WO2018000242A1 - 自修复材料在3d打印中的应用 - Google Patents
自修复材料在3d打印中的应用 Download PDFInfo
- Publication number
- WO2018000242A1 WO2018000242A1 PCT/CN2016/087670 CN2016087670W WO2018000242A1 WO 2018000242 A1 WO2018000242 A1 WO 2018000242A1 CN 2016087670 W CN2016087670 W CN 2016087670W WO 2018000242 A1 WO2018000242 A1 WO 2018000242A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- self
- healing
- present
- polysiloxane
- printing
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 238
- 238000007639 printing Methods 0.000 title description 20
- 238000010146 3D printing Methods 0.000 claims abstract description 42
- 230000008439 repair process Effects 0.000 claims abstract description 32
- -1 polysiloxane Polymers 0.000 claims description 112
- 229920001296 polysiloxane Polymers 0.000 claims description 109
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 230000003993 interaction Effects 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 230000002441 reversible effect Effects 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000009881 electrostatic interaction Effects 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 238000007259 addition reaction Methods 0.000 claims description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 230000000638 stimulation Effects 0.000 claims description 2
- 230000006378 damage Effects 0.000 abstract description 7
- 238000012423 maintenance Methods 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 57
- 239000000047 product Substances 0.000 description 57
- 238000010438 heat treatment Methods 0.000 description 38
- 239000002904 solvent Substances 0.000 description 35
- 238000004132 cross linking Methods 0.000 description 32
- 239000000654 additive Substances 0.000 description 29
- 230000000996 additive effect Effects 0.000 description 29
- 239000004014 plasticizer Substances 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- 238000010907 mechanical stirring Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 239000003002 pH adjusting agent Substances 0.000 description 8
- 238000005292 vacuum distillation Methods 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000011534 incubation Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 4
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 244000119461 Garcinia xanthochymus Species 0.000 description 1
- 235000000885 Garcinia xanthochymus Nutrition 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- CZJCMXPZSYNVLP-UHFFFAOYSA-N antimony zinc Chemical compound [Zn].[Sb] CZJCMXPZSYNVLP-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052956 cinnabar Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- WZWSOGGTVQXXSN-UHFFFAOYSA-N cyclohexanone;toluene Chemical compound CC1=CC=CC=C1.O=C1CCCCC1 WZWSOGGTVQXXSN-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000007648 laser printing Methods 0.000 description 1
- 229910001710 laterite Inorganic materials 0.000 description 1
- 239000011504 laterite Substances 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 125000005498 phthalate group Chemical group 0.000 description 1
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052957 realgar Inorganic materials 0.000 description 1
- 230000008263 repair mechanism Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
- B29C73/16—Auto-repairing or self-sealing arrangements or agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
- B29C73/16—Auto-repairing or self-sealing arrangements or agents
- B29C73/18—Auto-repairing or self-sealing arrangements or agents the article material itself being self-sealing, e.g. by compression
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2083/00—Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
Definitions
- the present invention relates to the field of 3D printing technology, and more particularly to the application of self-healing materials in 3D printing.
- 3D Printing is an emerging technology that has developed rapidly in the manufacturing industry in this century. It is called “manufacturing technology with industrial revolution significance.” This technology is one of the rapid prototyping technologies and is also known as additive manufacturing.
- the basic principle of 3D printing technology is similar to inkjet printing technology or laser printing technology. Based on the digital model file, the 3D model made by design or scanning is cut into an infinite number of sections according to a certain coordinate axis, and then The corresponding material is printed one by one from the printer nozzle, molded by cooling or photocuring, or selectively laser sintered or melted, and stacked together in the original position to form a three-dimensional entity.
- 3D printing technology simplifies the manufacturing process of products, shortens the product development cycle, improves efficiency and reduces costs. It has been widely used in product prototype, model making, art creation, jewelry making, bioengineering and medicine, construction, clothing, etc. field.
- 3D printing technology has achieved remarkable development, but still faces some challenges.
- the products obtained by 3D printing are generally a combination of many parts in ordinary mechanical manufacturing, which has the advantages of increasing the overall performance of the product and reducing the resources and energy consumption generated during the assembly process of the parts. It can produce and produce products that cannot be realized by process or technology, and increase the dexterity of production. While reflecting its advantages, its shortcomings are also obvious.
- the products prepared by 3D printing materials are integrally formed. After the micro cracks or external damage occur, the functionality of the whole product will be affected, so you can only choose to replace them. Increase the maintenance cost of the product and cause great waste.
- the solid or component printed by the existing 3D printing material cannot be restored to the normal state after it is microcracked or damaged by the outside, thereby directly affecting the service life of the product and causing safety hazards.
- the present invention provides the use of self-healing materials in 3D printing, with self-healing materials as 3D printed materials.
- the self-healing material is one of the following materials: a self-healing material that utilizes a reversible covalent bond to achieve a self-healing function, a self-healing material that utilizes a non-covalent interaction to achieve a self-healing function, and utilizes coordination.
- the self-healing material that implements the self-repair function is one of the following materials: a self-healing material that utilizes a reversible covalent bond to achieve a self-healing function, a self-healing material that utilizes a non-covalent interaction to achieve a self-healing function, and utilizes coordination.
- the self-healing material that implements the self-repair function is one of the following materials: a self-healing material that utilizes a reversible covalent bond to achieve a self-healing function, a self-healing material that utilizes a non-covalent interaction to achieve a self-healing
- the covalent bond in the self-healing material that realizes the self-healing function by using a reversible covalent bond is a carbon-carbon covalent bond formed by a disulfide bond, an imine bond or a diene addition reaction.
- the non-covalent interaction in the self-healing material that utilizes non-covalent interaction to achieve self-healing function is hydrogen bonding, halogen bonding, electrostatic interaction, hydrophobic interaction, ⁇ - ⁇ stacking or crystallization.
- the coordination bond in the self-healing material that realizes the self-healing function by using a coordination bond is a coordination bond formed by nitrogen, oxygen, carbon, boron, sulfur or phosphorus with a metal.
- the self-healing material is self-repairing one or more of heat repair, light repair, auxiliary repair and non-stimulation automatic repair.
- the self-healing material is prepared from a raw material comprising a polysiloxane having the structure of formula I:
- p 1 is 0 to 1000, and p 2 is 1 to 1000;
- R 1 to R 7 are independently selected from the group consisting of a C1-C8 alkyl group, a phenyl group, and one of the formulae II to X;
- p 3 to p 11 are independently selected from 0 to 50;
- G is -NH-, -O-, -S- or -CH(O)CH-;
- R 8 to R 9 are independently selected from a hydrogen atom or an alkyl group having 1 to 30 carbon atoms;
- X is a halogen atom.
- the ratio of p 1 to p 2 is 1/3 to 100.
- the p 1 is 10 to 800, and the p 2 is 10 to 800.
- the R 1 to R 7 are independently selected from the group consisting of a methyl group, a phenyl group, and one of the formulae II to X.
- the self-repairing material provided by the invention is applied in 3D printing, and the self-healing material is used as a 3D printing material to intelligently detect and spontaneously complete the repair of the material, thereby preventing potential damage of the material due to the generation of micro-cracks.
- the conditions required for self-repair are mild and mild. During the whole repair process, until the repair is completed, the overall performance of the product will not be affected, the maintenance cost of the product will be reduced, and the use thereof will be increased. Life expectancy increases resource utilization.
- the test results show that the repaired rate of the product printed by the self-healing material as 3D printing material after 6h self-repair can reach 98%.
- the present invention provides the use of self-healing materials in 3D printing, with self-healing materials as 3D printed materials.
- the self-healing material is preferably one of the following materials: a self-healing material that utilizes a reversible covalent bond to achieve a self-healing function, a self-healing material that utilizes a non-covalent interaction to achieve a self-healing function, and A self-healing material that uses a coordination key to achieve self-healing.
- the covalent bond in the self-healing material which realizes the self-healing function by using a reversible covalent bond is preferably a carbon-carbon covalent bond formed by a disulfide bond, an imine bond or a diene addition reaction.
- the non-covalent interaction in the self-healing material that utilizes non-covalent interaction to achieve self-healing function is preferably hydrogen bonding, halogen bonding, electrostatic interaction, hydrophobic interaction, ⁇ - ⁇ stacking or crystallization, More preferably, it is a hydrogen bond or an electrostatic action.
- the coordination bond in the self-healing material which realizes the self-healing function by using a coordinate bond is a coordination bond formed of nitrogen, oxygen, carbon, boron, sulfur or phosphorus with a metal.
- the self-healing means of the self-healing material is preferably one or more of heat repair, light repair, auxiliary repair, and non-irritant automatic repair, and more preferably heat repair or light repair.
- the self-healing material is preferably prepared from a raw material comprising a polysiloxane having the structure of the formula I:
- p 1 is preferably from 0 to 1000, more preferably from 10 to 800, most preferably from 100 to 200;
- p 2 is preferably from 1 to 1000, more preferably from 10 to 800, most preferably from 100 to 200;
- the ratio of p 1 to p 2 is preferably from 1/3 to 100, more preferably from 1 to 50, most preferably from 5 to 15;
- R 1 to R 7 are preferably independently selected from the group consisting of a C1-C8 alkyl group, a phenyl group, and one of the formulae II to X, more preferably independently selected from the group consisting of a methyl group, a phenyl group, and one of the formulae II to X. ;
- p 3 to p 11 are preferably independently selected from 0 to 50, more preferably independently selected from 3 to 20, and most preferably independently selected from 5 to 10;
- G is preferably -NH-, -O-, -S- or -CH(O)CH-;
- R 8 to R 9 are independently selected from a hydrogen atom or an alkyl group having 1 to 30 carbon atoms;
- X is a halogen atom.
- the self-healing material is preferably a self-healing material that realizes a self-healing function by a carbon-carbon covalent bond generated by a diene addition reaction, that is, a self-healing material based on a D-A reaction.
- the raw material of the D-A reaction-based self-healing material preferably includes polysiloxane A and polysiloxane B having different structures.
- the polysiloxane A is preferably a polysiloxane having a structure represented by the formula I, and in the formula I, R 1 to R 7 are preferably at least one of the formula II; 3 is preferably 0 to 10, and more preferably 1 to 3.
- the polysiloxane B is preferably a polysiloxane having a structure represented by the formula I, wherein R 1 to R 7 in the formula I are preferably at least one of the formula III; 3 is preferably 0 to 10, and more preferably 1 to 3.
- the application of the D-A reaction-based self-healing material in 3D printing preferably includes the following steps:
- the solvent is not particularly limited in the present invention, and an organic solvent well known to those skilled in the art may be employed.
- the solvent is preferably an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, a halogenated hydrocarbon solvent, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, or a diol derivative.
- nitrogen-containing solvents more preferably benzene, toluene, xylene, styrene, pentane, hexane, octane, cyclohexane, cyclohexanone, toluene cyclohexanone, chlorobenzene , dichlorobenzene, dichloromethane, chloroform, perchloroethylene, trichloroethylene, methanol, ethanol, isopropanol, diethyl ether, propylene oxide, ethylene glycol ether, methyl acetate, ethyl acetate, propyl acetate
- the operation of the mixing of the present invention is not particularly limited, and a mixed technical solution well known to those skilled in the art may be employed.
- the present invention preferably mixes the polysiloxane A solution and the polysiloxane B solution to obtain a preprinted material.
- the mass concentration of the polysiloxane A in the polysiloxane A solution is preferably 40 to 60%, more preferably 45 to 55%, and most preferably 48 to 52%.
- the mass concentration of the polysiloxane B in the polysiloxane B solution is preferably 40 to 60%, more preferably 45 to 55%, and most preferably 48 to 52%.
- the mass ratio of the polysiloxane A to the polysiloxane B is preferably from 1:0.8 to 1.2, more preferably from 1:0.9 to 1.1.
- the temperature of the mixing is preferably from 20 to 30 ° C, more preferably from 23 to 26 ° C.
- the mixing is preferably carried out under stirring.
- the agitation is preferably mechanical agitation; the agitation rate is preferably 800 to 1200 rpm/m, more preferably 900 to 1100 rpm/m, most preferably 950 to 1050 rpm/min; It is 1.5 to 2.5 h, and more preferably 1.8 to 2.2 h.
- the present invention preferably heats the pre-printed material and cross-links the reaction to obtain a 3D printed material.
- the invention has no particular limitation on the manner of heating, and adopts the field.
- the technical solution of heating known to the skilled person is sufficient.
- the heating is preferably oil bath heating; the heating rate is preferably 8 to 12 ° C / min, more preferably 9 to 11 ° C / min.
- the temperature of the crosslinking reaction is preferably 70 to 80 ° C, more preferably 74 to 76 ° C; and the time for holding the crosslinking reaction temperature is preferably 10 to 14 h, more preferably 11 to 13 h. Most preferably, it is from 11.5 to 12.5 h.
- the crosslinking reaction is preferably carried out under stirring; the stirring rate is preferably from 800 to 1200 rmp/min, more preferably from 900 to 1100 rmp/min, and most preferably from 950 to 1050 rmp/min.
- the present invention preferably mixes the preprinted material with a plasticizer prior to heating.
- the mass of the plasticizer is preferably from 1 to 10%, more preferably from 3 to 6%, based on the total mass of the polysiloxane.
- the type of the plasticizer is not particularly limited in the present invention, and a plasticizer well known to those skilled in the art may be used.
- the plasticizer is preferably a Phthalate Esters (PAEs), more preferably di-n-octyl phthalate (DNOP or DnOP), butyl benzyl phthalate ( BBP), dioctyl phthalate (DCP), dicyclohexyl phthalate (DCHP), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), One of dimethyl phthalate (DMP), diethyl phthalate (DEP), diisononyl phthalate (DINP), and diisononyl phthalate (DIDP) or A variety.
- PAEs Phthalate Esters
- DMP dimethyl phthalate
- DEP diethyl phthalate
- DEP diisononyl phthalate
- DIDP diisononyl phthalate
- the present invention preferably mixes the pre-printed material with a color additive prior to heating.
- the mass of the color additive is preferably from 1 to 5%, more preferably from 2 to 3%, based on the total mass of the polysiloxane.
- the type of the color additive is not particularly limited in the present invention, and a color additive well known to those skilled in the art may be used.
- the color additive is preferably one or more of a natural inorganic color additive, an artificial inorganic color additive, a natural organic color additive, and an artificial organic color additive.
- the natural inorganic color additive is one or more of soot, chalk, cinnabar, laterite, realgar, natural iron oxide, wollastonite, barite powder, talc powder, mica powder and kaolin;
- the artificial inorganic color additive is one or more of titanium white, zinc antimony white, lead chrome yellow and iron blue;
- the natural organic color additive is one or more of garcinia, alizarin red and indigo
- the artificial organic color additive is one or more of macro red powder, even pale yellow, phthalocyanine blue, and quinacridone.
- the present invention preferably removes excess solvent from the reaction product to obtain a 3D printed material.
- the invention has no particular limitation on the operation of removing the solvent, and adopts the skill. The solvent removal operation well known to those skilled in the art is sufficient.
- the temperature of the vacuum distillation is preferably 45 to 55 ° C, more preferably 48 to 52 ° C; the pressure of the vacuum distillation is preferably 0.009 to 0.011 kPa; and the time of the vacuum distillation is preferably It is 1.5 to 2.5 h, and more preferably 1.8 to 2.2 h.
- the present invention preferably prints the 3D printed material to obtain a product.
- the printing temperature is preferably from 140 to 160 ° C, more preferably from 145 to 155 ° C.
- the self-healing mechanism of the D-A reaction-based self-healing material 3D printing product is preferably as shown in the reaction formula (1):
- R 1 to R 8 are a substituent on a double bond.
- the diene is connected by covalent bond.
- the covalent bond between the diene is destroyed.
- the DA reaction can be re-directed to the closed loop. In turn, the material is repaired.
- the self-healing material is preferably a self-healing material that utilizes an imine bond to achieve a self-healing function, ie, an imine bond-based self-healing material.
- the raw material of the imine bond-based self-healing material preferably includes polysiloxane C and polysiloxane D having different structures.
- the polysiloxane C is preferably a polysiloxane having a structure represented by the formula I, wherein R 1 to R 7 in the formula I are preferably at least one of the formula IV; 5 is preferably 0 to 10, more preferably 1 to 3; and G in the formula IV is preferably -NH-.
- the polysiloxane D is preferably a polysiloxane having a structure represented by the formula I, and in the formula I, R 1 to R 7 are preferably at least one of the formula V; 6 is preferably 0 to 10, and more preferably 1 to 3.
- the application of the imine bond-based self-healing material in 3D printing is preferred Includes the following steps:
- the present invention preferably mixes the polysiloxane C and the polysiloxane D with a solvent to obtain a preprinted material.
- the mass ratio of the polysiloxane C to the polysiloxane D is preferably from 1:0.8 to 1.2, more preferably from 1:0.9 to 1.1.
- the operation of preparing the pre-printed material is preferably the same as the above technical solution, and details are not described herein again.
- the present invention preferably heats the pre-printed material and cross-links the reaction to obtain a 3D printed material.
- the operation of the heating is preferably the same as the above technical solution, and details are not described herein again.
- the temperature of the crosslinking reaction is preferably from 90 to 110 ° C, more preferably from 95 to 115 ° C; and the incubation time at the crosslinking reaction temperature is preferably from 5 to 7 h, more preferably from 5.5 to 6.5 h. .
- the crosslinking reaction is preferably carried out under stirring; the stirring rate is preferably from 800 to 1200 rmp/min, more preferably from 900 to 1100 rmp/min, and most preferably from 950 to 1050 rmp/min.
- the present invention preferably mixes the preprinted material with a plasticizer prior to heating.
- the present invention preferably mixes the pre-printed material with a color additive prior to heating.
- the type and amount of the plasticizer and the color additive are preferably the same as those of the plasticizer and the color additive described in the above technical solutions, and are not described herein again.
- the present invention preferably removes excess solvent from the reaction product to obtain a 3D printed material.
- the present invention preferably removes excess solvent from the reaction product by the method described in the above technical scheme.
- the present invention preferably prints the 3D printed material to obtain a product.
- the printing temperature is preferably from 120 to 140 ° C, more preferably from 125 to 135 ° C.
- the self-healing mechanism of the imine bond-based self-healing material 3D printing product is preferably as shown in the reaction formula (2):
- R is a substituent on the N atom
- R' is a substituent on the double bond C.
- an aldehyde group and an amino group are condensed to form an imine bond.
- the imine bond at the interface is at In dynamic equilibrium; when heat-treating a region where microcracks or external damage occurs, the imine bond exchanges with an adjacent amino or aldehyde group to form a new imine bond and a new amino group and aldehyde group. Repair of materials.
- the self-healing material is preferably a self-healing material that utilizes a disulfide bond to achieve a self-healing function, that is, a self-healing material based on a disulfide bond.
- the raw material of the imine bond-based self-healing material preferably includes polysiloxane E.
- the polysiloxane is a polysiloxane E preferably has the structure shown in formula I, in the formula I R 1 ⁇ R 7 is preferably at least one type VI; p 7 the formula It is preferably 0 to 10, and more preferably 1 to 3.
- the application of the disulfide bond-based self-healing material in 3D printing preferably includes the following steps:
- the polysiloxane E is preferably mixed with a solvent to obtain a preprinted material.
- the operation of preparing the pre-printed material is preferably the same as the above technical solution, and details are not described herein again.
- the pre-printed material is preferably heated and mixed with H 2 O 2 to obtain a 3D printed material.
- the mass is preferably 0.8 to 1.2 times the mass of the polysiloxane, more preferably 0.9 to 1.1 times, and most preferably 0.95 to 1.05 times.
- the operation of the heating is preferably the same as the above technical solution, and details are not described herein again.
- the temperature of the crosslinking reaction is preferably 40 to 60 ° C, more preferably 45 to 55 ° C; and the incubation time at the crosslinking reaction temperature is preferably 5 to 7 h, more preferably 5.5 to 6.5 h. .
- the crosslinking reaction is preferably carried out under stirring; the stirring rate is preferably from 800 to 1200 rmp/min, more preferably from 900 to 1100 rmp/min, and most preferably from 950 to 1050 rmp/min.
- the present invention preferably pre-prints the material and plasticizes it before heating. Mix the agents.
- the present invention preferably mixes the pre-printed material with a color additive prior to heating.
- the type and amount of the plasticizer and the color additive are preferably the same as those of the plasticizer and the color additive described in the above technical solutions, and are not described herein again.
- the present invention preferably removes excess solvent from the reaction product to obtain a 3D printed material.
- the present invention preferably removes excess solvent from the reaction product by the method described in the above technical scheme.
- the present invention preferably prints the 3D printed material to obtain a product.
- the printing temperature is preferably from 90 to 110 ° C, more preferably from 95 to 105 ° C.
- the self-healing mechanism of the 3D printed product of the disulfide-based self-healing material is preferably as shown in the reaction formula (3):
- R and R' are substituents on the S atom.
- a sulfur atom and a sulfur atom are connected by a covalent bond, that is, a disulfide bond is formed, when a microcrack is generated in the material or is exposed to the outside.
- the disulfide bond is destroyed to form a reduced-SH bond; by controlling the light or temperature, the reaction can be carried out in the direction of generating a disulfide bond, thereby realizing the repair of the material.
- the self-healing material is preferably a self-healing material that utilizes hydrogen bonding to achieve a self-healing function, that is, a self-healing material based on hydrogen bonding.
- the raw material of the hydrogen bond-based self-healing material preferably includes polysiloxane F.
- the polysiloxane F is preferably a polysiloxane having a structure represented by the formula I, and in the formula I, R 1 to R 7 are preferably at least one of the formula VII and the formula VIII. Or both; in the formula VII, p 8 and p 9 are preferably independently selected from 0 to 10, more preferably from 1 to 5.
- the application of the hydrogen bond-based self-healing material in 3D printing preferably includes the following steps:
- the polysiloxane F is preferably mixed with a solvent to obtain a preprinted material.
- the operation of preparing the pre-printed material is preferably the same as the above technical solution, and details are not described herein again.
- the present invention preferably heats the pre-printed material and cross-links the reaction to obtain a 3D printed material.
- the operation of the heating is preferably the same as the above technical solution, and details are not described herein again.
- the temperature of the crosslinking reaction is preferably 40 to 60 ° C, more preferably 45 to 55 ° C; and the incubation time at the crosslinking reaction temperature is preferably 5 to 7 h, more preferably 5.5 to 6.5 h. .
- the crosslinking reaction is preferably carried out under stirring; the stirring rate is preferably from 800 to 1200 rmp/min, more preferably from 900 to 1100 rmp/min, and most preferably from 950 to 1050 rmp/min.
- the present invention preferably mixes the preprinted material with a plasticizer prior to heating.
- the present invention preferably mixes the pre-printed material with a color additive prior to heating.
- the type and amount of the plasticizer and the color additive are preferably the same as those of the plasticizer and the color additive described in the above technical solutions, and are not described herein again.
- the pH of the crosslinking reaction is preferably from 3 to 11, more preferably from 5 to 9.
- the present invention preferably mixes the preprinted material with a pH adjusting agent prior to heating.
- the pH adjusting agent is preferably used in an amount of from 1 to 30%, more preferably from 5 to 10%, based on the total mass of the polysiloxane.
- the type of the pH adjuster is not particularly limited in the present invention, and a pH-adjusting agent well known to those skilled in the art may be used.
- the pH adjusting agent is one or more of an organic acid, an organic base, an inorganic acid, and an inorganic base; and the organic acid preferably includes a carboxyl group (-COOH), a sulfonic acid (-SO3H), An organic acid of sulfinic acid (RSOOH) or sulfuric acid (RCOSH), more preferably p-toluenesulfonic acid and/or trifluoroacetic acid;
- the organic base is preferably an organic base including an amino group and/or an amine group, more preferably Is triethylamine and/or ethylenediamine;
- the inorganic acid is preferably hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, perchloric acid, hypochlorous acid, permanganic acid and carbonic acid.
- the inorganic base is preferably one or more of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal weak acid salt, and an alkaline earth metal weak acid salt. It is preferably one or more of potassium hydrogencarbonate, sodium hydrogencarbonate, potassium carbonate, sodium carbonate, sodium hydroxide and potassium hydroxide.
- the present invention preferably removes excess solvent from the reaction product to obtain a 3D printed material.
- the present invention preferably removes more of the reaction products by the method described in the above technical solution. The remaining solvent.
- the present invention preferably prints the 3D printed material to obtain a product.
- the printing temperature is preferably from 50 to 70 ° C, more preferably from 55 to 65 ° C.
- the self-healing mechanism of the self-healing material 3D printing product based on hydrogen bonding interaction is preferably as shown in the reaction formula (4):
- X is an electron donor in a hydrogen bond
- R is a substituent attached to a hydrogen bond electron donor
- H is a hydrogen atom
- R' is a substituent attached to a hydrogen atom
- a solid line is a covalent bond.
- the dotted line is a hydrogen bond.
- the self-healing material is preferably a self-healing material that achieves a self-healing function by electrostatic action, that is, a self-healing material based on electrostatic action.
- the raw material of the electrostatically acting self-healing material preferably includes polysiloxane G and polysiloxane H having different structures.
- the polysiloxane G is preferably a polysiloxane having a structure represented by the formula I, and in the formula I, R 1 to R 7 are preferably at least one of the formula IX; 10 is preferably 0 to 10, and more preferably 1 to 3.
- the polysiloxane H is preferably a polysiloxane having a structure of the formula I, wherein R 1 to R 7 in the formula I are preferably at least one of the formula VII; 8 and p 9 are preferably independently selected from 0 to 10, more preferably from 1 to 5.
- the application of the electrostatic-based self-healing material in 3D printing preferably includes the following steps:
- the mass ratio of the polysiloxane H to the polysiloxane G is preferably from 1:0.8 to 1.2, more preferably from 1:0.9 to 1.1.
- the present invention preferably heats the pre-printed material and cross-links the reaction to obtain a 3D printed material.
- the operation of the heating is preferably the same as the above technical solution, and details are not described herein again.
- the temperature of the crosslinking reaction is preferably 40 to 60 ° C, more preferably 45 to 55 ° C; and the incubation time at the crosslinking reaction temperature is preferably 5 to 7 h, more preferably 5.5 to 6.5 h. .
- the crosslinking reaction is preferably carried out under stirring; the stirring rate is preferably from 800 to 1200 rmp/min, more preferably from 900 to 1100 rmp/min, and most preferably from 950 to 1050 rmp/min.
- the present invention preferably mixes the preprinted material with a plasticizer prior to heating.
- the present invention preferably mixes the pre-printed material with a color additive prior to heating.
- the pH of the crosslinking reaction is preferably from 3 to 11, more preferably from 5 to 9.
- the present invention preferably mixes the preprinted material with a pH adjusting agent prior to heating.
- the type and amount of the plasticizer, the color additive and the pH adjuster are preferably the same as those of the plasticizer, the color additive and the pH adjuster described in the above technical solutions, and are not described herein again.
- the present invention preferably removes excess solvent from the reaction product to obtain a 3D printed material.
- the present invention preferably removes excess solvent from the reaction product by the method described in the above technical scheme.
- the present invention preferably prints the 3D printed material to obtain a product.
- the printing temperature is preferably from 50 to 70 ° C, more preferably from 55 to 65 ° C.
- the self-healing mechanism of the electrostatically acting self-healing material 3D printing product is preferably as shown in the reaction formula (5):
- X - is an anion
- Y + is a cation
- R is a substituent on an anion
- R' is a substituent on a cation
- a solid line is a covalent bond
- a broken line is an ionic bond.
- the anion and cation are connected by ionic bond; when microcracks are generated in the material or damaged by the outside, the ionic bond will be destroyed to form the corresponding yin and yang.
- the anions and cations can be combined again to form corresponding ionic bonds, thereby realizing the repair of the material.
- the self-healing material is preferably a self-healing material that utilizes metal coordination to achieve a self-healing function, that is, a self-healing material based on metal coordination.
- the raw material of the metal complex-based self-healing material preferably includes polysiloxane J.
- the polysiloxane J is preferably a polysiloxane having a structure represented by the formula I, and in the formula I, R 1 to R 7 are preferably at least one of the formula X; 11 is preferably 0 to 10, and more preferably 1 to 3.
- the application of the metal coordination-based self-healing material in 3D printing preferably includes the following steps:
- the mass of the metal salt is preferably from 2 to 50%, more preferably from 5 to 30%, most preferably from 10 to 20% by mass of the polysiloxane.
- the metal salt is preferably an alkali metal, an alkaline earth metal, a transition metal, and a rare earth metal chloride, nitrate, sulfate, acetate, phosphate, perchlorate, permanganate.
- the operation of preparing the pre-printed material is preferably the same as the above technical solution, and details are not described herein again.
- the present invention preferably heats the pre-printed material and cross-links the reaction to obtain a 3D printed material.
- the operation of the heating is preferably the same as the above technical solution, and details are not described herein again.
- the temperature of the crosslinking reaction is preferably 40 to 60 ° C, more preferably 45 to 55 ° C; and the incubation time at the crosslinking reaction temperature is preferably 5 to 7 h, more preferably 5.5 to 6.5 h. .
- the crosslinking reaction is preferably under stirring conditions
- the rate of agitation is preferably from 800 to 1200 rpm/m, more preferably from 900 to 1100 rpm/m, most preferably from 950 to 1050 rpm/min.
- the present invention preferably mixes the preprinted material with a plasticizer prior to heating.
- the present invention preferably mixes the pre-printed material with a color additive prior to heating.
- the type and amount of the plasticizer and the color additive are preferably the same as those of the plasticizer and the color additive described in the above technical solutions, and are not described herein again.
- the present invention preferably removes excess solvent from the reaction product to obtain a 3D printed material.
- the present invention preferably removes excess solvent from the reaction product by the method described in the above technical scheme.
- the present invention preferably prints the 3D printed material to obtain a product.
- the printing temperature is preferably from 110 to 130 ° C, more preferably from 115 to 125 ° C.
- the repair mechanism of the metal-based coordination-based self-healing material 3D printing product is preferably as shown in the reaction formula (6):
- L is a coordination group having a coordination point
- R is a substituent attached to the coordination group
- Mn + is a metal ion
- n + is a positive valence state exhibited by a metal atom
- a solid line is a covalent state
- the key, the dotted line is the coordination key.
- a coordination bond is formed between a coordination group and a metal ion, and is in a coordination state; when a microcrack is generated in the material or is damaged by the outside, The bond is broken, the coordinating group and the metal ion are in a free state; by heat-treating the region where microcracks are generated or damaged by the external environment, the coordination bond can be reformed, thereby realizing the repair of the material.
- R 1 to R 6 are a methyl group
- Polysiloxane A, R 7 is a formula II, wherein p 1 is equal to p 2 , a value of 80 to 100, and p 3 is 1;
- Polysiloxane B, R 7 is a formula III, wherein p 1 is equal to p 2 , a value of 80 to 100, and p 4 is 1;
- the product printed by the printed material can be self-repaired by heating at 80 ° C, and the repair efficiency of repairing 6 h is 98%.
- R 2 to R 7 are a methyl group
- R 1 is Formula IV, wherein p 1 is equal to p 2 , is a value in the range of 80 to 100, p 5 is 3, and G is -NH-;
- Polysiloxane B, R 1 is Formula V, wherein p 1 is equal to p 2 , a value of 80 to 100, and p 6 is 1;
- the preprinted material obtained in (1) is at an oil bath at a rate of 10 ° C / min Heating, raising the temperature to 75 ° C, reacting under mechanical agitation at 1000 rpm / min for 6 h; further heating at a rate of 10 ° C / min, raising the temperature to 100 ° C, reacting under mechanical agitation at 1000 rpm / min 6h; after the end of the reaction, after 2 hours of vacuum distillation at 50 ° C, wherein the pressure value is 0.01 kPa, an imine bond-based polysiloxane material is obtained, the yield is 98.5%, and the purity is 97%; Self-healing 3D printed material based on imine bonds;
- the product printed by the printed material can be self-repaired by heating at 70 ° C, and the repair efficiency of repairing 6 h is 98%.
- R 2 to R 7 are a methyl group, R 1 is a formula VI, p 7 is 3, and p 1 is equal to p 2 and is a value in the range of 80 to 100;
- Polysiloxane B, R 1 to R 6 are a methyl group, R 7 is a formula VI, p 7 is 3, and p 1 is equal to p 2 and is a value in the range of 80 to 100;
- the product printed by the printing material can be self-repaired by heating at 50 ° C, and the repair efficiency of repairing 6 h reaches 98%;
- the printed product of the printed material can be self-repaired by a 10W fluorescent lamp at a temperature of 25 ° C and a distance of 20 cm, and the repair efficiency of repairing for 6 hours is 98%.
- R 1 to R 6 are methyl, R 7 is a formula VII, R 8 is a methyl group, p 8 is 1, and when p 9 is 5, p 1 is equal to p 2 and is 80 to 100. value;
- Polysiloxane B, R 1 to R 6 are a methyl group, and when R 7 is a formula VIII, p 1 is equal to p 2 and is a value in the range of 80 to 100;
- the product printed by the printed material can be self-repaired by heating at 50 ° C, and the repair efficiency of repairing 6 h is 98%.
- R 2 to R 7 are a methyl group, R 1 is a formula IX, p 10 is 3, and when X is Cl, p 1 is equal to p 2 and is a value in the range of 80 to 100;
- Polysiloxane B, R 1 to R 6 are methyl groups, when R 7 is a formula VII, R 8 is a methyl group, p 8 is 1, and when p 9 is 5, p 1 is equal to p 2 and is 80 to 100. Value
- the product printed by the printed material can be self-repaired by heating at 25 ° C, and the repair efficiency of repairing 6 h is 98%.
- R 1 to R 6 are methyl groups, when R 7 is Formula X, R 9 is a methyl group, and when p 11 is 1, p 1 is equal to p 2 and is a value of 80 to 100;
- the product printed by the printed material can be self-repaired by heating at 75 ° C, and the repair efficiency of repairing 6 h is 98%.
- the self-healing material 3D printing product provided by the invention has good self-repairing performance, and the repairing efficiency of repairing 6h reaches 98%.
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims (10)
- 自修复材料在3D打印中的应用,其特征在于,以自修复材料作为3D打印材料。
- 根据权利要求1所述的应用,其特征在于,所述自修复材料为以下几种材料中的一种:利用可逆共价键实现自修复功能的自修复材料、利用非共价相互作用实现自修复功能的自修复材料和利用配位键实现自修复功能的自修复材料。
- 根据权利要求2所述的应用,其特征在于,所述利用可逆共价键实现自修复功能的自修复材料中的共价键为二硫键、亚胺键或双烯加成反应生成的碳碳共价键。
- 根据权利要求2所述的应用,其特征在于,所述利用非共价相互作用实现自修复功能的自修复材料中的非共价相互作用为氢键、卤键、静电作用、疏水作用、π-π堆叠或结晶作用。
- 根据权利要求2所述的应用,其特征在于,所述利用配位键实现自修复功能的自修复材料中的配位键为氮、氧、碳、硼、硫或磷与金属形成的配位键。
- 根据权利要求3~5任意一项所述的应用,其特征在于,所述自修复材料的自修复方式为热修复、光修复、助剂修复和无刺激自动修复中的一种或几种。
- 根据权利要求7所述的应用,其特征在于,所述p1与p2的比值为1/3~100。
- 根据权利要求7所述的应用,其特征在于,所述p1为10~800,p2为10~800;
- 根据权利要求7所述的应用,其特征在于,所述R1~R7独立地选自甲基、苯基和式Ⅱ~式Ⅹ中的一种。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018543416A JP6669886B2 (ja) | 2016-06-29 | 2016-06-29 | 自己修復材料の3d印刷における応用 |
PCT/CN2016/087670 WO2018000242A1 (zh) | 2016-06-29 | 2016-06-29 | 自修复材料在3d打印中的应用 |
EP16906643.8A EP3418331A4 (en) | 2016-06-29 | 2016-06-29 | APPLY SELF-REPAIRING MATERIAL IN 3D PRINTING |
US16/084,619 US10744728B2 (en) | 2016-06-29 | 2016-06-29 | Application of self-healing material in 3D printing |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2016/087670 WO2018000242A1 (zh) | 2016-06-29 | 2016-06-29 | 自修复材料在3d打印中的应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018000242A1 true WO2018000242A1 (zh) | 2018-01-04 |
Family
ID=60785926
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2016/087670 WO2018000242A1 (zh) | 2016-06-29 | 2016-06-29 | 自修复材料在3d打印中的应用 |
Country Status (4)
Country | Link |
---|---|
US (1) | US10744728B2 (zh) |
EP (1) | EP3418331A4 (zh) |
JP (1) | JP6669886B2 (zh) |
WO (1) | WO2018000242A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110643058A (zh) * | 2018-06-22 | 2020-01-03 | 苏州大学 | 一种受损的透明可卷曲折叠聚硅氧烷膜的自修复方法 |
CN110857359A (zh) * | 2018-08-23 | 2020-03-03 | 天津大学 | 一种聚硅氧烷纳米复合材料的制备方法 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110218329B (zh) * | 2018-03-04 | 2021-03-19 | 南京大学 | 一类改性的聚硅氧烷及其应用 |
CN109233571B (zh) * | 2018-10-12 | 2021-01-15 | 南宁本吉生物科技有限公司 | 一种无溶剂自修复环氧树脂及其制备方法 |
US11692068B2 (en) * | 2019-03-26 | 2023-07-04 | Xerox Corporation | Functionalized silicone materials for three-dimensional printing |
WO2022168277A1 (ja) * | 2021-02-05 | 2022-08-11 | パナソニックIpマネジメント株式会社 | 樹脂組成物及び成形体 |
JP2022191594A (ja) * | 2021-06-16 | 2022-12-28 | 信越化学工業株式会社 | フラニル基含有オルガノポリシロキサン及びその製造方法 |
WO2024090189A1 (ja) * | 2022-10-27 | 2024-05-02 | 信越化学工業株式会社 | リサイクル可能な硬化性シリコーン樹脂組成物 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104961881A (zh) * | 2015-06-03 | 2015-10-07 | 四川大学 | 用于3d打印、含动态键的聚氨酯材料及其制备方法和用途 |
CN105088043A (zh) * | 2015-09-17 | 2015-11-25 | 河北安耐哲新能源技术有限公司 | 一种液态合金及其制备方法和应用 |
CN105111470A (zh) * | 2015-08-13 | 2015-12-02 | 四川大学 | 一种可逆共价交联聚硅氧烷弹性体及其制备方法与应用 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005023331A2 (en) * | 2003-09-04 | 2005-03-17 | The United States Of America As Represented By The Department Of Veterans Affairs | Hydrogel nanocompsites for ophthalmic applications |
JP4888095B2 (ja) * | 2005-12-14 | 2012-02-29 | 日本電気株式会社 | 再成形可能かつ優れた形状回復能を有する形状記憶樹脂の高強度化 |
EP3116935B1 (en) * | 2014-03-12 | 2024-06-19 | The Regents of the University of Colorado, a body corporate | Novel covalently cross-linked malleable polymers and methods of use |
US20150337147A1 (en) * | 2014-05-22 | 2015-11-26 | Xerox Corporation | Reversible polymers in 3-d printing |
JP6528390B2 (ja) * | 2014-11-21 | 2019-06-12 | セイコーエプソン株式会社 | セルロース系材料、造形物製造用組成物セット、造形物、ダイアライザー、透析装置、透析方法および造形物の製造方法 |
CN105294936B (zh) * | 2015-10-19 | 2017-07-18 | 杭州龙勤新材料科技有限公司 | 二官能度丙烯酸酯类交联剂及其在3d打印中的应用 |
JP6813147B2 (ja) * | 2016-05-09 | 2021-01-13 | 国立大学法人東京工業大学 | 動的共有結合化合物及びその組換え方法 |
-
2016
- 2016-06-29 JP JP2018543416A patent/JP6669886B2/ja active Active
- 2016-06-29 EP EP16906643.8A patent/EP3418331A4/en not_active Withdrawn
- 2016-06-29 US US16/084,619 patent/US10744728B2/en active Active
- 2016-06-29 WO PCT/CN2016/087670 patent/WO2018000242A1/zh active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104961881A (zh) * | 2015-06-03 | 2015-10-07 | 四川大学 | 用于3d打印、含动态键的聚氨酯材料及其制备方法和用途 |
CN105111470A (zh) * | 2015-08-13 | 2015-12-02 | 四川大学 | 一种可逆共价交联聚硅氧烷弹性体及其制备方法与应用 |
CN105088043A (zh) * | 2015-09-17 | 2015-11-25 | 河北安耐哲新能源技术有限公司 | 一种液态合金及其制备方法和应用 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3418331A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110643058A (zh) * | 2018-06-22 | 2020-01-03 | 苏州大学 | 一种受损的透明可卷曲折叠聚硅氧烷膜的自修复方法 |
CN110643058B (zh) * | 2018-06-22 | 2022-02-11 | 苏州大学 | 一种受损的透明可卷曲折叠聚硅氧烷膜的自修复方法 |
CN110857359A (zh) * | 2018-08-23 | 2020-03-03 | 天津大学 | 一种聚硅氧烷纳米复合材料的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US20190077100A1 (en) | 2019-03-14 |
JP6669886B2 (ja) | 2020-03-18 |
US10744728B2 (en) | 2020-08-18 |
EP3418331A4 (en) | 2019-10-09 |
JP2018535304A (ja) | 2018-11-29 |
EP3418331A1 (en) | 2018-12-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2018000242A1 (zh) | 自修复材料在3d打印中的应用 | |
CN106009702B (zh) | 自修复材料在3d打印中的应用 | |
CN107129580A (zh) | 一种动态聚合物材料及其应用 | |
WO2018028365A1 (zh) | 具有杂化交联网络的动态聚合物及其应用 | |
TWI458746B (zh) | Novel copolymer | |
TW201716483A (zh) | 組合物 | |
CN106750342B (zh) | 一种梳型超分散剂、制备方法及应用 | |
CN109666168A (zh) | 一种自修复性固态杂化动态聚合物及其应用 | |
CN110240679B (zh) | 一种高性能光固化3d打印材料及其制备方法 | |
CN109206576A (zh) | 一种杂化交联动态聚合物 | |
CN109563266B (zh) | 可聚合组合物 | |
CN109666121A (zh) | 一种杂化动态交联聚合物及其应用 | |
CN107311889A (zh) | 化合物及其制造方法 | |
CN109320521A (zh) | 环氧单体及其制备方法、环氧树脂 | |
CN111378090A (zh) | 一种杂化作用动态聚合物 | |
DE1930526A1 (de) | Organische Peroxyverbindungen und Verfahren zu deren Herstellung | |
CN108341963A (zh) | 一种具有杂化结构的动态聚合物组成及其应用 | |
CN109206626A (zh) | 一种杂化交联动态聚合物 | |
CN108341974A (zh) | 一种具有杂化交联结构的动态聚合物及其应用 | |
US20040079924A1 (en) | Blue light-emitting, ladder-type polymer with excellent heat stability | |
CN110272365B (zh) | 一种橡胶促进剂二乙基二硫代氨基甲酸硒的制备方法 | |
KR101687396B1 (ko) | 전도성 고분자 나노 물질의 제조 방법 | |
CN106750230B (zh) | 一种用于3d打印的改性聚乳酸材料的制备方法 | |
US20210324269A1 (en) | Fabrication of Luminescent Quantum Dot Thiol-yne Nanocomposites With Tailorable Optical, Thermal and Mechanical Properties | |
CN110330647B (zh) | 可重塑形状记忆双马来酰亚胺树脂及其应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 2018543416 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2016906643 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2016906643 Country of ref document: EP Effective date: 20180919 |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16906643 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |