CN1075103C - Polyurethane adhesives/sealant composition, precursor and preparation process thereof - Google Patents
Polyurethane adhesives/sealant composition, precursor and preparation process thereof Download PDFInfo
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- CN1075103C CN1075103C CN98119666A CN98119666A CN1075103C CN 1075103 C CN1075103 C CN 1075103C CN 98119666 A CN98119666 A CN 98119666A CN 98119666 A CN98119666 A CN 98119666A CN 1075103 C CN1075103 C CN 1075103C
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- Prior art keywords
- binder
- parts
- polyether
- sealant
- precursor
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- 239000000565 sealant Substances 0.000 title claims abstract description 119
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 239000002243 precursor Substances 0.000 title claims abstract description 60
- 239000004814 polyurethane Substances 0.000 title claims abstract description 38
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000000853 adhesive Substances 0.000 title abstract description 6
- 230000001070 adhesive effect Effects 0.000 title abstract description 6
- 229920000570 polyether Polymers 0.000 claims abstract description 66
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 65
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- 229920000098 polyolefin Polymers 0.000 claims abstract description 11
- 229920001519 homopolymer Polymers 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims description 115
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 62
- 239000007788 liquid Substances 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000000047 product Substances 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 239000005062 Polybutadiene Substances 0.000 claims description 34
- 229920002857 polybutadiene Polymers 0.000 claims description 34
- 239000004135 Bone phosphate Substances 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 150000002334 glycols Chemical class 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 31
- 229920001228 polyisocyanate Polymers 0.000 claims description 31
- 239000005056 polyisocyanate Substances 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 31
- 239000000945 filler Substances 0.000 claims description 30
- 239000007795 chemical reaction product Substances 0.000 claims description 29
- -1 methylethyl malonic ester Chemical compound 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000654 additive Substances 0.000 claims description 22
- 238000013008 moisture curing Methods 0.000 claims description 21
- 239000004014 plasticizer Substances 0.000 claims description 21
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000010025 steaming Methods 0.000 claims description 19
- 239000012442 inert solvent Substances 0.000 claims description 15
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 13
- 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 12
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 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 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 7
- ZKBBUZRGPULIRN-UHFFFAOYSA-N diethyl 2,2-diethylpropanedioate Chemical compound CCOC(=O)C(CC)(CC)C(=O)OCC ZKBBUZRGPULIRN-UHFFFAOYSA-N 0.000 claims description 6
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 5
- 229920002367 Polyisobutene Polymers 0.000 claims description 5
- 229920001195 polyisoprene Polymers 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 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 2
- 230000003712 anti-aging effect Effects 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract 2
- 230000008023 solidification Effects 0.000 abstract 2
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 98
- 239000002994 raw material Substances 0.000 description 34
- 238000012360 testing method Methods 0.000 description 27
- 229920001451 polypropylene glycol Polymers 0.000 description 24
- 239000000523 sample Substances 0.000 description 21
- 230000008859 change Effects 0.000 description 19
- 239000005357 flat glass Substances 0.000 description 12
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 11
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 11
- 239000003292 glue Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 9
- 230000006837 decompression Effects 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 239000004902 Softening Agent Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002390 adhesive tape Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003613 toluenes Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000010009 beating Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920001281 polyalkylene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- JJKMIZGENPMJRC-UHFFFAOYSA-N 3-oxo-3-propan-2-yloxypropanoic acid Chemical compound CC(C)OC(=O)CC(O)=O JJKMIZGENPMJRC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- ZNBQMNLJFTYCHC-UHFFFAOYSA-N 1,1'-biphenyl;isocyanic acid Chemical compound N=C=O.C1=CC=CC=C1C1=CC=CC=C1 ZNBQMNLJFTYCHC-UHFFFAOYSA-N 0.000 description 1
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000838698 Togo Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004588 polyurethane sealant Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- Sealing Material Composition (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention discloses a novel single-component wet solidification polyurethane adhesive/sealant composition, a precursor and a preparation method thereof. The adhesive/sealant composition of the present invention belongs to a polyether and polyurethane type which is modified by polyolefin and/or polydiolefin. Due to the fact that polyolefin, a polydiolefin homopolymer, or a high molecular polymer of a copolymer thereof are added during a preparation process and unique synthesis technology is adopted, the performance of the novel single-component wet solidification polyurethane adhesive/sealant composition is greatly improved.
Description
The present invention relates to the polyurethane binder/sealant compositions field.Particularly, the present invention relates to a kind of monocomponent moisture cure polyether-polyurethane binder/sealant composition, its precursor and preparation method.
Polyurethane binder/sealant is of a great variety, is widely used, and can be used for the bonding between glass, metal, timber, leather and the fiber.Various bonding occasion can be used the polyurethane binder/sealant of different components, to satisfy different bonding requirements.The important polyurethane binder/sealant of one class is the single-component moisture curing polyurethane binder/sealant, be widely used in bonding and seal automobile component as jointing material and sealing material, such as windshield glass and back glass and car body, and be used for bonded building materials, for example glass curtain wall inlays and inlaying of other wallboards or the like.This type of binder/sealant is normally by polyether glycol and the reaction of excessive polyisocyanates, under block agent effect, makes residual active isocyanate group go polymerization again the prepolymer that obtains, adds the product that filler, softening agent and thinner etc. obtain.After the product coating, under the effect of water in air part, solidify.
The special public clear 63-8155 of Japanese Patent discloses a kind of monocomponent moisture cure automobile polyurethane binder/sealant composition.The polyalkylene ether triol that it contains by molecular-weight average 5000-8000 reacts the prepolymer that obtains with the aromatic diisocyanate compound that has isocyanate group.Japanese Patent discloses clear 52-17560 and discloses a kind of single-component moisture curing polyurethane binder/sealant, is reacted and residual active isocyanate group is carried out block with the alkyl malonic ester by dihydroxyl polyalkylene ether, trihydroxy-polyalkylene ether and excess fats family or aromatic diisocyanate to make.In the component of the single-component moisture curing polyurethane binder/sealant of these bibliographical informations, do not contain except that urethane itself and macromolecular material.
U.S. Pat 5,061,749 disclose a kind of single-component moisture curing polyurethane sealant composition, it contains as the base polyurethane prepolymer for use as of the free isocyanate groups that contains 0.5%-13% (weight) that is obtained by the reaction of polyvalent alcohol and excessive polyisocyanates of main component and contains the vinyl polymer of siloxanes, and as the filler and the softening agent of additive; The vinyl polymer that contains siloxanes wherein contacts with water and is hydrolyzed to oxy-compound, thus with the further polymerization of the compound that contains isocyanate group.
The Japanese Patent spy opens clear 61-250083 and discloses a kind of one-package adhesive that is suitable for bonding motor car engine circumferential component, is mixed by following compositions: (A) the free-NCO group content is the urethane of 1.5%-4%; (B) vinyl-vinyl acetate copolymer; (C) oxazolidine potential cross-linking agent.
Chinese patent application 96106661.X mention contain at least a kind of containing-OH or-the NCO end group with methacrylic ester or Lustrex or copolymer-modified urethane and preparation method thereof.But in specification sheets and embodiment and claims, openly do not use the polyurethane binder/sealant composition and method of making the same of polyolefine and/or polydiolefin modification.Tackiness agent in this patent application is transparent.
Japanese patent laid-open 9-31438 discloses a kind of binder composition that is used for bonding steel plate and polyvinyl chloride, by vibrin, solvent, inconsistent resin mixes mutually with polyisocyanates and makes with it.
Japanese patent laid-open 4-164985 discloses the modified polyurethane that is made by the vibrin that contains isocyanic ester, chloroprene nitrile, specific polysiloxane and halogenating agent.
Above document all unexposed single-component moisture curing polyurethane binder/sealant composition and method for making thereof with polyolefine and/or polydiolefin modification.
The single-component moisture curing polyurethane binder/sealant composition of prior art often has following shortcoming: tensile strength is not enough; The toluene level height can dissolve primer and cause bonding not firm and big to the murder by poisoning of operative employee's health; Hardness is big, and elasticity is little after solidifying, the glass of crushing easily; It is too high that binder/sealant is got back viscosity, can not soak into glass preferably, causes roof leaking; Can play glue after the heating; It is big perhaps to beat glue laminated power.
Therefore the objective of the invention is to overcome the above-mentioned defective of prior art, a kind of novel single-component moisture curing polyurethane binder/sealant composition is provided.
Another object of the present invention is to provide a kind of precursor of single-component moisture curing polyurethane binder/sealant.
A further object of the present invention is to provide the preparation method of this new type monocomponent moist-set polyurethane binder/sealant and precursor thereof.
New type monocomponent moist-set polyurethane binder/sealant composition of the present invention, by weight, contain:
I) the binder/sealant precursor is 100 parts; And
II) block agent 0.04-1.78 part;
III) inert filler 32-76 part;
IV) inert plasticizer 24-134 part;
V) other additives 1.2-3.6 part; With
VI) inert solvent is less than 9 parts greater than 0 part;
Wherein said binder/sealant precursor contains according to the weight meter:
ⅰ) being selected from molecular-weight average is 3,000-8, and the polyether glycol of the mixture of 000 polyether-tribasic alcohol or polyether Glycols and polyether-tribasic alcohol, with the polymerisate that excessive polyisocyanates reaction generates, it contains the free isocyanate groups of 3%-7%; With with respect to per 100 parts of polyether glycols
ⅱ) be selected from high molecular polymer 0.1-1.5 part of polyolefine, polydiolefin homopolymer or multipolymer.
Preferred binder/sealant composition, wherein by weight, contain: I) the binder/sealant precursor is 100 parts; And II) block agent 0.5-1.5 part; III) inert filler 40-60 part; IV) inert plasticizer 35-130 part; V) other additives 0.8-2.5 part; And VI) inert solvent is less than 9 parts greater than 0 part.
Preferred binder/sealant composition, wherein by weight, contain: I) the binder/sealant precursor is 100 parts; And II) the block agent is 0.9 part; III) inert filler is 55 parts; IV) inert plasticizer is 45 parts; V) other additives are 2.2 parts; And VI) inert solvent is less than 9 parts greater than 0 part.
A kind of preparation method of new type monocomponent moist-set polyurethane binder/sealant of the present invention comprises the steps:
I) by weight, add in reactor that to be selected from molecular-weight average be 3,000-8, the polyether glycol of the mixture of 000 polyether-tribasic alcohol or polyether Glycols and polyether-tribasic alcohol and with respect to inert solvent 30-50 parts of per 100 parts of polyether glycols steams solvent and water to steaming the thing water content less than 4ppm by underpressure distillation;
II) by weight, add the polyisocyanates 12-25 part with respect to per 100 parts of polyether glycols in reactor, high molecular polymer 0.1-1.5 part makes it reaction under heating, makes the binder/sealant precursor;
III) by weight, in precursor, add the block agent that is selected from methyl aceto acetate, methyl acetoacetate, methylethyl malonic ester, diethyl malonic ester, dimethyl malonic ester, its amount is 0.05-2.0 part with respect to per 100 parts of polyether glycols, be selected from the catalyzer of dibutyl tin dilaurate, N-alkyl benzene amine, N-alkyl morpholine, N-alkyl croak piperazine, aluminum napthenate, manganese naphthenate, cobalt naphthenate, stannous octoate, its amount is carried out block polymerization for respect to per 100 parts of polyether glycol 0.005-0.1 parts;
IV) to III) reaction product in add exsiccant inert plasticizer and exsiccant inert filler and other additives, fully mixing is promptly.
The another kind of preparation method of new type monocomponent moist-set polyurethane binder/sealant of the present invention comprises the steps:
I) by weight, add in reactor: being selected from molecular-weight average is 3,000-8, the polyether glycol of the mixture of 000 polyether-tribasic alcohol or polyether Glycols and polyether-tribasic alcohol; Inert plasticizer 30-150 part with respect to per 100 parts of polyether glycols; Inert filler 40-85 part and inert solvent 50-90 part steam solvent and water to steaming the thing water content less than 4ppm by underpressure distillation;
II) by weight, add the polyisocyanates 12-25 part with respect to per 100 parts of polyether glycols in reactor, high molecular polymer 0.1-1.5 part makes it reaction under heating, makes the binder/sealant precursor;
III) by weight, to II) product in add the block agent be selected from methyl aceto acetate, methyl acetoacetate, methylethyl malonic ester, diethyl malonic ester, dimethyl malonic ester, its amount is for being 0.05-2.0 part with respect to per 100 parts of polyether glycols, be selected from the catalyzer of dibutyl tin dilaurate, N-alkyl benzene amine, N-alkyl morpholine, N-alkyl croak piperazine, aluminum napthenate, manganese naphthenate, cobalt naphthenate, stannous octoate, its amount is 0.005-0.1 part with respect to per 100 parts of polyether glycols, carries out block polymerization;
IV) to III) reaction product in add other additives of exsiccant, fully mixing is promptly.
Unless otherwise noted, all herein umbers all by weight, the equal index average molecular weight of all molecular-weight average.
Fig. 1 is the internal temperature T of reactor among a kind of preparation method of single-component moisture curing polyurethane binder/sealant of the present invention
i(℃), outside temperature T
o(℃), still internal pressure P
i(MPa) graphic representation that changes with the toluene amount of steaming W (kilogram) and time.
Fig. 2 is a kind of specimen preparation synoptic diagram when among the present invention the binder/sealant composition being tested.
Fig. 3 is a kind of sample synoptic diagram of preparation when among the present invention the binder/sealant composition being tested.
Fig. 4 is a kind of sample synoptic diagram of preparation when among the present invention the binder/sealant composition being tested.
I. new type monocomponent moist-set polyurethane binder/sealant composition of the present invention and precursor thereof
Binder/sealant of the present invention contains the binder/sealant precursor, and used PPG can be the mixture of polyether-tribasic alcohol or polyether Glycols and polyether-tribasic alcohol in the described precursor, and its mean molecule quantity is 3,000-8 between 000, is preferably 4,500-5 is between 500. In the single-component moisture curing polyurethane binder/sealant of prior art, in order to guarantee the performance of product, the common molecular weight of the PPG of use is higher, is 5,000-8, and 000. This type of PPG also can adopt in the present invention, but comparatively expensive. The PPG of lower molecular weight relatively easily obtains, and is the preferred PPG of the present invention. The following product produced of chemical plant, Shenyang for example:
| Product grade | Product category | Mean molecule quantity |
| SPC-350 | Polyether-tribasic alcohol | 5,000 |
| SPC-230 | Polyether Glycols | 3,000 |
| SPC-330 | Polyether-tribasic alcohol | 3,000 |
| SPC-TR5000 | Polyether-tribasic alcohol | 5,000 |
| SPC-TR3010 | Polyether-tribasic alcohol | 3,000 |
Used polyisocyanates comprises fragrant polyisocyanates and aliphatic polyisocyanate in the described precursor, be preferably vulcabond, its limiting examples is such as triphenylmethane triisocyanate (Desmodur R) (III), polymethylene multi-phenenyl isocyanate (PAPI), hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), naphthalene diisocyanate (NDI), toluene di-isocyanate(TDI) (TDI), methylenediphenyl-4,4 '-vulcabond (MDI) and biphenyl isocyanate are preferably MDI, TDI, NDI or two or three mixture wherein.
PPG (A) reacts with polyisocyanates (B), generates polyether-polyurethane precursor (P). Take polyether Glycols as example, its reaction equation is as follows:
The reaction of polyether-tribasic alcohol similarly just obtains the large molecular product of branch, when adopting the mixture of polyether Glycols and polyether-tribasic alcohol, the skeleton structure of polyether-tribasic alcohol both can be arranged on the product chain, and the skeleton structure of polyether Glycols can be arranged again.
The total hydroxy of setting in the PPG is H, the NCO of the polyisocyanates of adding add up to R. Generally speaking, R＞H should be arranged, namely NCO is excessive with respect to hydroxyl, contains a small amount of free isocyanate groups in the binder/sealant precursor of generation. Generally should control the consumption of isocyanates, so that the amount of the free isocyanate groups in the precursor is 3 %-7%.
Used high molecular polymer comprises polyolefin, polydiene or their various copolymers in the described precursor. These polymer can be natural or synthetic, can be atactic, also can have the height stereospecificity. Preferred high molecular polymer is on sale on market among the present invention, comprises polyolefin and polydiene, for example liquid butyl rubber, liquid polybutadiene, liquid polyisoprene and liquid polyisobutene, its mean molecule quantity is 10,000-100,000, be preferably 30,000-40,000. More preferably liquid polybutadiene and liquid polyisobutene, its mean molecule quantity is 10,000-100,000, be preferably 30,000-40,000. Liquid polybutadiene most preferably, its mean molecule quantity is 10,000-100,000, is preferably 30,000-40,000. The high molecular polymerization raw material of technical grade can directly adopt, and can directly add, and also can add with the form of its solution, need not further purifying.
In the precursor of binder/sealant of the present invention, with respect to per 100 parts of PPGs, the consumption of high molecular polymer is 0.1-1.5 part, is preferably 0.4-1.0 part. Add very little, for example be lower than 0.1 part, the contribution of the physical and mechanical properties after then using for finished product is little; Addition is too large, for example is higher than 1.5 parts, and the hardness after then binder/sealant solidifies is too large, and poor flexibility affects its mechanical performance and serviceability. For the amount of the polyether-polyurethane that generates with respect to PPG and polyisocyanates, its consumption is little. Yet amazing is that a small amount of this type of high molecular polymer of adding can obviously improve physical property and the serviceability of binder/sealant composition. In order to improve the performance of polyurethane binder/sealant, the mean molecule quantity of the PPG that common requirement is adopted is higher, for example is 5,000-8 in the prior art, and 000. The present invention is by adding the polymer of other kinds in precursor, especially add higher molecular weight, for example mean molecule quantity is 10,000-100,000, be preferably 30,000-40,000 polyolefin, polydiene homopolymers or copolymer, for example preferred liquid butyl rubber, liquid polybutadiene, liquid polyisoprene and liquid polyisobutene, more preferably liquid polybutadiene and liquid polyisobutene most preferably are the high molecular polymer of liquid polybutadiene, under the condition that obtains same good end-product performance, can use the PPG of lower molecular weight, for example mean molecule quantity is 3,000-5,000 PPG, thereby the cost of reduction product. Although should not stick to theory, but it is believed that this is because a small amount of high molecular polymer and the long-chain of PPG/polyisocyanic acid ester polymer twine interspersed each other, form a kind of interpenetrating polymer networks or semi-interpenetrating polymer network, close together in the network between the large molecule, stronger active force is arranged each other, thereby give the better physical and mechanical properties of product and serviceability, for example stretching strength, percentage elongation, tensile strength, tearing strength and peel strength and thixotroping conformality.
The binder/sealant precursor that obtains can directly be used as binder/sealant, also can add inert filler, inert additwe and inert plasticizer, makes monocomponent moisture cure binder/sealant composition of the present invention and uses afterwards.
In order to control NCO in the precursor and the cross-linking reaction between the carbamate groups, improve bin stability, carry out using after the block better to the free isocyanate groups in the precursor. So contain block copolymer in the composition of the present invention. Used block agent can include but not limited to: contain the compound of active methylene group, for example dimethyl malonic ester, ethyl acetoacetate, methyl acetoacetate, Methylethyl malonate and diethylmalonate.
NCO is converted into carbamate groups in the reaction, thereby makes the precursor stabilisation. With respect to per 100 parts of binder/sealant precursors, the consumption of block agent is 0.04-1.78 part, is preferably 0.5-1.5 part.
Used inert additwe includes but not limited in the binder/sealant composition of the present invention: furnace black, in super carbon black, printing ink carbon black, talcum powder, sintering kaolin, calcium carbonate, White Carbon black etc., super carbon black in being preferably, its consumption changes to some extent with the different performance of the binder/sealant of required application scenario, but the binder/sealant precursor with respect to 100 parts, its consumption are 32-76 part. Be preferably 40-60 part.
Inert plasticizer comprises the plasticizer various commonly used in binder/sealant field, and its non-limitative example is such as dibutyl phthalate, BBP(Butyl Benzyl Phthalate, dioctyl phthalate, dinonyl phthalate, chlorinated paraffin wax, partial hydrogenation petroleum benzene, diethylene glycol dibenzoate etc. They do not react with precursor and block agent, but improve physical property and the serviceability of finished product. Its consumption requires and different with the difference to the finished product binder/sealant, and with respect to per 100 parts of binder/sealant precursors, its consumption is 24-134 part.
In order further to improve the serviceability of finished product composition, for example in order to prevent the aging of product, can contain a small amount of age resistor and UV resistant agent in the binder/sealant composition of the present invention. Examples of such additives commonly used in the binder/sealant field all can adopt, antioxidant D (alpha-naphthylamine for example, the mixture of beta-naphthylamine), UV resistant agent YW-590 (three (1,2,2,6,6-pentamethyl-4-piperidines) phosphite ester) etc., its consumption is 1.2-3.6 part with respect to per 100 parts of binder/sealant precursors.
In addition, also contain atent solvent in the binder/sealant composition of the present invention, it can be not with product in any solvent of other compositions reaction, for example the mixture of toluene, dimethylbenzene, ethyl acetate, aromatic ester, ketone and these solvents is preferably toluene. Consider toxicity and the smell of solvent, its content in finished product should strictly be controlled, and with respect to per 100 parts of binder/sealant precursors, its consumption is greater than 0 part, is less than 9 parts.
Certainly, binder/sealant composition of the present invention can also contain other a small amount of compositions, the catalyst that for example adds in the preparation process and other impurity of bringing into, because its content is less, for composition properties of the present invention and unsubstantial impact, so their existence does not exceed scope of the present invention.
II. the preparation method of single-component moisture curing polyurethane binder/sealant composition of the present invention and precursor thereof
Single-component moisture curing polyurethane binder/sealant composition of the present invention comprises its precursor, block agent, inert filler and inert additwe. Because various fillers, additive do not participate in polymerisation, so can after at first making the binder/sealant precursor by PPG, polyisocyanates and high molecular polymer, add again the block agent, add again anhydrous filler, plasticizer and other additives after finishing block polymerization, make finished product; Also can under the condition that filler, plasticizer exist, directly make precursor by PPG, polyisocyanates and high molecular polymer, go again block polymerization, then add other additive and make finished product. The below describes respectively it in detail to these two kinds of methods.
Method one
Comprise the steps:
I) by weight, add that to be selected from mean molecule quantity be 3 in the reactor, 000-8, the PPG of the mixture of 000 polyether-tribasic alcohol or polyether Glycols and polyether-tribasic alcohol and with respect to atent solvent 30-50 parts of per 100 parts of PPGs, be preferably 35-45 part, decompression distillation steams solvent and water to steaming the thing water content less than 4ppm;
II) by weight, add the polyisocyanates 12-25 part with respect to per 100 parts of PPGs in the reactor, high molecular polymer 0.1-1.5 part makes it reaction under heating, makes the binder/sealant precursor;
III) by weight, in precursor, add the block agent that is selected from ethyl acetoacetate, methyl acetoacetate, Methylethyl malonate, diethylmalonate, dimethyl malonic ester, its amount is 0.05-2.0 part with respect to per 100 parts of PPGs, be selected from the catalyst of dibutyl tin dilaurate, N-alkyl benzene amine, N-alkyl morpholine, N-alkyl croak piperazine, aluminium napthenate, manganese naphthenate, cobalt naphthenate, stannous octoate, its amount is 0.005-0.1 part with respect to per 100 parts of PPGs, carries out block polymerization;
IV) to III) product in add dry inert plasticizer and dry inert filler and other additives, abundant mixing and get final product.
The initiation material that adopts is as indicated above, on demand also will be through operations such as purification and grindings. Reactor is batch type still reactor. Owing to often contain a certain amount of moisture content in the PPG that adopts and the solvent, and the existence of a large amount of moisture content can make the polyisocyanates implode, can not obtain needed product, so need to carry out drying to raw material, so that the water content in the reaction system is below the 4ppm when adding polyisocyanates. Dry run can be undertaken by decompression distillation, makes atent solvent and water form azeotropic mixture and removes. Through distillation after a while, the solvent that steams reach a certain amount of after, the drying of raw material namely reaches requirement. Can add foregoing polyisocyanates and high molecular polymer this moment in still, its consumption is for per 100 parts of PPGs, and polyisocyanates is 12-25 part, is preferably 15-20 part, high molecular polymer is 0.1-1.5 part, is preferably 0.4-1.0 part. Heating is stirred, and makes the precursor of binder/sealant. In course of reaction, the viscosity of system constantly raises, and the strand of polyether-polyurethane progressively increases formation, and gradually mutually twines with the linear long-chain molecule of the high molecular polymer that adds and to intert, and forms interpenetrating polymer networks or semi-interpenetrating polymer network.
The PPG reaction is complete, contains the free isocyanate groups of 3%-5% in the precursor that makes; Add block agent as indicated above this moment in still, its amount is 0.04-1.78 part with respect to per 100 parts of precursors, is preferably 0.5-1.5 part. In order to make block polymerization reaction acceleration, can heat reaction system, and can be to wherein adding a small amount of catalyst. Used catalyst includes but not limited to: dibutyl tin dilaurate, N-alkyl benzene amine, N-alkyl morpholine, N-alkyl croak piperazine, aluminium napthenate, manganese naphthenate, cobalt naphthenate and stannous octoate, its consumption is 0.005-0.1 part with respect to per 100 parts of PPGs, is preferably 0.01-0.05 part.
After block reaction is finished, in reaction system, add inert plasticizer and inert filler and other additive mentioned above.Additive wherein and filler must be dry in advance, and grind as required.Because this type of material does not participate in chemical reaction, so use mechanical stirring to mix, promptly can make single-component moisture curing polyurethane binder/sealant composition of the present invention, after Vacuum Package, promptly can be used as finished product storage transportation, the storage period under its room temperature can reach 9 months.
Because raw material and product in the inventive method are very responsive to airborne moisture content, reaction all should be carried out under the condition of secluding air.A kind of preferred method of secluding air is airtight and decompression with reaction system, plays the effect that the moisture content that will exist in the reaction system and solvent are extracted out simultaneously.The quantity of solvent of initial adding is bigger in the reaction system, can reduce the viscosity of system, thereby helps stirring, and makes that reaction is more abundant.But the content that should control solvent in the finished product is below a certain numerical value, so in reaction process it is progressively steamed.
In a preferred embodiment of present method, the raw material that is adopted is:
Inert solvent: toluene
Polyether glycol: the polyethers ternary of molecular-weight average about 5,000
Alcohol
Polyisocyanates: MDI
High molecular polymer: molecular-weight average 30,000-40,000 liquid
The body polyhutadiene
Block agent: methyl aceto acetate
Catalyzer: dibutyl tin dilaurate
Softening agent: dioctyl phthalate (DOP)
Inert filler: in super carbon black
Other additives: antioxidant D, anti UV agent YW-590
At first in still, add toluene and polyether glycol, mix, heating, underpressure distillation, the moisture content in the raw material progressively steams with toluene, steams water content in the solvent with the measurement of trace water determinator.Treat solvent steam a certain amount of after, the water content of raw material just is lower than 4ppm in the still.Carry out II this moment) step, in still, add MDI toluene solution and the liquid high molecular polymer for preparing in advance, continue under the condition of decompression and heating, to react, still there is solvent constantly to steam in the reaction process.After the amount of steaming of solvent reached a certain ratio, precursor preparation promptly came to an end.Carry out III this moment) step.Keep heating and decompression, treat that the solvent amount of steaming reaches after a certain ratio, reaction is promptly accused fully, and can carry out IV this moment) step.The product in this step is a kind of monocomponent moist-set polyurethane adhesive/sealant composition of the present invention.
Method two
Comprise the steps:
I) by weight, add in reactor: being selected from molecular-weight average is 3,000-8, the polyether glycol of the mixture of 000 polyether-tribasic alcohol or polyether Glycols and polyether-tribasic alcohol; Inert plasticizer 30-150 part with respect to per 100 parts of polyether glycols is preferably 35-130 part; Inert filler 40-85 part, preferred 50-70 part and inert solvent 50-90 part, preferred 70-90 part, underpressure distillation goes out solvent and water to steaming the thing water content less than 4ppm;
II) by weight, in reactor, add polyisocyanates 12-25 part, be preferably 15-20 part with respect to per 100 parts of polyether glycols, high molecular polymer 0.1-1.5 part, be preferably 0.4-1.0 part, make it reaction under heating, make the binder/sealant precursor;
III) by weight, to II) product in add and to be selected from methyl aceto acetate, methyl acetoacetate, the methylethyl malonic ester, diethyl malonic ester, the block agent of dimethyl malonic ester, its amount is 0.05-2.0 part with respect to per 100 parts of polyether glycols, be preferably 0.5-1.5 part, be selected from dibutyl tin dilaurate, the N-alkyl benzene amine, the N-alkyl morpholine, N-alkyl croak piperazine, aluminum napthenate, manganese naphthenate, cobalt naphthenate, the catalyzer of stannous octoate, its amount is with respect to per 100 parts of polyether glycol 0.005-0.1 parts, be preferably 0.01-0.05 part, carry out block polymerization;
IV) to III) reaction product in add other additives of exsiccant, fully mixing is promptly.
Different with method one is the I of present method) the step beginning, except in reactor, adding polyether glycol and the inert solvent, also added inert filler and inert plasticizer, IV) need not to add in addition again this two classes raw material in the step.Like this, the preparation process of precursor and block reaction step all are to carry out in the presence of inert filler and inert plasticizer.Remaining operation all is similar to method one.Owing to all contain a certain amount of moisture content, method one IV in filler and the softening agent) filler and the softening agent that add in the step must be dry in advance, and this needs expensive drying plant, has increased material consumption and energy consumption.In method two, the drying of softening agent, filler and polyether glycol merges carries out, thereby has simplified equipment, has reduced cost, can't produce detrimentally affect to the performance of product.Temperature and pressure in the control entire reaction course is very important for the good end product of obtained performance stable homogeneous.In a kind of preferred version of present method, the solvent that is adopted is a toluene, should control the outside temperature T of reactor in the reaction process
o, internal temperature T
i, pressure P
iThe amount of steaming W and the change curve of time with toluene in the vacuum distillation process conform to Fig. 1.
In a preferred embodiment of present method, the raw material that is adopted is:
Inert solvent: toluene
Polyether glycol: the polyether-tribasic alcohol of molecular-weight average 5,000
Polyisocyanates: MDI
High molecular polymer: molecular-weight average 30,000-40,000 liquid
The body polyhutadiene
Block agent: methyl aceto acetate
Catalyzer: dibutyl tin dilaurate
Softening agent: dioctyl phthalate (DOP)
Inert filler: in super carbon black
Other additives: antioxidant D, anti UV agent YW-590
At first in still, add toluene, polyether glycol, inert filler and inert plasticizer, mix, heating, underpressure distillation, the moisture content in the raw material progressively steams with toluene, steams water content in the solvent with the measurement of trace water determinator.Treat solvent steam a certain amount of after, the water content of raw material just is lower than 4ppm in the still.Carry out II this moment) step, in still, add MDI toluene solution and the liquid high molecular polymer for preparing in advance, continue under the condition of decompression and heating, to react, still there is solvent constantly to steam in the reaction process.After the amount of steaming of solvent reached a certain ratio, precursor preparation promptly came to an end.Carry out III this moment) step.Keep heating and decompression, treat that the solvent amount of steaming reaches after a certain ratio, reaction is promptly accused fully, and can carry out IV this moment) step.The product in this step is monocomponent moisture cure binder/sealant composition end product of the present invention.
In this preferred version of present method, adopt wherein that processing condition are controlled to be the what is called " three-way method for making " that meets accompanying drawing 1, promptly in the process of preparation, should control the outside temperature T of reactor
o, internal temperature T
i, pressure P
iThree kinds of processing parameters make it to conform to Fig. 1 along with the amount of the steaming W and the change curve of time of toluene in the vacuum distillation process.
Embodiment
One. the preparation of product
Use one 240 liters be furnished with that charging opening, discharge port, solvent steam mouthful, the reactor of electronic stirring and heating jacket, its center and periphery are furnished with temp probe, in order to measure the interior temperature T of still
iWith outer temperature T
o, and have with still in the weather gauge that communicates, in order to measure the interior pressure P of still
iAccurately take by weighing 85 kilograms of polyether-tribasic alcohol TR5000,78 kilograms of toluene add in the still, start stirring, airtight still, and heating, the vacuum pump decompression when toluene steams, whenever steams 2Kg toluene, regulates heating power, with outer temperature T
o(℃) be controlled at T among Fig. 1
oOn the numerical value of curve corresponding to this toluene amount of steaming, the adjustment vacuum pump is with pressure P
i(MPa) be controlled at P among Fig. 1
iOn the numerical value of curve corresponding to this toluene amount of steaming, this moment read in warm Ti (℃) numerical value, thereby control T
o, P
iAnd T
iVariation with the toluene amount of steaming W (Kg) and time conforms to Fig. 1.When temperature in the kettle rises to more than 70 ℃, negative pressure steams a large amount of toluene and toluene-water azeotrope when 0.07MPa (gauge pressure).Steam the water content of thing with the measurement of trace water tester, when being low to moderate 4ppm, slowly add the ready MDI12 kilogram that is dissolved in 1-2 kilogram dry toluene in advance from charging opening, add molecular-weight average 35 simultaneously, 0.4 kilogram of 000 liquid polybutadiene, keep interior temperature 70-80 ℃ of still, and constantly stir, the precursor preparation reaction finishes after 1-2 hour, the free isocyanate groups of nearly 3%-5% in the material in the still adds 0.015 kilogram of 0.8 kilogram of methyl aceto acetate and catalyzer dibutyl tin dilaurate this moment.Constantly stir.After 1 hour, make temperature in the kettle reduce to 50-55 ℃.In still, add 36 kilograms of exsiccant dioctyl phthalate (DOP)s this moment, super carbon black is 50 kilograms in the thorough drying, 0.9 kilogram of antioxidant D, 0.4 kilogram of anti UV agent YW-590, stir, it is canned to go out still, is the finished product of a kind of single-component moisture curing polyurethane binder/sealant composition of the present invention, and its code name is E1.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Equipment and operation are with embodiment 1, and different is, it is the mixture of 45 kilograms of polyether-tribasic alcohol TR5000 and 40 kilograms of SPC-230 that 85 kilograms of polyether-tribasic alcohols are changed, and the molecular-weight average of polyhutadiene changes 15,000 into, and its consumption is constant.Other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E2.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Equipment and operation are with embodiment 1, and different is, change the consumption of liquid polybutadiene into 0.1 kilogram, and other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E3.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 4
Equipment and operation are with embodiment 1, different is, change the consumption of liquid polybutadiene into 0.8 kilogram, catalyzer changes stannous octoate into, consumption is 0.006 kilogram, and block agent methyl aceto acetate changes dimethyl malonic ester into, and consumption is constant, other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E4.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 5
Equipment and operation are with embodiment 1, and different is, change the consumption of liquid polybutadiene into 1.5 kilograms, and molecular-weight average changes 90,000 into, and other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E5.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 6 (comparative example)
Equipment and operation are with embodiment 1, and different is, adding after 1-2 hour is carried out in the reaction that liquid polybutadiene is changed into MDI and polyether glycol, and its consumption is constant, and other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E6.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 7 (comparative example)
Equipment and operation are with embodiment 1, and different is, change the consumption of liquid polybutadiene into 0 kilogram, and other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E7.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 8 (comparative example)
Equipment and operation are with embodiment 1, and different is, liquid polybutadiene are changed in the reaction of MDI/ polyether glycol reactive polymeric finish, and add after further finishing with block agent reaction, and its consumption is constant.Other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E8.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 9
Equipment and operation are with embodiment 1, and different is, change liquid polybutadiene the liquid polybutene of molecular-weight average 40,000 into, and its consumption is constant, and other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E9.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Equipment and operation are with embodiment 1, and different is, change liquid polybutadiene the liquid polyisoprene of molecular-weight average 40,000 into, and its consumption is constant, and other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E10.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 11
Equipment and operation are with embodiment 1, and different is, change liquid polybutadiene the liquid isoprene-isobutylene rubber of molecular-weight average 40,000 into, and its consumption is constant, and other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E11.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 12
Equipment used sees the following form with embodiment 1. raw materials and consumption thereof:
| Raw material type | Material name | Raw material consumption (kilogram) |
| Inert solvent | Toluene | 78 |
| Polyether glycol | The polyether-tribasic alcohol SPC-350 of molecular-weight average 5,000 | 85 |
| Polyisocyanates | MDI | 12 |
| High molecular polymer | Molecular-weight average 30, the liquid polybutadiene of 000-40,000 | 0.4 |
| The block agent | Methyl aceto acetate | 0.8 |
| Catalyzer | Dibutyl tin dilaurate | 0.015 |
| Softening agent | Dioctyl phthalate (DOP) | 36 |
| Inert filler | In super carbon black | 50 |
| Other additives | Antioxidant D | 0.9 |
| Anti UV agent YW-590 | 0.4 |
According to the consumption in the last table, accurately take by weighing polyether-tribasic alcohol, toluene, dioctyl phthalate (DOP) and in super carbon black, mixing, grind with colloidal mill, when granularity is viewed as less than 2 microns under electron microscope, add in the still, start stirring, airtight still, heating, vacuum pump decompression, when toluene steams, whenever steam 2Kg toluene, regulate heating power, outer temperature T
o(℃) be controlled at T among Fig. 1
oOn the numerical value of curve corresponding to this toluene amount of steaming, the adjustment vacuum pump is with pressure P
i(MPa) be controlled at P among Fig. 1
iOn the numerical value of curve corresponding to this toluene amount of steaming, warm T in reading this moment
i(℃) numerical value, thereby control T
o, P
iAnd T
iVariation with the toluene amount of steaming W (Kg) and time conforms to Fig. 1.Following preparation process is all controlled its condition according to this method.When temperature in the kettle rises to more than 70 ℃, negative pressure steams a large amount of toluene and toluene-water azeotrope when 0.07MPa (gauge pressure).Distilled about 7-8 hour, steam the water content of thing with the measurement of trace water tester, when the about 7-8 of distillation hour for being low to moderate 4ppm approximately, slowly splash into the ready MDI12 kilogram that is dissolved in 2 kilograms of dry toluene in advance from charging opening, the molecular-weight average that adds above-mentioned amount simultaneously is 35,000 liquid polybutadiene, this moment, still Wen Weiyue was 60-70 ℃, make the interior temperature of still go up to about 70-80 ℃, and constantly stir, the precursor preparation reaction finishes after 1-2 hour, in the material excessive free isocyanate groups is arranged in the still, adds the methyl aceto acetate and the catalyzer dibutyl tin dilaurate of above-mentioned amount this moment.Constantly stir.Add the antioxidant D and the anti UV agent YW-590 of above-mentioned amount after 30 minutes, stir, it is canned to go out still, is the finished product of a kind of single-component moisture curing polyurethane binder/sealant composition of the present invention, and its code name is E12.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.Ti, To and the Pi of monitoring reaction system make it to conform to Fig. 1 with W and the variation of time in the whole process of preparation, and the total amount that steams of toluene is about 70 kilograms.
Embodiment 13
Equipment and operation are with embodiment 12, and different is, it is the mixture of 45 kilograms of polyether-tribasic alcohol TR5000 and 40 kilograms of SPC-230 that 85 kilograms of polyether-tribasic alcohols are changed, and the molecular-weight average of liquid polybutadiene changes 10,000 into, and its consumption is constant.Other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E13.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 14
Equipment and operation are with embodiment 12, and different is, change the consumption of liquid polybutadiene into 0.1 kilogram, and other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E14.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 15
Equipment and operation are with embodiment 12, different is, change the consumption of liquid polybutadiene into 0.8 kilogram, catalyzer changes stannous octoate into, its consumption is 0.006 kilogram, and the block agent changes dimethyl malonic ester into, and consumption is constant, other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E15.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 16
Equipment and operation are with embodiment 12, and different is, change the consumption of liquid polybutadiene into 1.5 kilograms, and molecular-weight average changes 90,000 into, and other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E15.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 17 (comparative example)
Equipment and operation are with embodiment 12, and different is, change the consumption of liquid polybutadiene into 0 kilogram, and other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E17.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 18
Equipment and operation are with embodiment 12, and different is, change liquid polybutadiene the liquid polybutene of molecular-weight average 40,000 into, and its consumption is constant, and other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E18.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 19
Equipment and operation are with embodiment 12, and different is, change liquid polybutadiene the liquid polyisoprene of molecular-weight average 40,000 into, and its consumption is constant, and other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E19.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 20
Equipment and operation are with embodiment 12, and different is, change liquid polybutadiene the liquid isoprene-isobutylene rubber of molecular-weight average 40,000 into, and its consumption is constant, and other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E20.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 21 (comparative example)
Equipment and operation are with embodiment 12, and different is, change liquid polybutadiene into block reaction is finished after adding, and its consumption is constant, and other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E21.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Embodiment 22 (comparative example)
Equipment and operation are with embodiment 12, and different is, change liquid polybutadiene into after the reaction of polyether glycol and MDI is finished adding, and its consumption is constant, and other raw materials and consumption thereof are constant, and resulting binder/sealant end product code name is E22.It is the paste that a kind of black homogeneous does not have the foreign matter gel-free.
Two. performance test
To the binder/sealant product of above-mentioned each embodiment and the TL-VW of commercially available First Automobile Works
52880, the following several aspects performance with products such as TOGO series product Switzerland EMS company Switzerland ESSEX company carried out test relatively: outward appearance, density, non-volatile part, Shore A hardness, solid time of table, curing speed (with expression in mm/24 hour), 100% tensile modulus, tensile strength, elongation, shearing resistance and tear strength.
(1) testing method
The general condition of 1 test
The envrionment conditions in test place
--standard state: 23 ± 2 ℃ of temperature, relative humidity 60 ± 5%.
--off-rating: temperature 5-35 ℃, relative humidity 45-85%.
2 sampling methods
Every still product is got three samples in upper, middle and lower according to the position of still and is tested.
3 test piece steel plates
Automobile cold-rolled calendering steel plate, every chip size are 25mm * 100mm * 0.1mm, steel plate is given handle and spray paint.
4 key instrument devices: WD-5 type electronic universal tester, hot-blast constant temperature oven, constant temperature and humidity cabinet, balance, glue beating apparatus, tension testing machine.
The detection of 5 outward appearances
The a device: scraper, sheet glass (200mm * 300mm * 5mm), glue beating apparatus.
B method: with the sheet glass dedusting, after the clean-out system degreasing, get glue from the glue bottle, discard initial 30-50g, on sheet glass, coat the long adhesive tape of 20～30cm then, glue is wipeed off with scraper with glue beating apparatus.By below the visual observations several: variable color, layering, solidify, whether impurity is arranged, can conformal.
C result: observations is reported as follows several: homogeneity, color, not gel and foreign matter and conformality are arranged.
The mensuration of 6 density
The a device: balance (range 500g, sensibility reciprocal 0.5g), weighing bottle (volume 100ml ± 0.5ml), constant temperature oven.
B method: glue is injected known weight exsiccant weighing bottle, fill with seal gum (not sneaking into bubble) and cover bottle cap, wipe the seal gum that overflows, under standard state, behind the placement 3h, claim its gross weight.
C data processing: calculate according to following formula:
In the formula: ρ-density
W
1The weight of-weighing bottle (g)
W
2-weighing bottle and seal gum weight (g)
V-weighing bottle volume (ml)
7 non-volatile parts mensuration
A device: air blast constant temperature oven, weighing bottle (the about 50mm of internal diameter, about deeply 30mm), balance (sensibility reciprocal 1mg), moisture eliminator.
B method: in the weighing bottle of known weight, put into the little blocky seal gum of 3～4g, cover bottle cap, and accurately weigh up its weight with glass stick.Remove bottle cap after having claimed, place in 105 ± 2 ℃ of constant temperature ovens dry 3h.After the taking-up, cover bottle cap, in moisture eliminator, cool off 1h, claim its weight.Be calculated as follows non-volatile part.
In the formula: non-volatile part of R-(%)
Residual seal gum heavy (g) in the A-weighing bottle
S-seal gum heavy (g)
C result: with the weight percentage is unit representation; Result's the arithmetical av of getting 3～5 replicate(determination)s is as net result.
The mensuration of 8 curing speeds
The a device: sheet glass (5mm * 200mm * 300mm), timing register, polyethylene film (50mm * 25mm, 0.1mm), controlled thermohygrostat, scraper.
B method: seal gum to be tested is coated on the sheet glass, makes it become thick 5mm, wide 6mm, the film of long 50mm and get long 100mm, the trilateral adhesive tape of wide 10mm, high 12mm.Place under the standard state,, one polyethylene film is affixed on the film, peel off polyethylene film, till not sticking, note during this period of time as the solid time of the table of binder/sealant composition along 180 degree directions every 5min from getting the moment of glue.After treating 24h, cut another adhesive tape with blade, measure cured layer thickness with milscale, this thickness is 24h curing speed (mm/24h).
C result: horizontal survey 3 times, get its arithmetical av.
The mensuration of 9 shearing resistances
A device: tension testing machine, constant temperature and humidity cabinet, painted steel sheet and glass coupon.
The b method:
The making of test piece: referring to Fig. 2, painted steel sheet 2 and glass coupon 1 removed surface dirt after, remove degrease with clean-out system.Be coated with car body primer 3 and glass primer 4 respectively, and back to be dried (3～5min), fix cushion block 5 (5mm thick) at the painted steel sheet upper surface with adhesive tape according to Fig. 2, coat seal gum 6 a little more than cushion block, sheet glass is compressed from above, fix with adhesive tape, the unnecessary seal gum of extruding is wiped off with scraper.The test piece for preparing place constant temperature and humidity cabinet (23 ± 2 ℃, 60 ± 5%RH), place 168h.Data unit among Fig. 2 is a millimeter.
Measure
After taking out test piece under the standard state, tear adhesive tape, take off cushion block 5 test fixture is fixed on the last clamper of puller system.An end that glues the sample sheet glass is inserted in the test fixture, and painted steel sheet one end is clipped on the lower gripper of puller system.Painted steel sheet one end is clipped on the lower gripper of puller system.Maximum load when measuring sample fail in shear under the draw speed of 50 ± 2mm/min.Measure the length of shear surface and wide with slide calliper rule, be accurate to 0.01mm.Be calculated as follows shearing resistance:
In the formula: T-shearing resistance (MPa)
Maximum load (N) when the P-bonding plane destroys
B-bonding plane width (mm)
L-bonding plane length (mm)
C result: 5 samples of parallel testing, get its arithmetical av.
The mensuration of 10 hardness
A device: Shore A hardness meter, sheet glass.
The b method: seal gum is applied on the clean sheet glass, and the film of painting is of a size of 6mm * 50mm * 50mm.Under standard state, place 168h.After the completely solidified as test piece.With Shore A hardness instrumentation amount hardness, the each point point of mensuration is apart from being not less than 6mm, and measurement point is not less than 10mm apart from sample edge.
C result: the arithmetical av of getting 5 measured values.
The mensuration of 11 tensile strength and elongation
A device: tension testing machine, blanking die, cut-off knife (the dumb-bell shape cut-off knife that meets 1 type in the standard GB 528).
B method: (on the 200mm * 300mm), seal gum is painted the thick glued membrane of 2.0 ± 0.3mm, under standard state, place 168h at sheet glass.Be cut into test piece with No. 1 dumb-bell shape cut-off knife as Fig. 3.
Measure the position at dumbbell-shaped test piece center with measurer, and mark vertical medullary ray aa ', again in the both sides, center at a distance of each 10mm place of medullary ray stroke vertical graticule bb ' and cc ', two clampers of tension testing machine are clipped on the standard lines respectively.Start tension testing machine, making translational speed is 500 ± 2mm/min.Load when the record sample extends one times, maximum load when sample destroys and tensile elongation (must not there be pore at the test position).
C result: press examination and calculate 100% tensile modulus, tensile strength and elongation.
In the formula: σ
1-sample extends 100% o'clock tensile modulus (MPa)
σ
2Tensile strength when-sample is broken (MPa)
P
1The load (N) that the elongation of-sample is one times
P
2Maximum load during-sample fracture (N)
The thickness (mm) of B-sample working portion
The width (mm) of D-sample working portion
ε-sample fracture elongation (%)
L
oLength between-sample graticule (mm)
Length (mm) between graticule during the L-sample fracture
The result gets the arithmetical av of 5 parallel samples.
The mensuration of 12 tear strengths
The a device: tension testing machine, sheet glass (200mm * 300mm), cut-off knife (the no scarfing square style that meets standard GB 530 regulations).
B method: on sheet glass, coat the thick glued membrane of 2.0 ± 0.3mm, under standard state, place 168h.Test piece is cut into the test piece of Fig. 4 with cut-off knife, accurately measures the thickness of right angle tip position, be accurate to 0.01mm.The clamp of tension testing machine is clamped two ends, breaks test piece with the draw speed of 500 ± 2mm/min, the maximum load when record is broken.Be calculated as follows tear strength:
In the formula: F
Sz-perpendicular type sample tear strength (N/mm)
F-tears the maximum force (N) of sample
D-sample thickness (mm)
C result: measure 5 samples, get its arithmetical av.The measured value of each sample and the difference of mean value must not be greater than 15%.
(2) test result
Test result is summarized in following table 1.
| The product code name | Conformality | Density (G/CM 3) | When table is solid (MIN) | Curing speed (MM/24HR) | Hardness (° A) | Tensile strength (MPA) | Elongation (%) | Non-volatile part (%) | Shearing resistance (MPA) | 100% tensile modulus (MPA) | Tear strength (N/MM) | Quality guaranteed period (moon) |
| E1 | Good | 1.18 | - | 4.2 | 60 | 11.8 | 505 | 96.3 | 6.5 | 1.6 | 39.0 | 9 |
| E2 | Good | 1.19 | - | 4.3 | 61 | 12.5 | 510 | 97.0 | 5.8 | 1.7 | 39.4 | 9 |
| E3 | Good | 1.18 | 30 | 4.5 | 61 | 11.2 | 500 | 96.9 | 5.9 | 1.6 | 37.9 | 9 |
| E4 | Good | 1.18 | 30 | 4.7 | 60 | 12.0 | 526 | 98.0 | 6.2 | 1.8 | 36.0 | 9 |
| E5 | Good | 1.19 | 40 | 4.4 | 64 | 13.0 | 480 | 97.2 | 6.9 | 2.4 | 39.1 | 9 |
| E6 | Difference | 1.18 | 60 | 4.2 | 58 | 5.1 | 500 | 95.1 | 2.9 | 1.4 | 28.0 | 9 |
| E7 | Difference | 1.19 | 50 | 4.4 | 62 | 4.7 | 507 | 96.0 | 2.4 | 1.2 | 29.9 | 9 |
| E8 | Difference | 1.19 | 60 | 4.0 | 60 | 4.3 | 515 | 97.2 | 2.7 | 1.3 | 29.1 | 9 |
| E9 | Good | 1.18 | 35 | 4.5 | 61 | 12.2 | 517 | 98.1 | 6.0 | 1.7 | 39.3 | 9 |
| E10 | Good | 1.18 | 40 | 4.6 | 62 | 11.8 | 520 | 97.7 | 6.4 | 1.7 | 37.0 | 9 |
| E11 | Good | 1.19 | 30 | 4.2 | 60 | 10.0 | 490 | 95.9 | 5.4 | 1.2 | 38.0 | 9 |
| E12 | Good | 1.19 | 40 | 4.6 | 60 | 12.7 | 515 | 97.2 | 6.0 | 1.9 | 38.2 | 9 |
| E13 | Good | 1.19 | 40 | 4.2 | 59 | 11.9 | 503 | 97.2 | 6.4 | 1.8 | 37.9 | 9 |
| E14 | Good | 1.20 | 40 | 4.4 | 61 | 12.0 | 510 | 95.0 | 5.9 | 1.7 | 38.1 | 9 |
| E15 | Good | 1.18 | 30 | 4.2 | 60 | 11.2 | 490 | 96.1 | 5.7 | 1.7 | 38.0 | 9 |
| E16 | Good | 1.18 | 30 | 4.0 | 64 | 13.0 | 480 | 97.0 | 6.2 | 2.2 | 39.0 | 9 |
| E17 | Difference | 1.19 | 50 | 4.4 | 59 | 5.1 | 530 | 96.1 | 2.8 | 1.2 | 32.2 | 9 |
| E18 | Good | 1.18 | 30 | 4.0 | 61 | 10.0 | 500 | 99.1 | 5.7 | 1.4 | 39.0 | 9 |
| E19 | Good | 1.18 | 35 | 4.4 | 62 | 10.9 | 505 | 98.0 | 6.1 | 1.7 | 41.9 | 9 |
| E20 | Good | 1.19 | 30 | 4.4 | 60 | 12.0 | 520 | 97.0 | 6.4 | 1.7 | 39.1 | 9 |
| E21 | Good | 1.19 | 80 | 4.0 | 61 | 4.9 | 560 | 96.1 | 2.9 | 2.4 | 39.9 | 9 |
| E22 | Difference | 1.19 | 60 | 4.2 | 62 | 4.5 | 540 | 97.2 | 3.0 | 2.1 | 38.0 | 9 |
| TL-VW 52880 | Good | 1.16- 1.28 | 25-40 | 4-5 | 55±5 | 6 | 500 | - | 5.0 | 6 | ||
| ESSEX | Good | 1.20 | 20-25 | 4-5 | 55±5 | 6-7 | 500 | - | 5.0 | 6 | ||
| EMS | Good | 1.20 | 20-25 | 3-4 | 70-75 | 10 | - | - | 7-8 | 9 |
From the data of last table as seen, monocomponent moisture cure binder/sealant composition of the present invention is compared with the composition that does not add accordingly the high molecular polymer modification, and performance has increased significantly; The addition sequence of high molecular polymer also has tangible influence for the performance of final composition: when high molecular polymer and polyisocyanates join in the reactor simultaneously, because it is interspersed that the macromole of the molecule of high molecular polymer and the polyisocyanates/polyether glycol polymkeric substance that progressively forms twines mutually, the use properties of the binder/sealant end product that obtains and mechanical property are all very superior.When high molecular polymer adds after finishing in polyisocyanates/polyether glycol reaction, perhaps add after polyisocyanates/polyether glycol polymkeric substance finishes with the reaction of block agent, the product that obtains is all less better in use properties and mechanical properties.In addition, binder/sealant composition of the present invention is compared with commercially available existing binder/sealant has same even more excellent performance, therefore has the potential industrial application value, can be applied to being bonded and sealed of automobile component and material of construction.
The embodiment that it should be understood that above detailed description only supplies the usefulness of explanation, and can not be interpreted as any limitation of the invention.Any accommodation and change for the embodiment among the present invention all will be covered by within the scope of claim of the present invention.
Claims (14)
1. single-component moisture curing polyurethane binder/sealant composition, wherein by weight, contain:
I) the binder/sealant precursor is 100 parts; And
II) block agent 0.04-1.78 part; It is selected from following a kind of material: methyl aceto acetate, methyl acetoacetate, methylethyl malonic ester, diethyl malonic ester, dimethyl malonic ester;
III) inert filler 32-76 part;
IV) inert plasticizer 24-134 part;
V) other additives 1.2-3.6 part; It is anti-aging agent and anti UV agent and
VI) inert solvent is less than 9 parts greater than 0 part, its be not with product in any solvent of other compositions reaction;
Described binder/sealant precursor contains according to the weight meter:
ⅰ) being selected from molecular-weight average is 3,000-8, and the polyether glycol of the mixture of 000 polyether-tribasic alcohol or polyether Glycols and polyether-tribasic alcohol, with the polymerisate that excessive polyisocyanates reaction generates, it contains the free isocyanate groups of 3%-7%; With with respect to per 100 parts of polyether glycols
ⅱ) be selected from the polyolefine of liquid isoprene-isobutylene rubber, liquid polybutadiene, liquid polyisoprene and liquid polyisobutene, high molecular polymer 0.1-1.5 part of polydiolefin, its molecular-weight average is 10,000-100,000.
2. the binder/sealant composition of claim 1, wherein by weight, contain:
I) the binder/sealant precursor is 100 parts; And
II) block agent 0.5-1.5 part;
III) inert filler 40-60 part;
IV) inert plasticizer 35-130 part;
V) other additives 0.8-2.5 part; With
VI) inert solvent is less than 9 parts greater than 0 part.
3. the binder/sealant composition of claim 1, wherein by weight, contain:
I) the binder/sealant precursor is 100 parts; And
II) the block agent is 0.9 part;
III) inert filler is 55 parts;
IV) inert plasticizer is 45 parts;
V) other additives are 2.2 parts; With
VI) inert solvent is less than 9 parts greater than 0 part.
4. each binder/sealant composition among the claim 1-3, wherein used polyether glycol molecular-weight average is 4 in the precursor, 500-5,500.
5. each binder/sealant composition among the claim 1-3, wherein said polyisocyanates is selected from naphthalene diisocyanate (NDI), tolylene diisocyanate (TDI) and methylenediphenyl-4,4 '-vulcabond (MDI) or two or three mixture wherein.
6. each binder/sealant composition among the claim 1-3, wherein contained high molecular polymer molecular-weight average is 30 in the binder/sealant precursor, 000-40,000.
7. each binder/sealant composition among the claim 1-3, wherein contained high molecular polymer is a liquid polybutadiene in the binder/sealant precursor, its molecular-weight average is 10,000-100,000.
8. the binder/sealant composition of claim 7, wherein the molecular-weight average of liquid polybutadiene is 30,000-40,000.
9. each binder/sealant composition among the claim 1-3, wherein the content of high molecular polymer is 0.4-1.0 part with respect to per 100 parts polyether glycol.
10. each binder/sealant composition among the claim 1-3, wherein the molecular-weight average of the polyether glycol of precursor is 4,500-5,500; Liquid high molecular polymer used in the precursor is a liquid polybutadiene, and its molecular-weight average is 30,000-40,000; The content of high molecular polymer is 0.4-1.0 part with respect to per 100 parts polyether glycol in the precursor.
11. the binder/sealant composition manufacturing method of claim 1 comprises the steps:
I) by weight, add in reactor that to be selected from molecular-weight average be 3,000-8, the polyether glycol of the mixture of 000 polyether-tribasic alcohol or polyether Glycols and polyether-tribasic alcohol and with respect to inert solvent 30-50 parts of per 100 parts of polyether glycols steams solvent and water to steaming the thing water content less than 4ppm by underpressure distillation;
II) by weight, in reactor, add polyisocyanates 12-25 part with respect to per 100 parts of polyether glycols, be selected from high molecular polymer 0.1-1.5 part of polyolefine, polydiolefin homopolymer or multipolymer, make it reaction under heating, make the binder/sealant precursor;
III) by weight, in precursor, add the block agent that is selected from methyl aceto acetate, methyl acetoacetate, methylethyl malonic ester, diethyl malonic ester, dimethyl malonic ester, its amount is 0.05-2.0 part with respect to per 100 parts of polyether glycols, be selected from the catalyzer of dibutyl tin dilaurate, N-alkyl benzene amine, N-alkyl morpholine, N-alkyl croak piperazine, aluminum napthenate, manganese naphthenate, cobalt naphthenate, stannous octoate, its amount is 0.005-0.1 part with respect to per 100 parts of polyether glycols, carries out block polymerization;
IV) to III) reaction product in add exsiccant inert plasticizer and exsiccant inert filler and other additives, fully mixing is promptly.
12. the method for claim 11, the molecular-weight average of wherein used polyether glycol are 4,500-5,500; Used liquid high molecular polymer is a liquid polybutadiene, and its molecular-weight average is 30,000-40,000; The consumption of high molecular polymer is 0.4-1.0 part with respect to per 100 parts polyether glycol.
13. the binder/sealant composition manufacturing method of claim 1 comprises the steps:
I) by weight, add in reactor: being selected from molecular-weight average is 3,000-8, the polyether glycol of the mixture of 000 polyether-tribasic alcohol or polyether Glycols and polyether-tribasic alcohol; Inert plasticizer 30-150 part with respect to per 100 parts of polyether glycols; Inert filler 40-85 part and inert solvent 50-90 part steam solvent and water to steaming the thing water content less than 4ppm by underpressure distillation;
II) by weight, in reactor, add polyisocyanates 12-25 part with respect to per 100 parts of polyether glycols, be selected from high molecular polymer 0.1-1.5 part of polyolefine, polydiolefin homopolymer or multipolymer, make it reaction under heating, make the binder/sealant precursor;
III) by weight, to II) product in add the block agent be selected from methyl aceto acetate, methyl acetoacetate, methylethyl malonic ester, diethyl malonic ester, dimethyl malonic ester, its amount is 0.05-2.0 part with respect to per 100 parts of polyether glycols, be selected from the catalyzer of dibutyl tin dilaurate, N-alkyl benzene amine, N-alkyl morpholine, N-alkyl croak piperazine, aluminum napthenate, manganese naphthenate, cobalt naphthenate, stannous octoate, its amount is 0.005-0.1 part with respect to per 100 parts of polyether glycols, carries out block polymerization;
IV) to III) reaction product in add other additives of exsiccant, fully mixing is promptly.
14. the method for claim 13, wherein the molecular-weight average of employed polyether glycol is 4,500-5,500; Used liquid high molecular polymer is a liquid polybutadiene, and its molecular-weight average is 30,000-40,000; The consumption of high molecular polymer is 0.4-1.0 part with respect to per 100 parts polyether glycol.
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| CN98119666A CN1075103C (en) | 1998-09-21 | 1998-09-21 | Polyurethane adhesives/sealant composition, precursor and preparation process thereof |
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| EP1595902A1 (en) * | 2004-05-10 | 2005-11-16 | Sika Technology AG | Polyurethane composition having high early strength |
| CN102131530A (en) | 2008-06-27 | 2011-07-20 | 心脏起搏器公司 | Polyisobutylene urethane, urea and urethane/urea copolymers and medical devices containing same |
| WO2010081132A1 (en) | 2009-01-12 | 2010-07-15 | University Of Massachusetts Lowell | Polyisobutylene-based polyurethanes |
| CN101638568B (en) * | 2009-06-09 | 2012-03-14 | 虞建放 | Modified polyurethane waterproof seal glue |
| AU2010284137B2 (en) | 2009-08-21 | 2014-11-27 | Cardiac Pacemakers, Inc. | Crosslinkable polyisobutylene-based polymers and medical devices containing the same |
| US8374704B2 (en) | 2009-09-02 | 2013-02-12 | Cardiac Pacemakers, Inc. | Polyisobutylene urethane, urea and urethane/urea copolymers and medical leads containing the same |
| US8644952B2 (en) | 2009-09-02 | 2014-02-04 | Cardiac Pacemakers, Inc. | Medical devices including polyisobutylene based polymers and derivatives thereof |
| EP2466030A1 (en) * | 2010-12-17 | 2012-06-20 | Sika Technology AG | Use of polyolefin membranes being coated by non-reactive hotmelt adhesives for sealing purposes |
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| JPS61250083A (en) * | 1985-04-27 | 1986-11-07 | Nippon Synthetic Chem Ind Co Ltd:The | Urethane sealant having improved heat resistance |
| US5061749A (en) * | 1989-07-28 | 1991-10-29 | Sunstar Giken Kabushiki Kaisha | One-pack type heat precurable moisture-curing sealant composition |
| CN1138077A (en) * | 1995-05-20 | 1996-12-18 | 莫顿国际有限公司 | Adhesive for solvent-free use |
| CN1161362A (en) * | 1997-02-21 | 1997-10-08 | 吉林省科技开发实业公司 | Method for preparing single component polyurethane adhesive/seal gum |
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|---|---|---|---|---|
| JPS61250083A (en) * | 1985-04-27 | 1986-11-07 | Nippon Synthetic Chem Ind Co Ltd:The | Urethane sealant having improved heat resistance |
| US5061749A (en) * | 1989-07-28 | 1991-10-29 | Sunstar Giken Kabushiki Kaisha | One-pack type heat precurable moisture-curing sealant composition |
| CN1138077A (en) * | 1995-05-20 | 1996-12-18 | 莫顿国际有限公司 | Adhesive for solvent-free use |
| CN1161362A (en) * | 1997-02-21 | 1997-10-08 | 吉林省科技开发实业公司 | Method for preparing single component polyurethane adhesive/seal gum |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1248606A (en) | 2000-03-29 |
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