CN113795531A - 不可燃水性自流平环氧地板 - Google Patents
不可燃水性自流平环氧地板 Download PDFInfo
- Publication number
- CN113795531A CN113795531A CN202080033485.8A CN202080033485A CN113795531A CN 113795531 A CN113795531 A CN 113795531A CN 202080033485 A CN202080033485 A CN 202080033485A CN 113795531 A CN113795531 A CN 113795531A
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- Prior art keywords
- amine
- epoxy
- weight
- composition
- resin
- 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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- 239000004593 Epoxy Substances 0.000 title claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 24
- 239000000203 mixture Substances 0.000 claims abstract description 95
- 150000001412 amines Chemical class 0.000 claims abstract description 69
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 239000012764 mineral filler Substances 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims abstract description 21
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 38
- 239000003822 epoxy resin Substances 0.000 claims description 34
- 239000000945 filler Substances 0.000 claims description 28
- -1 Polyoxypropylene Polymers 0.000 claims description 27
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 23
- 229920000570 polyether Polymers 0.000 claims description 23
- 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 18
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 18
- 239000004615 ingredient Substances 0.000 claims description 16
- 150000003141 primary amines Chemical group 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 239000006004 Quartz sand Substances 0.000 claims description 10
- 239000003085 diluting agent Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 150000003512 tertiary amines Chemical group 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229920001281 polyalkylene Polymers 0.000 claims description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 14
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 15
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 11
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 10
- 238000009408 flooring Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 8
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229930185605 Bisphenol Natural products 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 5
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 5
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 5
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 5
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 150000003335 secondary amines Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 4
- QGMGHALXLXKCBD-UHFFFAOYSA-N 4-amino-n-(2-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC=C1N QGMGHALXLXKCBD-UHFFFAOYSA-N 0.000 description 4
- 239000009261 D 400 Substances 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 239000011083 cement mortar Substances 0.000 description 4
- 239000004567 concrete Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 description 3
- HSDVRWZKEDRBAG-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COC(CCCCC)OCC1CO1 HSDVRWZKEDRBAG-UHFFFAOYSA-N 0.000 description 3
- RREANTFLPGEWEN-MBLPBCRHSA-N 7-[4-[[(3z)-3-[4-amino-5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidin-2-yl]imino-5-fluoro-2-oxoindol-1-yl]methyl]piperazin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(\N=C/3C4=CC(F)=CC=C4N(CN4CCN(CC4)C=4C(=CC=5C(=O)C(C(O)=O)=CN(C=5C=4)C4CC4)F)C\3=O)=NC=2)N)=C1 RREANTFLPGEWEN-MBLPBCRHSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 3
