CN111019510A - 一种改性外露型单组分聚氨酯防水涂料及其制备方法 - Google Patents
一种改性外露型单组分聚氨酯防水涂料及其制备方法 Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 34
- 239000011248 coating agent Substances 0.000 title claims abstract description 32
- 239000004814 polyurethane Substances 0.000 title abstract description 15
- 229920002635 polyurethane Polymers 0.000 title abstract description 15
- 238000002360 preparation method Methods 0.000 title description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 20
- 229920000570 polyether Polymers 0.000 claims abstract description 20
- 239000004014 plasticizer Substances 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 8
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- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 18
- -1 acrylic ester Chemical class 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 229920005862 polyol Polymers 0.000 claims description 13
- 150000003077 polyols Chemical class 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 7
- 239000012188 paraffin wax Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 239000002608 ionic liquid Substances 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- WGESJTHIONWBDD-UHFFFAOYSA-N 2-propan-2-yl-1,3-oxazolidine Chemical compound CC(C)C1NCCO1 WGESJTHIONWBDD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 3
- DZARITHRMKPIQB-UHFFFAOYSA-N 2-(2-propan-2-yl-1,3-oxazolidin-3-yl)ethanol Chemical compound CC(C)C1OCCN1CCO DZARITHRMKPIQB-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 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 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 claims description 2
- ISPIHWORPMENMZ-UHFFFAOYSA-N 3-(1h-imidazol-2-yl)propan-1-ol Chemical compound OCCCC1=NC=CN1 ISPIHWORPMENMZ-UHFFFAOYSA-N 0.000 claims description 2
- RQFUZUMFPRMVDX-UHFFFAOYSA-N 3-Bromo-1-propanol Chemical compound OCCCBr RQFUZUMFPRMVDX-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims description 2
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 claims description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 2
- OCSUTSDNCHFJDN-UHFFFAOYSA-N [Na].FC(F)(F)C1C(C(=O)NC1=O)C(F)(F)F Chemical compound [Na].FC(F)(F)C1C(C(=O)NC1=O)C(F)(F)F OCSUTSDNCHFJDN-UHFFFAOYSA-N 0.000 claims description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 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 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229940097275 indigo Drugs 0.000 claims description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 2
- DMTRWFMFBIMXBX-UHFFFAOYSA-L lead(2+);6-methylheptanoate Chemical compound [Pb+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O DMTRWFMFBIMXBX-UHFFFAOYSA-L 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 2
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- 150000001450 anions Chemical class 0.000 abstract description 5
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract 1
- 238000010276 construction Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XBXFGOSIPGWNLZ-UHFFFAOYSA-N O=C1C=C(CC(C)(C)C1)C.N=C=O Chemical compound O=C1C=C(CC(C)(C)C1)C.N=C=O XBXFGOSIPGWNLZ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- SFIDCIGCQMGWKT-UHFFFAOYSA-N OCCCC1=C(N=CN1)CCCO Chemical compound OCCCC1=C(N=CN1)CCCO SFIDCIGCQMGWKT-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3848—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing two nitrogen atoms in the ring
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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
- 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
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- 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
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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Abstract
本发明属于涂料技术领域,具体涉及一种外漏型单组分聚氨酯防水涂料,所述涂料包括如下重量份数组成:二异氰酸酯15‑30份,端羟基聚醚20‑35份、丙烯酸酯2‑8份、潜固化剂0.5‑3份,增塑剂6‑14份、颜填料15‑35份、溶剂8‑24份、抗氧剂0.5‑3份、引发剂1‑3份、高性能改性助剂3‑10份;所述高性能改性助剂为双羟基离子液体结构,其阳离子为对称的双羟基结构,可与二异氰酸酯和端羟基聚醚聚合形成嵌段结构;阴离子为NTf2 ¯结构,分子体积较大,聚合时由于其静电作用可以均匀的吸附在链的两端,从而增大了链与链间的空隙,进而增加了高分子链的运动幅度提高韧性;另一方面,阴离子具有较高的耐温性能,C‑F键还具有较强的耐磨性能,进一步提高了涂料的耐高温和耐磨性能。
Description
技术领域
本发明属于涂料技术领域,具体涉及一种外露型单组分聚氨酯防水涂料及其制备方法
背景技术
聚氨酯防水涂料是聚氨酯合成材料应用重要组成部分之一。由于聚氨酯涂料涂膜具有弹性且延伸性好,抗拉强度高,粘结性好,体积收缩小,涂膜防水层无接缝,对基层裂缝伸缩性的变形有较强的适应性,施工维修方便、在任何结构复杂的基层表面均易于施工等特点,可用于建筑物不同部位的防水堵漏,故成为建筑防水的主要材料之一。
单组分聚氨酯防水涂料施工时不存在计量误差,对施工操作人员的素质要求不高,粘度较低,施工容易,同时适用期长、性能稳定、使用方便、适用面广。因此,近年来单组分聚氨酯防水涂料的使用量越来越大,也越来越受到用户的肯定。单组份聚氨酯防水涂料已经成为聚氨酯防水涂料的发展方向。
为解决聚氨酯防水涂料耐老化性差,不能外露的情况,中国专利CN201610843230.3公开了一种单组份外露型聚氨酯防水涂料及其制备方法,在反应容器内加入聚醚多元醇、聚碳酸酯多元醇、增塑剂、颜填料,分散均匀,搅拌升温,真空脱水;降温后加入二异氰酸酯,搅拌升温反应;加入扩链剂反应;加入二异氰酸酯三聚体继续反应;降温后加入溶剂,搅拌;降温后加入催化剂、紫外线吸收剂、紫外线稳定剂、抗氧剂、消泡剂,搅拌均匀后,在真空下脱泡出料,制得成品。本发明大幅提升了涂料的力学性能和耐候性能,但其环境适应性和耐磨性能还有待进一步改进。
发明内容
为解决现有技术的不足,本发明提供了一种改性外露型单组分防水涂料,其特征在于包括如下重量份数组成:二异氰酸酯15-30份,端羟基聚醚20-35份、丙烯酸酯2-8份、潜固化剂0.5-3份,增塑剂6-14份、颜填料15-35份、溶剂8-24份、抗氧剂0.5-3份、引发剂1-3份、高性能改性助剂3-10份。
所述高性能助剂为双羟基离子液体结构,具体结构为:
该结构阳离子为对称的双羟基结构,可与二异氰酸酯和端羟基聚醚聚合形成嵌段结构;阴离子为NTf2 -结构,分子体积较大,聚合时由于其静电作用可以均匀的吸附在链的两端,从而增大了链与链间的空隙,进而增加了高分子链的运动幅度提高韧性;另一方面,阴离子具有较高的耐温性能,C-F键还具有较强的耐磨性能,进一步提高了涂料的耐高温和耐磨性能。
进一步的所述二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯的脂肪族异氰酸酯中的一种或多种的混合物;
所述端羟基聚醚为PPG类聚醚多元醇、POP类聚合物聚醚多元醇和PTMEG类聚四氢呋喃型多元醇中的一种或两种以上的混合物;
所述丙烯酸酯包括丙烯酸羟乙酯、甲基丙烯酸羟乙酯和二甲基丙烯酸乙酯中一种或两种以上的混合物;
所述潜固化剂包括2-异丙基恶唑烷、2,2-二氢恶唑烷、2-异丙基-N-羟乙基-恶唑烷或2,2-二氢-N-羟乙基恶唑烷中的至少一种;
所述增塑剂包括壬酯、氯化石蜡、柠檬酸酯类增塑剂中的至少一种;
所述颜填料包括炭黑、钛白粉、靛蓝、铁黄、铁棕、高岭土、重钙、硫酸钡、氧化镁、氧化钙、硅灰石、硅微粉和滑石粉中的一种或两种以上的混合物;
所述溶剂为醋酸乙酯、醋酸丁酯或丙酮中的至少一种。
所述抗氧剂为丁基羟基茴香醚、二丁基羟基甲苯、叔丁基对苯二酚中至少一种;
所述引发剂为二月桂酸二丁基锡、辛酸亚锡、异辛酸铅中的一种或多种的混合物。
本发明还提供了一种所述改性外露型单组分防水涂料的制备方法,包括如下步骤:
(1)在反应器内加入端羟基聚醚,增塑剂、颜填料、高性能改性助剂,分散均匀,搅拌升温至100-110℃,抽真空脱水,真空度-0.08-0.1MPa;
(2)将温度降至60-70℃,高速搅拌下滴加异氰酸酯,滴加完毕后保温反应1-2h,然后升温到80-90℃,继续搅拌反应2-3h;
(3)将反应体系降温到70-80℃,缓慢滴加丙烯酸酯,滴加完毕后保温反应1-2h,然后加入引发剂,继续保温反应1-2h;
(4)向步骤(3)所得的反应体系中依次加入潜固化剂、抗氧剂、溶剂、高速搅拌分散均匀,然后降低温度到40℃以下,抽真空除气泡,充氮气保护出料得最终涂料。
本发明所制备的涂料具有如下优点:(1)双羟基离子液体改性提高了涂料的韧性,长期使用时不易出现裂纹;(2)掺入NTf2 -阴离子改性还可提高涂层的耐磨性能;(3)本发明提高涂料的制备方法,各物料分散均匀,操作简便,易于工业化。
具体实施方式
以下对本发明的原理和特征进行描述,所举实施例只用于解释本发明,并非用于限定本发明的范围。
本发明实施例所用高性能改性助剂为双羟基离子液体结构,具体结构为:
所述双羟基离子液体的具体制备方法如下:
(1)将1mol羟丙基咪唑与1mol3-溴丙醇加入500mL乙腈中,回流反应24h,过滤洗涤得双羟丙基咪唑溴盐;
(2)双羟丙基吡唑溴盐与双三氟甲黄酰亚胺钠盐按摩尔比1:1加入去离子水中,搅拌反应2h后,体系分为两层,分液后将下层产品用去离子水洗涤3次得双羟丙基咪唑双三氟甲黄酰胺盐产品。所得产品用1HNMR进行表表征确认结构,1H NMR(600MHz,DMSO)δ=2.20(t,4H,CH2),3.49(t,4H,CH2),4.06(t,4H,CH2),4.06(s,2H,OH),7.75(d,2H,CH),8.92(s,1H,CH).
下面以具体实施例对本发明进行详细说明,
实施例1:
本实施例提供一种改性外露型单组分防水涂料,包括如下重量份数组成:异佛尔酮异氰酸酯20份,PPG类聚醚多元醇26份、丙烯酸羟乙酯4份、2-异丙基恶唑烷1份,氯化石蜡8份、钛白粉20份、醋酸乙酯16份、丁基羟基茴香醚1份、二月桂酸二丁基锡1份、双羟丙基咪唑双三氟甲黄酰胺盐5份。所述外露型单组分防水涂料的制备方法,具体包括如下步骤:
(1)在反应器内加入PPG类聚醚多元醇,氯化石蜡、钛白粉、双羟丙基咪唑双三氟甲黄酰胺盐,分散均匀,搅拌升温至100-110℃,抽真空脱水,真空度-0.08-0.1MPa;
(2)将温度降至60-70℃,高速搅拌下滴加异佛尔酮异氰酸酯,滴加完毕后保温反应1-2h,然后升温到80-90℃,继续搅拌反应2-3h;
(3)将反应体系降温到70-80℃,缓慢滴加丙烯酸羟乙酯,滴加完毕后保温反应1-2h,然后加入二月桂酸二丁基锡,继续保温反应1-2h;
(4)向步骤(3)所得的反应体系中依次加入2-异丙基恶唑烷、丁基羟基茴香醚、醋酸乙酯、高速搅拌分散均匀,然后降低温度到40℃以下,抽真空除气泡,充氮气保护出料得最终涂料。
实施例2:
本实施例提供一种改性外露型单组分防水涂料,包括如下重量份数组成:六亚甲基二异氰酸酯25份,POP类聚合物聚醚多元醇30份、丙烯酸羟乙酯6份、2,2-二氢恶唑烷2份,氯化石蜡8份、高岭土20份、醋酸乙酯20份、丁基羟基茴香醚1份、二月桂酸二丁基锡2份、双羟丙基咪唑双三氟甲黄酰胺盐8份。本实施例制备方法同实施例1。
实施例3:
本实施例提供一种改性外露型单组分防水涂料,包括如下重量份数组成:苯二亚甲基二异氰酸酯20份,POP类聚合物聚醚多元醇28份、甲基丙烯酸羟乙酯3份、2,2-二氢恶唑烷1份,壬酯10份、高岭土30份、醋酸丁酯20份、丁基羟基茴香醚1份、辛酸亚锡2份、双羟丙基咪唑双三氟甲黄酰胺盐10份。本实施例制备方法同实施例1。
实施例4:
本实施例提供一种改性外露型单组分防水涂料,包括如下重量份数组成:二环己基甲烷二异氰酸酯25份,PTMEG类聚四氢呋喃型多元醇30份、甲基丙烯酸羟乙酯5份、2-异丙基-N-羟乙基-恶唑烷2份,氯化石蜡10份、硅微粉26份、醋酸丁酯20份、丁基羟基茴香醚3份、二月桂酸二丁基锡2份、双羟丙基咪唑双三氟甲黄酰胺盐5份。本实施例制备方法同实施例1。
对比例1
为进一步验证本发明的技术效果,将现有专利技术CN201611121394.1的实施例制备的样品与本发明进行比较,采用的技术方案为:异氰酸酯IPDI 6.5份;聚醚二元醇2000D20份,聚醚三元醇330N 14份,氯化石蜡10份,丙烯酸羟易酯2.5份,偶氮二异丁腈0.2份,甲基丙烯酸乙酯5份,十二烷基硫醇0.2份,潜固化剂2959 0.8份,太白粉0.3份,铁红0.2份,重钙30份,有机锡催化剂T-12 0.2份,抗氧剂0.1份,溶剂10份。
为进一步验证本发明的技术效果,将合成的改性聚氨酯防水涂料进行涂膜,厚度约为1.5mm,按照GB/T19250-2013《聚氨酯防水涂料》外露型聚氨酯进行测试,测的拉伸强度,断裂伸长率和2000h加速老化性能,结果如表1所示,可以发现本发明制备的涂料具有较强的力学性能和环境适应性。
表1.外露型聚氨酯涂料性能参数
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (4)
2.根据权利要求1所述一种改性外露型单组分防水涂料,其特征在于所述二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯中的一种或多种的混合物;
所述端羟基聚醚为PPG类聚醚多元醇、POP类聚合物聚醚多元醇和PTMEG类聚四氢呋喃型多元醇中的一种或两种以上的混合物;
所述丙烯酸酯包括丙烯酸羟乙酯、甲基丙烯酸羟乙酯和二甲基丙烯酸乙酯中一种或两种以上的混合物;
所述潜固化剂包括2-异丙基恶唑烷、2,2-二氢恶唑烷、2-异丙基-N-羟乙基-恶唑烷或2,2-二氢-N-羟乙基恶唑烷中的至少一种;
所述增塑剂包括壬酯、氯化石蜡、柠檬酸酯类增塑剂中的至少一种;
所述颜填料包括炭黑、钛白粉、靛蓝、铁黄、铁棕、高岭土、重钙、硫酸钡、氧化镁、氧化钙、硅灰石、硅微粉和滑石粉中的一种或两种以上的混合物;
所述溶剂为醋酸乙酯、醋酸丁酯或丙酮中的至少一种。
所述抗氧剂为丁基羟基茴香醚、二丁基羟基甲苯、叔丁基对苯二酚中至少一种;
所述引发剂为二月桂酸二丁基锡、辛酸亚锡、异辛酸铅中的一种或多种的混合物。
3.权利要求1或2所述的双羟基离子液体的制备方法,具体包括如下步骤:
(1)将1mol羟丙基咪唑与1mol 3-溴丙醇加入500mL乙腈中,回流反应24h,过滤洗涤得双羟丙基咪唑溴盐;
(2)双羟丙基吡唑溴盐与双三氟甲黄酰亚胺钠盐按摩尔比1:1加入去离子水中,搅拌反应2h后,体系分为两层,分液后将下层产品用去离子水洗涤3次得双羟丙基咪唑双三氟甲黄酰胺盐产品。
4.权利要求1或2所述的一种改性外露型单组分防水涂料的制备方法,包括如下步骤:
(1)在反应器内加入端羟基聚醚,增塑剂、颜填料、高性能改性助剂,分散均匀,搅拌升温至100-110℃,抽真空脱水,真空度-0.08-0.1MPa;
(2)将温度降至60-70℃,高速搅拌下滴加异氰酸酯,滴加完毕后保温反应1-2h,然后升温到80-90℃,继续搅拌反应2-3h;
(3)将反应体系降温到70-80℃,缓慢滴加丙烯酸酯,滴加完毕后保温反应1-2h,然后加入引发剂,继续保温反应1-2h;
(4)向步骤(3)所得的反应体系中依次加入潜固化剂、抗氧剂、溶剂、高速搅拌分散均匀,然后降低温度到40℃以下,抽真空除气泡,充氮气保护出料得最终涂料。
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