CN117343235A - Degradable polydicyclopentadiene thermosetting material containing silyl ether primitives and preparation method thereof - Google Patents
Degradable polydicyclopentadiene thermosetting material containing silyl ether primitives and preparation method thereof Download PDFInfo
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000000463 material Substances 0.000 title claims abstract description 105
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 82
- 229920001153 Polydicyclopentadiene Polymers 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 114
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003112 inhibitor Substances 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 20
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims abstract description 18
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 claims abstract description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims abstract description 4
- 239000008204 material by function Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 81
- 238000006243 chemical reaction Methods 0.000 claims description 52
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 39
- 230000015556 catabolic process Effects 0.000 claims description 30
- 238000006731 degradation reaction Methods 0.000 claims description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 150000002430 hydrocarbons Chemical group 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 238000004440 column chromatography Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 13
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 13
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 125000004185 ester group Chemical group 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 150000008301 phosphite esters Chemical group 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- YWZHEUFCDPRCAD-OWOJBTEDSA-N (e)-pent-2-ene-1,5-diol Chemical compound OCC\C=C\CO YWZHEUFCDPRCAD-OWOJBTEDSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- GUVXZFRDPCKWEM-UHFFFAOYSA-N pentalene Chemical compound C1=CC2=CC=CC2=C1 GUVXZFRDPCKWEM-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 4
- 230000000593 degrading effect Effects 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000012634 fragment Substances 0.000 abstract description 6
- 230000009477 glass transition Effects 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- -1 cyclic olefin Chemical class 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 125000001033 ether group Chemical group 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 30
- 238000001816 cooling Methods 0.000 description 14
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 description 13
- 239000011986 second-generation catalyst Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 11
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 7
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- WEIMJSIRDZDHAH-UHFFFAOYSA-N cyclopent-3-en-1-ol Chemical compound OC1CC=CC1 WEIMJSIRDZDHAH-UHFFFAOYSA-N 0.000 description 5
- 229920000548 poly(silane) polymer Polymers 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- UCPDHOTYYDHPEN-UHFFFAOYSA-N cyclooct-4-en-1-ol Chemical compound OC1CCCC=CCC1 UCPDHOTYYDHPEN-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 239000005051 trimethylchlorosilane Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical group C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical group C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- 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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a degradable polydicyclopentadiene thermosetting material containing silyl ether primitives and a preparation method thereof. The polydicyclopentadiene thermosetting material is prepared with dicyclopentadiene, 5-ethylidene-2-norbornene and trifunctional cyclosilyl ether structure (COSIO) 3 ) The catalyst is prepared from monomers, catalysts and inhibitors by front-end ring opening metathesis polymerization (FROMP). Wherein, COSiO 3 The cyclic olefin with the middle cleavable silyl ether bond and lower ring strain energy endows the copolymer dicyclopentadiene thermosetting material with the degradability in the mixed solution of tetrabutylammonium fluoride and tetrahydrofuran. When COSiO 3 At a comonomer content of 7.5wt%, the material was able to degrade completely into soluble fragments, while the polydicyclopentadiene material was excellent in mechanical properties, tensile strength, elongation at break andthe initial decomposition temperature reaches 49.3MPa, 103% and 413 ℃, the glass transition temperature reaches 149 ℃, and the material can be applied to functional materials in the fields of biomedicine, catalysis and sensing.
Description
Technical Field
The invention belongs to the technical field of high polymer materials and engineering, and particularly relates to a degradable polydicyclopentadiene thermosetting material containing silyl ether primitives, and meanwhile relates to preparation of a monomer containing trifunctional silyl ether primitives.
Background
Polydicyclopentadiene is a high-performance thermosetting engineering material, has the advantages of high strength, excellent heat resistance, excellent chemical resistance, excellent coating and bonding performance and the like, and is widely applied to the fields of automobiles, machinery, medical equipment and chlor-alkali industry. However, polydicyclopentadiene has the characteristics of full hydrocarbon composition and high crosslinking density, and is difficult to degrade in a traditional mild mode, so that a large amount of waste is generated, and the ecological environment is greatly influenced.
In order to solve the problems, technological workers at home and abroad have made a great deal of researches on the degradability of thermosetting engineering materials. CN 110218294A discloses a method for preparing a degradable imine epoxy resin curing agent through an amine aldehyde condensation reaction, and introduces a c=n group through a crosslinking curing reaction, so that the degradable epoxy resin has better mechanical properties, but needs to be degraded under the condition of heating and stirring. The CN 115505085A patent discloses a method for introducing acid-sensitive groups hexahydrotriazine ring into polyurethane containing quercetin structure, and the structure can be rapidly decomposed under acidic condition, so that the thermosetting polyurethane material has good comprehensive performance and degradability, but the curing time is longer.
The invention provides a monomer containing silyl ether, which is mixed with dicyclopentadiene and 5-The mixed liquor of the ethylidene-2-norbornene is used for preparing the degradable polydicyclopentadiene thermosetting material through FROMP. COSiO 3 The comonomer ensures that the polydicyclopentadiene material has good degradation performance, the material can be completely degraded into soluble fragments in a mixed solution of tetrabutylammonium fluoride and tetrahydrofuran, meanwhile, the material has excellent strength and thermal stability, and the introduction of a silyl ether structure endows the material with good toughness, the tensile strength, the elongation at break and the initial decomposition temperature respectively reach 49.3MPa, 103% and 413 ℃, and the glass transition temperature reaches 149 ℃.
Disclosure of Invention
One of the purposes of the invention is to provide a degradable polydicyclopentadiene thermosetting material containing a silyl ether group.
The second purpose of the invention is to provide a monomer containing trifunctional silyl ether, which solves the problem that the existing polydicyclopentadiene thermosetting material is not easy to degrade.
The invention discloses a degradable polydicyclopentadiene thermosetting material containing silyl ether primitives and a preparation method thereof. The material can be completely degraded into soluble fragments in a mixed solution of tetrabutylammonium fluoride and tetrahydrofuran, the tensile strength, the elongation at break and the initial decomposition temperature respectively reach 49.3MPa, 103% and 413 ℃, the glass transition temperature reaches 149 ℃, and the material has excellent strength and thermal stability while having degradation performance.
The structural formula of the degradable polydicyclopentadiene thermosetting material containing the silyl ether primitives is shown as formula 1:
wherein m, n, p are each independently integers ranging from 100 to 1000; r is a hydrocarbon group with the number of carbon atoms being an integer between 0 and 6 or a hydrocarbon group with a lateral group having a hydroxyl group, a carboxyl group, an amino group, an ester group and the like; x, y, z are the number of methylene groups, wherein x=1, 2 or 3; y=1, 2 or 3; z=1 or 2.
Wherein the sum of the mass percentages of the raw materials for preparing the degradable polydicyclopentadiene thermosetting material containing the silyl ether primitives is 100 weight percent, and the mass percentages of the raw materials are as follows:
the catalyst is a ruthenium catalyst;
the inhibitor is phosphite esters, and the mass percentage ratio of the catalyst to the inhibitor is 1:1-4:1;
the structural formula of the silyl ether-containing monomer is shown as formula 2:
wherein R is a hydrocarbon group with the number of carbon atoms being an integer between 0 and 6 or a hydrocarbon group with a lateral group having a hydroxyl group, a carboxyl group, an amino group, an ester group and the like; x, y, z are the number of methylene groups, wherein x=1, 2 or 3; y=1, 2 or 3; z=1 or 2.
Further, wherein in structural formulas 1 and 2, the hydrocarbon group includes an alkyl group, an alkenyl group, an alkynyl group.
Further, the preparation method of the thermosetting material comprises the following steps:
(1) Adding the inhibitor into a mixed solution of dicyclopentadiene and 5-ethylidene-2-norbornene according to a proportion, uniformly mixing, adding a monomer containing a silyl ether unit, adding the catalyst, and ultrasonically mixing the mixed solution under the ice water bath condition to obtain a dispersion liquid;
(2) And (3) injecting the dispersion liquid into a mould, thermally initiating at 120-250 ℃, and obtaining the degradable polydicyclopentadiene thermosetting material containing the silyl ether primitives through front-end ring-opening metathesis polymerization.
Further, the method also comprises the step of preparing the monomer containing the silyl ether, and specifically comprises the following steps:
dissolving methyltrichlorosilane and cycloolefin-alcohol shown in structural formula 3 with organic solvent, respectively, dripping the dissolved methyltrichlorosilane into cycloolefin-alcohol solution shown in structural formula 3, and introducing N 2 In the presence of a catalyst, the reaction is carried out at 0-5 ℃, the dropwise adding time is 1-2h, the temperature is raised to the room temperature, the reaction is carried out for 0.5-2h under the stirring condition, and after the reaction is finished, the monosubstituted silyl ether monomer shown in the structural formula 4 is obtained through the operations of filtration, drying, rotary evaporation and column chromatography.
Wherein in the structural formulas 3 and 4, R is a hydrocarbon group with the number of carbon atoms being an integer between 0 and 6 or a hydrocarbon group with a lateral group having a hydroxyl group, a carboxyl group, an amino group, an ester group and the like; x, y is the number of methylene groups, wherein x=1, 2 or 3; y=1, 2 or 3;
dissolving the monosubstituted silyl ether monomer and alkene-diol shown in the structural formula 5 by using an organic solvent respectively, dripping the dissolved monosubstituted silyl ether monomer into the alkene-diol solution, and introducing N 2 In the presence of a catalyst, the reaction is carried out at 0-5 ℃, the dropwise adding time is 1-2h, the temperature is raised to the room temperature, the reaction is carried out for 0.5-36h under the stirring condition, and after the reaction is finished, the silicon-containing ether primitive monomer is obtained through the operations of filtration, drying, rotary evaporation and column chromatography.
In the structural formula 5, z is the number of methylene groups, and z=1 or 2.
Further, the alkene-diol is one of cis-1, 2-dimethylol ethylene, (2E) -2-pentene-1, 5-diol;
the catalyst is one of imidazole, 4-N, N-lutidine, 4-dimethylaminopyridine, N-dimethylaniline, quinoline and 1-methylimidazole.
The required organic solvent is one or more of dichloromethane, n-hexane, ethyl acetate, methanol, ethanol, acetone, chloroform, benzene, xylene, cyclohexane and tetrahydrofuran.
Further, a degradation method of the thermosetting material is characterized in that:
placing the thermosetting material in an organic solvent containing a degradation reagent, wherein the organic solvent is tetrahydrofuran; the degradation reagent is tetrabutylammonium fluoride.
Under the heating condition, the mixed solution of the degradation reagent and the solvent is adopted as the degradation solution, and under the stirring condition, the degradation of the degradable polydicyclopentadiene thermosetting material containing the silyl ether primitive is realized.
Wherein the mass concentration of the degradation reagent is 0.1-100%; the heating temperature is 0-200 ℃; the heating time is 1-120 h.
Further, the application of the thermosetting material is that the thermosetting material is used for intelligent robot equipment structural members, protective equipment in the military field and functional materials in the biomedical, catalytic and sensing fields, and can realize recycling after material discarding.
Further, the application of the silyl ether group-containing monomer in the preparation process of the degradable polydicyclopentadiene thermosetting material is characterized in that the silyl ether group-containing monomer is used as a raw material for preparing the degradable polydicyclopentadiene thermosetting material, and the degradable polydicyclopentadiene thermosetting material is shown in a structural formula 1:
wherein m, n, p are each independently integers ranging from 100 to 1000; r is a hydrocarbon group with the number of carbon atoms being an integer between 0 and 6 or a hydrocarbon group with a lateral group having a hydroxyl group, a carboxyl group, an amino group, an ester group and the like; x, y, z are the number of methylene groups, wherein x=1, 2 or 3; y=1, 2 or 3; z=1 or 2.
A silyl ether monomer for preparing degradable polydicyclopentadiene thermosetting material is shown in structural formula 2
Wherein R is a hydrocarbon group with the number of carbon atoms being an integer between 0 and 6 or a hydrocarbon group with a lateral group having a hydroxyl group, a carboxyl group, an amino group, an ester group and the like; x, y, z are the number of methylene groups, wherein x=1, 2 or 3; y=1, 2 or 3; z=1 or 2.
Further, the synthetic method of the monomer containing the silyl ether moieties comprises the following steps:
is synthesized by nucleophilic substitution reaction of cycloolefin-alcohol and methyltrichlorosilane, and the reaction equation is shown in formula 6;
dissolving reactants with anhydrous dichloromethane, dripping the dissolved methyltrichlorosilane into 3-cyclopenten-1-alcohol, and introducing N 2 The reaction is carried out at 0-5 ℃ for 1-2h, the temperature is raised to room temperature, the reaction is carried out for 0.5-2h under the stirring condition, and after the reaction is finished, the monosubstituted silyl ether monomer (COSIO) is obtained through the operations of filtration, drying, rotary evaporation and column chromatography.
The COSiO monomer and the butadiene (pentalene) -diol are synthesized through nucleophilic substitution reaction, and the reaction equation is shown in formula 7; dissolving the reactants with anhydrous dichloromethane, respectively, adding the dissolved COSiO into cis-1, 2-dimethylol ethylene, and introducing N 2 The reaction is carried out at 0-5 ℃ for 1-2h, the temperature is raised to room temperature, the reaction is carried out for 0.5-36h under the stirring condition, and after the reaction is finished, the silicon ether monomer is obtained through the operations of filtration, drying, rotary evaporation and column chromatography, and is the silicon ether monomer (COSiO 3 )。
The invention has the following beneficial effects:
compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a monomer containing trifunctional silyl ether primitives, which has Si-O bond in the structure, and introduces degradable primitives on the main chain of polydicyclopentadiene molecules, so that polydicyclopentadiene thermosetting material is completely chemically degraded into soluble fragments in the mixed solution of tetrabutylammonium fluoride and tetrahydrofuran. In addition, COSIO 3 The unsaturated double-ring structure in the structure can increase the crosslinking density of polydicyclopentadiene, the material has excellent strength and thermal stability while having degradation performance, and the introduction of the silyl ether structure endows the material with better toughness. When COSiO 3 At a comonomer content of 7.5 wt.%, the tensile strength, elongation at break and initial decomposition temperature of the material reached 49.3MPa, 103% and 413 c, respectively, and the glass transition temperature reached 149 c.
(2) The invention provides a monomer containing trifunctional silyl ether element, when the structure contains low-ring strain energy ring such as cyclopentene, the polydicyclopentadiene thermosetting material has lower polymerization critical temperature (T) c ) The material can be depolymerized into micromolecular cycloolefin derivatives by regulating the temperature in the presence of a catalyst, so that the material degradation is further promoted, and a new idea is provided for controllable degradation and high-value recovery of polydicyclopentadiene thermosetting materials.
(3) Compared with the traditional reaction injection molding curing process, the polymerization process of the degradable polydicyclopentadiene thermosetting material containing the silyl ether primitives is simple, secondary curing is not needed, and the industrial process flow is simple.
Drawings
FIG. 1 is a block diagram of a trifunctional silyl ether-containing monomer A 1 H-NMR spectra
FIG. 2 is a block diagram of a monomer B containing a trifunctional silyl ether moiety 1 H-NMR spectra
FIG. 3 is a schematic illustration of a monomer C containing a monosubstituted silyl ether 1 H-NMR spectra
FIG. 4 shows a containerMonosubstituted silyl ether monomer D 1 H-NMR spectra
FIG. 5 is a block diagram of a trifunctional silyl ether-containing monomer E 1 H-NMR spectra
FIG. 6 is a synthetic scheme of a trifunctional silyl ether-containing monomer A
FIG. 7 is a synthetic scheme of a trifunctional silyl ether-containing monomer B
FIG. 8 is a synthetic scheme for monomer C containing monosubstituted silyl ether
FIG. 9 is a synthetic scheme for monomer D containing monosubstituted silyl ether
FIG. 10 is a synthetic scheme of a trifunctional silyl ether-containing monomer E
FIG. 11 is a graph comparing the before and after degradation of a polydicyclopentadiene thermoset containing a trifunctional silyl monomer A (20 ℃ C.; from left to right: 1. Polydicyclopentadiene; 2. Containing 2.5wt% silyl monomer A;3. Containing 5wt% silyl monomer A;4. Containing 7.5wt% silyl monomer A;5. Containing 10wt% silyl monomer A)
Detailed Description
The invention is further described below in connection with the following detailed description. The scope of the present invention is not limited to the following embodiments, but rather, various modifications and variations can be made without departing from the spirit and scope of the present invention.
The following examples and comparative examples were prepared from the following raw materials:
dicyclopentadiene and 5-ethylidene-2-norbornene are preferably manufactured by Sigma-Aldrich company;
the silyl ether monomers A and B are the self-synthesized tri-functional silyl ether unit-containing monomers of the patent, the structural formulas are shown in the examples 1 and 7, the silyl ether monomers C and D are the self-synthesized mono-substituted silyl ether structural monomers of the patent, the structural formulas are shown in the comparative examples 2 and 3, and the silyl ether monomer E is the self-synthesized tri-functional silyl ether unit-containing monomers of the patent, and the structural formulas are shown in the comparative example 4.
The synthetic raw materials and the catalyst comprise: 3-cyclopenten-1-ol, cycloocta-4-en-1-ol, methyltrichlorosilane, cis-1, 2-dimethylolethane, 1, 4-butanediol, trimethylchlorosilane, imidazole, preferably Shanghai Ala Di Biochemical technologies Co., ltd;
the organic solvent used for synthesis is dichloromethane, n-hexane and ethyl acetate, preferably Shanghai Ala Latin Biochemical technology Co., ltd;
the organic solvent used for degradation is tetrahydrofuran, preferably Shanghai Ala Biochemical technology Co., ltd;
the degradation reagent is tetrabutylammonium fluoride, preferably Shanghai Ala Latin Biochemical technology Co., ltd;
t-butyldimethylallyl silyl ether, preferably Shanghai Meilin Biochemical technologies Co., ltd;
the Grubbs second generation catalyst is ruthenium catalyst, and the inhibitor is phosphite esters, preferably Sigma-Aldrich company product.
Table 1 shows the raw materials and the amounts used in the examples
To demonstrate the effect of the present invention, 6 comparative examples are now provided:
table 2 shows the raw materials and the amounts used in each comparative example
Example 1
The degradable polydicyclopentadiene thermosetting material containing the silyl ether primitives comprises the following raw materials: dicyclopentadiene was 92.435wt%, 5-ethylidene-2-norbornene was 4.865wt%, silyl ether monomer A was 2.5wt%, grubbs' second generation catalyst was 0.16wt%, and inhibitor was 0.04wt%. Wherein the degradable primitive is a monomer A containing trifunctional silyl ether primitive.
The structural formula is as follows:
preparation of silyl ether monomer A (synthetic scheme see FIG. 6):
(1) 50mmol of 3-cyclopenten-1-ol was weighed into a 500mL three-necked flask, and 100mL of anhydrous methylene chloride was added to dissolve. Then 50mmol of catalyst imidazole was added and stirred. Cooling to 0deg.C, introducing N 2 50mmol of methyltrichlorosilane was weighed, diluted with 100mL of anhydrous dichloromethane, placed in a dropping funnel, and added dropwise to a three-necked flask at a rate of 3 drops/sec, and during the addition, the internal temperature of the three-necked flask was maintained at about 0 ℃. The dropping time was 1h.
(2) The reaction was stirred at room temperature for 2h. After the reaction is finished, filtering, drying, rotary evaporation and column chromatography are carried out, and then the product is enriched, thus obtaining the monosubstituted silyl ether monomer (COSIO).
(3) 40mmol of cis-1, 2-dimethylol ethylene was weighed into a 1000mL three-necked flask, and 200mL of anhydrous methylene chloride was added to dissolve thoroughly. Then 80mmol of catalyst imidazole was weighed and added to a three-necked flask for stirring. Cooling to 0deg.C, maintaining temperature, and introducing N 2 40mmol of the COSiO obtained in step (1) was diluted with 200mL of anhydrous methylene chloride, transferred to a dropping funnel, and added dropwise to a three-necked flask at a rate of 2 drops/sec. The dropping time was 2 hours. After completion of the dropwise addition, the reaction was carried out at room temperature for 24 hours.
(4) After the reaction is finished, filtering, drying and rotary evaporating, using the mixed solution of normal hexane and ethyl acetate as eluent, performing column chromatography on the organic phase, then enriching the product, 1 h NMR characterization gave a trifunctional silyl-containing monomer A.
Preparation of a degradable polydicyclopentadiene thermosetting material containing a silyl ether group:
(1) Adding 0.04wt% of inhibitor into a mixed solution of 92.435wt% of dicyclopentadiene and 4.865wt% of 5-ethylidene-2-norbornene, uniformly mixing, adding 2.5wt% of trifunctional silyl ether primitive monomer A into the mixed solution, adding 0.16wt% of catalyst into the mixed solution, and ultrasonically mixing the mixed solution under ice water bath condition for 1min to obtain a dispersion;
(2) And (3) injecting the dispersion liquid into a special mold, thermally initiating at 120 ℃, and performing ring-opening metathesis polymerization on the front end to obtain the degradable polydicyclopentadiene thermosetting material containing the silyl ether primitives.
Example 2
The degradable polydicyclopentadiene thermosetting material containing the silyl ether primitives comprises the following raw materials: dicyclopentadiene was 90.06wt%, 5-ethylidene-2-norbornene was 4.74wt%, a silyl ether containing monomer was 5.0wt%, a Grubbs second generation catalyst was 0.16wt%, and an inhibitor was 0.04wt%. Wherein the silyl ether monomer is a trifunctional silyl ether monomer A.
The preparation process of the degradable polydicyclopentadiene thermosetting material of the embodiment is the same as that of the embodiment 1.
Example 3
The degradable polydicyclopentadiene thermosetting material containing the silyl ether primitives comprises the following raw materials: dicyclopentadiene was 87.685wt%, 5-ethylidene-2-norbornene was 4.615wt%, a silyl ether containing monomer was 7.5wt%, a Grubbs second generation catalyst was 0.16wt%, and an inhibitor was 0.04wt%. Wherein the silyl ether monomer is a trifunctional silyl ether monomer A.
The preparation process of the degradable polydicyclopentadiene thermosetting material of the embodiment is the same as that of the embodiment 1.
Example 4
The degradable polydicyclopentadiene thermosetting material containing the silyl ether primitives comprises the following raw materials: dicyclopentadiene was 85.31wt%, 5-ethylidene-2-norbornene was 4.49wt%, a silyl-containing monomer was 10wt%, a Grubbs second generation catalyst was 0.16wt%, and an inhibitor was 0.04wt%. Wherein the silyl ether monomer is a trifunctional silyl ether monomer A.
The preparation process of the degradable polydicyclopentadiene thermosetting material of the embodiment is the same as that of the embodiment 1.
Example 5
The degradable polydicyclopentadiene thermosetting material containing the silyl ether primitives comprises the following raw materials: dicyclopentadiene was 75.81wt%, 5-ethylidene-2-norbornene was 3.99wt%, a silyl ether containing monomer was 20wt%, a Grubbs second generation catalyst was 0.16wt%, and an inhibitor was 0.04wt%. Wherein the silyl ether monomer is a trifunctional silyl ether monomer A.
The preparation process of the degradable polydicyclopentadiene thermosetting material of the embodiment is the same as that of the embodiment 1.
Example 6
The degradable polydicyclopentadiene thermosetting material containing the silyl ether primitives comprises the following raw materials: dicyclopentadiene was 66.31wt%, 5-ethylidene-2-norbornene was 3.49wt%, a silyl ether containing monomer was 30wt%, a Grubbs second generation catalyst was 0.16wt%, and an inhibitor was 0.04wt%. Wherein the silyl ether monomer is a trifunctional silyl ether monomer A.
The preparation process of the degradable polydicyclopentadiene thermosetting material of the embodiment is the same as that of the embodiment 1.
Example 7
The degradable polydicyclopentadiene thermosetting material containing the silyl ether primitives comprises the following raw materials: dicyclopentadiene was 87.685wt%, 5-ethylidene-2-norbornene was 4.615wt%, a silyl ether containing monomer was 7.5wt%, a Grubbs second generation catalyst was 0.16wt%, and an inhibitor was 0.04wt%. Wherein the silyl ether monomer is a trifunctional silyl ether monomer B.
The structural formula is as follows:
preparation of silyl ether monomer B (synthetic scheme see FIG. 7):
(1) 50mmol of cycloocta-4-en-1-ol was weighed into a 500mL three-necked flask, and 100mL of anhydrous dichloromethane was added to dissolve. Then 50mmol of catalyst imidazole was added and stirred. Cooling to 0deg.C, introducing N 2 50mmol of methyltrichlorosilane was weighed, diluted with 100mL of anhydrous dichloromethane, and placed in a dripIn the funnel, the mixture was dropped into a three-necked flask at a rate of 3 drops/sec, and the internal temperature of the three-necked flask was maintained at about 0℃during the dropping. The dropping time was 1h.
(2) The reaction was stirred at room temperature for 2h. After the reaction is finished, filtering, drying, rotary evaporation and column chromatography are carried out, and then the product is enriched, thus obtaining the monosubstituted silyl ether monomer (COSIO).
(3) 40mmol of cis-1, 2-dimethylol ethylene was weighed into a 1000mL three-necked flask, and 200mL of anhydrous methylene chloride was added to dissolve thoroughly. Then 80mmol of catalyst imidazole was weighed and added to a three-necked flask for stirring. Cooling to 0deg.C, maintaining temperature, and introducing N 2 40mmol of the COSiO obtained in step (1) was diluted with 200mL of anhydrous methylene chloride, transferred to a dropping funnel, and added dropwise to a three-necked flask at a rate of 2 drops/sec. The dropping time was 2 hours. After completion of the dropwise addition, the reaction was carried out at room temperature for 24 hours.
(4) After the reaction is finished, filtering, drying and rotary evaporating, using the mixed solution of normal hexane and ethyl acetate as eluent, performing column chromatography on the organic phase, then enriching the product, 1 h NMR characterization gave a trifunctional silyl-containing monomer B.
The preparation process of the degradable polydicyclopentadiene thermosetting material of the embodiment is the same as that of the embodiment 1.
Comparative example 1
The basic process, target structure and preparation method in this comparative example are the same as in example 1, but the preparation method is different, and the specific preparation process is as follows:
(1) 50mmol of cis-1, 2-dimethylol ethylene was weighed out and dissolved in 100mL of anhydrous dichloromethane, and then 100mmol of the catalyst imidazole was added. Cooling to 0deg.C, introducing N 2 50mmol of methyltrichlorosilane was weighed in 100mL of anhydrous dichloromethane and added dropwise for 1h.
(2) The reaction was stirred at room temperature for 2h. After the reaction is finished, the intermediate is obtained by filtering, drying, rotary evaporation and column chromatography, and then enriching the product.
(3) 40mmol of 3-cyclopenten-1-ol was weighed into a 1000mL three-necked flask, and 200mL of anhydrous dichloromethane was added for sufficient dissolution. Hereafter called40mmol of catalyst imidazole was taken and added to a three-necked flask and stirred. Cooling to 0deg.C, maintaining temperature, and introducing N 2 40mmol of the intermediate obtained in step (1) was diluted with 200mL of anhydrous methylene chloride, transferred to a dropping funnel, and added dropwise to a three-necked flask at a rate of 2 drops/sec. The dropping time was 2 hours. After completion of the dropwise addition, the reaction was carried out at room temperature for 24 hours.
(4) After the reaction is finished, filtering, drying and rotary evaporating, using the mixed solution of normal hexane and ethyl acetate as eluent, performing column chromatography on the organic phase, then enriching the product, 1 h NMR characterization found that the target product could not be obtained.
Comparative example 2
The polysilane group-containing polydicyclopentadiene thermosetting material of the comparative example comprises the following raw materials: 94.81wt% dicyclopentadiene, 4.99wt% 5-ethylidene-2-norbornene, 0wt% silyl ether monomer A, 0.16wt% Grubbs second generation catalyst and 0.04wt% inhibitor.
The procedure for the preparation of the polydicyclopentadiene thermosetting material of this comparative example was the same as in example 1.
Comparative example 3
The polysilane group-containing polydicyclopentadiene thermosetting material of the comparative example comprises the following raw materials: dicyclopentadiene was 87.685wt%, 5-ethylidene-2-norbornene was 4.615wt%, silyl ether monomer C was 7.5wt%, grubbs' second generation catalyst was 0.16wt%, and inhibitor was 0.04wt%.
The structural formula is as follows:
preparation of silyl ether monomer C (synthetic scheme see FIG. 8):
50mmol of 3-cyclopenten-1-ol was weighed into a 500mL three-necked flask, and 100mL of anhydrous methylene chloride was added to dissolve. Then 50mmol of catalyst imidazole was added and stirred. Cooling to 0deg.C, introducing N 2 50mmol of trimethylchlorosilane was weighed, diluted with 100mL of anhydrous dichloromethane, placed in a dropping funnel, and added dropwise to a three-necked flask at a rate of 3 drops/sec, followed by additionDuring the addition, the internal temperature of the three-neck flask was kept at about 0 ℃. The dropping time was 1h. The reaction was stirred at room temperature for 2h. After the reaction is finished, filtering, drying and rotary evaporating, using the mixed solution of normal hexane and ethyl acetate as eluent, performing column chromatography on the organic phase, then enriching the product, 1 h NMR characterization gave a monomer C containing a monosubstituted silyl ether.
The procedure for the preparation of the polydicyclopentadiene thermosetting material of this comparative example was the same as in example 1.
Comparative example 4
The polysilane group-containing polydicyclopentadiene thermosetting material of the comparative example comprises the following raw materials: dicyclopentadiene was 87.685wt%, 5-ethylidene-2-norbornene was 4.615wt%, silyl ether monomer D was 7.5wt%, grubbs' second generation catalyst was 0.16wt%, and inhibitor was 0.04wt%.
The structural formula is as follows:
preparation of silyl ether monomer D (synthetic scheme see FIG. 9):
50mmol of cycloocta-4-en-1-ol was weighed into a 500mL three-necked flask, and 100mL of anhydrous dichloromethane was added to dissolve. Then 50mmol of catalyst imidazole was added and stirred. Cooling to 0deg.C, introducing N 2 50mmol of trimethylchlorosilane was weighed, diluted with 100mL of anhydrous dichloromethane, placed in a dropping funnel, and added dropwise into a three-necked flask at a rate of 3 drops/sec, and during the addition, the internal temperature of the three-necked flask was kept at about 0 ℃. The dropping time was 1h. The reaction was stirred at room temperature for 2h. After the reaction is finished, filtering, drying and rotary evaporating, using the mixed solution of normal hexane and ethyl acetate as eluent, performing column chromatography on the organic phase, then enriching the product, 1 h NMR characterization gave a monomer D containing a monosubstituted silyl ether.
The procedure for the preparation of the polydicyclopentadiene thermosetting material of this comparative example was the same as in example 1.
Comparative example 5
The polysilane group-containing polydicyclopentadiene thermosetting material of the comparative example comprises the following raw materials: dicyclopentadiene was 87.685wt%, 5-ethylidene-2-norbornene was 4.615wt%, silyl ether monomer E was 7.5wt%, grubbs' second generation catalyst was 0.16wt%, and inhibitor was 0.04wt%.
The structural formula is as follows:
preparation of silyl ether monomer E (synthetic scheme see FIG. 10):
(1) 50mmol of 3-cyclopenten-1-ol (4.2195 g,1eq, 84.12) was weighed into a 500mL three-necked flask, and 100mL of anhydrous dichloromethane was added to dissolve. Then 50mmol of catalyst imidazole was added and stirred. Cooling to 0deg.C, introducing N 2 50mmol of methyltrichlorosilane was weighed, diluted with 100mL of anhydrous dichloromethane, placed in a dropping funnel, and added dropwise to a three-necked flask at a rate of 3 drops/sec, and during the addition, the internal temperature of the three-necked flask was maintained at about 0 ℃. The dropping time was 1h.
(2) The reaction was stirred at room temperature for 2h. After the reaction is finished, filtering, drying, rotary evaporation and column chromatography are carried out, and then the product is enriched, thus obtaining the monosubstituted silyl ether monomer (COSIO).
(3) 40mmol of 1, 4-butanediol was weighed into a 1000mL three-necked flask, and 200mL of anhydrous methylene chloride was added to dissolve thoroughly. Then 80mmol of catalyst imidazole was weighed and added to a three-necked flask for stirring. Cooling to 0deg.C, maintaining temperature, and introducing N 2 40mmol of the COSiO obtained in step (1) was diluted with 200mL of anhydrous methylene chloride, transferred to a dropping funnel, and added dropwise to a three-necked flask at a rate of 2 drops/sec. The dropping time was 2 hours. After completion of the dropwise addition, the reaction was carried out at room temperature for 24 hours.
(4) After the reaction is finished, filtering, drying and rotary evaporating, using the mixed solution of normal hexane and ethyl acetate as eluent, performing column chromatography on the organic phase, then enriching the product, 1 HNMR characterization, gives a trifunctional silyl ether-containing monomer E.
The procedure for the preparation of the polydicyclopentadiene thermosetting material of this comparative example was the same as in example 1.
Comparative example 6
The polysilane group-containing polydicyclopentadiene thermosetting material of the comparative example comprises the following raw materials: dicyclopentadiene was 87.685wt%, 5-ethylidene-2-norbornene was 4.615wt%, silyl ether monomer was 7.5wt%, grubbs second generation catalyst was 0.16wt%, and inhibitor was 0.04wt%. Wherein the silyl ether monomer is tert-butyl dimethyl allyl silyl ether.
The procedure for the preparation of the polydicyclopentadiene thermosetting material of this comparative example was the same as in example 1.
Testing and results
Cutting the materials prepared in the above examples and comparative examples to prepare test bars, wherein the test method comprises the following steps:
enthalpy of polymerization and degree of cure: at N 2 The polymerization enthalpy and the curing degree were measured in the atmosphere. And (3) testing polymerization enthalpy, namely weighing about 10mg of samples, cooling to-10 ℃, preserving heat for 5min, and then heating to 200 ℃, wherein the temperature rising and cooling rate in the whole process is 5 ℃/min. And (3) testing reaction waste heat, namely weighing about 10mg of samples, heating to 250 ℃, preserving heat for 5min, cooling to-20 ℃, and finally heating from-20 ℃ to 250 ℃, wherein the heating and cooling rate in the whole process is 10 ℃/min. Obtaining the reaction polymerization enthalpy (H) r ) And reaction waste heat (H) res ) The curing degree alpha of the sample is calculated according to the following formula, wherein the calculation formula is shown as follows:
molecular weight M between crosslinking points c ，M c Calculated according to the following formula:
wherein ρ is 1g cm -3 R is an ideal gas constant, and has a value of 8.314 J.mol -1 ·K -1 T is T g +50K，E′ Tg+50K Is warmDegree of T g Storage modulus of the sample at +50k.
Tensile strength: the speed was 50mm/min as measured according to ISO 527-2:1993.
Elongation at break: the speed was 50mm/min as measured according to ISO 527-2:1993.
Thermal decomposition temperature: about 10mg of sample was weighed out and put into N 2 In the environment, the initial temperature is room temperature, the heating rate is 10 ℃/min, and the end temperature is 800 ℃.
Degradability: about 0.2g square samples were immersed in 0.2M TBAF (5 mL THF) and subjected to degradation testing at 20, 30 and 50℃respectively.
Residual mass: after immersing the sample in 0.2M TBAF (5 mL THF) at 20 ℃, 30 ℃ and 50 ℃ for 8 hours, the sample was left to stand in a vacuum oven at 60 ℃ for 48 hours, and the remaining mass was weighed and compared with the initial mass.
TABLE 3 polymerization kinetics, mechanical Properties, thermal stability and degradation Performance index of the degradable polydicyclopentadiene thermosetting materials containing the silyl Ether moiety prepared in examples 1 to 7
TABLE 4 polymerization kinetics, mechanical Properties, thermal stability and degradation Performance index of the degradable polydicyclopentadiene thermosetting materials containing the silyl Ether moiety prepared in comparative examples 1 to 6
Tables 1 and 2 show experimental formulations of examples 1 to 7 and comparative examples 1 to 6, and tables 3 and 4 show polymerization kinetics, mechanical properties, thermal stability and degradation performance indexes of the degradable polydicyclopentadiene thermosetting materials containing the silyl ether moieties prepared in the corresponding examples 1 to 7 and comparative examples 1 to 6.
The data for the polymerization kinetics of examples 1-7 in Table 3 show that the introduction of the comonomer reduces the heat of polymerization and the degree of cure to some extent because the ring strain energy of the trifunctional cyclosilyl containing monomers is lower than that of dicyclopentadiene and thus the ring opening capability of the silyl monomer is relatively low. However, the curing degree of the examples is over 96.5%, and the materials still have higher curing degree. In examples 1-6, the glass transition temperature of the polydicyclopentadiene thermoset decreases as the silyl ether monomer content increases, but the glass transition temperature of example 3 can reach 149 ℃. And the molecular weight between the crosslinking points decreases with increasing silyl ether monomer content, because of the COSiO 3 The unsaturated double-ring structure in the structure increases the crosslinking density of polydicyclopentadiene. Characterization of the mechanical properties of the material shows that the tensile strength of example 3 can reach 49.2MPa, and the introduction of the trifunctional cyclosilyl ether monomer can obviously increase the elongation at break of the material, because the introduction of the silyl ether structure gives the material better toughness. The thermal gravimetric analysis is carried out on the material, and the decomposition temperatures of the materials are similar, which shows that the introduction of the silyl ether monomer does not have great influence on the thermal stability of the material. Finally, the degradation performance of the material is tested, and when the COSiO is found 3 When the comonomer accounts for more than 7.5 weight percent of the total content of the copolymer, the polydicyclopentadiene thermosetting material is placed in a mixed solution of tetrabutylammonium fluoride and tetrahydrofuran, and the residual mass of the sample is 0 after 10 hours at 20 ℃ and is completely chemically degraded into soluble fragments. And as the silyl ether monomer content increases, the time to complete degradation of the polydicyclopentadiene thermoset decreases. Due to COSIO 3 The cyclopentene on the side group has lower ring strain energy, so that the T of the polydicyclopentadiene thermosetting material c And the material can be depolymerized into small-molecule cycloolefin derivatives by controlling the temperature in the presence of a catalyst, so that the degradation of the material is further promoted. Example 3 completely chemically degraded into soluble fragments within 8.5h at 30 c, and only required 5h for complete degradation when the temperature was raised to 50 c. Polydicyclopentadiene thermoset materials when the silyl ether monomer content is increased to 30wt%The material can be completely degraded within 3.5 hours. Whereas examples 1 and 2, due to the low incorporation of the degradable silyl monomer, were only partially soluble within a week at 50 ℃. Although the mechanical properties and thermal stability of example 7 are similar to those of example 3, since the side group of the silyl ether monomer is cyclooctene, the ring strain energy is slightly higher than that of cyclopentene, so that the capability of depolymerizing into small-molecule cycloolefin derivatives under the condition of a catalyst is weaker, the example 7 can not be completely degraded under the same condition (20 ℃) and the residual mass is 9.2%, but when the temperature is raised to 50 ℃, the material can be completely degraded within 6 hours. The above results indicate that the introduction of the monomer containing the trifunctional cyclic silyl ether group imparts excellent degradation performance to the polydicyclopentadiene thermosetting material.
Table 4 shows the results of the data relating to comparative examples 1-6. In comparative examples 3 to 4, the monosubstituted silyl ether monomer was introduced, and after copolymerization, since the si—o bond was in the side chain of the polymer, the residual mass was more than 100% (since the solvent was left in the matrix structure) by the same treatment as in example 3, and thus the mechanical properties and thermal stability of the material were inferior to those of the examples in this patent. In comparative example 5, although the introduced monomer had a trifunctional silyl ether structure, it also had no main chain degradability because only the ring on the side group contained a double bond capable of participating in FROMP, and the residual mass after treatment was 113.6% under the same conditions. Comparative example 6 is a silyl ether structural monomer having a double bond at the end, and the residual mass after treatment under the same conditions is 105.7%, and also has no degradability. The results indicate that the material degradability is only imparted when the silyl ether structure is in the backbone of the copolymer.
In conclusion, the introduction of the monomer containing the trifunctional cyclic silyl ether group can endow the polydicyclopentadiene thermosetting material with the degradation performance, simultaneously has excellent strength and thermal stability, endows the material with better toughness, and has good application prospect.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention.
Claims (10)
1. A degradable polydicyclopentadiene thermosetting material containing silyl ether primitives is characterized in that:
the structural formula of the degradable polydicyclopentadiene thermosetting material containing the silyl ether motif is shown as formula 1:
wherein m, n, p are each independently integers ranging from 100 to 1000; r is a hydrocarbon group with the number of carbon atoms being an integer between 0 and 6 or a hydrocarbon group with a lateral group having a hydroxyl group, a carboxyl group, an amino group, an ester group and the like; x, y, z are the number of methylene groups, wherein x=1, 2 or 3; y=1, 2 or 3; z=1 or 2;
wherein the sum of the mass percentages of the raw materials for preparing the degradable polydicyclopentadiene thermosetting material containing the silyl ether primitives is 100 weight percent, and the mass percentages of the raw materials are as follows:
the catalyst is a ruthenium catalyst;
the inhibitor is phosphite esters, and the mass percentage ratio of the catalyst to the inhibitor is 1:1-4:1;
the structural formula of the silyl ether-containing monomer is shown as formula 2:
wherein R is a hydrocarbon group with the number of carbon atoms being an integer between 0 and 6 or a hydrocarbon group with a lateral group containing hydroxyl, carboxyl, amino and ester groups; x, y, z are the number of methylene groups, wherein x=1, 2 or 3; y=1, 2 or 3; z=1 or 2.
2. The thermoset of claim 1, wherein:
in structural formulas 1 and 2, the hydrocarbon group includes an alkyl group, an alkenyl group, or an alkynyl group.
3. A method of preparing a thermoset according to any one of claims 1-2, comprising the steps of:
(1) Adding the inhibitor into a mixed solution of dicyclopentadiene and 5-ethylidene-2-norbornene according to a proportion, uniformly mixing, adding a monomer containing a silyl ether unit, adding the catalyst, and ultrasonically mixing the mixed solution under the ice water bath condition to obtain a dispersion liquid;
(2) And (3) injecting the dispersion liquid into a mould, thermally initiating at 120-250 ℃, and obtaining the degradable polydicyclopentadiene thermosetting material containing the silyl ether primitives through front-end ring-opening metathesis polymerization.
4. A method of preparation as claimed in claim 3, wherein: the method also comprises the steps of preparing the monomer containing the silyl ether, and specifically comprises the following steps:
dissolving methyltrichlorosilane and cycloolefin-alcohol shown in structural formula 3 with organic solvent, respectively, dripping the dissolved methyltrichlorosilane into cycloolefin-alcohol solution shown in structural formula 3, and introducing N 2 In the presence of a catalyst, the reaction is carried out at 0-5 ℃, the dripping time is 1-2h, the temperature is raised to the room temperature, the reaction is carried out for 0.5-2h under the stirring condition, after the reaction is finished, the monosubstituted silyl ether monomer shown in the structural formula 4 is obtained through the operations of filtration, drying, rotary evaporation and column chromatography,
wherein in the structural formulas 3 and 4, R is a hydrocarbon group with the number of carbon atoms being an integer between 0 and 6 or a hydrocarbon group with a lateral group containing hydroxyl, carboxyl, amino and ester groups; x, y is the number of methylene groups, wherein x=1, 2 or 3; y=1, 2 or 3;
dissolving the monosubstituted silyl ether monomer and alkene-diol shown in the structural formula 5 by using an organic solvent respectively, dripping the dissolved monosubstituted silyl ether monomer into the alkene-diol solution, and introducing N 2 In the presence of a catalyst, the reaction is carried out at 0-5 ℃, the dripping time is 1-2h, the temperature is raised to the room temperature, the reaction is carried out for 0.5-36h under the stirring condition, after the reaction is finished, the silicon-containing ether monomer is obtained through the operations of filtration, drying, rotary evaporation and column chromatography,
in the structural formula 5, z is the number of methylene groups, and z=1 or 2.
5. The method of manufacturing according to claim 4, wherein:
the alkene-diol is one of cis-1, 2-dimethylol ethylene and (2E) -2-pentene-1, 5-diol;
the catalyst is one of imidazole, 4-N, N-lutidine, 4-dimethylaminopyridine, N-dimethylaniline, quinoline and 1-methylimidazole;
the organic solvent is one or more of dichloromethane, n-hexane, ethyl acetate, methanol, ethanol, acetone, chloroform, benzene, xylene, cyclohexane and tetrahydrofuran.
6. A method of degrading a thermoset according to any one of claims 1 to 2 or a thermoset obtainable by a method of preparation according to any one of claims 3 to 5, wherein:
placing the thermosetting material in an organic solvent containing a degradation reagent, wherein the organic solvent is tetrahydrofuran; the degradation reagent is tetrabutylammonium fluoride;
under the heating condition, the mixed solution of the degradation reagent and the organic solvent is adopted as degradation solution, and under the stirring condition, the degradation of the degradable polydicyclopentadiene thermosetting material containing the silyl ether primitive is realized;
wherein the mass concentration of the degradation reagent is 0.1-100%; the heating temperature is 0-200 ℃; the heating time is 1-120 h.
7. Use of a thermoset material as claimed in claims 1-2 or as prepared by the preparation method as claimed in any one of claims 3-5, characterized in that: the thermosetting material is used for intelligent robot equipment structural members, protective equipment in the military field and functional materials in the biomedical, catalytic and sensing fields, and can realize recycling of waste materials.
8. The application of a silyl ether group-containing monomer in the preparation process of a degradable polydicyclopentadiene thermosetting material is characterized in that the silyl ether group-containing monomer is used as a raw material for preparing the degradable polydicyclopentadiene thermosetting material, wherein the degradable polydicyclopentadiene thermosetting material is shown as a structural formula 1:
wherein m, n, p are integers between 100 and 1000; r is a hydrocarbon group with the number of carbon atoms being an integer between 0 and 6 or a hydrocarbon group with a lateral group containing hydroxyl, carboxyl, amino and ester groups; x, y, z are the number of methylene groups, wherein x=1, 2 or 3; y=1, 2 or 3; z=1 or 2;
the silyl ether-containing monomer is shown as a structural formula 2
Wherein R is a hydrocarbon group with the number of carbon atoms being an integer between 0 and 6 or a hydrocarbon group with a lateral group having a hydroxyl group, a carboxyl group, an amino group, an ester group and the like; x, y, z are the number of methylene groups, wherein x=1, 2 or 3; y=1, 2 or 3; z=1 or 2.
9. A silyl ether monomer for preparing degradable polydicyclopentadiene thermosetting material is shown in structural formula 2
Wherein in the structural formula 2, R is a hydrocarbon group with the number of carbon atoms being an integer between 0 and 6 or a hydrocarbon group with a lateral group containing hydroxyl, carboxyl, amino and ester groups; x, y, z are the number of methylene groups, wherein x=1, 2 or 3; y=1, 2 or 3; z=1 or 2.
10. The method for synthesizing the monomer containing the silyl ether moieties according to claim 9 comprises the following steps:
is synthesized by nucleophilic substitution reaction of cycloolefin-alcohol and methyltrichlorosilane, and the reaction equation is shown in formula 6; dissolving reactants with anhydrous dichloromethane, dripping the dissolved methyltrichlorosilane into 3-cyclopenten-1-alcohol, and introducing N 2 The reaction is carried out at 0-5 ℃ for 1-2h, the temperature is raised to room temperature, the reaction is carried out for 0.5-2h under the stirring condition, and after the reaction is finished, the monosubstituted silyl ether monomer (COSIO) is obtained through the operations of filtration, drying, rotary evaporation and column chromatography;
the monomer is synthesized by nucleophilic substitution reaction of monosubstituted silyl ether monomer and butadiene (pentalene) -diol, and the reaction equation is shown in formula 7; dissolving the reactants with anhydrous dichloromethane, respectively, adding the dissolved COSiO into cis-1, 2-dimethylol ethylene, and introducing N 2 The reaction is carried out at 0-5 ℃ for 1-2h, the temperature is raised to room temperature, the reaction is carried out for 0.5-36h under the stirring condition, and the operation of filtration, drying, rotary evaporation and column chromatography is carried out after the reaction is finished, namelyTo give a silyl ether-containing monomer which is a trifunctional silyl ether-containing monomer (COSIO 3 )；
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