CN117343262A - 一种紫外光照调控力学性能的聚氨酯脲薄膜及其制备方法 - Google Patents
一种紫外光照调控力学性能的聚氨酯脲薄膜及其制备方法 Download PDFInfo
- Publication number
- CN117343262A CN117343262A CN202311432860.8A CN202311432860A CN117343262A CN 117343262 A CN117343262 A CN 117343262A CN 202311432860 A CN202311432860 A CN 202311432860A CN 117343262 A CN117343262 A CN 117343262A
- Authority
- CN
- China
- Prior art keywords
- film
- polyurethane urea
- diisocyanate
- ultraviolet
- dihydric alcohol
- 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
Links
- 229920003226 polyurethane urea Polymers 0.000 title claims abstract description 80
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 150000004985 diamines Chemical class 0.000 claims abstract description 19
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 239000004970 Chain extender Substances 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000003277 amino group Chemical group 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 19
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 15
- 229920001451 polypropylene glycol Polymers 0.000 claims description 15
- 150000002009 diols Chemical class 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 10
- 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 10
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 10
- -1 polydimethylsiloxane Polymers 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 8
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 7
- 229920001610 polycaprolactone Polymers 0.000 claims description 7
- 239000004632 polycaprolactone Substances 0.000 claims description 7
- LTOVZUHVYHATET-UHFFFAOYSA-N 1,2-diisocyanatoethylcyclohexane Chemical compound O=C=NCC(N=C=O)C1CCCCC1 LTOVZUHVYHATET-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 6
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical group [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 claims description 6
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 6
- 239000004417 polycarbonate Substances 0.000 claims description 6
- 229920000515 polycarbonate Polymers 0.000 claims description 6
- 239000004626 polylactic acid Substances 0.000 claims description 6
- 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 6
