙酯=2:1(Rf=0.75,TLC洗脱液石油醚:乙酸乙酯=1:2)得到N-(1H-2-苯基-吲哚-3-甲基)丙烯酰胺(NPI,产率73%)。NPI谱图数据如下:
1H NMR (600 MHz, DMSO-d6): δ = 11。373 (s, NH), 8.412 (s, NH), 7.701(s, ArH), 7.598 (s, ArH), 7.529 (t, ArH), 7.404 (m ArH), 7.137 (t, ArH),7.031 ( t, ArH), 6.291 (m, CH), 6.178 (d, CH2, 5.591 (d, CH2, 4.509 (d, CH2。13CNMR (125 MHz, DMSO-d6): δ (ppm) = 164.853 (C), 136.414 (C), 132.634 (C),132.223 (CH), 129.249 (C), 128.830 (CH) , 128.600 (CH), 128.228 (CH2, 125.601(C), 122.321 (CH), 119.596 (CH), 119.416 (CH), 111.703 (C), 108.761 (CH),33.944 (CH2)。 HRMS (m/z):计算值:277.1331 [MH]+,实测值:277.1296 [MH]+。
(2)制备4,4'-(4,4'-二苯基亚甲基)-双-(1,2,4-三唑啉-3,5-二酮)(MDI-TAD)
MDI-TAD的合成路线如式(1-2)所示。具体方法如下:
首先,将肼基甲酸乙酯(40.0 g,0.384 mol,2 eq)和甲苯(300 mL)的混合物放入1L的三颈烧瓶中,在冰浴中冷却;三颈烧瓶配有一个加料漏斗,加料漏斗中装有48.0g 4,4'-亚甲基双(苯基异氰酸酯)(0.192 mol,1 eq)溶解于200 mL甲苯后所形成的溶液;三颈烧瓶还连接有机械搅拌器和冷凝器。用氮气置换三颈烧瓶中的空气,然后在剧烈搅拌下缓慢加入4,4'-亚甲基双(苯基异氰酸酯)溶液。加入后,在室温下搅拌反应2小时,然后升温至90℃,继续搅拌反应2小时,随后冷却到室温,过滤产物并用甲苯洗涤,得到双官能度氨基脲。
然后,在1L烧瓶中,在惰性气氛下将双官能度氨基脲(86.2 g,0.188 mol)溶于330mL氢氧化钾水溶液(4M)中,然后在100℃下回流1.5小时,再入氯化氢至pH=1,随后过滤,得到双官能度脲唑(白色固体粉末)。
最后,将双官能度脲唑(2 g,5.46 mmol,1 eq),DABCO-Br(5g,3.18 mmol,0.58eq)和二氯甲烷(30 mL)的共同加入到100 mL的烧瓶中,并在室温下搅拌反应2h。随后过滤,固体用二氯甲烷(2×30 mL)洗涤,滤液真空浓缩得到MDI-TAD。
DABCO-Br的制备:在500 mL双颈烧瓶中,将三乙烯二胺(6.73 g,60.0 mmol,1 eq)溶解在氯仿(100 mL)中,然后用加料漏斗逐滴添加Br2(20.0 g,0.125 mol,2.1 eq)的氯仿(100 mL)溶液。添加完成后混合物在惰性气氛下搅拌反应1小时,然后过滤出黄色沉淀物,用氯仿(50 mL)洗涤,并在40℃的真空烘箱中干燥过夜,得DABCO-Br。
(3)向配备有磁力搅拌器、氮气出口和入口的双颈烧瓶中加入丙烯酸甲酯(MA,100mmol)、NPI(5mmol)、偶氮二异丁腈(AIBN)(MA与NPI总质量的0.015%)和N,N-二甲基甲酰胺(DMF,3mL),用高纯度氮气冲洗双颈烧瓶。将反应混合物在氮气氛下加热至75℃,搅拌反应0.5小时,得预聚物溶液;然后将偶氮二异庚腈(ABVN,MA与NPI总质量的0.1wt%)添加到预聚物溶液中,并在55℃下加热反应24小时;再将反应后的物质在120℃加热2h,随后将加热后的聚合物置于真空干燥器中,在80℃、0.09MPa下干燥12小时,得到LPMA。
(4)将MDI-TAD(2.5mmol)溶于1,4-二氧六环中,并放入冰箱降温;在80℃下将LPMA溶解在30mL的1,4-二氧六环中,然后将聚合物溶液置于冰箱中以降低聚合物溶液的温度(约15℃),这个过程减慢了混合过程中的交联速度;将聚合物溶液置于具有高搅拌速度(1000rpm)的搅拌器上,将MDI-TAD溶液加入到聚合物溶液中,搅拌20秒;然后将混合溶液浇铸到硅橡胶片上,并放入真空箱中,于80℃下蒸发12h,得到可逆应力响应材料(CPMA,约0.2mm厚)。
CPMA的核磁共振氢谱如图2所示,其中图2a为CPMA在DMSO-
d 6中的谱图,图2b为在7.8-6.8ppm范围内的局部放大图。
实施例2
一种可逆应力响应材料,其经过以下步骤制得:
(1)合成N-(1H-2-苯基-吲哚-3-甲基)丙烯酰胺(NPI)
NPI的合成方法同实施例1;
(2)制备4,4'-(4,4'-二苯基亚甲基)-双-(1,2,4-三唑啉-3,5-二酮)(MDI-TAD)
MDI-TAD的合成方法同实施例1;
(3)向配备有磁力搅拌器、氮气出口和入口的双颈烧瓶中加入丙烯酸甲酯(MMA,87.8mmol)、NPI(4.4mmol)、偶氮二异丁腈(AIBN)(MMA与NPI总质量的0.01%)和N,N-二甲基甲酰胺(DMF,3mL),用高纯度氮气冲洗双颈烧瓶。将反应混合物在氮气氛下加热至80℃,搅拌反应0.5小时,得预聚物溶液;然后将偶氮二异庚腈(ABVN,MMA与NPI总质量的0.05wt%)添加到预聚物溶液中,并在60℃下加热反应20小时;再将反应后的物质在120℃加热2h,随后将加热后的聚合物置于真空干燥器中,在75℃、0.1MPa下干燥15小时,得到LPMMA。
(4)将MDI-TAD(2.2mmol)溶于N,N-二甲基甲酰胺中,并放入冰箱降温;在80℃下将LPMMA溶解在30mL的N,N-二甲基甲酰胺中,然后将聚合物溶液置于冰箱中以降低聚合物溶液的温度(约15℃),这个过程减慢了混合过程中的交联速度;将聚合物溶液置于具有高搅拌速度(1000rpm)的搅拌器上,将MDI-TAD溶液加入到聚合物溶液中,搅拌20秒;然后将混合溶液浇铸到硅橡胶片上,并放入真空箱中,于80℃下蒸发12h,得到可逆应力响应材料(CPMMA,约0.2mm厚)。
CPMMA的核磁共振氢谱如图3所示,其中图3a为CPMMA在DMSO-d6中的谱图,图3b为在7.8-6.8ppm范围内的局部放大图。
实施例3
一种可逆应力响应材料,其经过以下步骤制得:
(1)合成N-(1H-吲哚-3-甲基)丙烯酰胺(NIAM)
NIAM的合成路线如式(1-3)所示。具体方法如下:
将吲哚(5.85g,0.05mol)、N-羟甲基丙烯酰胺(7.2g,0.07mol)和无水乙醇(100mL)依次加入250cm3锥形瓶中,待N-羟甲基丙烯酰胺完全溶解,缓慢加入无水三氯化铝(4.0g);然后在25℃的水浴中搅拌反应3天;在此期间,体系逐渐由无色变为红色。反应完成后,旋转蒸发除去大部分乙醇,再向浓缩液中倒入稀硫酸溶液(硫酸与三氯化铝的摩尔比为3:2),搅拌除去催化剂三氯化铝;然后抽滤、干燥后得到砖红色粗品,柱层析纯化,石油醚/乙酸乙酯=2:1为洗脱液(Rf=0.45,TLC洗脱液石油醚:乙酸乙酯)=1:2)得到纯的N-(1H-吲哚-3-甲基)丙烯酰胺(NIAM,收率:65.5%)。NIAM谱图数据如下:
1H NMR (600 MHz, DMSO-d6: δ = 10.930 (s, NH), 8.331 (s, NH), 7.549 (d,ArH), 7.367 (d, ArH), 7.272 (d , ArH), 7.082 (d, ArH), 6.984 (d, ArH), 6.249(m, -CH=CH2, 6.139 (m, -CH=CH2, 5.572 (d, -CH =CH2, 4.486 (d, Ar-CH2-)。13CNMR(125 MHz, DMSO-d6: δ (ppm) = 164.648 (C), 136.497 (C), 132.719 (CH), 126.705(C), 125.198 (C), 124.069 (CH) , 122.020 (CH), 119.139 (CH), 119.002 (CH),112.564 (C), 111.717 (CH), 34.539 (CH2。 HRMS (m/z):计算值:201.1024 [MH]+,实测值:201.0983 [MH]+。
(2)制备4,4'-(4,4'-二苯基亚甲基)-双-(1,2,4-三唑啉-3,5-二酮)(MDI-TAD)
MDI-TAD的合成方法同实施例1;
(3)向配备有磁力搅拌器、氮气出口和入口的双颈烧瓶中加入丙烯酸甲酯(MA,104.2mmol)、NIAM(5.21mmol)、偶氮二异丁腈(AIBN)(MA与NPI总质量的0.02%)和N,N-二甲基甲酰胺(DMF,3mL),用高纯度氮气冲洗双颈烧瓶。将反应混合物在氮气氛下加热至80℃,搅拌反应1小时,得预聚物溶液;然后将偶氮二异庚腈(ABVN,MA与NPI总质量的0.2wt%)添加到预聚物溶液中,并在50℃下加热反应25小时;再将反应后的物质在130℃加热2h,随后将加热后的聚合物置于真空干燥器中,在85℃、0.05MPa下干燥15小时,得到LPMA。
(4)将MDI-TAD(2.6mmol)溶于1,4-二氧六环中,并放入冰箱降温;在80℃下将LPMA溶解在30mL的1,4-二氧六环中,然后将聚合物溶液置于冰箱中以降低聚合物溶液的温度(约15℃),这个过程减慢了混合过程中的交联速度;将聚合物溶液置于具有高搅拌速度(1000rpm)的搅拌器上,将MDI-TAD溶液加入到聚合物溶液中,搅拌20秒;然后将混合溶液浇铸到硅橡胶片上,并放入真空箱中,于85℃下蒸发10h,得到可逆应力响应材料(ir-CPMA,约0.2mm厚)。
实施例4
一种可逆应力响应材料,其经过以下步骤制得:
(1)合成N-(1H-2-苯基-吲哚-3-甲基)丙烯酰胺(NPI)和N-(1H-吲哚-3-甲基)丙烯酰胺(NIAM)
NPI的合成方法同实施例1;NIAM的合成方法同实施例3;
(2)制备4,4'-(4,4'-二苯基亚甲基)-双-(1,2,4-三唑啉-3,5-二酮)(MDI-TAD)
MDI-TAD的合成方法同实施例1;
(3)向配备有磁力搅拌器、氮气出口和入口的双颈烧瓶中加入丙烯酸甲酯(MA,102mmol)、NPI(2.55mmol)、NIAM(2.55mmol)、偶氮二异丁腈(AIBN)(MA与NPI和NIAM总质量的0.015%)和N,N-二甲基甲酰胺(DMF,3mL),用高纯度氮气冲洗双颈烧瓶。将反应混合物在氮气氛下加热至80℃,搅拌反应1小时,得预聚物溶液;然后将偶氮二异庚腈(ABVN,MA与NPI和NIAM总质量的0.1wt%)添加到预聚物溶液中,并在60℃下加热反应20小时;再将反应后的物质在110℃加热2h,随后将加热后的聚合物置于真空干燥器中,在75℃、0.1MPa下干燥12小时,得到LPMA。
(4)将MDI-TAD(2.55mmol)溶于1,4-二氧六环中,并放入冰箱降温;在80℃下将LPMA溶解在30mL的1,4-二氧六环中,然后将聚合物溶液置于冰箱中以降低聚合物溶液的温度(约15℃),这个过程减慢了混合过程中的交联速度;将聚合物溶液置于具有高搅拌速度(1000rpm)的搅拌器上,将MDI-TAD溶液加入到聚合物溶液中,搅拌20秒;然后将混合溶液浇铸到硅橡胶片上,并放入真空箱中,于75℃下蒸发15h,得到可逆应力响应材料(du-CPMA,约0.2mm厚)。
结果分析
观察实施例1制得的LPMA、CPMA,实施例2制得的LPMMA、CPMMA,实施例3制得的ir-CPMA以及实施例4制得的du-CPMA的透明度,并用不同的溶剂在不同温度下(室温和120℃)对它们进行溶解,结果如表1所示。
表1 可逆应力响应材料的透明度及溶解性能
注:e++:聚合物在室温下可完全溶解;+–:聚合物只能在120℃下溶解;--:聚合物在高温和室温下不溶。
从表1中可以看出,本发明所制备的可逆应力响应材料在室温环境下为半透明、非粘性的不溶性固体。线性聚合物(LPMMA,LPMA)在不同极性溶剂中均可以完全溶解。不同交联类型的聚合物(CPMA,CPMMA,ir-CPMA,du-CPMA)均表现出极低的溶解质量百分比(<5wt%可认为聚合物不可溶),即使是长达七天的浸泡也不能使其溶解,说明MDI-TAD的引入使原本含吲哚侧基线性的聚合物交联成网状结构。同时,对上述材料进行了差示扫描量热法(DSC)分析,结果如图4所示,从图中可以看出,CPMMA可视为典型的硬质热固性材料(Tg=120℃),CPMA为软材料(Tg=18℃),MDI-TAD的引入使得原先线性聚合物链通过各个交联点结合,限制了聚合物链段的运动,提高了使聚合物链段“解冻”的温度。
对材料力致可逆C-N键的断裂进行核磁氢谱表征,结果如图5所示,从图中可以看出在研磨后C-N键断裂并产生新的产物。通过对交联密度进行筛选得到当交联密度为5%时PMA和PMMA材料具有最佳的力学性能(图6)。对CPMA-5%和CPMMA-5%进行原位松弛-荧光和紫外吸收光谱,结果如图7和图8所示,结果展示在拉伸力作用下可逆C-N键断裂和重构展示出紫外和荧光强度的变化。为阐明力可逆C-N交联聚合物的动力学,对两种薄膜进行原位拉伸-荧光光谱,结果如图9所示。上述结果反映材料动力学变化如图10示意图,当应变小于40%时,力可逆C-N键未发生断裂;当应变大约60%时,力可逆C-N键开始断裂并在松弛后在原位点重新成键;当应变大于80%时,力可逆C-N键断裂后在新的位点重新成键。对C-N键交联聚合物材料进行反复的松弛测试,结果如图11所示,当应变大于60%时多余的聚合物内应力可以被完全松弛,这是因为力可逆C-N键在交联聚合物网络中不断断裂和重构时进行了能量耗散。
虽然结合实施例对本发明的具体实施方式进行了详细地描述,但不应理解为对本专利的保护范围的限定。在权利要求书所描述的范围内,本领域技术人员不经创造性劳动即可作出的各种修改和变形仍属本专利的保护范围。
Claims (10)
1.一种可逆应力响应材料的制备方法,其特征在于,包括以下步骤:
S1:合成NPI和NIAM,取其中一种或两种作为吲哚基结构单元;所述NPI的结构式如下所示:
;
所述NIAM的结构式如下所示:
;
S2:将线性聚合物原料、吲哚基结构单元以及AIBN共溶于有机溶剂中,然后于保护气氛围中加热至70~80℃,并保温反应0.5~1h,得预聚物溶液;所述线性聚合物原料为丙烯酸甲酯和甲基丙烯酸甲酯中的至少一种;
S3:向预聚物溶液中加入ABVN,于50~60℃下反应20~25h,再将反应后的物质在110~130℃下加热2h,然后在75~85℃、0.05~0.1MPa下干燥12~15h,得含有吲哚侧基的线性聚合物;
S4:将含有吲哚侧基的线性聚合物溶解于有机溶剂中,并将溶液温度调节至15~20℃,然后在搅拌条件下加入MDI-TAD,然后将混合均匀的聚合物溶液浇注到玻璃板上,并于75~85℃的真空环境中蒸发10~15h,即得;所述MDI-TAD的结构式如下所示:
。
2.根据权利要求1所述的可逆应力响应材料的制备方法,其特征在于,NPI的合成包括以下步骤:
将2-苯基吲哚和N-羟甲基丙烯酰胺按1:1~1.5的摩尔比共溶于有机溶剂中,在搅拌条件下加入氯化铝,然后于冰浴下反应2h,再升温至室温,并在室温下继续反应45~50h,随后加入稀硫酸,并用DCM进行提取,收集有机相,再浓缩、纯化,即得;所加入的氯化铝与2-苯基吲哚的摩尔比为1:10;所加入的硫酸与氯化铝的摩尔比为3:2。
3.根据权利要求1所述的可逆应力响应材料的制备方法,其特征在于,NIAM的合成包括以下步骤:
将吲哚和N-羟甲基丙烯酰胺按5:5~10的摩尔比共溶于有机溶剂中,在搅拌条件下加入氯化铝,然后于25~30℃下反应2~3天;随后加入稀硫酸,再抽滤、纯化,即得;所加入的氯化铝与吲哚的摩尔比为3:5;所加入的硫酸与氯化铝的摩尔比为3:2。
4.根据权利要求2或3所述的可逆应力响应材料的制备方法,其特征在于:所述线性聚合物原料与吲哚基结构单元的摩尔比为20:0.5~2;含有吲哚侧基的线性聚合物与MDI-TAD的摩尔比为0.5~2:0.1~1。
5.根据权利要求4所述的可逆应力响应材料的制备方法,其特征在于:所述线性聚合物原料为MA,所述吲哚基结构单元为NPI,所述MA与NPI的摩尔比为20:1,含有吲哚侧基的线性聚合物与MDI-TAD的摩尔比为1:0.5;或者是,所述线性聚合物原料为MA,所述吲哚基结构单元为NIAM,所述MA与NIAM的摩尔比为20:1,含有吲哚侧基的线性聚合物与MDI-TAD的摩尔比为1:0.5;或者是,所述线性聚合物原料为MA,所述吲哚基结构单元为NPI和NIAM,所述MA与NPI和NIAM的摩尔比为20:0.5:0.5,含有吲哚侧基的线性聚合物与MDI-TAD的摩尔比为0.5:0.5;或者是,所述线性聚合物原料为MMA,所述吲哚基结构单元为NPI,所述MMA与NPI的摩尔比为20:1,含有吲哚侧基的线性聚合物与MDI-TAD的摩尔比为1:0.5。
6.根据权利要求1所述的可逆应力响应材料的制备方法,其特征在于:所述AIBN占线性聚合物原料和吲哚基结构单元总质量的0.01%~0.02%;所述ABVN的加入量占线性聚合物原料和吲哚基结构单元总质量的0.05%~0.2%。
7.根据权利要求1所述的可逆应力响应材料的制备方法,其特征在于:S2中所述有机溶剂为N,N-二甲基甲酰胺;S4中所述有机溶剂为1,4-二氧六环或N,N-二甲基甲酰胺。
8.根据权利要求1所述的可逆应力响应材料的制备方法,其特征在于,所述MDI-TAD经过以下步骤制得:
S1:分别将肼基甲酸乙酯和4,4'-亚甲基双(苯基异氰酸酯)溶解于有机溶剂中,再在保护气氛围中将两种溶液混合,混合后先在室温下搅拌反应1~3h,再升温至85~95℃,继续搅拌反应1~3h,随后过滤、洗涤,得双官能度氨基脲;
S2:将双官能度氨基脲溶解于碱液中,在90~120℃下回流1~3h,然后酸化、过滤,得双官能度脲唑;
S3:将双官能度脲唑和DABCO-Br共溶于有机溶剂中,室温下搅拌反应1~3h,随后过滤、真空浓缩,即得;
所述DABCO-Br的制备方法为:分别将三乙烯二胺和Br2溶解于有机溶剂中,再在保护气氛围中将两种溶液混合,混合后室温搅拌反应1~3h,然后过滤、洗涤、干燥,即得。
9.采用权利要求1~8任一项所述的制备方法制得的可逆应力响应材料。
10.如权利要求9所述的可逆应力响应材料在制备高强韧聚合物的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/891,160 US20230391963A1 (en) | 2022-06-02 | 2022-08-19 | Reversible stress-responsive material, preparation method, and use thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210623223 | 2022-06-02 | ||
CN2022106232238 | 2022-06-02 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114957898A CN114957898A (zh) | 2022-08-30 |
CN114957898B true CN114957898B (zh) | 2023-04-25 |
Family
ID=82961059
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210669588.4A Active CN114957898B (zh) | 2022-06-02 | 2022-06-14 | 一种可逆应力响应材料及其制备方法和应用 |
Country Status (2)
Country | Link |
---|---|
US (1) | US20230391963A1 (zh) |
CN (1) | CN114957898B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117683184B (zh) * | 2024-02-01 | 2024-04-12 | 广东工业大学 | 一种可逆交联共价含硫聚合物弹性体及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017206671A1 (zh) * | 2016-06-01 | 2017-12-07 | 翁秋梅 | 具有动态交联结构的动态聚合物 |
WO2019183140A1 (en) * | 2018-03-19 | 2019-09-26 | The Regents Of The University Of Colorado, A Body Corporate | Tough, healable composites displaying stress relaxation at the resin-filler interface |
CN111378163A (zh) * | 2019-01-01 | 2020-07-07 | 翁秋梅 | 一种组合杂化动态聚合物及其应用 |
CN113896677A (zh) * | 2021-08-23 | 2022-01-07 | 浙江科技学院 | 具有聚集诱导发光性质的可逆力致变色材料及其制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11390710B2 (en) * | 2012-04-27 | 2022-07-19 | Wisys Technology Foundation, Inc. | Reversible crosslinked polymers |
-
2022
- 2022-06-14 CN CN202210669588.4A patent/CN114957898B/zh active Active
- 2022-08-19 US US17/891,160 patent/US20230391963A1/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017206671A1 (zh) * | 2016-06-01 | 2017-12-07 | 翁秋梅 | 具有动态交联结构的动态聚合物 |
WO2019183140A1 (en) * | 2018-03-19 | 2019-09-26 | The Regents Of The University Of Colorado, A Body Corporate | Tough, healable composites displaying stress relaxation at the resin-filler interface |
CN111378163A (zh) * | 2019-01-01 | 2020-07-07 | 翁秋梅 | 一种组合杂化动态聚合物及其应用 |
CN113896677A (zh) * | 2021-08-23 | 2022-01-07 | 浙江科技学院 | 具有聚集诱导发光性质的可逆力致变色材料及其制备方法 |
Non-Patent Citations (3)
Title |
---|
Force–Reversible Chemical Reaction at Ambient Temperature for Designing Toughened Dynamic Covalent Polymer Networks;Mengqi Du 等;Nature communications;第1-9页 * |
Synthesis and evaluation of acrylate resins suspending indole derivative structure in the side chain for marine antifouling;Feng, Kang等;Colloids and Surfaces B: Biointerfaces;第184卷;第1-8页 * |
陈凤等.基于点击化学制备高强韧可再加工环氧弹性体.第36卷(第3期),25-32. * |
Also Published As
Publication number | Publication date |
---|---|
US20230391963A1 (en) | 2023-12-07 |
CN114957898A (zh) | 2022-08-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN114957898B (zh) | 一种可逆应力响应材料及其制备方法和应用 | |
CN105646876B (zh) | 一种有机催化制备聚酯酰胺的方法 | |
US8058358B2 (en) | Method and formula for forming hyper-branched polymer | |
CN112940283B (zh) | 一种基于酰腙键的自修复聚合物水凝胶及其制备方法 | |
CN114605345B (zh) | 含噁二唑环桥连二硝基甲基含能盐及其制备方法 | |
CN117088919B (zh) | 一种噻吩类单体聚合用催化剂及聚噻吩 | |
CN109694476B (zh) | 一种制备含脲基自催化型聚邻苯二甲腈树脂的方法 | |
US4900805A (en) | Rigid rod aromatic benzthiazole heterocyclic polymer | |
CN113773489B (zh) | 一种聚(酰胺-硫代酰胺)聚合物及其合成方法和应用 | |
CN113429629B (zh) | Schiff-HCCP阻燃剂及其制备方法和改性环氧树脂 | |
CN108314799A (zh) | 一种含磷杂吖嗪基和马来酰亚胺基的化合物、环氧树脂材料及其制备方法和应用 | |
CN111944145B (zh) | 热固性聚三唑酯树脂及其复合材料、制备方法 | |
CN114133391A (zh) | 母核取代萘二酰亚胺电化学聚合单体及其制备方法 | |
KR101646341B1 (ko) | 테트라하이드라진이 도입된 칼릭스[4]아렌과 비스페닐알데하이드가 도입된 사이클로헥산의 하이드라존 공중합체, 이의 제조방법 및 이를 포함하는 자외선 차단용 조성물 | |
CN102786718B (zh) | 一种含磷氮杂环的有机无卤阻燃剂及其制备方法 | |
CN115093565B (zh) | 一种聚苯砜醚三唑及其制备方法和应用 | |
CN111647153B (zh) | 一种络合显色聚酰胺的制备方法 | |
CN115028834B (zh) | 一种聚芳基三唑及其制备方法和应用 | |
CN115960288B (zh) | 交联增强的复分解聚烯烃及其制备方法 | |
US4960853A (en) | Rigid rod aromatic benzoxazole/thiazole heterocyclic copolymers | |
CN116515105B (zh) | 一种聚联苯醚高分子化合物及其制备方法和应用 | |
RU2676767C2 (ru) | Политриазол и способ его получения | |
CN116574017A (zh) | 一种双羟基改性反式pbo复合单体及其合成方法 | |
US4960854A (en) | Rigid rod aromatic benzthiazole/oxazole heterocyclic polymer | |
CN108101847B (zh) | 蒽双咪唑盐化合物及其制备方法与应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |