CN116444786A - 高密度含氟多元醇及其在双重自修复含氟聚氨酯中的应用 - Google Patents
高密度含氟多元醇及其在双重自修复含氟聚氨酯中的应用 Download PDFInfo
- Publication number
- CN116444786A CN116444786A CN202310436672.6A CN202310436672A CN116444786A CN 116444786 A CN116444786 A CN 116444786A CN 202310436672 A CN202310436672 A CN 202310436672A CN 116444786 A CN116444786 A CN 116444786A
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- China
- Prior art keywords
- fluorine
- polyol
- repairing
- self
- containing polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 102
- 239000011737 fluorine Substances 0.000 title claims abstract description 102
- 229920005862 polyol Polymers 0.000 title claims abstract description 53
- 150000003077 polyols Chemical class 0.000 title claims abstract description 53
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 33
- 239000004814 polyurethane Substances 0.000 title claims abstract description 33
- 230000009977 dual effect Effects 0.000 title claims abstract description 11
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 28
- 239000012948 isocyanate Substances 0.000 claims abstract description 14
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 12
- 239000004970 Chain extender Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 68
- 238000006243 chemical reaction Methods 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 17
- PHQYMDAUTAXXFZ-UHFFFAOYSA-N 4-[2-(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C=C1 PHQYMDAUTAXXFZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000008859 change Effects 0.000 claims description 16
- 238000005070 sampling Methods 0.000 claims description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002329 infrared spectrum Methods 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 12
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- YPCSMEGZIYWAAZ-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecanedioic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(O)=O YPCSMEGZIYWAAZ-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- PIVAHSCRTJPWJU-UHFFFAOYSA-N 2,2-difluoropentanedioic acid Chemical compound OC(=O)CCC(F)(F)C(O)=O PIVAHSCRTJPWJU-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- QYCPVKMFWNBDPV-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorooctanedioic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(O)=O QYCPVKMFWNBDPV-UHFFFAOYSA-N 0.000 claims description 2
- CCUWGJDGLACFQT-UHFFFAOYSA-N 2,2,3,3,4,4-hexafluoropentanedioic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(O)=O CCUWGJDGLACFQT-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- XGKGITBBMXTKTE-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)disulfanyl]phenol Chemical compound C1=CC(O)=CC=C1SSC1=CC=C(O)C=C1 XGKGITBBMXTKTE-UHFFFAOYSA-N 0.000 claims description 2
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229960003067 cystine Drugs 0.000 claims description 2
- -1 polybutylene adipate Polymers 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 26
- 230000008439 repair process Effects 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 238000005979 thermal decomposition reaction Methods 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 13
- MERLDGDYUMSLAY-UHFFFAOYSA-N 4-[(4-aminophenyl)disulfanyl]aniline Chemical compound C1=CC(N)=CC=C1SSC1=CC=C(N)C=C1 MERLDGDYUMSLAY-UHFFFAOYSA-N 0.000 description 12
- 238000010998 test method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 6
- 239000006260 foam Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 229960002050 hydrofluoric acid Drugs 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ALXIOUGHHXXLKX-UHFFFAOYSA-N n,n-dimethyl-2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C)C ALXIOUGHHXXLKX-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NZUNWRVHLLQLSX-UHFFFAOYSA-N 2-[2-(6-hydroxyhexanoyloxy)ethoxy]ethyl 6-hydroxyhexanoate Chemical compound OCCCCCC(=O)OCCOCCOC(=O)CCCCCO NZUNWRVHLLQLSX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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- 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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4607—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen having halogens
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- 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
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- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
-
- 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
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- 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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- 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
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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Abstract
本发明属于高分子材料制备技术领域,具体涉及一种高密度含氟多元醇及其在双重自修复含氟聚氨酯中的应用。通过将多元醇与高含氟量羧酸反应得到高密度含氟多元醇,再加入异氰酸酯,制备含氟聚氨酯预聚物,再加入含二硫键的扩链剂、糠胺通过逐步聚合制得双重自修复含氟聚氨酯。高密度含氟多元醇的引入使材料具备卓越的疏水性、耐腐蚀性及热稳定性,二硫键及糠胺的引入赋予材料光热双重修复性能,从而制备出同时具备优异的力学性能、耐高温、耐溶剂性、耐热性及光热双重自修复性的含氟聚氨酯。
Description
技术领域
本发明属于高分子材料制备技术领域,具体涉及一种高密度含氟多元醇及其在双重自修复含氟聚氨酯中的应用。
背景技术
多元醇是分子中含有二个或二个以上羟基的一大类醇类。多元醇一般溶于水,大多数多元醇都是具有沸点高,对极性物质溶解能力强,毒性和挥发性小等特性的黏性液体或结晶状固体。其沸点、黏度、相对密度和熔点等随分子量增加而增加。多元醇主要用在聚氨酯泡沫塑料中,可提高聚氨酯软泡的硬度,改进泡沫综合性能。为了增加泡沫硬度,早期常采用的方法有:在多元醇中掺无机填料,提高异氰酸酯指数,或使用高2,6-异构体含量的TDI。在多元醇中掺无机填料造成物料粘度增大,体系不稳定,加工困难,并在增加泡沫体硬度、提高制品密度的同时,明显降低了其它物性。
聚氨酯是由多异氰酸酯和多羟基聚合物加聚而成,在高分子主链上含有许多重复的氨基甲酸酯链段(-NHCOO-)的高分子化合物。聚氨酯材料的优异性能,如耐磨、高机械强度、高弹性、耐老化、耐腐蚀等,与其分子结构密切相关。聚氨酯分子主链是由柔性的长链多元醇和刚性的异氰酸酯嵌段而成,可以有效分散应力,极性和非极性链段的共存也提高了聚氨酯的化学稳定性。同时,聚合物内广泛存在的氢键,也进一步提高了材料的机械性能。此外,异氰酸酯的-NCO基团非常活泼,可以和醇、水、有机胺等迅速反应,使材料的加工性能保持良好的状态。通过对反应条件和催化剂的控制,可以得到不同硬度、不同结构的多种聚氨酯产品,如类似橡胶或塑料的弹性体、开孔结构的海绵、闭孔结构的硬质泡沫、黏合剂、涂料、密封剂等,在国民生产生活的各个领域得到广泛应用。与此同时,聚氨酯在生产过程中内生热大,耐高温性能一般,特别是耐湿热性能不好。正常使用温度范围是-40~120℃使用,若需在高频振荡或高温条件下长期作用,则必须在结构设计或配方上采取相应改性措施。
含氟聚氨酯是指聚合物主链结构上除含有-CF2基团外,还含有众多氨基甲酸酯基团(软段和硬段均可)的含氟高聚物,是制备氟橡胶、氟塑料、氟碳涂料最常用的材料之一,具有聚氨酯弹性体通用特性:高强度、高弹性、高耐磨性、优良的低温性能和粘结性能;又具有含氟高聚物的耐热性、耐化学品、耐溶剂、耐油、低污染等优良性能,但其仍难以满足极端环境下的使用需求。含氟聚氨酯虽然有很多优点,可以应用于众多领域,但是在一些极端环境,例如:在太空中高温高辐射、固体火箭强光照射的环境因素的影响,传统含氟聚氨酯无法同时满足这些极端环境的力学性能、耐辐射、耐高温及耐溶剂性要求。必须对含氟聚氨酯进行一定的物理和化学改性,使其各项性能得到进一步提高。
发明内容
本发明针对现有技术的不足,首先提供了一种高密度含氟多元醇,然后将其用于制备一种同时具备优异的力学性能、耐高温、耐溶剂性、耐热性及光热双重自修复性的含氟聚氨酯,解决了大部分含氟聚氨酯无法满足极端领域如固体火箭发动机的推进粘合剂、舱门密封圈的性能要求。
本发明将多元醇与高含氟量羧酸反应得到高密度含氟多元醇,再加入异氰酸酯、含二硫键扩链剂、糠胺通过逐步聚合制备含氟聚氨酯(FPU)。高密度含氟多元醇的引入使材料具备卓越的疏水性、耐腐蚀性及热稳定性,二硫键及糠胺的引入赋予材料光热双重修复性能,从而制备出同时具备优异的力学性能、耐高温、耐溶剂性、耐热性及光热双重自修复性的含氟聚氨酯。
双重自修复含氟聚氨酯制备方法为:首先,多元醇与高含氟量羧酸反应得到高密度含氟多元醇。而后,加入异氰酸酯、含二硫键扩链剂、糠胺通过逐步聚合制备含氟聚氨酯(FPU)。
其反应方程式为:
其中,
高密度含氟多元醇的具体制备方法为:将多元醇和高含氟量羧酸加入三口烧瓶中,在70-80℃及1.3-2.6kPa下抽空脱水2h,加入催化剂,搅拌0.5h,开始聚合,观察到明显粘稠,则停止反应,得到高密度含氟多元醇。
其中,多元醇为聚四氢呋喃二醇、聚己二酸乙二醇酯、聚己二酸丁二醇酯、聚己二酸己二醇酯、聚己内酯二醇中的一种;
高含氟量羧酸为2,2-双(4-羧基苯基)六氟丙烷、六氟戊二酸、全氟癸二酸、全氟辛二酸、2,2-二氟戊二酸中的一种。
多元醇、高含氟量羧酸的摩尔比为3.5-4.0:2.5-3.0。
催化剂为四氟硼酸、丙烯酸、乙酸钠中的一种。
双重自修复含氟聚氨酯的具体制备方法步骤如下:
(1)将上述的高密度含氟多元醇降温至50-60℃,加入异氰酸酯,通氮气,反应期间,每隔半小时取样,用红外光谱分析仪观察-NCO基团峰的变化,直到-NCO基团不再降低,得到异氰酸酯封端的含氟聚氨酯预聚物;
其中,异氰酸酯为异佛尔酮二异氰酸酯、2,4甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的一种。
多元醇、异氰酸酯的摩尔比为1:1。
(2)将含二硫键扩链剂和糠胺缓慢加入到步骤(1)的产物中,在60℃下反应2h;在氮气的保护下,控制温度75-85℃,搅拌反应直至明显粘稠,而后继续平衡化反应3h;加入酸性中和剂,控制温度在75-85℃,抽真空去除体系中的小分子物质,得到所需产物。
其中,含二硫键扩链剂为胱氨酸、4,4’-二氨基二苯二硫醚、双(4-羟苯基)二硫醚中的一种。
含二硫键扩链剂与糠胺的摩尔比为1-1.5:1-1.5。
酸性中和剂为氢氧化钠、碳酸钠、碳酸钙中的一种。
有益效果:
本发明通过将多元醇与高含氟量羧酸反应得到高密度含氟多元醇,再加入异氰酸酯、含二硫键扩链剂、糠胺通过逐步聚合制备含氟聚氨酯(FPU)。高密度含氟多元醇的引入使材料具备卓越的疏水性、耐腐蚀性及热稳定性,二硫键及糠胺的引入赋予材料光热双重修复性能,从而制备出同时具备优异的力学性能、耐高温、耐溶剂性、耐热性及光热双重自修复性的含氟聚氨酯,制备的聚氨酯可以在大多极端环境中使用,材料的各项性能可以满足固体火箭推进粘合剂、航天设备密封圈等领域的要求。
附图说明:
图1为实施例1-8及对照例1-5所得产物的水接触角柱状对比图。
图2为实施例1-8及对照例1-5所得产物的拉伸强度对比折线图。
图3为实施例1-8及对照例1-5所得产物5%热分解温度对比折线图。
图4为实施例1-8及对照例1-5所得产物断裂伸长率对比折线图。
图5为实施例1中使用2,2-双(4-羧基苯基)六氟丙烷为高含氟量羧酸时所制得的自修复含氟聚氨酯的自修复效果图。
图6为实施例1中使用2,2-双(4-羧基苯基)六氟丙烷为高含氟量羧酸时所制得高密度含氟多元醇和自修复含氟聚氨酯的红外谱图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅是本发明的一部分实施例,而不是全部的实施例。基于本发明的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其它实施方式,都属于本发明保护的范围。
实施例1
取100g聚四氢呋喃二醇(CAS号:25190-06-1)于抽真空通氮气反复处理三次的250ml三口烧瓶中,加入0.3g 2,2-双(4-羧基苯基)六氟丙烷(CAS号:1171-47-7),在75℃及2.5kPa下抽空脱水2h,加入四硼氟酸(0.4g),搅拌0.5h,开始聚合,观察到明显粘稠,则停止反应,降温至55℃,加入0.25g异佛尔酮二异氰酸酯(EC号:223-861-6),通氮气,反应期间,每隔半小时取样,用红外光谱分析仪观察-NCO基团峰的变化,直到-NCO基团不再降低,得到异氰酸酯封端的含氟聚氨酯预聚物;将0.25g 4,4’-二氨基二苯二硫醚(CAS号:139-65-1)和0.1g糠胺(CAS:617-89-0)缓慢加入到异氰酸酯封端的含氟聚氨酯预聚物中,在60℃下反应2h;在氮气的保护下,控制温度80℃,搅拌反应直至明显粘稠,而后继续平衡化反应3h;加入氢氧化钠(0.4g),控制温度在80℃,抽真空去除体系中的小分子物质,得到所需产物。
图6红外分析显示在2890cm-1左右为-NH2的特征峰,1500cm-1附近的峰为R-OH的特征峰,560cm-1、1080cm-1及1310cm-1出现的强吸收带为-NCO-的特征峰,1150左右为R-O-R的特征峰,500cm-1为-S-S-的特征峰,以上特征峰的出现说明高密度含氟多元醇、二硫键和糠胺的成功引入,以及自修复含氟聚氨酯的成功合成。
为了验证该材料的自修复性能,用力度可控的划痕设备将制得的产物划伤后置于室温环境下,实验发现在25℃下产物可以在45min完成自修复,在60℃加热条件下,可在10min内完成自修复过程。
采用JC2000D1型接触角测量仪对产物疏水性进行测试,测得材料水接触角为131°。
制得的产物加入交联剂固化后按照ASTM D882制样测试,测试速度500mm/min,拉伸强度为17.76MPa,断裂伸长率为245%。
采用STA6000型同步热分析分析仪对产物进行耐热性测试,称取试样10mg,升温速率20℃/min,温度变化范围50~600℃,在氮气氛围中测试,气体流量为20ml/min,测得产物百分之五热分解温度为345℃。
制得的产物加入交联剂固化后取小块试样浸泡于有机溶剂环己烷中,浸泡168h后称量试样并计算质量损失率,测得产物质量损失率为0.15%。
实施例2
取100g聚四氢呋喃二醇(CAS号:25190-06-1)于抽真空通氮气反复处理三次的250ml三口烧瓶中,加入0.4g全氟癸二酸(CAS号:307-78-8),在75℃及2.5kPa下抽空脱水2h,加入四硼氟酸(0.4g),搅拌0.5h,开始聚合,观察到明显粘稠,则停止反应,降温至55℃,加入0.25g异佛尔酮二异氰酸酯(EC号:223-861-6),通氮气,反应期间,每隔半小时取样,用红外光谱分析仪观察-NCO基团峰的变化,直到-NCO基团不再降低,得到异氰酸酯封端的含氟聚氨酯预聚物;将0.25g 4,4’-二氨基二苯二硫醚(CAS号:139-65-1)和0.1g糠胺(CAS:617-89-0)缓慢加入到异氰酸酯封端的含氟聚氨酯预聚物中,在60℃下反应2h;在氮气的保护下,控制温度80℃,搅拌反应直至明显粘稠,而后继续平衡化反应3h;加入氢氧化钠(0.4g),控制温度在80℃,抽真空去除体系中的小分子物质,得到所需产物。
具体测试方法同实施例1,实验发现在25℃下产物可以在45min完成自修复,在60℃加热条件下,可在10min内完成自修复过程;测得材料水接触角为129°;拉伸强度为17.53MPa,断裂伸长率为276%;测得产物百分之五热分解温度为352℃;测得产物质量损失率为0.13%。
实施例3
取100g聚四氢呋喃二醇(CAS号:25190-06-1)于抽真空通氮气反复处理三次的250ml三口烧瓶中,加入0.14g 2,2-二氟戊二酸(CAS号:681-57-2),在75℃及2.5kPa下抽空脱水2h,加入四硼氟酸(0.4g),搅拌0.5h,开始聚合,观察到明显粘稠,则停止反应,降温至55℃,加入0.25g异佛尔酮二异氰酸酯(EC号:223-861-6),通氮气,反应期间,每隔半小时取样,用红外光谱分析仪观察-NCO基团峰的变化,直到-NCO基团不再降低,得到异氰酸酯封端的含氟聚氨酯预聚物;将0.25g 4,4’-二氨基二苯二硫醚(CAS号:139-65-1)和0.1g糠胺(CAS:617-89-0)缓慢加入到异氰酸酯封端的含氟聚氨酯预聚物中,在60℃下反应2h;在氮气的保护下,控制温度80℃,搅拌反应直至明显粘稠,而后继续平衡化反应3h;加入氢氧化钠(0.4g),控制温度在80℃,抽真空去除体系中的小分子物质,得到所需产物。
具体测试方法同实施例1,实验发现在25℃下产物可以在45min完成自修复,在60℃加热条件下,可在10min内完成自修复过程;测得材料水接触角为132°;拉伸强度为16.78MPa,断裂伸长率为236%;测得产物百分之五热分解温度为347℃;测得产物质量损失率为0.16%。
实施例4
取100g聚己二酸乙二醇酯(CAS号:24938-37-2)于抽真空通氮气反复处理三次的250ml三口烧瓶中,加入0.15g 2,2-双(4-羧基苯基)六氟丙烷(CAS号:1171-47-7),在75℃及2.5kPa下抽空脱水2h,加入四硼氟酸(0.4g),搅拌0.5h,开始聚合,观察到明显粘稠,则停止反应,降温至55℃,加入0.12g异佛尔酮二异氰酸酯(EC号:223-861-6),通氮气,反应期间,每隔半小时取样,用红外光谱分析仪观察-NCO基团峰的变化,直到-NCO基团不再降低,得到异氰酸酯封端的含氟聚氨酯预聚物;将0.25g 4,4’-二氨基二苯二硫醚(CAS号:139-65-1)和0.1g糠胺(CAS号:617-89-0)缓慢加入到异氰酸酯封端的含氟聚氨酯预聚物中,在60℃下反应2h;在氮气的保护下,控制温度80℃,搅拌反应直至明显粘稠,而后继续平衡化反应3h;加入氢氧化钠(0.4g),控制温度在80℃,抽真空去除体系中的小分子物质,得到所需产物。
具体测试方法同实施例1,实验发现在25℃下产物可以在45min完成自修复,在60℃加热条件下,可在10min内完成自修复过程;测得材料水接触角为133°;拉伸强度为16.48MPa,断裂伸长率为264%;测得产物百分之五热分解温度为349℃;测得产物质量损失率为0.18%。
实施例5
含氟多元醇的制备同实施例1,停止反应,降温至55℃,加入0.2g 2,4甲苯二异氰酸酯(CAS号:584-84-9),通氮气,反应期间,每隔半小时取样,用红外光谱分析仪观察-NCO基团峰的变化,直到-NCO基团不再降低,得到异氰酸酯封端的含氟聚氨酯预聚物;将0.25g4,4’-二氨基二苯二硫醚(CAS号:139-65-1)和0.1g糠胺(CAS号:617-89-0)缓慢加入到异氰酸酯封端的含氟聚氨酯预聚物中,在60℃下反应2h;在氮气的保护下,控制温度80℃,搅拌反应直至明显粘稠,而后继续平衡化反应3h;加入氢氧化钠(0.4g),控制温度在80℃,抽真空去除体系中的小分子物质,得到所需产物。
具体测试方法同实施例1,实验发现在25℃下产物可以在45min完成自修复,在60℃加热条件下,可在10min内完成自修复过程;测得材料水接触角为128°;拉伸强度为17.12MPa,断裂伸长率为238%;测得产物百分之五热分解温度为351℃;测得产物质量损失率为0.12%。
实施例6
含氟多元醇的制备同实施例1,停止反应,降温至55℃,加入0.28g二苯基甲烷二异氰酸酯(CAS号:101-68-8),通氮气,反应期间,每隔半小时取样,用红外光谱分析仪观察-NCO基团峰的变化,直到-NCO基团不再降低,得到异氰酸酯封端的含氟聚氨酯预聚物;将0.25g 4,4’-二氨基二苯二硫醚(CAS号:139-65-1)和0.1g糠胺(CAS号:617-89-0)缓慢加入到异氰酸酯封端的含氟聚氨酯预聚物中,在60℃下反应2h;在氮气的保护下,控制温度80℃,搅拌反应直至明显粘稠,而后继续平衡化反应3h;加入氢氧化钠(0.4g),控制温度在80℃,抽真空去除体系中的小分子物质,得到所需产物。
具体测试方法同实施例1,实验发现在25℃下产物可以在45min完成自修复,在60℃加热条件下,可在10min内完成自修复过程;测得材料水接触角为126°;拉伸强度为16.84MPa,断裂伸长率为274%;测得产物百分之五热分解温度为344℃。
制得的产物加入交联剂固化后取小块试样浸泡于有机溶剂环己烷中,浸泡168h后称量试样并计算质量损失率,测得产物质量损失率为0.11%。
实施例7
含氟多元醇的制备同实施例1,停止反应,降温至55℃,加入0.18g六亚甲基二异氰酸酯(CAS号:822-06-0),通氮气,反应期间,每隔半小时取样,用红外光谱分析仪观察-NCO基团峰的变化,直到-NCO基团不再降低,得到异氰酸酯封端的含氟聚氨酯预聚物;将0.25g4,4’-二氨基二苯二硫醚(CAS号:139-65-1)和0.1g糠胺(CAS号:617-89-0)缓慢加入到异氰酸酯封端的含氟聚氨酯预聚物中,在60℃下反应2h;在氮气的保护下,控制温度80℃,搅拌反应直至明显粘稠,而后继续平衡化反应3h;加入氢氧化钠(0.4g),控制温度在80℃,抽真空去除体系中的小分子物质,得到所需产物。
具体测试方法同实施例1,实验发现在25℃下产物可以在45min完成自修复,在60℃加热条件下,可在10min内完成自修复过程;测得材料水接触角为134°;拉伸强度为16.53MPa,断裂伸长率为284%;测得产物百分之五热分解温度为348℃;测得产物质量损失率为0.19%。
实施例8
取100g聚己内酯二醇(CAS号:36890-68-3)于抽真空通氮气反复处理三次的250ml三口烧瓶中,加入0.18g 2,2-双(4-羧基苯基)六氟丙烷(CAS号:1171-47-7),在75℃及2.5kPa下抽空脱水2h,加入四硼氟酸(0.4g),搅拌0.5h,开始聚合,观察到明显粘稠,则停止反应,降温至55℃,加入0.17g异佛尔酮二异氰酸酯(EC号:223-861-6),通氮气,反应期间,每隔半小时取样,用红外光谱分析仪观察-NCO基团峰的变化,直到-NCO基团不再降低,得到异氰酸酯封端的含氟聚氨酯预聚物;将0.25g 4,4’-二氨基二苯二硫醚(CAS号:139-65-1)和0.1g糠胺(CAS号:617-89-0)缓慢加入到异氰酸酯封端的含氟聚氨酯预聚物中,在60℃下反应2h;在氮气的保护下,控制温度80℃,搅拌反应直至明显粘稠,而后继续平衡化反应3h;加入氢氧化钠(0.4g),控制温度在80℃,抽真空去除体系中的小分子物质,得到所需产物。
具体测试方法同实施例1,实验发现在25℃下产物可以在45min完成自修复,在60℃加热条件下,可在10min内完成自修复过程;测得材料水接触角为133°;拉伸强度为16.32MPa,断裂伸长率为262%;测得产物百分之五热分解温度为347℃;测得产物质量损失率为0.14%。
对照例1
取100g聚四氢呋喃二醇(CAS号:25190-06-1)于抽真空通氮气反复处理三次的250ml三口烧瓶中,在75℃及2.5kPa下抽空脱水2h,加入四硼氟酸(0.4g),搅拌0.5h,开始聚合,观察到明显粘稠,则停止反应,降温至55℃,加入0.25g异佛尔酮二异氰酸酯(EC号:223-861-6),通氮气,反应期间,每隔半小时取样,用红外光谱分析仪观察-NCO基团峰的变化,直到-NCO基团不再降低,得到异氰酸酯封端的含氟聚氨酯预聚物;将0.25g 4,4’-二氨基二苯二硫醚(CAS号:139-65-1)和0.1g糠胺(CAS号:617-89-0)缓慢加入到异氰酸酯封端的含氟聚氨酯预聚物中,在60℃下反应2h;在氮气的保护下,控制温度80℃,搅拌反应直至明显粘稠,而后继续平衡化反应3h;加入氢氧化钠(0.4g),控制温度在80℃,抽真空去除体系中的小分子物质,得到所需产物。
具体测试方法同实施例1,实验发现在25℃下产物可以在45min完成自修复,在60℃加热条件下,可在10min内完成自修复过程;测得材料水接触角为92°;拉伸强度为8.34MPa,断裂伸长率为368%;测得产物百分之五热分解温度为256℃;测得产物质量损失率为3.78%。
对照例2
取100g聚四氢呋喃二醇(CAS号:25190-06-1)于抽真空通氮气反复处理三次的250ml三口烧瓶中,加入0.1g二氟乙酸(CAS号:381-73-7),在75℃及2.5kPa下抽空脱水2h,加入四硼氟酸(0.4g),搅拌0.5h,开始聚合,观察到明显粘稠,则停止反应,降温至55℃,加入0.25g异佛尔酮二异氰酸酯(EC号:223-861-6),通氮气,反应期间,每隔半小时取样,用红外光谱分析仪观察-NCO基团峰的变化,直到-NCO基团不再降低,得到异氰酸酯封端的含氟聚氨酯预聚物;将0.25g 4,4’-二氨基二苯二硫醚(CAS号:139-65-1)和0.1g糠胺(CAS:617-89-0)缓慢加入到异氰酸酯封端的含氟聚氨酯预聚物中,在60℃下反应2h;在氮气的保护下,控制温度80℃,搅拌反应直至明显粘稠,而后继续平衡化反应3h;加入氢氧化钠(0.4g),控制温度在80℃,抽真空去除体系中的小分子物质,得到所需产物。
具体测试方法同实施例1,实验发现在25℃下产物可以在45min完成自修复,在60℃加热条件下,可在10min内完成自修复过程;测得材料水接触角为97°;拉伸强度为8.52MPa,断裂伸长率为365%;测得产物百分之五热分解温度为265℃;测得产物质量损失率为3.12%。
对照例3
取100g聚四氢呋喃二醇(CAS号:25190-06-1)于抽真空通氮气反复处理三次的250ml三口烧瓶中,加入0.3g 2,2-双(4-羧基苯基)六氟丙烷(CAS号:1171-47-7),在75℃及2.5kPa下抽空脱水2h,加入四硼氟酸(0.4g),搅拌0.5h,开始聚合,观察到明显粘稠,则停止反应,降温至55℃,加入0.25g异佛尔酮二异氰酸酯(EC号:223-861-6),通氮气,反应期间,每隔半小时取样,用红外光谱分析仪观察-NCO基团峰的变化,直到-NCO基团不再降低,得到异氰酸酯封端的含氟聚氨酯预聚物;将0.25g 4,4’-二氨基二苯二硫醚(CAS号:139-65-1)缓慢加入到异氰酸酯封端的含氟聚氨酯预聚物中,在60℃下反应2h;在氮气的保护下,控制温度80℃,搅拌反应直至明显粘稠,而后继续平衡化反应3h;加入氢氧化钠(0.4g),控制温度在80℃,抽真空去除体系中的小分子物质,得到所需产物。
具体测试方法同实施例1,实验发现在25℃下产物可以在45min完成自修复,在60℃加热条件下,可在5min内完成自修复过程;测得材料水接触角为130°;拉伸强度为8.23MPa,断裂伸长率为388%;测得产物百分之五热分解温度为354℃;测得产物质量损失率为1.17%。
对照例4
取100g聚四氢呋喃二醇(CAS号:25190-06-1)于抽真空通氮气反复处理三次的250ml三口烧瓶中,加入0.3g 2,2-双(4-羧基苯基)六氟丙烷(CAS号:1171-47-7),在75℃及2.5kPa下抽空脱水2h,加入四硼氟酸(0.4g),搅拌0.5h,开始聚合,观察到明显粘稠,则停止反应,降温至55℃,加入0.25g异佛尔酮二异氰酸酯(EC号:223-861-6),通氮气,反应期间,每隔半小时取样,用红外光谱分析仪观察-NCO基团峰的变化,直到-NCO基团不再降低,得到异氰酸酯封端的含氟聚氨酯预聚物;将0.1g糠胺(CAS号:617-89-0)缓慢加入到异氰酸酯封端的含氟聚氨酯预聚物中,在60℃下反应2h;在氮气的保护下,控制温度80℃,搅拌反应直至明显粘稠,而后继续平衡化反应3h;加入氢氧化钠(0.4g),控制温度在80℃,抽真空去除体系中的小分子物质,得到所需产物。
具体测试方法同实施例1,实验发现在25℃下产物可以在45min完成自修复,在60℃加热条件下,可在5min内完成自修复过程;测得材料水接触角为127°;拉伸强度为8.85MPa,断裂伸长率为367%;测得产物百分之五热分解温度为347℃;测得产物质量损失率为0.68%。
表1为实施例及对照例中所制备的一系列产物在有机溶剂环己烷中浸泡168h后的质量损失率。
对照例5
取100g聚四氢呋喃二醇(CAS号:25190-06-1)于抽真空通氮气反复处理三次的250ml三口烧瓶中,加入0.3g 2,2-双(4-羧基苯基)六氟丙烷(CAS号:1171-47-7),在75℃及2.5kPa下抽空脱水2h,加入四硼氟酸(0.4g),搅拌0.5h,开始聚合,观察到明显粘稠,则停止反应,降温至55℃,加入0.25g异佛尔酮二异氰酸酯(EC号:223-861-6),通氮气,反应期间,每隔半小时取样,用红外光谱分析仪观察-NCO基团峰的变化,直到-NCO基团不再降低,得到异氰酸酯封端的含氟聚氨酯预聚物;将0.25g 4,4’-二氨基二苯二硫醚(CAS号:139-65-1)和0.1g2,6-二异丙基-N,N-二甲基苯胺(CAS号:2909-77-5)缓慢加入到异氰酸酯封端的含氟聚氨酯预聚物中,在60℃下反应2h;在氮气的保护下,控制温度80℃,搅拌反应直至明显粘稠,而后继续平衡化反应3h;加入氢氧化钠(0.4g),控制温度在80℃,抽真空去除体系中的小分子物质,得到所需产物。
具体测试方法同实施例1,实验发现在25℃下产物可以在45min完成自修复,在60℃加热条件下,可在7min内完成自修复过程;测得材料水接触角为126°;拉伸强度为8.25MPa,断裂伸长率为384%;测得产物百分之五热分解温度为351℃;测得产物质量损失率为0.89%。
表1
Claims (10)
1.一种高密度含氟多元醇,其特征在于:所述高密度含氟多元醇的制备方法为:将多元醇和高含氟量羧酸加入三口烧瓶中,在70-80℃及1.3-2.6kPa下抽空脱水2h,加入催化剂,搅拌0.5h开始聚合,观察到明显粘稠,则停止反应得到高密度含氟多元醇。
2.如权利要求1所述高密度含氟多元醇,其特征在于:所述多元醇为聚四氢呋喃二醇、聚己二酸乙二醇酯、聚己二酸丁二醇酯、聚己二酸己二醇酯、聚己内酯二醇中的一种;高含氟量羧酸为2,2-双(4-羧基苯基)六氟丙烷、六氟戊二酸、全氟癸二酸、全氟辛二酸、2,2-二氟戊二酸中的一种;催化剂为四氟硼酸、丙烯酸、乙酸钠中的一种。
3.如权利要求1所述高密度含氟多元醇,其特征在于:所述多元醇和高含氟量羧酸的摩尔比为3.5-4.0:2.5-3.0。
4.一种如权利要求1所述高密度含氟多元醇的应用,其特征在于:所述高密度含氟多元醇用于制备双重自修复含氟聚氨酯。
5.如权利要求4所述高密度含氟多元醇的应用,其特征在于:所述双重自修复含氟聚氨酯的具体制备方法步骤如下:
(1)将高密度含氟多元醇降温至50-60℃,加入异氰酸酯,通氮气,反应期间,每隔半小时取样,用红外光谱分析仪观察-NCO基团峰的变化,直到-NCO基团不再降低,得到异氰酸酯封端的含氟聚氨酯预聚物;
(2)将含二硫键的扩链剂和糠胺加入到步骤(1)的产物中,在60℃下反应2h;在氮气保护下,控制温度75-85℃,搅拌反应直至粘稠,而后继续平衡化反应3h;加入酸性中和剂,控制温度在75-85℃,抽真空去除体系中的小分子物质,得到双重自修复含氟聚氨酯。
6.如权利要求5所述高密度含氟多元醇的应用,其特征在于:步骤(1)异氰酸酯为异佛尔酮二异氰酸酯、2,4甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的一种。
7.如权利要求5所述高密度含氟多元醇的应用,其特征在于:步骤(1)多元醇和异氰酸酯的摩尔比为1∶1。
8.如权利要求5所述高密度含氟多元醇的应用,其特征在于:步骤(2)含二硫键扩链剂为胱氨酸、4,4’-二氨基二苯二硫醚、双(4-羟苯基)二硫醚中的一种;酸性中和剂为氢氧化钠、碳酸钠、碳酸钙中的一种。
9.如权利要求5所述高密度含氟多元醇的应用,其特征在于:步骤(2)含二硫键扩链剂与糠胺的摩尔比为1-1.5∶1-1.5。
10.一种双重自修复含氟聚氨酯,其特征在于:所述自修复含氟聚氨酯的结构通式如下:
R4-OOCHN-R3-NHCOOR2-NHCOO-R1-NHCOO-R2-NHCOO-R3-NHCOO-R4;
或
R4-HNOCHN-R3-NHCONH-R2-NHCOO-R1-NHCOOR2-NHCONH-R3-NHCONH-R4
其中,
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