CN109021190A - A kind of nano modified polyurethane adhesive of high-fire resistance and preparation method thereof - Google Patents
A kind of nano modified polyurethane adhesive of high-fire resistance and preparation method thereof Download PDFInfo
- Publication number
- CN109021190A CN109021190A CN201710427756.8A CN201710427756A CN109021190A CN 109021190 A CN109021190 A CN 109021190A CN 201710427756 A CN201710427756 A CN 201710427756A CN 109021190 A CN109021190 A CN 109021190A
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- CN
- China
- Prior art keywords
- aqueous solution
- nano
- fire resistance
- modified polyurethane
- adhesive
- 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.)
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- 239000000853 adhesive Substances 0.000 title claims abstract description 45
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 45
- 239000004814 polyurethane Substances 0.000 title claims abstract description 43
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 44
- 239000007864 aqueous solution Substances 0.000 claims abstract description 39
- 239000004970 Chain extender Substances 0.000 claims abstract description 38
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 32
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 30
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 17
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 55
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 20
- 229920000728 polyester Polymers 0.000 claims description 17
- 239000000839 emulsion Substances 0.000 claims description 14
- -1 ester polyol Chemical class 0.000 claims description 13
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 150000002009 diols Chemical class 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 11
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 10
- 239000002253 acid 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 8
- QDPMLKBAQOZXEF-UHFFFAOYSA-N ethanesulfonic acid;sodium Chemical compound [Na].CCS(O)(=O)=O QDPMLKBAQOZXEF-UHFFFAOYSA-N 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- YADSWTKOIHUSDX-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-disulfonic acid Chemical compound NC1=CC(N)=C(S(O)(=O)=O)C=C1S(O)(=O)=O YADSWTKOIHUSDX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 2
- KPTLPIAOSCGETM-UHFFFAOYSA-N benzene 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O.c1ccccc1 KPTLPIAOSCGETM-UHFFFAOYSA-N 0.000 claims description 2
- 229940106691 bisphenol a Drugs 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical class CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims 2
- COTZVJGHVRNXLY-UHFFFAOYSA-N 1,1-diisocyanatoheptane Chemical compound CCCCCCC(N=C=O)N=C=O COTZVJGHVRNXLY-UHFFFAOYSA-N 0.000 claims 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical class OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims 1
- 229920005862 polyol Polymers 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 13
- 239000003292 glue Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000004026 adhesive bonding Methods 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 230000006837 decompression Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 229940083957 1,2-butanediol Drugs 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical group CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- DIVDFFZHCJEHGG-UHFFFAOYSA-N oxidopamine Chemical compound NCCC1=CC(O)=C(O)C=C1O DIVDFFZHCJEHGG-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007666 vacuum forming 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic 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
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- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
-
- 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
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
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- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
-
- 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
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids 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
- 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
- C08G18/74—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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The present invention relates to nano modified polyurethane adhesive of a kind of high-fire resistance and preparation method thereof, the raw material of the adhesive includes: polyester polyol, polyisocyanates, sulfonate chain extender, amine chainextender and nano silica aqueous solution.The adhesive the preparation method comprises the following steps: S1: polyester polyol reacts to obtain prepolymer with polyisocyanates；S2: prepolymer is dissolved, and the reactant aqueous solution of sulfonate chain extender is added, and is added amine chainextender dispersion, is removed organic solvent；S3: being added nano silica aqueous solution, stirs evenly the nano modified polyurethane adhesive up to high-fire resistance.Adhesive of the invention is able to maintain very low viscosity while with high solids content, this improves the thixotropy of glue greatly, and it is more easy that the production of product can be made to control, and better assures that the stability of properties of product, adhesive force is strong.
Description
Technical field
The present invention relates to fine polymer Material Fields, and in particular to a kind of nano modified polyurethane gluing of high-fire resistance
Agent and preparation method thereof.
Background technique
Polyurethane is a kind of important high molecular material, with hardness is high, flexibility is good, wear-resisting, adhesive force is strong, film forming temperature
The excellent properties such as low and ambient temperature curable are spent, the fields such as fabric, leather finish and adhesive, coating are widely used in.Its
In, it is one of main application as adhesive.Polyurethane binder includes solvent type and aqueous two class, and solvent borne polyurethane is viscous
Solvent volatilization in mixture not only causes environmental pollution, can also bring security risk；Commercially available aqueous polyurethane adhesive bonding
High temperature will lead to composite base material and come unglued after substrate, and especially temperature is higher than 85 DEG C and becomes apparent.In recent years, as the mankind are to environment
The continuous of protection and safety requirements is promoted and to being bonded persistent request under high temperature, to the adhesive for polyurethane of high-fire resistance
Research and development have become the important research direction of current polyurethane field.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of nano modified polyurethane adhesive of high-fire resistance and its preparations
Method solves the deficiencies in the prior art.
The purpose of the present invention is be achieved through the following technical solutions:
A kind of nano modified polyurethane adhesive of high-fire resistance, the raw material of the adhesive includes: polyester polyol, more
Isocyanates, sulfonate chain extender, amine chainextender and nano silica aqueous solution；
The dosage of above-mentioned various raw materials are as follows: the dosage relation satisfaction with polyester polyol in polyisocyanates: NCO/OH
Molar ratio be 1:0.3-0.8, i.e. OH equivalent proportion in NCO and polyester polyol in polyisocyanates is 1:0.3-0.8；Sulphur
The quality of hydrochlorate chain extender is the 3-10% of polyester polyol quality；The quality of amine chainextender is the 0.1- of polyester polyol quality
1%；The quality of nano silica aqueous solution is the 3-10% of polyester polyol quality.
Further, the nano-silica-containing aqueous solution is the aqueous silica solution that partial size is 30-100nm.
Further, the nano silica that the solid content of the nano silica aqueous solution is 15~60% is water-soluble
Liquid.
Further, the polyisocyanates is any polyisocyanate compound.
Further, the polyisocyanates includes isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI)
(TDI), hexamethylene diisocyanate (HDI), diphenyl methane -4,4- diisocyanate (MDI), phenylenedimethylidyne diisocyanate
Ester (XDI), poly methylene poly phenyl poly isocyanate (PAPI), 4,4'- dicyclohexyl methyl hydride diisocyanate (HMDI) and four
At least one of xylylene diisocyanate (TMXDI).
Further, the polyisocyanates is isophorone diisocyanate (IPDI) and 1, hexamethylene-diisocyanate
One or both of (HDI) mixture.
Further, the sulfonate chain extender includes ethylenediamine base ethanesulfonic acid sodium, 1,3 one phenylenediamine -4,6, one or two sulphur
Acid, two amido fourth sulfonic acid or two amido benzene sulfonates.
Further, the sulfonate chain extender is ethylenediamine base ethanesulfonic acid sodium.
Further, the nano silica aqueous solution includes dispercoll S3030, dispercoll
S4510, dispercoll S4020 or dispercoll S5005 aqueous silica solution.
Further, the nano silica aqueous solution is dispercoll S5005 aqueous silica solution.
Further, the polyester polyol includes polyester diol and/or polycarbonate glycol；The polyester diol
Number-average molecular weight be 1000-4000, preferred number average molecular weight 2000-3000；
Further, the polyester polyol is polyester diol.
Further, the polyester diol is to be made by acid and low molecular polylol by polycondensation reaction；
Stating acid includes phthalic acid, M-phthalic acid, terephthalic acid (TPA), glutaric acid, adipic acid, azelaic acid, carbonic acid diethyl
At least one of ester and sebacic acid；The low molecular polylol includes ethylene glycol, propylene glycol, 1,2- butanediol, 1,3- fourth two
At least one in alcohol, 1,4- butanediol, neopentyl glycol, 1,6-HD, diethylene glycol, dipropylene glycol, bisphenol-A and glycerol
Kind.
Further, the polyester diol is polyadipate -1,4-butanediol esterdiol (PBA), polyadipate second two
At least one of alcohol esterdiol (PEA) and polycarbonate glycol (PCDL)；
Further, the solid content of the nano modified polyurethane adhesive is not less than 50%；
Further, the amine chainextender is small molecule amine chain extender, preferably ethylenediamine.
A kind of preparation method of the nano modified polyurethane adhesive of high-fire resistance, it is characterised in that: this method include with
Lower key step:
S1: polyester polyol, polyisocyanates, sulfonate chain extender, amine chain extension the preparation of raw material: are weighed according to the above ratio
Agent and nano silica aqueous solution；
S2: the preparation of prepolymer: polyester polyol is added into reactor, and polyester polyol heating is dissolved, very
0.5~2h is dehydrated under reciprocal of duty cycle；When then cooling the temperature to 70-80 DEG C, polyisocyanates is added, then react at 75-85 DEG C
1.5-4h obtaining prepolymer；
S3: carrying out dissolved dilution for prepolymer using organic solvent, and prepolymer is then cooled to 5~55 DEG C, and sulphur is added
The aqueous solution of hydrochlorate chain extender adds amine chainextender and water to carry out 15~40min of emulsion dispersion, removes organic after reacting 15-35min
Solvent obtains first product adhesive for polyurethane；
S4: nano silica aqueous solution is added in above-mentioned resulting first product adhesive for polyurethane, is stirred evenly to obtain the final product
The nano modified polyurethane adhesive of high-fire resistance.
Further, in step s 2, the pure and mild polyisocyanates of polyester polyols reacts in resulting substance ,-NCO content
It is just prepared prepolymer that (i.e. isocyanate-terminated content), which reaches the 95% of theoretical value,.
Further, in step s 2, the polyester polyol is dissolved at 90~150 DEG C, is then small in vacuum degree
The vacuum dehydration under 1.1kPa.
Further, organic matter described in step S3 includes acetone.
The present invention at least has the advantages that
The present invention uses a certain amount of polyester polyol, polyisocyanates, sulfonate chain extender, amine chainextender and nanometer two
Silica aqueous solution, and chain extension processing is carried out to polyurethane prepolymer using sulfonate chain extender by means of the present invention, together
When compound nano silica aqueous solution and polyisocyanates etc., the nano modified polyurethane gluing of the high-fire resistance finally prepared
Agent is able to maintain very low viscosity while with high solids content, this improves the thixotropy of glue greatly, and can make
The production control of product is more easy, better assures that the stability of properties of product, it is often more important that the adhesive heat resistance
Excellent, adhesion strength is high, excellent in mechanical performance；The adhesive can be used for the bonding of PVC, PU, EVA, TPR, be especially suitable in PVC
The vacuum forming of decorations is bonded.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
It is a part of the embodiment of the present invention, instead of all the embodiments.The detailed description of the embodiment of the present invention presented below is simultaneously
It is not intended to be limiting the range of claimed invention, but is merely representative of selected embodiment of the invention.Based in the present invention
Embodiment, this field commonsense method personnel every other embodiment obtained without creative efforts,
It shall fall within the protection scope of the present invention.
Embodiment 1
A kind of nano modified polyurethane adhesive of high-fire resistance, the raw material of the adhesive are polyester polyol, polyisocyanate cyanogen
Acid esters, sulfonate chain extender, amine chainextender and nano silica aqueous solution；The dosage of various raw materials are as follows: in polyisocyanates
The dosage relation with polyester polyol are as follows: the molar ratio of NCO/OH be 1:(0.3-0.8), i.e. NCO in polyisocyanates with
OH equivalent proportion in polyester polyol is 1:(0.3-0.8), preferably 1:(0.4-0.7), such as 1:0.4,1:0.5,1:0.6,1:0.7
Etc.；The quality of sulfonate chain extender be polyester polyol quality 3-10%, preferably 4-8%, such as 4%, 5%, 6%, 7% or
8%；The quality of amine chainextender be polyester polyol quality 0.1-1%, preferably 0.1-0.8%, such as 0.1%, 0.2%,
0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%；The quality of nano silica aqueous solution is polyester polyol quality
3-10%, preferably 3-8%, such as 3%, 4%, 5%, 6%, 7% or 8%.
The solid content of the nano modified polyurethane adhesive is not less than 50%, such as any value in 50%~80%.
The polyester polyol is preferably polyester diol, and the number-average molecular weight of the polyester diol is 1000-
4000, preferably 2000-3000, such as 2000,2500 or 3000.The polyester diol is more preferably by acid and low molecule
First alcohol is made by polycondensation reaction；The acid include phthalic acid, M-phthalic acid, terephthalic acid (TPA), glutaric acid,
At least one of adipic acid, azelaic acid, diethyl carbonate and sebacic acid；The low molecular polylol includes ethylene glycol, the third two
It is alcohol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, neopentyl glycol, 1,6-HD, diethylene glycol, dipropylene glycol, double
At least one of phenol A and glycerol.It is highly preferred that passing through the anti-of above-mentioned certain specific acids and low molecular polylol
It answers, prepares resulting polyadipate -1,4-butanediol esterdiol (PBA), polyethylene glycol adipate glycol (PEA) or poly- carbonic acid
The effect of esterdiol (PCDL) is best.
The polyisocyanates be isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI), 1,6- oneself two
Isocyanates (HDI), diphenyl methane -4,4- diisocyanate (MDI), benzene dimethylene diisocyanate (XDI), more methylenes
Quito polyphenyl polyisocyanate (PAPI), 4,4'- dicyclohexyl methyl hydride diisocyanate (HMDI) and durol dimethyl two
At least one of isocyanates (TMXDI)；It is highly preferred that the polyisocyanates is isophorone diisocyanate (IPDI)
Or 1, the mixture of hexamethylene-diisocyanate (HDI) or IPDI and HDI；
The sulfonate chain extender is ethylenediamine base ethanesulfonic acid sodium, 1,3- phenylenediamine -4,6- disulfonic acid, two amido fourth sulfonic acid
Or two amido benzene sulfonate；It is highly preferred that the sulfonate chain extender is ethylenediamine base ethanesulfonic acid sodium.
The nano silica aqueous solution is the nano silica aqueous solution of solid content 15-60%, including contains admittedly
The nano silica aqueous solution that amount is 30 ± 1%, 40 ± 1%, 45 ± 1% or 50 ± 1%, as Bayer Bitterfeld GmbH produces
Dispercoll S3030 (30 ± 1%), dispercoll S4510 (45 ± 1%), dispercoll S4020 (40 ± 1%)
Or dispercoll S5005 (50 ± 1%) etc.；It is highly preferred that the nano silica aqueous solution is dispercoll
S5005 (solid content is 50 ± 1%) aqueous silica solution.It is 30- that nano-silica-containing aqueous solution, which is partial size, in the present invention
The aqueous silica solution of 100nm, preferably 50-80nm, such as 50nm, 60nm, 70nm, 80nm.
The amine chainextender is preferably small molecule amine chain extender, preferably ethylenediamine.
As further preferred embodiment, the solid content of the nano silica aqueous solution is 15~60% to receive
Rice aqueous silica solution.
In the present embodiment, the polyester polyol can also be polycarbonate glycol, as Bayer Bitterfeld GmbH produces
Desmophen C 1200。
Embodiment 2
In the reactor with blender, thermometer, cooler and nitrogen-sealed pipe, 100g polyadipate fourth two is added
Alcohol esterdiol (hydroxyl value 56mg/g, number-average molecular weight 2000) dissolves at 110 DEG C, the vacuum dehydration at pressure 0.95kPa
1h, sampling cools down when surveying moisture less than 0.1%, when temperature is down to 70 DEG C, 25.0gIPDI is added, stirs evenly, is warming up to 80
DEG C isothermal reaction 2h, when-NCO content (i.e. isocyanate-terminated content) reaches the 95% of theoretical value, reaction was completed, obtains
Prepolymer.
The acetone that 100.0g is added carries out dissolved dilution to prepolymer, when the prepolymer for having added acetone is cooled to 50 DEG C,
8.0g ethylenediamine base ethanesulfonic acid sodium solution (solid content is 50% aqueous solution) is added in above-mentioned prepolymer, 15min is reacted
Afterwards, 116.0g deionized water is added and 0.3g ethylenediamine carries out emulsion dispersion 20min, continues to stir 0.5h after emulsion dispersion, so
Decompression steams acetone at 50 DEG C afterwards.3g aqueous silica solution dispercoll S5005 is added, receiving for high-fire resistance is obtained
Rice modified polyurethane adhesive, is denoted as WPU-1.
The solid content of WPU-1 is 51.8%, appearance milky white band blue light, pH value 7.7, the viscosity 40mPa.s at 25 DEG C,
Average grain diameter is 110nm.
Embodiment 3
In the reactor with blender, thermometer, cooler and nitrogen-sealed pipe, 100g polyadipate second two is added
Alcohol esterdiol (hydroxyl value 56mg/g, number-average molecular weight 2000) melts at 120 DEG C, the vacuum dehydration in the case where pressure is 0.9kPa
1.5h, sampling cools down when surveying moisture less than 0.1%, when temperature is about 75 DEG C, 20.0g HDI is added, stirs evenly, is warming up to
85 DEG C of isothermal reaction 2h terminate anti-when-NCO content (i.e. isocyanate-terminated content) reaches 95% or more of theoretical value
It answers, obtains prepolymer.
The acetone that 100.0g is added carries out dissolved dilution to prepolymer；When prepolymer is cooled to 40 DEG C, by 7.0g1,3 one
Phenylenediamine -4,6- disulphonic acid (50% aqueous solution) is added in above-mentioned prepolymer, and after reacting 20min, 116.0g is added
Deionized water and 0.1g ethylenediamine carry out emulsion dispersion 30min, continue to stir 0.5h after emulsion dispersion, then depressurize at 50 DEG C
Steam acetone；9g aqueous silica solution dispercoll S5005 is added, the nano modified polyurethane glue of high-fire resistance is obtained
Glutinous agent, is denoted as WPU-2.
The solid content of WPU-2 is 50.8%, appearance milky white band blue light, pH value 7.8, the viscosity 50mPa.s at 25 DEG C,
Average grain diameter is 120nm.
Embodiment 4
In the reactor with blender, thermometer, cooler and nitrogen-sealed pipe, polyadipate -1 100g is added,
4- butyl glycol ester diol (PBA) (hydroxyl value 56mg/g, number-average molecular weight 2000) is dissolved at 115 DEG C, is in pressure
Vacuum dehydration 2h under 0.87kPa, sampling cools down when surveying moisture less than 0.1%, and when temperature is about 75 DEG C, 14.0g IPDI is added
And 5gHDI, it stirs evenly, is warming up to 80 DEG C of isothermal reaction 2h, when-NCO content (i.e. isocyanate-terminated content) reaches reason
By value 95% or more when reaction was completed, obtain prepolymer.
The acetone that 100.0g is added carries out dissolved dilution to prepolymer, when prepolymer is cooled to 30 DEG C, by 8.0g diamines
Base fourth sulfonic acid solutions (50% aqueous solution) are added in above-mentioned prepolymer, react 25min after, be added 116.0g deionized water and
0.1g ethylenediamine carries out emulsion dispersion 30min, continues to stir 0.5h after emulsion dispersion, then decompression steams acetone at 55 DEG C.
8g aqueous silica solution dispercoll S3030 is added, the nano modified polyurethane gluing of high-fire resistance is obtained
Agent is denoted as WPU-3.
The solid content of WPU-3 is 50.6%, appearance milky white band blue light, pH value 8.3, the viscosity at 25 DEG C
100mPa.s, average grain diameter 140nm.
Embodiment 5
In the reactor with blender, thermometer, cooler and nitrogen-sealed pipe, 100g polyadipate fourth two is added
Alcohol esterdiol (hydroxyl value 37mg/g, number-average molecular weight 3000) dissolves at 100 DEG C, the vacuum dehydration in the case where pressure is 0.9kPa
1h, sampling cools down when surveying moisture less than 0.1%, when temperature is about 70 DEG C, 5.0gIPDI and 12.0gHDI is added, stirring is equal
It is even, 80 DEG C of isothermal reaction 2h are warming up to, when-NCO content (i.e. isocyanate-terminated content) reaches 95% or more of theoretical value
When reaction was completed, obtain prepolymer.
The acetone that 100.0g is added carries out dissolved dilution to prepolymer, when prepolymer is cooled to 45 DEG C, by 6.0g second two
Amido ethanesulfonic acid sodium solution (50% aqueous solution) is added in above-mentioned prepolymer, and after reacting 35min, 116.0g deionization is added
Water and 0.8g ethylenediamine carry out emulsion dispersion 25min；Continue to stir 25min after emulsion dispersion, then depressurizes and steam at 50 DEG C
Acetone.
6g aqueous silica solution dispercoll S5005 is added, the nano modified polyurethane gluing of high-fire resistance is obtained
Agent is denoted as WPU-4.
Then the solid content of WPU-4 is 50.3%, appearance milky white band blue light, pH value 7.3, the viscosity at 25 DEG C
80mPa.s, average grain diameter 110nm.
Embodiment 6
In the reactor with blender, thermometer, cooler and nitrogen-sealed pipe, polyadipate -1 100g is added,
4- butyl glycol ester diol (PBA) (hydroxyl value 37mg/g, number-average molecular weight 3000) melts at 100-120 DEG C, is in pressure
Vacuum dehydration 1.5h under 0.95kPa, sampling cools down when surveying moisture less than 0.1%, and when temperature is about 75 DEG C, 4.0g is added
IPDI and 10gHDI, stirs evenly, and is warming up to 80 DEG C of isothermal reaction 2h, when-NCO content (i.e. isocyanate-terminated content) reaches
To theoretical value 95% or more when reaction was completed, obtain prepolymer.
The acetone that 100.0g is added carries out dissolved dilution to prepolymer, when prepolymer is cooled to 38 DEG C, by 4.0g diamines
Base benzene sulfonate solution (50% aqueous solution) is added in above-mentioned prepolymer, and after reacting 30min, 116.0g deionized water is added
Emulsion dispersion 35min is carried out with 0.1g ethylenediamine；Continue to stir 0.5h after emulsion dispersion, then decompression steams third at 50 DEG C
Ketone.
5g aqueous silica solution dispercoll S4020 is added, the nano modified polyurethane gluing of high-fire resistance is obtained
Agent is denoted as WPU-5.
The solid content of WPU-5 is 50.0%, appearance milky white band blue light, pH value 8.5, the viscosity at 25 DEG C
120mPa.s, average grain diameter 60nm.
Embodiment 7
In the reactor with blender, thermometer, cooler and nitrogen-sealed pipe, 100g polyadipate fourth two is added
Alcohol esterdiol (hydroxyl value 37mg/g, number-average molecular weight 3000) melts at 105 DEG C, and in the case where pressure is 0.92kPa, vacuum is de-
Water, sampling cools down when surveying moisture less than 0.1%, when temperature is about 70 DEG C, 5.0g IPDI and 9gHDI is added, stirs evenly,
80 DEG C of isothermal reaction 2h are warming up to, the knot when-NCO content (i.e. isocyanate-terminated content) reaches 95% or more of theoretical value
Shu Fanying obtains prepolymer.
The acetone that 100.0g is added carries out dissolved dilution to prepolymer, when prepolymer is cooled to 50 DEG C, by 7.0g second two
Amido ethanesulfonic acid sodium solution (50% aqueous solution) is added in above-mentioned prepolymer, and after reacting 25min, 116.0g deionization is added
Water and 0.5g ethylenediamine carry out emulsion dispersion 25min, continue to stir 0.5h after emulsion dispersion, then decompression steams third at 50 DEG C
Ketone.
4g aqueous silica solution dispercoll S5005 is added, the nano modified polyurethane gluing of high-fire resistance is obtained
Agent is denoted as WPU-6.
The solid content of WPU-6 is 50.0%, appearance milky white band blue light, pH value 7.9, the viscosity at 25 DEG C
150mPa.s, average grain diameter 50nm.
Embodiment 8
By 100g aqueous polyurethane dispersion (i.e. the nano modified polyurethane adhesive of high-fire resistance) WPU-1, WPU-2,
WPU-3, WPU-4, WPU-5, WPU-6 and commercially available Bayer Bitterfeld GmbH U54 use manual gluing.The PVC sample of 25X200mm is taken, is used
After acetone wipes surface contaminants, the adhesive of preparation is respectively coated in two sticky surfaces, is uniformly brushed secondary.It is coated with postposition
10min is activated at 60 DEG C, bonding plane mutually fits after activation, then applies the uniform pressure of 1MPa, and the time is 15 seconds, is put
Progress T-type disbonded test after a certain period of time is set, the separating rate of specimen holder is (100 ± 10) mm/min.Experiment is put into perseverance
Whether warm drying box is for 24 hours to come unglued and judge heat resistance.Result of implementation is as shown in the table.The adhesive of the application adhesive is heat-resisting
Property it is excellent, adhesion strength is high, excellent in mechanical performance, and the performance of WPU-1, WPU-2, WPU-3, WPU-4, WPU-5 and WPU-6
Common and excellent effect the Bayer U54 obviously higher than market.
The above description is only a preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For, the invention can have various changes and changes.All any modifications made within the spirit and principles of the present invention are equal
Replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of nano modified polyurethane adhesive of high-fire resistance, it is characterised in that: the raw material of the adhesive includes: polyester
Polyalcohol, polyisocyanates, sulfonate chain extender, amine chainextender and nano silica aqueous solution；
The dosage of above-mentioned various raw materials are as follows: the dosage relation satisfaction with polyester polyol in polyisocyanates: NCO/OH's rubs
You are than being 1:0.3-0.8；The quality of sulfonate chain extender is the 3-10% of polyester polyol quality；The quality of amine chainextender is poly-
The 0.1-1% of ester polyol quality；The quality of nano silica aqueous solution is the 3-10% of polyester polyol quality.
2. the nano modified polyurethane adhesive of high-fire resistance according to claim 1, it is characterised in that: the polyester is more
First alcohol includes polyester diol and/or polycarbonate glycol；The number-average molecular weight of the polyester diol is 1000-4000；
The polyisocyanates is any polyisocyanate compound；
The aqueous solution of nano-silica-containing is the nano silica aqueous solution that partial size is 30-100nm；The nanometer titanium dioxide
The nano silica aqueous solution that the solid content of silicon aqueous solution is 15 ~ 60%.
3. the nano modified polyurethane adhesive of high-fire resistance according to claim 2, it is characterised in that: the polyester is more
First alcohol is polyester diol, and the molecular weight of the polyester diol is 2000-3000；
The polyisocyanates includes isophorone diisocyanate, toluene di-isocyanate(TDI), hexamethylene diisocyanate, hexichol
Methylmethane -4,4- diisocyanate, benzene dimethylene diisocyanate, poly methylene poly phenyl poly isocyanate, bis- ring of 4,4'-
At least one of hexyl methane diisocyanate and tetramethyl xylylene diisocyanate；
The sulfonate chain extender include ethylenediamine base ethanesulfonic acid sodium, 1,3- phenylenediamine -4,6- disulfonic acid, two amido fourth sulfonic acid or
Two amido benzene sulfonates；
The nano silica aqueous solution includes dispercoll S3030, dispercoll S4510, dispercoll
S4020 or dispercoll S5005 aqueous silica solution；
The amine chainextender is small molecule amine chain extender.
4. the nano modified polyurethane adhesive of high-fire resistance according to claim 3, it is characterised in that: the polyester two
First alcohol is to be made by acid and low molecular polylol by polycondensation reaction；
The acid includes phthalic acid, M-phthalic acid, terephthalic acid (TPA), glutaric acid, adipic acid, azelaic acid, carbon
At least one of diethyl phthalate and sebacic acid；
The low molecular polylol includes ethylene glycol, propylene glycol, 1,2 1 butanediols, 1,3 1 butanediols, 1,4 1 butanediols, new
At least one of pentanediol, 1,6 1 hexylene glycols, diethylene glycol, dipropylene glycol, bisphenol-A and glycerol.
5. the nano modified polyurethane adhesive of high-fire resistance according to claim 4, it is characterised in that: the polyester two
First alcohol is polyadipate -1,4- butyl glycol ester diol (PBA), polyethylene glycol adipate glycol (PEA) and polycarbonate glycol
At least one of (PCDL)；
The polyisocyanates is in isophorone diisocyanate (IPDI) and 1,6 1 hexamethylene diisocyanates (HDI)
One or two kinds of mixtures；
The sulfonate chain extender is ethylenediamine base ethanesulfonic acid sodium；
The nano silica aqueous solution is dispercoll S5005 aqueous silica solution.
6. the nano modified polyurethane adhesive of high-fire resistance according to claim 5, it is characterised in that: the nanometer changes
Property adhesive for polyurethane solid content be not less than 50%；
The small molecule amine chain extender is ethylenediamine.
7. a kind of preparation method of the nano modified polyurethane adhesive of high-fire resistance, it is characterised in that: this method includes following
Key step:
S1: the preparation of raw material: in the ratio in claim 1 weigh polyester polyol, polyisocyanates, sulfonate chain extender,
Amine chainextender and nano silica aqueous solution；
S2: the preparation of prepolymer: polyester polyol is added into reactor, and polyester polyol heating is dissolved, vacuum degree
0.5 ~ 2h of lower dehydration；When then cooling the temperature to 70-80 DEG C, polyisocyanates is added, then react 1.5-4h at 75-85 DEG C,
Obtain prepolymer；
S3: carrying out dissolved dilution for prepolymer using organic solvent, and prepolymer is then cooled to 5 ~ 55 DEG C, and sulfonate is added and expands
The aqueous solution of chain agent adds amine chainextender and water to carry out 15 ~ 40min of emulsion dispersion, removes organic solvent, obtain after reacting 15-35min
First product adhesive for polyurethane；
S4: nano silica aqueous solution is added in above-mentioned resulting first product adhesive for polyurethane, is stirred evenly up to high resistance to
Hot nano modified polyurethane adhesive.
8. the preparation method of the nano modified polyurethane adhesive of high-fire resistance according to claim 7, which is characterized in that
In step s 2, the pure and mild polyisocyanates of polyester polyols reacts in resulting substance, and what-NCO content reached theoretical value 95% is just
Prepared prepolymer.
9. the preparation method of the nano modified polyurethane adhesive of high-fire resistance according to claim 8, which is characterized in that
In step s 2, the polyester polyol is dissolved at 90 ~ 150 DEG C, is then less than vacuum dehydration under 1.1kPa in vacuum degree.
10. the preparation method of the nano modified polyurethane adhesive of high-fire resistance according to claim 9, feature exist
In in step S3, the organic matter includes acetone.
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