- DPNYVVLIXCRDQZ-UHFFFAOYSA-N [5-(aminomethyl)-2-bicyclo[2.2.1]heptanyl]methanamine [6-(aminomethyl)-2-bicyclo[2.2.1]heptanyl]methanamine Chemical compound NCC1CC2CC1CC2CN.NCC1CC2CC(CN)C1C2 DPNYVVLIXCRDQZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- UOWSVNMPHMJCBZ-UHFFFAOYSA-N 1-[2-(2-butoxypropoxy)propoxy]butane Chemical compound CCCCOCC(C)OCC(C)OCCCC UOWSVNMPHMJCBZ-UHFFFAOYSA-N 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 2
- VGKUQBORKKSJMG-UHFFFAOYSA-N 2,2,6-trimethylcyclohexane-1,4-diamine Chemical compound CC1CC(N)CC(C)(C)C1N VGKUQBORKKSJMG-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 2
- KOGSPLLRMRSADR-UHFFFAOYSA-N 4-(2-aminopropan-2-yl)-1-methylcyclohexan-1-amine Chemical compound CC(C)(N)C1CCC(C)(N)CC1 KOGSPLLRMRSADR-UHFFFAOYSA-N 0.000 description 2
- JHCBFGGESJQAIQ-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylcyclohexyl)methyl]-2,6-dimethylcyclohexan-1-amine Chemical compound C1C(C)C(N)C(C)CC1CC1CC(C)C(N)C(C)C1 JHCBFGGESJQAIQ-UHFFFAOYSA-N 0.000 description 2
- OZTBUYKEBWNOKR-UHFFFAOYSA-N 4-[(4-amino-3-ethyl-5-methylcyclohexyl)methyl]-2-ethyl-6-methylcyclohexan-1-amine Chemical compound C1C(C)C(N)C(CC)CC1CC1CC(CC)C(N)C(C)C1 OZTBUYKEBWNOKR-UHFFFAOYSA-N 0.000 description 2
- HCJLTNJVGXHKTN-UHFFFAOYSA-N 4-[(4-amino-3-ethylcyclohexyl)methyl]-2-ethylcyclohexan-1-amine Chemical compound C1CC(N)C(CC)CC1CC1CC(CC)C(N)CC1 HCJLTNJVGXHKTN-UHFFFAOYSA-N 0.000 description 2
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GIXXQTYGFOHYPT-UHFFFAOYSA-N Bisphenol P Chemical compound C=1C=C(C(C)(C)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 GIXXQTYGFOHYPT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- GMTFURRRXIRGLH-UHFFFAOYSA-N C12CCCC2C2(CN)CC1CC2 Chemical compound C12CCCC2C2(CN)CC1CC2 GMTFURRRXIRGLH-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000003677 Sheet moulding compound Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229920006272 aromatic hydrocarbon resin Chemical class 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 239000010428 baryte Substances 0.000 description 2
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Abstract
本发明涉及环氧组合物,包括–含有胺官能加合物的水性硬化剂组分,所述胺官能加合物是至少一种聚醚胺、至少一种聚亚烷基胺、至少一种芳基脂族或脂环族胺、至少一种聚醚环氧树脂和至少一种芳族液体环氧树脂的反应产物,–树脂组分,所述树脂组分含有至少一种液体环氧树脂,和–矿物填料,其中所述组合物含有在以组合物的总固体为基础的85至95重量%的范围内的矿物填料。本发明的环氧组合物能够使地板涂层具有低的排放、低的收缩和高的耐冲击性,其可以至3mm或更大的层厚度在一个步骤中施加,固化为装饰性、无缺陷且有光泽的表面而不需要顶涂覆,并在燃烧时产生足够低的热以满足根据EN 13501‑1的火灾等级A2fl。
Description
技术领域
环氧组合物和它们作为地板涂层的用途。
现有技术
用于装饰目的的环氧地板广泛使用在例如工业地板或停车板的应用中。这样的地板通常通过将两种液体组分,任选地与填料组分一起混合,之后以大约1至3mm的层厚度施加混合的组分作为自流平涂层来加工。这样的地板的完工表面必须是硬的,高度耐机械和化学侵蚀,并必须满足高的美学标准,即均匀光泽的外观,没有斑点、裂纹或其它缺陷。如果固化的表面不满足这些美学标准,则地板不可用于装饰目的并必须用顶涂层顶涂覆,顶涂层通常以大约0.1至0.5mm的层厚度施加。施加顶涂层可确保高品质表面,但它还意味着额外的工作步骤和因此额外的时间和成本。
需要具有高耐火性的建筑。为了实现这点,建筑的所有材料都根据它们的耐火性分类,包括地板。需要环氧地板满足根据EN 13501-1的A2fl火灾等级。满足这点的一个要求是当如所述燃烧地板材料时小于3MJ/kg的低热量产生。满足这个要求的现有技术环氧地板或者粘度不够低,不够以1至3mm的层厚度施加作为自流平涂层(在足够低的溶剂或水含量下以这个层厚度可用而没有太多收缩),或者它们发展为无光泽的分布不均的表面,不可用于装饰目的,即必须其必须进行顶涂覆。
WO 2018/166897描述适合于地板涂层的具有良好加工性、优良的表面和相对高矿物填料含量的环氧组合物。良好的实施例的填料含量以固体为基础低于70重量%,并且组合物含有在复杂的多阶段方法中制备的加合物。使用这些组合物,不能够实现足够高的填料含量以使环氧地板能够具有足够低的热量产生从而满足根据EN 13501-1的A2fl火灾等级。
EP 2'961'784描述通过使二伯胺、单伯胺和聚环氧化合物反应获得的用于环氧树脂的水可还原的固化剂。这种固化剂使基于环氧的涂层能够在相对高的填料含量下(实施例1中基于固体79重量%矿物填料)具有好的加工性和流动性质。但是这些涂层发展为无光泽的分布不均的表面并需要进行顶涂覆用于装饰目的,并且它们在燃烧时仍产生过多的热从而不满足根据EN 13501-1的A2fl火灾等级。
在市场上没有这样的自流平的环氧地板,其可以1至3mm或更大的层厚度施加并实现用于装饰目的的高品质表面并在燃烧时产生足够低的热以满足根据EN 13501-1的A2fl火灾等级。
发明概述
本发明的任务是提供具有好的流动和自流平性质的环氧组合物,其可用作装饰目的地板涂层而不需要顶涂覆,并且当如EN 13501-1中描述燃烧地板材料时产生小于3MJ/kg热。
这个任务通过根据权利要求1的环氧组合物实现,其包括水性硬化剂组分,该水性硬化剂组分含有特定的胺官能加合物和在以固体为基础的85至95重量%范围内的非常高含量的矿物填料。令人惊讶地发现,基于(a)至少一种聚醚胺、(b)至少一种聚亚烷基胺、(c)至少一种芳基脂族或脂环族胺、(d)至少一种聚醚环氧树脂和(e)至少一种芳族液体环氧树脂的特定的胺官能加合物允许在这个高填料含量下良好的流动和自流平性质与在环境条件下固化后均匀且有光泽的表面而没有缺陷的独特组合。加合物能够在低的水含量下实现低粘性硬化剂组分而不需要高的有机溶剂或稀释剂量。根据权利要求1的组合物能够在高的层厚度例如1至3mm下实现高的固化速度和长的开放时间、低的收缩而没有裂纹形成,良好的耐冲击性和在环境条件下固化后光泽且均匀的表面。硬化剂组分中的加合物特别容易生产,而不需要多步骤方法,而多步骤方法对于高品质表面的现有技术的水性硬化剂经常是必需的。本发明的加合物可在简单且快速的一步方法中通过使混合的胺与混合的环氧树脂反应制成。
本发明的环氧组合物能够使地板涂层具有低的排放、低的收缩和高的耐冲击性,其可以1至3mm或更大的层厚度在一个步骤中施加,固化为装饰性、无缺陷且有光泽的表面而不需要顶涂覆,并在燃烧时产生足够低的热以满足根据EN 13501-1的火灾等级A2fl。
在其它独立权利要求中描述本发明的其它方面。在从属权利要求中描述本发明的优选方面。
发明详述
本发明的主题是环氧组合物,包括
–水性硬化剂组分,所述水性硬化剂组分含有胺官能加合物,其为以下物质的反应产物
(a)至少一种聚醚胺,
(b)至少一种聚亚烷基胺,
(c)至少一种芳基脂族或脂环族胺,
(d)至少一种聚醚环氧树脂,和
(e)至少一种芳族液体环氧树脂,
–树脂组分,所述树脂组分含有至少一种液体环氧树脂,和
–矿物填料,
其中所述组合物含有在以组合物的总固体为基础的85至95重量%的范围内的矿物填料。
在本文件中,硬化剂如果它含有大量的水,通常至少5重量%,则被称作“水性的”。
在本文件中,树脂组分如果它含有大量的水,优选至少20重量%,其中树脂是乳化的,则被称作“水性的”。
术语“聚醚胺”是指胺官能的聚醚。
术语“聚亚烷基胺”是指含有彼此通过亚烷基基团分开的至少三个胺基的线性聚胺。
术语“芳基脂族胺”是指具有与芳基脂族结构部分的脂族碳原子连接的胺基团的分子。
术语“脂环族胺”是指具有与脂环族结构部分的脂族碳原子连接的胺基团的分子。
术语“固体”或“固体含量”是指从其中蒸发了所有挥发性成分例如水或溶剂的组合物的比例。它可用算数方法确定或通过在红外干燥器中或在循环空气烘箱中干燥组合物至恒定重量来测定。
术语“伯胺”是指与仅一个有机结构部分连接并带有两个氢的胺基团;术语“仲胺”是指与两个有机结构部分(其还可以共同是环的一部分)连接并带有一个氢的胺基团;和术语“叔胺”是指与三个有机结构部分(其还可以是一个或多个环的部分)连接并不带有氢的胺基团。
术语“胺氢”是指伯胺基团和仲胺基团的氢。
术语“胺氢当量”是指含有一摩尔当量的胺氢的胺或含胺组合物的质量。
以“聚(多)”开始的物质名称例如多胺或聚环氧化物是指每个分子带有两个或更多个各自官能团的物质。
术语“分子量”是指分子的摩尔质量(以克/摩尔为单位给出)。术语“平均分子量”是指低聚物或聚合物分子或分子结构部分的多分散混合物的数均分子量Mn。它经常通过凝胶渗透色谱法(GPC)相对于聚苯乙烯标准物测定。
在本文件中,术语“室温”是指23℃的温度。
术语“适用期”是指可在没有缺陷的情况下混合组分之后施加多组分组合物的时间段。适用期的通常量度可为粘度的两倍。
胺官能加合物基于(a)至少一种聚醚胺。聚醚胺能够实现特别低的粘度和低的收缩。
优选的是不含仲胺或叔胺基团并含有两个或三个,特别是两个伯胺基团的聚醚胺。
合适的聚醚胺优选含有选自1,2-亚乙基氧基、1,2-亚丙基氧基、1,3-亚丙基氧基、1,2-亚丁基氧基和1,4-亚丁基氧基的重复单元。
优选的是具有1,2-亚乙基氧基和/或1,2-亚丙基氧基作为重复单元的聚醚胺。
特别优选的是仅含有1,2-亚丙基氧基作为聚醚链中重复单元的聚醚胺。这样的聚醚胺是疏水的并能够实现长的适用期。
优选的聚醚胺具有平均分子量Mn在200至5'000g/mol、更优选200至2'000g/mol、特别是200至500g/mol的范围内。
最优选的是具有平均分子量Mn在200至2'000g/mol、优选200至500g/mol范围内的聚氧化亚丙基二胺。这样的聚醚胺可作为例如D-230、D-400或D-2000(都来自Huntsman)商购得到。
胺官能加合物还基于(b)至少一种聚亚烷基胺。聚亚烷基胺能够实现良好的颜料分散性质、硬化剂组分的良好稳定性而没有分离,和固化的环氧组合物的高光泽度。
优选地,聚亚烷基胺是式(I)的胺,
其中
x是1-6的整数,和
B彼此独立地为C2-C6亚烷基基团。
这样的聚亚烷基胺通常以工业级使用。
合适的聚亚烷基胺特别是二亚乙基三胺(DETA)、三亚乙基四胺(TETA)、四亚乙基五胺(TEPA)、五亚乙基六胺(PEHA)、线性聚亚乙基胺的高级同系物、二亚丙基三胺(DPTA)、N-(2-氨基乙基)-1,3-丙二胺(N3-胺)、N,N'-双(3-氨基丙基)乙二胺(N4-胺)、N,N'-双(3-氨基丙基)-1,4-二氨基丁烷、N5-(3-氨基丙基)-2-甲基-1,5-戊二胺、N3-(3-氨基戊基)-1,3-戊二胺、N5-(3-氨基-1-乙基丙基)-2-甲基-1,5-戊二胺、N,N'-双(3-氨基-1-乙基丙基)-2-甲基-1,5-戊二胺或双(6-氨基己基)胺(BHMT)。
优选x是2或3或4。
优选地B是1,2-亚乙基和/或1,3-亚丙基,特别是1,2-亚乙基。
特别优选的聚亚烷基胺是TETA、TEPA、PEHA或N4-胺,特别是TETA、TEPA或PEHA。它们能够实现特别好的颜料润湿和高的固化速率。最优选的是TEPA。
胺官能加合物还基于(c)至少一种芳基脂族或脂环族胺。
芳基脂族或脂环族胺优选具有两个伯胺基团并不含仲胺或叔胺基团。它优选具有在100至300g/mol范围内的分子量。
优选地,芳基脂族或脂环族胺具有两个伯胺基团,除这些外不含另外的杂原子。
合适的芳基脂族或脂环族胺特别是1,2-二氨基环己烷,1,3-二氨基环己烷,1,4-二氨基环己烷,1,3-双(氨基甲基)环己烷,1,4-双(氨基甲基)环己烷,双(4-氨基环己基)甲烷,4-(4-氨基环己基甲基)苯胺,双(4-氨基-3-甲基环己基)甲烷,双(4-氨基-3-乙基环己基)甲烷,双(4-氨基-3,5-二甲基环己基)甲烷,双(4-氨基-3-乙基-5-甲基环己基)甲烷,1-氨基-3-氨基甲基-3,5,5-三甲基环己烷(异佛尔酮二胺或IPDA),2(4)-甲基-1,3-二氨基环己烷,2,5(2,6)-双(氨基甲基)双环[2.2.1]庚烷(降冰片烷二胺或NBDA),3(4),8(9)-双(氨基甲基)三环[5.2.1.02,6]癸烷,1,4-二氨基-2,2,6-三甲基环己烷(TMCDA),1,8-薄荷烷二胺、1,3-双(氨基甲基)苯(MXDA)、1,4-双(氨基甲基)苯、基于二聚体脂肪酸的胺例如1071或1074(均来自Croda),或酚醛胺(phenalkamine),例如腰果酚、甲醛和伯二胺的反应产物,可从Cardolite商购得到。
优选地芳基脂族或脂环族胺选自以下:1,3-双(氨基甲基)环己烷、1,4-双(氨基甲基)环己烷、1-氨基-3-氨基甲基-3,5,5-三甲基环己烷、2(4)-甲基-1,3-二氨基环己烷、2,5(2,6)-双(氨基甲基)双环[2.2.1]庚烷和1,3-双(氨基甲基)苯。
它们中特别优选的是1-氨基-3-氨基甲基-3,5,5-三甲基环己烷或1,3-双(氨基甲基)苯。最优选是1,3-双(氨基甲基)苯。
优选的胺能够实现平衡的亲水性质、低粘度和高反应性。
胺官能加合物还基于(d)至少一种聚醚环氧树脂。聚醚环氧树脂能够实现良好的流动行为和高耐冲击性。
优选地聚醚环氧树脂具有平均分子量Mn在200至2'000g/mol、特别地300至1'500g/mol的范围内。
合适的聚醚环氧树脂特别是聚乙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、聚四氢呋喃二缩水甘油醚或它们的混合物。
聚醚环氧树脂优选是聚丙二醇二缩水甘油醚。
最优选的,聚醚环氧树脂是具有环氧当量在150至750g/mol、特别是300至500g/mol范围内的工业级聚丙二醇二缩水甘油醚。
可有益的使用两个或更多个牌号的聚醚环氧树脂的混合物从而在加合物中得到最平衡的亲水性质和低粘度。
胺官能加合物还基于(e)至少一种芳族液体环氧树脂。
芳族液体环氧树脂通常是具有玻璃化转变温度低于25℃的工业级芳族聚环氧化物树脂。与此相反,固体环氧树脂具有玻璃化转变温度大于25℃并可粉碎为粉末。
合适的芳族液体环氧树脂是以下物质的缩水甘油醚
-双酚A、双酚F或双酚A/F,其中A意为丙酮和F意为甲醛,其用于生产这些双酚。工业级双酚F还可含有位置异构体,特别是来源于2,4'-或2,2'-羟苯基甲烷的;
-间苯二酚、对苯二酚或邻苯二酚;或
-其它双酚。
优选地芳族液体环氧树脂是双酚A和/或F二缩水甘油醚。这样的环氧树脂可从例如Dow、Huntsman、Hexion、Allnex或Momentive得到。
为了制备加合物,除已经提到的之外,还可以使用其它的胺和/或其它缩水甘油醚。
在本发明的优选实施方案中,除液体芳族环氧树脂之外,还使用固体芳族环氧树脂。这能够使涂层具有特别高的光泽度。优选地固体芳族环氧树脂以5至15重量%范围内的量使用,基于加合物中所有环氧官能物质的总重量。
在本发明另外优选的实施方案中,环氧官能反应性稀释剂与液体芳族环氧树脂一起使用,特别是1,4-丁二醇、1,6-己二醇或1,4-环己二甲醇的二缩水甘油醚,或C12-C14醇、C13-C15醇、苯酚、甲酚、对叔丁基苯酚的单缩水甘油醚。这能够使加合物具有特别低粘度。优选的是二缩水甘油醚,特别是工业级1,6-己二醇二缩水甘油醚。
含有一定量的反应性稀释剂的双酚A和/或F二缩水甘油醚可商购得到。
胺官能加合物优选通过使(a)聚醚胺、(b)聚亚烷基胺、(c)芳基脂族或脂环族胺和任选另外的胺官能物质与(d)聚醚环氧树脂、(e)芳族液体环氧树脂和任选另外的环氧官能物质以这样的方式反应制成,使得伯胺基团和环氧基之间的比大于1。
优选地在形成胺官能加合物的反应中伯胺基团和环氧基之间的总比率在1.5至4、优选2至3的范围内。这个比率范围使低粘度加合物能够在环境条件下固化成具有均匀、有光泽表面的涂层。
胺官能加合物优选通过在15至120℃、优选40至100℃、更优选60至90℃的范围内的温度下使含有胺基团的化合物与含有环氧基的化合物反应制成。反应的时间顺序是自由的,只要在反应混合物中总是存在相对环氧基过量的伯胺基团。
在优选实施方案中,胺官能加合物在一锅反应中通过将所有反应物混合在一起并使它们在50至130℃、优选60至100℃之间的温度范围内反应制成。优选预混合胺类,任选地与固体环氧树脂一起,加热这个混合物到至少50℃并在良好搅拌和温度控制下缓慢添加聚醚环氧树脂、液体芳族环氧树脂和任选的反应性稀释剂。这样的一锅反应特别容易且快速。
可以通过使胺官能加合物与单环氧化物例如对-叔丁基苯基缩水甘油醚反应来向生产方法添加第二步骤。这样的第二步骤是可能的,但对于得到环氧组合物的所述良好性能是不必要的。
优选地,加合物在一锅反应中仅在一个步骤中制成。这样的方法特别容易且快速。
优选地,在聚醚环氧树脂和液体芳族环氧树脂之间的重量比在30/70至80/20、优选50/50至75/25的范围内。
优选地,在聚醚胺和聚亚烷基胺之间的重量比在30/70至80/20、优选50/50至75/25的范围内。
优选地,在芳基脂族或脂环族胺与聚醚胺加上聚亚烷基胺之和之间的重量比在5/95至40/60、优选10/90至30/70的范围内。
优选的重量比能够实现低的粘度、平衡的亲水和疏水性质和具有高光泽度的装饰表面。
优选地,在胺和环氧树脂之间的反应完成之后用第一部分的水稀释加合物。使用这第一部分的水,优选将加合物稀释至固体含量在55至90重量%、优选60至80重量%的范围内。像这样,加合物是储存稳定的并容易用作环氧树脂的一部分水性硬化剂组分。
优选地水性硬化剂组分含有另外的水。
除胺官能加合物之外,水性硬化剂组分优选还含有至少一种另外的胺。
合适的另外的胺是具有至少3个胺氢的脂族、脂环族或芳基脂族多胺,特别是2,2-二甲基-1,3-丙二胺、1,3-戊二胺(DAMP)、1,5-戊二胺、1,5-二氨基-2-甲基戊烷(MPMD)、2-丁基-2-乙基-1,5-戊二胺(C11-新二胺)、1,6-己二胺、2,5-二甲基-1,6-己二胺、2,2(4),4-三甲基-1,6-己二胺(TMD)、1,7-庚二胺、1,8-辛二胺、1,9-壬二胺、1,10-癸二胺、1,11-十一烷二胺、1,12-十二烷二胺、1,2-、1,3-或1,4-二氨基环己烷、1,3-双(氨基甲基)环己烷、1,4-双(氨基甲基)环己烷、双(4-氨基环己基)甲烷、双(4-氨基-3-甲基环己基)甲烷、双(4-氨基-3-乙基环己基)甲烷、双(4-氨基-3,5-二甲基环己基)甲烷、双(4-氨基-3-乙基-5-甲基环己基)甲烷、1-氨基-3-氨基甲基-3,5,5-三甲基环己烷(IPDA)、2(4)-甲基-1,3-二氨基环己烷、2,5(2,6)-双(氨基甲基)双环[2.2.1]庚烷(NBDA)、3(4),8(9)-双(氨基甲基)三环[5.2.1.02,6]癸烷、1,4-二氨基-2,2,6-三甲基环己烷(TMCDA)、1,8-薄荷烷二胺、3,9-双(3-氨丙基)-2,4,8,10-四氧杂螺[5.5]十一烷、1,3-双(氨基甲基)苯(MXDA)、1,4-双(氨基甲基)苯、双(2-氨基乙基)醚、3,6-二氧杂辛烷-1,8-二胺、4,7-二氧杂癸烷-1,10-二胺、4,7-二氧杂癸烷-2,9-二胺、4,9-二氧杂十二烷-1,12-二胺、5,8-二氧杂十二烷-3,10-二胺、4,7,10-三氧杂十三烷-1,13-二胺,或这些胺的高级低聚物、双(3-氨基丙基)聚四氢呋喃或其它聚四氢呋喃二胺、聚氧化亚烷基二胺或三胺,特别是D-230、D-400、D-2000、EDR-104、EDR-148、EDR-176、T-403、T-3000、T-5000或THF-100(都来自Huntsman),2-氨基乙基哌嗪、N-苄基二亚乙基二胺、N-苄基三亚乙基四胺、N,N'-二苄基三亚乙基四胺、N”-苄基-N,N'-双(3-氨基丙基)乙二胺、N”,N”'-二苄基-N,N'-双(3-氨基丙基)乙二胺、N-苄基-1,3-双(氨基甲基)苯、N,N'-二苄基-1,3-双(氨基甲基)苯、N-(2-乙基己基)-1,3-双(氨基甲基)苯、N,N'-双(2-乙基己基)-1,3-双(氨基甲基)苯、苯乙烯化(styrolinated)MXDA(以240从Mitsubishi Gas Chem得到),辛基、癸基、异癸基、十二烷基、十四烷基或异十三烷基作为烷基的烷氧基丙基-1,3-二氨基丙烷,可以DA-1214、DA-14、DA-1618或DA-17(都来自Evonik)得到。
它们中优选的是2,2(4),4-三甲基-1,6-己二胺(TMD)、1,2-、1,3-或1,4-二氨基环己烷、1,3-双(氨基甲基)环己烷、1,4-双(氨基甲基)环己烷、1-氨基-3-氨基甲基-3,5,5-三甲基环己烷(IPDA)、2(4)-甲基-1,3-二氨基环己烷、2,5(2,6)-双(氨基甲基)双环[2.2.1]庚烷(NBDA)、1,3-双(氨基甲基)苯(MXDA)、和具有平均分子量Mn在200至500g/mol范围内的聚氧化亚烷基二胺或三胺,特别是D-230、D-400或T-403(都来自Huntsman)。
特别优选的是IPDA、MXDA和/或具有平均分子量Mn在200至500g/mol范围内的聚氧化亚烷基二胺或三胺。
树脂组分含有至少一种液体环氧树脂。
合适的液体环氧树脂特别是芳族环氧树脂,特别是以下物质的缩水甘油醚
-双酚A、双酚F或双酚A/F;
-间苯二酚、对苯二酚或邻苯二酚;
-其它双酚或多元酚例如双(4-羟基-3-甲基苯基)甲烷、2,2-双(4-羟基-3-甲基苯基)丙烷(双酚C)、双(3,5-二甲基-4-羟基苯基)甲烷、2,2-双(3,5-二甲基-4-羟基苯基)丙烷、2,2-双(3,5-二溴-4-羟基苯基)丙烷、2,2-双(4-羟基-3-叔丁基苯基)丙烷、2,2-双(4-羟基苯基)丁烷(双酚B)、3,3-双(4-羟基苯基)戊烷、3,4-双(4-羟基苯基)己烷、4,4-双(4-羟基苯基)庚烷、2,4-双(4-羟基苯基)-2-甲基丁烷、2,4-双(3,5-二甲基-4-羟基苯基)-2-甲基丁烷、1,1-双(4-羟基苯基)环己烷(双酚Z)、1,1-双(4-羟基苯基)-3,3,5-三甲基环己烷(双酚TMC)、1,1-双(4-羟基苯基)-1-苯基乙烷、1,4-双[2-(4-羟基苯基)-2-丙基]苯(双酚P)、1,3-双[2-(4-羟基苯基)-2-丙基]苯(双酚M)、4,4'-二羟基联苯(DOD)、4,4'-二羟基二苯甲酮、双(2-羟基萘-1-基)甲烷、双(4-羟基萘-1-基)甲烷、1,5-二羟基萘、三(4-羟基苯基)甲烷、1,1,2,2-四(4-羟基苯基)乙烷、双(4-羟基苯基)醚或双(4-羟基苯基)砜。
-酚醛清漆,其优选是苯酚或甲酚与甲醛、多聚甲醛、乙醛、巴豆醛、异丁醛、2-乙基己醛、苯甲醛或糠醛的缩合产物;
-芳族胺例如苯胺、甲苯胺、4-氨基苯酚、4,4'-亚甲基二苯基二胺、4,4'-亚甲基二苯基二(N-甲基)胺、4,4'-[1,4-亚苯基-双(1-甲基乙叉基)]双苯胺(双苯胺P)或4,4'-[1,3-亚苯基-双(1-甲基乙叉基)]双苯胺(双苯胺M)。
合适的液体环氧树脂是另外的脂族或脂环族聚环氧化物,特别是
-以下物质的缩水甘油醚:二-、三-或四官能C2-C30-醇,特别是乙二醇、丙二醇、丁二醇、己二醇、辛二醇、聚丙二醇、二羟甲基环己烷、新戊二醇、二溴新戊二醇、蓖麻油、三羟甲基丙烷、三羟甲基乙烷、季戊四醇、山梨糖醇或甘油,或烷氧基化甘油或三羟甲基丙烷;
-基于以下的水合的液体环氧树脂:双酚A、F或A/F,或水合的双酚A、F或A/F各自的缩水甘油醚;
-酰胺或杂环氮碱的N-缩水甘油基衍生物,例如氰尿酸三缩水甘油酯或异氰尿酸三缩水甘油酯,或表氯醇与乙内酰脲的反应产物;
-由烯烃例如特别是乙烯基己烯、二环戊二烯、环己二烯、环十二碳二烯、环十二碳三烯、异戊二烯、1,5-己二烯、丁二烯、聚丁二烯或二乙烯基苯的氧化得到的环氧树脂。
树脂组分的液体环氧树脂优选是芳族的。优选基于双酚。特别地,它是双酚A、F或A/F二缩水甘油醚。这些树脂是低粘度的并能够实现快速固化和高硬度。
任选地它们含有一定量的固体双酚A树脂或酚醛清漆缩水甘油醚。
优选地树脂组分还含有反应性稀释剂,特别是丁二醇二缩水甘油醚,己二醇二缩水甘油醚,环己烷二甲醇二缩水甘油醚,三羟甲基丙烷二-或三缩水甘油醚,苯基缩水甘油醚,甲苯基缩水甘油醚,对-叔丁基苯基缩水甘油醚,壬基苯基缩水甘油醚,十二烷基苯基缩水甘油醚,腰果酚缩水甘油醚,苄基缩水甘油醚,烯丙基缩水甘油醚,丁基缩水甘油醚,己基缩水甘油醚,2-乙基己基缩水甘油醚或天然醇例如C8-C10醇、C12-C14醇或C13-C15醇的单缩水甘油醚。
它们中优选的是丁二醇二缩水甘油醚、己二醇二缩水甘油醚、对-叔丁基苯基缩水甘油醚、腰果酚缩水甘油醚或C12-C14-或C13-C15烷基缩水甘油醚。
优选地树脂组分还含有水。
优选地,树脂组分是水性树脂组分并含有在20至50重量%、优选30至40重量%的范围内的水,基于树脂组分的总量。
优选地,水性树脂组分还含有至少一种表面活性添加剂,优选至少一种乳化剂。
环氧组合物含有在以组合物的总固体为基础的85至95重量%的范围内的矿物填料。
合适的矿物填料特别是碳酸钙、重晶石、滑石、石英粉、石英砂、碳化硅、云母、白云石、硅灰石、高岭土、矿物颜料例如二氧化钛、铁氧化物或铬氧化物、分子筛、氧化铝、氢氧化铝、氢氧化镁、硅酸、水泥、石膏、飞灰、金属粉末例如铝、铜、铁、锌、银或钢。
优选的矿物填料是碳酸钙、重晶石、石英粉、石英砂、二氧化钛和它们的组合。
矿物填料可为硬化剂和/或树脂组分的一部分,和/或它们可以分开包装并储存的填料组分的形式存在。
优选地环氧组合物除硬化剂和树脂组分之外还包括填料组分。填料组分优选是主要由矿物填料组成的粉末状材料。
优选地,填料组分含有至少一种石英粉和/或石英砂,特别是它含有具有粒度在0.05至0.5mm范围内的石英砂。
优选地填料组分含有在50至100重量%、优选70至100重量%、更优选90至100重量%的范围内的石英粉和/或石英砂,基于填料组分的总量。
最优选地,填料组分基本上由具有粒度在0.05至0.5mm范围内的工业级石英砂组成。
本发明的环氧组合物中矿物填料的总量在以组合物的总固体为基础的85至95重量%、优选88至93重量%的范围内。这样的组合物能够实现热产生小于3MJ/kg并具有以1-3mm或更大的范围内的层厚度可施加的足够好的流动行为。
在包括水的环氧组合物中,矿物填料的总量在70至90重量%、优选75至85重量%的范围内。
优选地,硬化剂组分含有60至90重量%、更优选70至90重量%、特别是75至88重量%矿物填料,优选它的至少一部分为重晶石粉、石英粉、二氧化钛和/或碳酸钙的形式。优选地,额外的矿物填料作为分开包装的填料组分使用,其优选基于石英砂。
任选地,环氧组合物含有另外的成分,特别是
-非反应性稀释剂或溶剂,特别是二甲苯、2-甲氧基乙醇、二甲氧基乙醇、2-乙氧基乙醇、2-丙氧基乙醇、2-异丙氧基乙醇、2-丁氧基乙醇、2-苯氧基乙醇、2-苄氧基乙醇、苄基醇、乙二醇、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚、乙二醇二苯醚、二甘醇、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单正丁醚、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二正丁醚、丙二醇单丁醚、丙二醇单苯醚、二丙二醇、二丙二醇单甲醚、二丙二醇二甲醚、二丙二醇二正丁醚、二苯基甲烷、二异丙基萘、矿物油馏分例如(来自Exxon)、烷基酚例如叔丁基苯酚、壬基苯酚、十二烷基苯酚、腰果酚(来自腰果壳油,含有3-(8,11,14-十五碳三烯基)苯酚作为主要成分)、苯乙烯化苯酚、双酚、芳族烃树脂,特别是含有酚基团的那些,烷氧基化苯酚,特别是乙氧基化或丙氧基化苯酚,特别是2-苯氧基乙醇,己二酸酯、癸二酸酯、邻苯二甲酸酯、苯甲酸酯、有机磷酸酯、有机磺酸酯或磺酰胺。它们中优选的是具有沸点大于200℃的稀释剂,特别是苄基醇、苯乙烯化苯酚、乙氧基化苯酚、含有酚基的芳族烃树脂,特别是LS 500、LX 200、LA 300或LA 700(均来自Ruetgers)、二异丙基萘或腰果酚。
-用于胺与环氧化物之间反应的促进剂,特别是酸或可水解成酸的物质,特别是碳酸例如乙酸、苯甲酸、水杨酸、2-硝基苯甲酸、乳酸,有机磺酸例如甲磺酸、对甲苯磺酸或4-十二烷基苯磺酸,磺酸的酯,其它有机或非有机酸例如磷酸,或之前提到的酸和酯;硝酸盐例如特别是硝酸钙;叔胺例如1,4-二氮杂双环[2.2.2]辛烷、苄基二甲胺、α-甲基苄基二甲胺、三乙醇胺、二甲基氨基丙胺,咪唑例如N-甲基咪唑、N-乙烯基咪唑或1,2-二甲基咪唑,这些叔胺的盐,季铵盐例如苄基三甲基氯化铵,脒例如1,8-二氮杂双环[5.4.0]十一碳-7-烯,胍例如1,1,3,3-四甲基胍,酚例如双酚,酚醛树脂或曼尼希碱例如2-(二甲基氨基甲基)苯酚、2,4,6-三(二甲基氨基甲基)苯酚或来自苯酚、甲醛和N,N-二甲基-1,3-丙二胺的聚合物,亚磷酸酯例如亚磷酸二-或三苯酯,或巯基官能化合物。它们中优选的是酸、硝酸盐、叔胺或曼尼希碱,特别是水杨酸、硝酸钙或2,4,6-三(二甲基氨基甲基)苯酚或它们的组合。
-其它填料例如炭黑、石墨、来自铝、铜、铁、锌、银或钢的金属粉末、PVC粉末或中空球。
-有机颜料;
-其它反应性稀释剂例如环氧化的大豆或亚麻子油,乙酰乙酸酯官能化合物例如乙酰乙酰基化的多元醇、丁内酯、碳酸酯、醛、异氰酸酯或含有反应性基团的硅酮;
-另外的胺,特别是前述胺与双环氧化物或单环氧化物的加合物,或聚酰胺胺,或曼尼希碱,特别是酚醛胺,或单胺例如苄胺或糠胺,或芳族多胺例如4,4'-、2,4'和/或2,2'-二氨基二苯基甲烷、2,4-和/或2,6-甲苯二胺、3,5-二甲基硫代-2,4-和/或-2,6-甲苯二胺、3,5-二乙基-2,4-和/或-2,6-甲苯二胺;
-巯基官能化合物,特别是液体巯基官能聚硫化物聚合物、巯基官能聚氧化烯、来自硫代碳酸的聚酯、2,4,6-三巯基-1,3,5-三嗪、三乙二醇二硫醇或乙二硫醇;
-聚合物,例如聚酰胺、聚硫化物、聚乙烯醇缩甲醛(PVF)、聚乙烯醇缩丁醛(PVB)、聚氨酯(PUR)、具有羧基的聚合物、聚酰胺、丁二烯-丙烯腈共聚物、苯乙烯-丙烯腈共聚物、丁二烯-苯乙烯共聚物、不饱和单体的均聚物或共聚物,所述不饱和单体特别是乙烯、丙烯、丁烯、异丁烯、异戊二烯、乙酸乙烯酯或(甲基)丙烯酸烷基酯,特别是氯磺化聚乙烯或含氟聚合物或磺酰胺改性三聚氰胺;
-纤维,特别是玻璃纤维、碳纤维、金属纤维、陶瓷纤维或塑料纤维例如聚酰胺纤维或聚乙烯纤维;
-流变改性剂,例如增稠剂或防沉剂;
-粘附促进剂,特别是有机烷氧基硅烷;
-阻燃剂,特别是已经提到的矿物填料氢氧化铝,特别是氢氧化铝(ATH),或氢氧化镁,另外的三氧化锑,五氧化二锑,硼酸(B(OH)3),硼酸锌,磷酸锌,硼酸三聚氰胺,氰尿酸三聚氰胺,多磷酸铵,磷酸三聚氰胺,焦磷酸三聚氰胺,多溴化二苯醚或二苯基醚,磷酸酯例如磷酸二苯甲苯酯,间苯二酚双(二苯基磷酸酯),间苯二酚二磷酸酯低聚物,四苯基间苯二酚二亚磷酸酯,二磷酸乙二胺,双酚A双(二苯基磷酸酯),磷酸三(氯乙基)酯,磷酸三(氯丙基)酯,磷酸三(二氯异丙基)酯,磷酸三[3-溴-2,2-双(溴甲基)丙基]酯,四溴双酚A,双酚A的双(2,3-二溴丙基醚),溴化环氧树脂,亚乙基双(四溴邻苯二甲酰亚胺),亚乙基双(二溴降冰片烷二甲酰亚胺),1,2-双(三溴苯氧基)乙烷,三(2,3-二溴丙基)异氰脲酸酯,三溴苯酚,六溴环十二烷,双(六氯环戊二烯基)环辛烷或氯化石蜡;
-添加剂例如分散石蜡,聚结剂,杀生物剂,抗氧化、热、光或UV辐射的稳定剂,或特别是表面活性添加剂例如润湿剂、消泡剂、脱气剂、分散助剂或流平剂。
这样的另外成分可为硬化剂和/或树脂和/或填料组分的一部分,而含有可与环氧化物反应的反应性基团的成分优选是硬化剂组分的一部分,环氧官能成分优选是树脂组分的一部分,和仅粉末状成分优选作为填料组分的一部分。还可以以分开包装的另外组分的形式使用这样的成分。
优选的水性硬化剂组分含有
-2至10重量%、优选4至8重量%的所描述胺官能加合物,
-60至90重量%矿物填料,
-5至20重量%、优选8至15重量%水,
-0至5重量%、优选0至2.5重量%其它的胺,
-0至5重量%、优选0.5至3重量%表面活性添加剂,和
任选另外的成分,
基于总水性硬化剂组分。
优选的树脂组分含有
-40至80重量%、优选50至70重量%基于双酚A、F或A/F的液体环氧树脂,
-0至15重量%、优选2至7重量%反应性稀释剂,
-20至60重量%、优选30至50重量%水,
-0.5至10重量%、优选1至5重量%表面活性添加剂,和
任选另外的成分,
基于总水性树脂组分。
优选的填料组分基本上由优选具有粒度在0.05至0.5mm范围内的工业级石英砂组成。
优选地,总组合物含有在5至20重量%、优选6至12重量%的范围内的水,基于总组合物。
优选地总组合物含有小于15重量%、优选小于12重量%、更优选小于11重量%的有机材料,基于组合物的总固体含量。
优选地,环氧涂层含有少量的挥发性有机溶剂,优选小于2重量%、更优选小于1重量%、最优选基本上不含具有沸点为200℃或更小的挥发性有机溶剂。
优选地,在总组合物中对环氧基有反应性的基团数与环氧基数之比在0.5至1.5、优选0.7至1.2的范围内。
环氧组合物中的伯胺和仲胺基团和任选另外的反应性基团与环氧基通过环氧基的开环(加成反应)反应。环氧组合物主要通过这个反应聚合从而硬化。
硬化剂和树脂组分通过混合所有成分从而获得均匀流体彼此分开生产。
硬化剂组分、树脂组分和如果存在的填料组分彼此分开地储存在分开包装的容器中。
用于储存硬化剂或树脂组分的合适容器特别是大桶、桶、罐、锡罐、管、防水袋或肠状袋(sausage)。填料组分储存的合适容器特别是袋或桶。
分开储存的组分是储存稳定的,即它们可在几个月直至一年或更长时期内储存而没有将它们的性质改变到与影响它们的使用的程度。
对于环氧组合物的使用而言,硬化剂、树脂和任选另外的组分,特别是填料组分在施加前不久或在施加期间混合在一起。如果存在填料组分,则可以任何合适的顺序混合组分。优选地,它们以这样的方式混合,使得预混合硬化剂和树脂组分,之后添加填料组分并再次混合。组分之间的混合比优选使得反应性基团之间的比率导致如之前给出的合适比率,并且使得矿物填料的总含量在要求保护的比率中。以重量份计,硬化剂和树脂组分之间的比率通常在10:1至1:1的范围内,并且硬化剂和树脂组分组合与填料组分之间的比率通常在4:1至1:2的范围内。
组分的混合通常分批完成,但是还可以以连续方法混合组分。如果不是在施加前立即进行混合,则需要注意在环氧组合物的适用期内完成施加。特别在环境温度下进行组分的混合,环境温度通常在约5至40℃、特别是约10至35℃的范围内。
环氧组合物在它的组分混合之后不久具有低粘度。优选地动态粘度在组分的混合完成之后5分钟在400mPa.s至4'000mPa.s的范围内,在20℃下使用锥板型粘度计以100s-1的剪切速率测量(锥直径50mm,锥角度1°,锥顶至板距离0.05mm)。
组分一经混合,如以上描述,环氧组合物的固化通过化学反应开始。固化通常发生在0至70℃范围内的温度下。优选地,固化发生在环境条件下并通常延续几天至几周,这取决于温度、成分的反应性和化学计量比和促进剂的含量。一经固化,水和其它挥发性非反应性成分蒸发至环境。
环氧组合物的施加在至少一个基材上进行。合适的基材优选是
-混凝土、灰浆、水泥砂浆、纤维水泥、砖、贴片、灰泥、石膏、天然石例如花岗岩或大理石、陶瓷或玻璃;
-基于PCC(聚合物改性水泥组合物)或ECC(环氧改性水泥组合物)的修复或流平材料;
-金属或合金例如铝、铁、钢、铜或其它非铁金属,包括表面处理的金属例如镀锌或镀铬金属。
另外可行的物质是
-柏油或沥青;
-皮革、纺织品、纸、木材、含有树脂粘合木材的复合材料,特别是具有基于酚、三聚氰胺或环氧树脂的树脂的、基于树脂和纺织品的复合材料,或其它复合材料;
-塑料,例如硬或软的PVC、聚碳酸酯、聚苯乙烯、聚酯、聚酰胺、PMMA、ABS、SAN、环氧材料、酚醛树脂、PUR、POM、TPO、PE、PP、EPM或EPDM,各自呈未处理或表面处理的形式,特别是通过等离子体、电晕或火焰处理;
-纤维增强塑料,例如碳纤维增强塑料(CFRP)、玻璃纤维增强塑料(GFRP)或片状模塑料(SMC);
-隔绝泡沫,特别是基于EPS、XPS、PUR、PIR、岩棉、玻璃棉或泡沫玻璃的;
-涂覆的或涂漆的基材,特别是上釉贴片、涂漆混凝土、粉末涂覆的金属或合金或涂清漆的金属片;
-涂层、油漆层或清漆层,特别是涂覆的地板,其待使用地板覆面层顶涂覆。
可有利的在施加环氧组合物之前预处理基材,特别是通过物理和/或化学清洁方法或通过施加底漆和/或底涂层预处理。
环氧组合物优选用作涂层、密封剂、粘合剂或浇铸化合物。优选地它用于涂覆地板、筒仓、管材或屋顶。
特别优选的是使用环氧组合物作为地板涂层。这样的地板涂层具有良好的耐火性质与燃烧时特别低的热量产生。优选地,固化的地板涂层产生根据EN 13501-1小于3MJ/kg的热,这能够满足火灾等级A2fl。
优选地,混合的环氧组合物在它的适用期内以液体状态施加,通常通过将其倾倒在基材上,之后用工具例如刮板、齿形抹刀或辊铺展,从而得到优选在1至3mm范围内的期望的干膜厚度。
混合的环氧组合物具有好的流动和自流平性质,这意味着在施加时它容易铺展并发展为平整表面。在固化之后,表面均匀、平整且有光泽,这能够将它用作具有装饰目的的地板覆面层的顶层。然而,如果需要,则将它顶涂覆。这样的顶涂层也可基于环氧树脂,或者它可基于另一材料例如聚氨酯、丙烯酸酯或聚脲。
本发明的另一主题是涂覆方法,包括以下步骤
(i)混合描述的环氧组合物的组分,
(ii)将混合的组合物在它的适用期内以0.5至5mm、优选1至3mm范围内的层厚度施加至基材上,
之后将体系固化。
将环氧组合物施加至其上的基材优选是地板,特别是混凝土地板、水泥砂浆、或任何其它不可燃的地板。可在施加根据本发明的环氧组合物之前用底漆或底涂层预处理基材。
优选地,施加的环氧组合物是地板涂层体系的一部分,该地板涂层体系任选地含有所谓的底漆,接着任选地含有所谓的底涂层,接着一层或多层根据本发明的环氧组合物。可以使用顶涂层作为最顶层,但这不是必要的,因为根据本发明的环氧组合物发展为可用于装饰目的的精美表面。
底漆通常是环氧组合物,其能够润湿基材例如混凝土地板或水泥砂浆的表面。它结合灰尘并渗入孔隙,并因此能够封闭孔隙。它通常以200至500g/m2的量使用。
底涂层通常也是环氧组合物。其可为填充的或未填充的。通常用于调节凸起或孔从而得到平整表面。
顶涂层以约0.1至0.5mm的层厚度使用。它可为环氧组合物或另一材料,例如聚氨酯。其可为水性的或不是水性的。
本发明的另一主题是制品,其含有由描述的涂覆方法获得的固化的环氧组合物。优选地,它含有呈地板涂层形式的固化的环氧组合物。制品可为建筑或建筑的一部分,例如工业大厅、楼梯井、办公室、实验室、会客室、休息室、储藏室、停车板、阳台、露台、屋顶或桥梁。
本发明的另一主题是水性硬化剂用于固化至少一种环氧树脂的用途,所述水性硬化剂含有胺官能加合物,其为以下物质的反应产物
(a)至少一种聚醚胺,
(b)至少一种聚亚烷基胺,
(c)至少一种芳基脂族或脂环族胺,
(d)至少一种聚醚环氧树脂,和
(e)至少一种芳族液体环氧树脂,
如以上描述,伯胺基团与环氧基的摩尔比在1.5至4、优选2至3的范围内。
这个用途能够使环氧组合物以组合物的总固体为基础在直至75至95重量%、优选80至95重量%、更优选85至95重量%的范围的异常高的矿物填料含量下具有好的流动和自流平性质,以及在环境条件下固化后具有平整且有光泽的表面而没有缺陷。
实施例
以下实施例说明本发明而不是限制本发明。
“AHEW”意为胺氢当量。
“EEW”意为环氧基当量。
“正常气候”意为23±1℃的温度和50±5%的相对大气湿度。
化学物质没有另外规定则来自Sigma-Aldrich Chemie GmbH。
粘度通过Brookfield粘度计使用转子数3以速度数5测定。
使用的物质:
TEPA: 四亚乙基五胺,AHEW 30g/mol,当量/伯胺基团95g/mol,工业级,来自Huntsman
MXDA: 1,3-双(氨基甲基)环己烷,AHEW 34g/mol,当量/伯胺基团68g/mol,来自Mitsubishi Gas Chem
D.E.R.TM 358: 含有己二醇二缩水甘油醚的双酚A/F二缩水甘油醚,EEW180g/mol,来自Dow
Epikote TM Resin 05447:双酚A/F二缩水甘油醚,EEW 177g/mol,来自Momentive
添加剂: 消泡剂和分散助剂
胺官能加合物的制备:
加合物A1:
将20.33wpt D-400、9.93重量份(wpt)TEPA、5.92wpt MXDA和4.59wpt EP 384w放在圆底烧瓶中并加热至70℃。然后,在良好搅拌下缓慢添加6.16wpt F 704、13.62wptDY-F和11.29wpt D.E.R.TM 358的预混物并且烧瓶中温度保持低于85℃。此后,在2小时期间内将反应混合物保持在80至85℃下,之后添加26.14wpt自来水和2.02wpt乙酸,各自在良好搅拌下。将获得的胺官能加合物冷却至室温。它具有固体含量为72重量%,粘度在20℃下为3.5Pa.s,计算AHEW为176.3g/eq,和透明的淡黄色外观。
加合物A2:
如对于加合物A1所述使用表1中给出的成分的量制备加合物A2。在完成添加F 704、DY-F和D.E.R.TM 358的预混物之后添加DY-P。然后,在2小时期间内将反应混合物保持在80至85℃下,之后添加自来水和乙酸。获得的胺官能加合物具有固体含量为72重量%,粘度在20℃下为3.2Pa.s,计算AHEW为172.6g/eq,和透明的淡黄色外观。
加合物R1:
如对于加合物A1所述使用表1中给出的成分的量制备加合物R1。获得的胺官能加合物具有固体含量为72重量%,粘度在20℃下为3.2Pa.s,计算AHEW为151.2g/eq,和透明的淡黄色外观。
加合物R2:
如对于加合物A1所述使用表1中给出的成分的量制备加合物R2。获得的胺官能加合物具有固体含量为72重量%,粘度在20℃下为8.9Pa.s,计算AHEW为129.2g/eq,和透明的淡黄色外观。
加合物R3:
如对于加合物A1所述使用表1中给出的成分的量制备加合物R3。获得的胺官能加合物具有固体含量为72重量%,粘度在20℃下为1.7Pa.s,计算AHEW为243.5g/eq,和透明的淡黄色外观。
加合物A1和A2是根据本发明的胺官能加合物。加合物R1至R3用于对比。
表1:加合物A1、A2和R1至R3的组成(以重量份计)和特征。
环氧组合物的制备:
实施例1至8:
通过混合表2和表3中给出的成分制备了每个实施例的硬化剂组分,储存在密闭的容器中。
通过混合3.294重量份(wpt)GY 250、4.942wpt Epikote TM Resin05447、0.539wpt DY-E、0.175wpt乳化剂和5.050wpt自来水另外制备了每个实施例的树脂组分,储存在密闭容器中。
由石英砂0.1至0.3mm组成另外制备了每个实施例的填料组分,储存在纸袋中。
树脂组分、硬化剂组分和填料组分以表2和表3中给出的比例(重量份)通过具有搅拌棒的钻机(drilling machine)混合在一起。通过齿状刮板以2mm的层厚度将新鲜混合的环氧组合物施加至水平放置的水泥砂浆板上并使其在正常气候下固化7天。
流动行为通过眼睛确定并以从1(差)至5(好)的等级评判。
自流平通过眼睛确定并以从1(差)至5(好)的等级评判。
收缩通过浇铸500mm x 30mm x 4mm的棒测量并以从1(差)至5(好)的等级评判。良好意为低收缩。
光泽度通过光泽计确定并以从1(差)至5(良好)的等级评判。
肖氏D硬度根据DIN 53505在正常气候下储存1天和7天之后测量。
如果在混合在一起之后硬化剂和环氧组分没有相分离,则相分离指定为“否”;并且如果存在,则指定为“是”。
通过弹式量热测试根据EN 13501-1测定地板的热产生。
在表2和表3中给出组成和测试结果。
具有“(Ref.)”的实施例是参考例。
表2:实施例1至5的组成(以重量份计)。
1如以上描述制备
2硬化剂比树脂比填料组分,以重量计
3基于总组合物
4基于总组合物的计算的固体含量
“n.d.”意为“未测定”
表3:实施例6至8的组成(以重量份计)。
1如以上描述制备
2硬化剂比树脂比填料组分,以重量计
3基于总组合物
4基于总组合物的计算的固体含量。
Claims (15)
1.环氧组合物,包括
–水性硬化剂组分,所述水性硬化剂组分含有胺官能加合物,其为以下物质的反应产物
(a)至少一种聚醚胺,
(b)至少一种聚亚烷基胺,
(c)至少一种芳基脂族或脂环族胺,
(d)至少一种聚醚环氧树脂,和
(e)至少一种芳族液体环氧树脂,
–树脂组分,所述树脂组分含有至少一种液体环氧树脂,和
–矿物填料,
其中所述组合物含有在以组合物的总固体为基础的85至95重量%的范围内的矿物填料。
2.根据权利要求1所述的环氧组合物,其中聚醚胺是具有平均分子量Mn在200至2'000g/mol、优选200至500g/mol范围内的聚氧化亚丙基二胺。
4.根据权利要求1至3中任一项所述的环氧组合物,其中芳基脂族或脂环族胺具有两个伯胺基团,不含仲胺或叔胺基团并具有分子量在100至300g/mol的范围内。
5.根据权利要求1至4中任一项所述的环氧组合物,其中聚醚环氧树脂是聚丙二醇二缩水甘油醚。
6.根据权利要求1至5中任一项所述的环氧组合物,其中在形成胺官能加合物的反应中伯胺基团和环氧基之间的总比率在1.5至4的范围内。
7.根据权利要求1至6中任一项所述的环氧组合物,其中树脂组分是水性树脂组分并含有在20至50重量%、优选30至40重量%的范围内的水,基于树脂组分的总量。
8.根据权利要求1至7中任一项所述的环氧组合物,其额外包括填料组分。
9.根据权利要求8所述的环氧组合物,其中填料组分基本上由具有粒度在0.05至0.5mm范围内的工业级石英砂组成。
10.根据权利要求1至9中任一项所述的环氧组合物,其中水性硬化剂组分含有
-2至10重量%的胺官能加合物,
-60至90重量%的矿物填料,
-5至20重量%的水,
-0至5重量%的其它胺硬化剂,
-0至5重量%的表面活性添加剂,
和任选另外的成分,
基于总水性硬化剂组分。
11.根据权利要求1至10中任一项所述的环氧组合物,其中树脂组分含有
-以双酚A、F或A/F为基础的40至80重量%、优选50至70重量%液体环氧树脂,
-0至15重量%、优选2至7重量%反应性稀释剂,
-20至60重量%、优选30至50重量%水,
-0.5至10重量%、优选1至5重量%表面活性添加剂,
和任选另外的成分,
基于总水性树脂组分。
12.涂覆方法,包括以下步骤
(i)混合根据权利要求1至11中任一项的环氧组合物的组分,
(ii)将混合的组合物在它的适用期内以0.5至5mm范围内的层厚度施加至基材上,
之后将体系固化。
13.根据权利要求12所述的方法,其中基材是地板。
14.含有固化的环氧组合物的制品,所述固化的环氧组合物通过根据权利要求12至13中任一项的方法获得。
15.水性硬化剂用于固化至少一种环氧树脂的用途,所述水性硬化剂含有胺官能加合物,其为以下物质的反应产物
(a)至少一种聚醚胺,
(b)至少一种聚亚烷基胺,和
(c)至少一种芳基脂族或脂环族胺,
(d)至少一种聚醚环氧树脂,和
(e)至少一种芳族液体环氧树脂,
伯胺基团与环氧基的摩尔比在1.5至4的范围内。
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EP19180191.9 | 2019-06-14 | ||
EP19180191.9A EP3750935A1 (en) | 2019-06-14 | 2019-06-14 | Non-combustible waterborne self levelling epoxy floor |
PCT/EP2020/066335 WO2020249751A1 (en) | 2019-06-14 | 2020-06-12 | Non-combustible waterborne self levelling epoxy floor |
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US (1) | US20220235220A1 (zh) |
EP (2) | EP3750935A1 (zh) |
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EP4269464A1 (en) * | 2022-04-25 | 2023-11-01 | Sika Technology AG | Epoxy-resin modified composition used for coating or sealing |
CN115011200A (zh) * | 2022-06-10 | 2022-09-06 | 烟台市北海海洋工程技术有限公司 | 一种船用轻型环氧甲板组合物、甲板敷料及甲板敷料施工方法 |
EP4372025A1 (en) * | 2022-11-21 | 2024-05-22 | Sika Technology AG | Multipurpose waterborne epoxy flooring composition |
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EP1647584A1 (en) * | 2004-10-13 | 2006-04-19 | Cytec Surface Specialties Austria GmbH | Aqueous epoxy resin systems |
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KR20150123795A (ko) | 2013-03-01 | 2015-11-04 | 시카 테크놀러지 아게 | 긴 가용 시간, 신속 경화 및 낮은 수축률 특성을 지니는 2성분 에폭시 셀프 레벨링 화합물에 이용하기 위한 수계 에폭시 경화제를 제조하는 방법 및 조성물 |
EP3375831A1 (de) | 2017-03-13 | 2018-09-19 | Sika Technology Ag | Epoxidharz-vergütete zusammensetzung als beschichtung oder versiegelung |
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- 2020-06-12 CA CA3136397A patent/CA3136397A1/en active Pending
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EP1647584A1 (en) * | 2004-10-13 | 2006-04-19 | Cytec Surface Specialties Austria GmbH | Aqueous epoxy resin systems |
US20090029175A1 (en) * | 2007-02-07 | 2009-01-29 | Air Products And Chemicals, Inc. | Alkylated Polyalkylene Polyamines And Uses Thereof |
EP1980542A2 (en) * | 2007-04-10 | 2008-10-15 | Air Products and Chemicals, Inc. | Polyalkyleneamine adducts as curing agents for thick layer water-based epoxy systems |
EP2159218A1 (en) * | 2008-08-25 | 2010-03-03 | Air Products and Chemicals, Inc. | Curing agent for low temperature cure applications |
EP2752437A1 (de) * | 2013-01-08 | 2014-07-09 | Sika Technology AG | Härter für emissionsarme Epoxidharz-Produkte |
CN104884496A (zh) * | 2013-01-08 | 2015-09-02 | Sika技术股份公司 | 用于低排放环氧树脂产品的固化剂 |
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US20170029364A1 (en) * | 2014-02-07 | 2017-02-02 | Sika Technology Ag | Amine for low-emission epoxy resin products |
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EP3983468A1 (en) | 2022-04-20 |
CA3136397A1 (en) | 2020-12-17 |
EP3983468B1 (en) | 2024-03-13 |
EP3983468C0 (en) | 2024-03-13 |
AU2020290769A1 (en) | 2021-10-28 |
EP3750935A1 (en) | 2020-12-16 |
US20220235220A1 (en) | 2022-07-28 |
WO2020249751A1 (en) | 2020-12-17 |
CN113795531B (zh) | 2023-11-03 |
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