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 5
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 34
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 abstract description 10
- 238000004132 cross linking Methods 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 3
- 230000000977 initiatory effect Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 83
- 239000000203 mixture Substances 0.000 description 21
- 238000002156 mixing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3237—Polyamines aromatic
- C08G18/324—Polyamines 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/428—Lactides
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 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
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 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
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- 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
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- 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
- C08G18/6666—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明提供了一种紫外光照调控力学性能的聚氨酯脲薄膜及其制备方法,本发明选用氨酯脲薄膜是以低聚物二元醇、低聚物二元胺、二异氰酸酯、扩链剂和紫外敏感单体为反应原料,经聚合反应得到;所述反应原料中,羟基+胺基与异氰酸酯基的摩尔比为1:0.8~1:1.2。二氨基二苯甲酮或二羟基二苯甲酮紫外光引发基团作为聚氨酯脲薄膜的制备原料之一,使得聚合形成的聚氨酯脲薄膜材料的分子链中存在紫外敏感单体,进而成型的聚氨酯脲薄膜材料在紫外光的作用下产生二次交联,得到强度韧性优异,力学性能可调控,且在日光长时间照射下可以实现刚度提升的聚氨酯脲薄膜。
Description
技术领域
本发明涉及高分子材料技术领域,尤其涉及一种紫外光照调控力学性能的聚氨酯脲薄膜及其制备方法。
背景技术
薄膜材料广泛用于高科技和生产生活等诸多领域。在传统的高分子加工中,常用线性或枝化的热塑性聚合物通过吹塑、模压、压延、流延或溶液涂布等方法制备薄膜。其可以单独使用,也可以附着在其他材料表面形成涂层。
聚氨酯脲(PU)薄膜由于其出色的性能和多样的特性,在众多领域中得到广泛应用。具体涉及包装、冷冻保鲜、薄膜电子学、医疗领域和分离膜等多个领域。不同应用领域对薄膜性能的要求不同,需要根据具体应用场景进行材料设计和制备。而更改高分子配方是调控薄膜材料性能的常用方法,比如化学结构、助剂、复合填料等的选择。这也就意味着一旦确定了材料配方,薄膜的性能几乎就无法再次调控。虽然定向拉伸、电晕等方法也可以在薄膜制备后进一步改变其力学和表面性质,但这些过程通常需要特殊的设备,难以满足复杂的定制化趋势和需求。
因此,开发一种力学性能可调控的聚合物薄膜十分重要的。
发明内容
针对现有技术中存在的上述问题,本发明提供一种紫外光照调控力学性能的聚氨酯脲薄膜以及制备方法,所获得的聚氨酯脲薄膜在紫外暴露下,不仅不会使材料性能劣化,反而会使薄膜性能得到提升。
具体发明内容如下:
第一方面,本发明提供一种紫外光照调控力学性能的聚氨酯脲薄膜,所述聚氨酯脲薄膜是以以摩尔比为1:1:4:0.6:1.4~1:1:6:2:2的低聚物二元醇、低聚物二元胺、二异氰酸酯、扩链剂和紫外敏感单体为反应原料,经聚合反应得到;
其中,所述低聚物二元醇选自聚四氢呋喃、聚己内酯二元醇、聚乙二醇、聚丙二醇、聚乳酸二元醇、聚二甲基硅氧烷二元醇和聚碳酸酯二元醇中的一种或多种;
所述低聚物二元胺选自胺基封端聚丙二醇、胺基封端聚四氢呋喃和胺基封端聚二甲基硅氧烷中的一种或多种;
所述二异氰酸酯选自异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、甲基环己基二异氰酸酯、环己基二亚甲基二异氰酸酯、二苯甲烷二异氰酸酯和甲苯二异氰酸酯中的一种或多种;
所述扩链剂选自乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、环己二醇、对苯二胺、4,4'-亚甲基二(2-氯苯胺)和N-甲基二乙醇胺中的一种或多种;
所述紫外敏感单体选自二氨基二苯甲酮或二羟基二苯甲酮。
可选地,所述低聚物二元醇选自聚四氢呋喃或聚己内酯。
可选地,所述低聚物二元胺选自胺基封端聚四氢呋喃。
可选地,所述二异氰酸酯选自异佛尔酮二异氰酸酯。
可选地,所述扩链剂选自1,4-丁二醇。
可选地,所述紫外敏感单体选自二氨基二苯甲酮。
可选地,所述聚氨酯脲薄膜中,羟基+胺基与异氰酸酯基的摩尔比为1:0.8~1:1.2。
第二方面,本发明一种上述第一方面所述的紫外光照调控力学性能的聚氨酯脲薄膜的制备方法,所述制备方法包括如下制备步骤:
S1、向低聚物二元醇、低聚物二元胺和二异氰酸酯的混合溶液中加入催化剂,并加热至50-100℃进行第一聚合反应,得到预聚物;
S2、向所述预聚物中继续加入紫外敏感单体、扩链剂和有机溶剂,形成固含量为10-50%的混合物质;将所述混合物质置于40~110℃条件下进行第二聚合反应,得到聚合物溶液;
S3、涂布所述聚合物溶液,充分烘干后得到聚氨酯脲薄膜;
S4、将所述聚氨酯脲薄膜置于紫外光照设备下进行1-30min的紫外光照,得到紫外光照调控力学性能的聚氨酯脲薄膜。
可选地,所述催化剂为新癸酸铋。
可选地,所述有机溶剂选自N,N’二甲基甲酰胺、N,N’二甲基乙酰胺、丁酮、二甲亚砜、二氧六环、甲苯、二甲苯中的一种或多。
与现有技术相比,本发明具有以下优点:
本发明提供了一种紫外光照调控力学性能的聚氨酯脲薄膜,本发明以紫外敏感单体作为制备聚氨酯脲薄膜的原料之一,聚合物分子链中紫外敏感单体的存在,可使成型的聚氨酯脲薄膜材料在紫外光的作用下产生二次交联,进而得到强度韧性优异,力学性能可调控,且在日光长时间照射下可以实现刚度提升的聚氨酯脲薄膜。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1示出了本发明实施例提供的聚氨酯脲薄膜的制备方法流程图;
图2示出了本发明实施例提供的未经紫外光照的聚氨酯脲薄膜的拉伸实验结果图;
图3示出了本发明实施例1提供的聚氨酯脲薄膜的拉伸实验结果图;
图4示出了本发明实施例3提供的聚氨酯脲薄膜的拉伸实验结果图;
图5示出了本发明实施例4提供的聚氨酯脲薄膜在自然日光照射后的杨氏模量变化图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。以下对至少一个示例性实施例的描述实际上仅仅是说明性的,决不作为对本发明及其应用或使用的任何限制。基于本发明中的实施例,任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品,均落在本发明的保护范围之内。以及,本领域普通技术人员在没有开展创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例中未注明具体实验步骤或者条件,按照本领域内的现有技术所描述的常规实验步骤的操作或条件即可进行。所用试剂以及其他仪器未注明生产厂商者,均为可以通过市购获得的常规试剂产品。此外,附图仅为本发明实施例的示意性图解,并非一定是按比例绘制。图中相同的附图标记表示相同或类似的部分,因而将省略对它们的重复描述。附图中所示的一些方框图是功能实体,不一定必须与物理或逻辑上独立的实体相对应。
对于相关领域普通技术人员已知的技术、方法和设备可能不作详细讨论,但在适当情况下,所述技术、方法和设备应当被视为本发明说明书的一部分。
在本发明的描述中,需要理解的是,使用“第一”、“第二”等词语来限定零部件,仅仅是为了便于对相应零部件进行区别,如没有另行声明,上述词语并没有特殊含义,因此不能理解为对本发明保护范围的限制。
此外,下面所描述的本发明不同实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互结合。
在对本发明所提供的一种紫外光照调控力学性能的聚氨酯脲薄膜及其制备方法进行详细说明之前,有必要对相关技术进行以下说明:
现有调控薄膜材料性能的常用方法中,通过选择合适的原料,优化配方,并控制反应条件,以调控薄膜材料的各项性能。例如,根据具体的应用需求,选择高质量的原料,如高分子量的聚氨酯和合适的脲交联剂,以提高薄膜材料的强度和耐久性;通过调整原料的比例和添加适量的助剂,以改善聚氨酯脲薄膜的机械性能,如添加增强剂或填充剂可以提高薄膜的强度、刚度和耐磨性;在制备过程中,控制好反应的温度、时间和pH值等条件,确保反应充分进行,产生致密的交联结构,有助于提高薄膜的强度和耐用性;进一步地,在制备薄膜的工艺中,使用更高级别的技术和设备,如采用真空技术、溶液旋涂、薄膜层压等方法,以确保薄膜的均匀性和致密性。
对于大多数聚合物材料而言,紫外光照射会缩减材料寿命。这主要是由于紫外光会诱发聚合物链的氧化、断裂等。因此,目前还没有用到紫外光照这一技术手段来强化聚氨酯脲薄膜性能。
本发明进行深入研究发现,聚氨酯脲由于其微相分离结构和氢键,本身力学性能优异,且可通过经典的加工方法获得各种尺寸的薄膜。进一步地,将紫外光引发基团引入到分子链当中,即可使材料在紫外照射下产生可相互耦合的自由基,从而形成交联键,提升薄膜的刚度。此外,交联键的产生有助于延长材料寿命,即使暴露于紫外光下(如强烈的日光)也不会使材料性能劣化,反而会使薄膜性能得到提升。这在聚氨酯脲薄膜材料用于防护涂层的应用场景下有重要意义。因此,本发明开发了一种紫外光调控力学性能的聚合物薄膜,且在紫外暴露下不影响材料寿命。本发明具体实施内容如下:
第一方面,本发明提供了一种紫外光照调控力学性能的聚氨酯脲薄膜,所述聚氨酯脲薄膜是以以摩尔比为1:1:4:0.6:1.4~1:1:6:2:2的低聚物二元醇、低聚物二元胺、二异氰酸酯、扩链剂和紫外敏感单体为反应原料,经聚合反应得到;其中,所述低聚物二元醇选自聚四氢呋喃、聚己内酯二元醇、聚乙二醇、聚丙二醇、聚乳酸二元醇、聚二甲基硅氧烷二元醇和聚碳酸酯二元醇中的一种或多种,优选聚四氢呋喃或聚己内酯;所述低聚物二元胺选自胺基封端聚丙二醇、胺基封端聚四氢呋喃和胺基封端聚二甲基硅氧烷中的一种或多种,优选胺基封端聚四氢呋喃;所述二异氰酸酯选自异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、甲基环己基二异氰酸酯、环己基二亚甲基二异氰酸酯、二苯甲烷二异氰酸酯和甲苯二异氰酸酯中的一种或多种,优选异佛尔酮二异氰酸酯;所述扩链剂选自乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、环己二醇、对苯二胺、4,4'-亚甲基二(2-氯苯胺)和N-甲基二乙醇胺中的一种或多种,优选1,4-丁二醇;所述紫外敏感单体选自二氨基二苯甲酮或二羟基二苯甲酮,优选二氨基二苯甲酮。
具体实施时,本发明选用二氨基二苯甲酮或二羟基二苯甲酮紫外光引发基团作为聚氨酯脲薄膜的制备原料之一,使得成型的聚氨酯脲薄膜在紫外照射下,紫外光引发基团产生可相互耦合的自由基,并发生二次交联,交联键的形成提升了薄膜的刚度。此外,交联键的产生也有助于延长材料寿命,即使暴露于紫外光下(如强烈的日光)不仅不会使材料性能劣化,反而会使薄膜性能得到提升。
在一些实施方式中,本实施例在反应原料的配比上进行了优化,羟基+胺基(包含在低聚物二元醇、低聚物二元胺以及紫外敏感单体中):异氰酸酯基(包含在二异氰酸酯基中)的摩尔比为1:0.8~1:1.2。摩尔比在上述范围内有利于材料的制备和良好的综合性能。如果二异氰酸酯含量过低会导致分子量过低,材料性能下降;实验验证表明,羟基+胺基(包含在低聚物二元醇、低聚物二元胺以及紫外敏感单体中):异氰酸酯基(包含在二异氰酸酯基中)的摩尔比不易小于1:0.8;如果异氰酸酯含量过高会导致大量不可逆交联产生,对薄膜加工不利;实验验证表明,羟基+胺基(包含在低聚物二元醇、低聚物二元胺以及紫外敏感单体中):异氰酸酯基(包含在二异氰酸酯基中)的摩尔比不易大于1:1.2。羟基+胺基(包含在低聚物二元醇、低聚物二元胺以及紫外敏感单体中):异氰酸酯基(包含在二异氰酸酯基中)的摩尔比优选范围为1:0.95~1:1.05。
第二方面,本发明提供一种上述第一方面所述的紫外光照调控力学性能的聚氨酯脲薄膜的制备方法,图1示出了本发明实施例提供的聚氨酯脲薄膜的制备方法流程图,如图1所示,所述制备方法包括如下制备步骤:
S1、向低聚物二元醇、低聚物二元胺和二异氰酸酯的混合溶液中加入催化剂,并加热至50-100℃进行第一聚合反应,得到预聚物;
具体实施时,本步骤涉及的反应原料低聚物二元醇选自聚四氢呋喃、聚己内酯二元醇、聚乙二醇、聚丙二醇、聚乳酸二元醇、聚二甲基硅氧烷二元醇和聚碳酸酯二元醇中的一种或多种;本步骤涉及的反应原料本步骤涉及的反应原料低聚物二元胺选自胺基封端聚丙二醇、胺基封端聚四氢呋喃和胺基封端聚二甲基硅氧烷中的一种或多种;本步骤涉及的反应原料二异氰酸酯选自异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、甲基环己基二异氰酸酯、环己基二亚甲基二异氰酸酯、二苯甲烷二异氰酸酯和甲苯二异氰酸酯中的一种或多种。
如上所列的低聚物二元醇、低聚物二元胺和二异氰酸酯原料组合物在催化剂新癸酸铋的作用下发生聚合(第一聚合反应)。反应所需温度条件为50-100℃,反应时间为1-6h,获得异氰酸酯基团封端的预聚物。其中,使用低聚物二元胺能够将氨酯键替换为脲键,增加硬段氢键数量,提升物理交联和能量耗散,提升材料性能。
S2、向所述预聚物中继续加入紫外敏感单体、扩链剂和有机溶剂,形成固含量为10-50%的混合物质;将所述混合物质置于40~110℃条件下进行第二聚合反应,得到聚合物溶液;
本步骤中,由预聚物、紫外敏感单体、扩链剂和有机溶剂组成的原料组合物中,控制有机溶剂的加入量,使混合物质中固含量的质量占比为10-50%,优选混合物质中固含量的质量占比为15-40%;上述原料组合物在40~110℃下进行6~48h聚合(第二聚合反应),得到聚合物溶液。其中,本步骤使用的反应原料光敏扩链剂为具有二苯甲酮单元和2个羟基或氨基的化合物,优选二氨基二苯甲酮或二羟基二苯甲酮;本步骤涉及的反应原料扩链剂选自乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、环己二醇、对苯二胺、4,4'-亚甲基二(2-氯苯胺)和N-甲基二乙醇胺中的一种或多种。
由于扩链剂以及紫外敏感单体(二氨基二苯甲酮或二羟基二苯甲酮)均可以与预聚物的链端发生反应,产生自由基(或离子),从而启动聚合链的生长增长和分子量的增加,从而形成高分子量的聚氨酯脲。
S3、涂布所述聚合物溶液,充分烘干后得到聚氨酯脲薄膜;
本步骤中,涂布优选涂布机涂布,涂布的厚度控制在50μm-80μm
S4、将所述聚氨酯脲薄膜置于紫外光照设备下进行1-30min的紫外光照,得到紫外光照调控力学性能的聚氨酯脲薄膜。
本步骤中,成型的聚氨酯脲薄膜进一步接受1-30min的紫外光照,其刚度明显提升。并且,上述聚氨酯脲薄膜材料在日常使用中,即使聚氨酯脲薄膜暴露于紫外光下(如强烈的日光)也不会使材料性能劣化,反而会使薄膜性能得到提升。这在防护涂层的应用场景下有重要意义。
为使本领域技术人员更加清楚地理解本发明,现通过以下实施例对本发明所述的一种紫外光照调控力学性能的聚氨酯脲薄膜及其制备方法进行详细说明。
以下实施例所用到的试剂中:聚四氢呋喃二元醇(分子量2000)、氨基封端聚丙二醇(分子量2000)购自阿拉丁公司;异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、新癸酸铋由Admas-beta公司生产;二羟基二苯甲酮、二氨基二苯甲酮购自安耐吉公司。
实施例1
将聚四氢呋喃二元醇(分子量2000)、氨基封端聚四氢呋喃(分子量1000)、异佛尔酮二异氰酸酯按摩尔比为1:1:6混合,加入0.1%质量分数的催化剂新癸酸铋,80℃预聚2小时得到预聚物。向预聚物中加入1,4-丁二醇、二氨基二苯甲酮,以及有机溶剂N,N’二甲基甲酰胺,以控制反应物粘度。使得聚四氢呋喃二元醇、氨基封端聚四氢呋喃、异佛尔酮二异氰酸酯、1,4-丁二醇和二氨基二苯甲酮摩尔比为1:1:6:2:2,混合均匀,形成固含量为80%的原料组合物,原料组合物中,羟基+胺基与异氰酸酯基的摩尔比为1:1将原料组合物在80℃的温度下进行聚合反应,反应时间为12小时。将得到的聚合物用热压机在100℃热压10分钟,得到200μm厚度的聚氨酯脲薄膜1。
利用功率为250W的紫外固化箱对聚氨酯脲薄膜1进行不同时长的光照处理,照射时间分别为0、5、10、15分钟。照射后在室温下放置3天以上,再进行相关性能测试。
实施例2
将聚丙二元醇(分子量2000)、氨基封端聚丙二醇(分子量2000)、甲苯二异氰酸酯按摩尔比为1:1:6混合,使羟基+氨基与异氰酸酯基的摩尔比为1:3,加入0.1%质量分数的催化剂新癸酸铋,80℃预聚2小时得到预聚物。向预聚物中加入乙二醇、二氨基二苯甲酮和有机溶剂N,N’二甲基乙酰胺,以控制反应物粘度。使得聚丙二元醇、氨基封端聚丙二醇、甲苯二异氰酸酯、乙二醇和二氨基二苯甲酮摩尔比为1:1:6:2:2,混合均匀,形成固含量为85%的原料组合物,原料组合物中,羟基+胺基与异氰酸酯基的摩尔比为1:1。将原料组合物在80℃的温度下进行聚合反应,反应时间为10小时。将得到的聚合物用热压机在100℃热压10分钟,得到50μm厚度的聚氨酯脲薄膜2。
利用功率为250W的紫外固化箱对聚氨酯脲薄膜2进行不同时长的光照处理,照射时间分别为0、5、10、15分钟。照射后在室温下放置3天以上,再进行相关性能测试。
实施例3
将聚碳酸酯二元醇(分子量1000)、氨基封端聚丙二醇(分子量2000)、环己基二亚甲基二异氰酸酯按摩尔比为1:1:4混合,使羟基+氨基与异氰酸酯基的摩尔比为1:2。85℃预聚2小时得到预聚物。向预聚物中加入对苯二胺、二羟基二苯甲酮和有机溶剂二甲亚砜,以控制反应物粘度。使得聚碳酸酯二元醇、氨基封端聚丙二醇、环己基二亚甲基二异氰酸酯、对苯二胺和二羟基二苯甲酮摩尔比为1:1:4:0.6:1.4,混合均匀,形成固含量为80%的原料组合物,原料组合物中,羟基+胺基与异氰酸酯基的摩尔比为1:1将原料组合物在80℃的温度下进行聚合反应,反应时间为24小时。将得到的聚合物用热压机在150℃热压10分钟,得到100μm厚度的聚氨酯脲薄膜3。
利用功率为250W的紫外固化箱对聚氨酯脲薄膜3进行不同时长的光照处理,照射时间分别为0、5、10、15分钟。照射后在室温下放置3天以上,再进行相关性能测试。
实施例4
将聚乳酸二元醇(分子量1000)、氨基封端聚二甲基硅氧烷(分子量2400)、二环己基甲烷二异氰酸酯按摩尔比为1:1:6混合,使羟基+氨基与异氰酸酯基的摩尔比为1:3,85℃预聚2小时得到预聚物。向预聚物中加入1,5-戊二醇、二羟基二苯甲酮和有机溶剂甲苯,以控制反应物粘度。使得聚乳酸二元醇、氨基封端聚二甲基硅氧烷、二环己基甲烷二异氰酸酯、对苯二胺和二羟基二苯甲酮摩尔比为1:1:6:2:2,混合均匀,形成固含量为75%的原料组合物,原料组合物中,羟基+胺基与异氰酸酯基的摩尔比为1:1。将原料组合物在80℃的温度下进行聚合反应,反应时间为24小时。将得到的聚合物溶解于四氢呋喃溶剂中,涂于金属表面形成约100μm厚度的聚氨酯脲薄膜4。
利用功率为250W的紫外固化箱对聚氨酯脲薄膜4进行不同时长的光照处理,照射时间分别为0、5、10、15分钟。照射后在室温下放置3天以上,再进行相关性能测试。
性能评价
1、力学性能评价
采用力学试验机对实施例1-4获得的未经紫外光照处理的聚氨酯脲薄膜进行拉伸实验,拉伸速率为10mm/min,拉伸应变为0-100%。
图2示出了本发明实施例提供的未经紫外光照的聚氨酯脲薄膜的拉伸实验结果图,如图2展示,聚氨酯脲薄膜未经紫外光照(照射时间分别为0)时薄膜的韧性,这说明,可以仅通过改变软硬段配方调节薄膜的力学性能,其中实施例4提供的原料配比下形成的聚氨酯脲薄膜具有更好的力学性能。
图3示出了本发明实施例1提供的聚氨酯脲薄膜的拉伸实验结果图,图4示出了本发明实施例3提供的聚氨酯脲薄膜的拉伸实验结果图,如图3、图4所示,紫外光照时间延长,薄膜的模量和100%定伸应力显著增加。这一结果证明了可以通过紫外光照定量调控薄膜的力学性能,从而实现材料的定制化。
2、自然日光照射硬化评价
将实施例4得到的紫外光照15min的聚氨酯脲薄膜涂层置于无遮挡的屋顶,持续测试3个月,每隔一月监测一次涂层薄膜的杨氏模量,遇阴雨天气则时间顺延。测试时间地点为2023年6-8月的北京。
图5示出了本发明实施例4提供的聚氨酯脲薄膜在自然光照射后的杨氏模量变化图,如图5所示,在日光的紫外照射下,涂层的刚度会随日光的紫外照射时长的增加而逐渐提升。这相对于常规材料的环境老化过程是逆向的,即存在后强化过程。此过程能够极大程度地延长涂层薄膜的防护寿命,并提升防护效果。
产业上的可利用性
本发明的紫外光照调控力学性能的聚氨酯脲薄膜可以广泛用于包装、涂层、柔性电子、结构件等领域。可以根据实际需要,调控制备具有各种定制力学性能的薄膜材料。
在本说明书的描述中,参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。此外,本领域的技术人员可以将本说明书中描述的不同实施例或示例进行结合和组合。
对于方法实施例,为了简单描述,故将其都表述为一系列的动作组合,但是本领域技术人员应该知悉,本发明并不受所描述的动作顺序的限制,因为依据本发明,某些步骤可以采用其他顺序或者同时进行。其次,本领域技术人员也应该知悉,说明书中所描述的实施例均属于优选实施例,所涉及的动作和部件并不一定是本发明所必须的。
以上对本发明所提供的一种紫外光照调控力学性能的聚氨酯脲薄膜及其制备方法进行了详细介绍,本文中应用了具体个例对本发明的原理及实施方式进行了阐述,以上实施例的说明只是用于帮助理解本发明的方法及其核心思想;同时,对于本领域的一般技术人员,依据本发明的思想,在具体实施方式及应用范围上均会有改变之处,综上所述,本说明书内容不应理解为对本发明的限制。
Claims (10)
1.一种紫外光照调控力学性能的聚氨酯脲薄膜,其特征在于,所述聚氨酯脲薄膜是以摩尔比为1:1:4:0.6:1.4~1:1:6:2:2的低聚物二元醇、低聚物二元胺、二异氰酸酯、扩链剂和紫外敏感单体为反应原料,经聚合反应得到;
其中,所述低聚物二元醇选自聚四氢呋喃、聚己内酯二元醇、聚乙二醇、聚丙二醇、聚乳酸二元醇、聚二甲基硅氧烷二元醇和聚碳酸酯二元醇中的一种或多种;
所述低聚物二元胺选自胺基封端聚丙二醇、胺基封端聚四氢呋喃和胺基封端聚二甲基硅氧烷中的一种或多种;
所述二异氰酸酯选自异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、甲基环己基二异氰酸酯、环己基二亚甲基二异氰酸酯、二苯甲烷二异氰酸酯和甲苯二异氰酸酯中的一种或多种;
所述扩链剂选自乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、环己二醇、对苯二胺、4,4'-亚甲基二(2-氯苯胺)和N-甲基二乙醇胺中的一种或多种;
所述紫外敏感单体选自二氨基二苯甲酮或二羟基二苯甲酮。
2.根据权利要求1所述的聚氨酯脲薄膜,其特征在于,所述低聚物二元醇选自聚四氢呋喃或聚己内酯。
3.根据权利要求1所述的聚氨酯脲薄膜,其特征在于,所述低聚物二元胺选自胺基封端聚四氢呋喃。
4.根据权利要求1所述的聚氨酯脲薄膜,其特征在于,所述二异氰酸酯选自异佛尔酮二异氰酸酯。
5.根据权利要求1所述的聚氨酯脲薄膜,其特征在于,所述扩链剂选自1,4-丁二醇。
6.根据权利要求1所述的聚氨酯脲薄膜,其特征在于,所述紫外敏感单体选自二氨基二苯甲酮。
7.根据权利要求1所述的聚氨酯脲薄膜,其特征在于,所述聚氨酯脲薄膜中,羟基+胺基与异氰酸酯基的摩尔比为1:0.8~1:1.2。
8.一种上述权利要求1所述的紫外光照调控力学性能的聚氨酯脲薄膜的制备方法,其特征在于,所述制备方法包括如下制备步骤:
S1、向低聚物二元醇、低聚物二元胺和二异氰酸酯的混合溶液中加入催化剂,并加热至50-100℃进行第一聚合反应,得到预聚物;
S2、向所述预聚物中继续加入紫外敏感单体、扩链剂和有机溶剂,形成固含量为10-50%的混合物质;将所述混合物质置于40~110℃条件下进行第二聚合反应,得到聚合物溶液;
S3、涂布所述聚合物溶液,充分烘干后得到聚氨酯脲薄膜;
S4、将所述聚氨酯脲薄膜置于紫外光照设备下进行1-30min的紫外光照,得到紫外光照调控力学性能的聚氨酯脲薄膜。
9.根据权利要求8所述的制备方法,其特征在于,所述催化剂为新癸酸铋。
10.根据权利要求8所述的制备方法,其特征在于,所述有机溶剂选自N,N’二甲基甲酰胺、N,N’二甲基乙酰胺、丁酮、二甲亚砜、二氧六环、甲苯、二甲苯中的一种或多。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311432860.8A CN117343262A (zh) | 2023-10-31 | 2023-10-31 | 一种紫外光照调控力学性能的聚氨酯脲薄膜及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311432860.8A CN117343262A (zh) | 2023-10-31 | 2023-10-31 | 一种紫外光照调控力学性能的聚氨酯脲薄膜及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117343262A true CN117343262A (zh) | 2024-01-05 |
Family
ID=89361256
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311432860.8A Pending CN117343262A (zh) | 2023-10-31 | 2023-10-31 | 一种紫外光照调控力学性能的聚氨酯脲薄膜及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117343262A (zh) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2730897A1 (de) * | 1977-07-08 | 1979-02-01 | Basf Ag | Photopolymerisierbare bindemittel |
CN102702475A (zh) * | 2012-01-05 | 2012-10-03 | 北京东方雨虹防水技术股份有限公司 | 一种高力学性能喷涂脂肪族聚脲弹性体及其制备方法、施工方法 |
CN104769022A (zh) * | 2012-09-28 | 2015-07-08 | 索菲昂生物科学有限公司 | 一种用于将涂料施涂到聚合物基底上的方法 |
CN106366277A (zh) * | 2016-08-29 | 2017-02-01 | 中山大学 | 一种紫外光交联固化水性聚氨酯的制备方法及应用 |
CN113185644A (zh) * | 2021-04-23 | 2021-07-30 | 清华大学 | 一种可进行光接枝的热可逆交联聚氨酯的制备方法 |
CN114456690A (zh) * | 2021-12-15 | 2022-05-10 | 浙江亚厦装饰股份有限公司 | 一种uv湿气双重固化漆及其制备方法和应用 |
CN115109223A (zh) * | 2022-07-14 | 2022-09-27 | 清华大学 | 一种自修复、表面图案化交联的聚氨酯弹性体 |
-
2023
- 2023-10-31 CN CN202311432860.8A patent/CN117343262A/zh active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2730897A1 (de) * | 1977-07-08 | 1979-02-01 | Basf Ag | Photopolymerisierbare bindemittel |
CN102702475A (zh) * | 2012-01-05 | 2012-10-03 | 北京东方雨虹防水技术股份有限公司 | 一种高力学性能喷涂脂肪族聚脲弹性体及其制备方法、施工方法 |
CN104769022A (zh) * | 2012-09-28 | 2015-07-08 | 索菲昂生物科学有限公司 | 一种用于将涂料施涂到聚合物基底上的方法 |
CN106366277A (zh) * | 2016-08-29 | 2017-02-01 | 中山大学 | 一种紫外光交联固化水性聚氨酯的制备方法及应用 |
CN113185644A (zh) * | 2021-04-23 | 2021-07-30 | 清华大学 | 一种可进行光接枝的热可逆交联聚氨酯的制备方法 |
CN114456690A (zh) * | 2021-12-15 | 2022-05-10 | 浙江亚厦装饰股份有限公司 | 一种uv湿气双重固化漆及其制备方法和应用 |
CN115109223A (zh) * | 2022-07-14 | 2022-09-27 | 清华大学 | 一种自修复、表面图案化交联的聚氨酯弹性体 |
Non-Patent Citations (2)
Title |
---|
JIAXIN SHI等: "Thermal and UV light adaptive polyurethane elastomers for photolithography-transfer printing of flexible circuits", 《MATERIALS HORIZONS》, vol. 9, 30 September 2022 (2022-09-30), pages 3070 * |
赵艳娜 等: "2, 4-二羟基二苯甲酮改性水性聚氨酯的制备与性能", 《精细化工》, vol. 35, no. 1, 31 January 2018 (2018-01-31), pages 124 - 129 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
RU2545457C2 (ru) | Сшиваемые термопластичные полиуретаны | |
JPH03128912A (ja) | 水分散性ポリウレタンの水性分散物 | |
CN110483730B (zh) | 一种聚氨酯丙烯酸酯齐聚物及其制备方法与应用方法 | |
CA2255832C (en) | Extrudable thermoplastic elastomeric urea-extended polyurethane | |
Wang et al. | A novel polyurethane elastomer with super mechanical strength and excellent self-healing performance of wide scratches | |
CN113185644B (zh) | 一种可进行光接枝的热可逆交联聚氨酯的制备方法 | |
CN115612051A (zh) | 一种高韧性可自修复聚硅氧烷弹性体及其制备方法 | |
Zhao et al. | A robust mechanochromic self-healing poly (dimethylsiloxane) elastomer | |
CN116003730A (zh) | 一种自修复聚氨酯材料 | |
CN117343262A (zh) | 一种紫外光照调控力学性能的聚氨酯脲薄膜及其制备方法 | |
NL2035909A (en) | Telechelic polyurethane, and preparation method and application thereof | |
Li et al. | Synthesis and characterization of radiation curable polyurethanes containing pendant acrylate groups | |
CN116284673A (zh) | 一种自修复聚氨酯及其制备方法和应用 | |
Ghosh et al. | Preparation and properties of UV-curable polyurethane methacrylate cationomers and their use as adhesives | |
Gao et al. | New poly (urethane-methacrylate) s obtained by adjusting the structure of the polyols moieties: synthesis, transparent, thermal and mechanical properties | |
CN109880040B (zh) | 一种机械性能可控且具有自修复能力的聚氨酯材料及其制备方法 | |
JP3603293B2 (ja) | 2液注型用ポリウレタンエラストマー組成物、及び該組成物を用いたポリウレタンエラストマーの製造方法 | |
CN115417969B (zh) | 一种分子结构中同时含有羧酸阴离子基团和季铵阳离子基团的亲水性聚氨酯及其水凝胶 | |
JPS6366218A (ja) | 熱可塑性ポリウレタンの製造法 | |
JPS62280214A (ja) | ポリウレタン樹脂組成物 | |
CN114656612B (zh) | 可逆氢键交联的形状记忆聚脲弹性体及其制备方法 | |
CN114957592B (zh) | 一种血液环境自愈合的聚氨酯弹性体及其制备方法和应用 | |
TW201139511A (en) | Process for producing lactone-modified single-terminal type silicone polyol, and urethane resin composition | |
CA2079169A1 (en) | Elastomers based on 4,4'-diisocyanato dicyclohexyl-methane enriched in the trans, trans isomer which contain essentially no chain extenders | |
RU2563878C1 (ru) | Эластомерный полиэфируретансилоксановый материал |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |