CN117186352A - 包含封闭型聚氨酯预聚物的单组分体系 - Google Patents
包含封闭型聚氨酯预聚物的单组分体系 Download PDFInfo
- Publication number
- CN117186352A CN117186352A CN202310664545.1A CN202310664545A CN117186352A CN 117186352 A CN117186352 A CN 117186352A CN 202310664545 A CN202310664545 A CN 202310664545A CN 117186352 A CN117186352 A CN 117186352A
- Authority
- CN
- China
- Prior art keywords
- component system
- diisocyanate
- glycol
- malonate
- diol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001730 Moisture cure polyurethane Polymers 0.000 title claims abstract description 27
- 150000002009 diols Chemical class 0.000 claims abstract description 67
- 229920005862 polyol Polymers 0.000 claims abstract description 59
- 150000003077 polyols Chemical class 0.000 claims abstract description 58
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 51
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 47
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 29
- 150000004985 diamines Chemical class 0.000 claims abstract description 26
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000002649 leather substitute Substances 0.000 claims abstract description 23
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 239000010985 leather Substances 0.000 claims abstract description 19
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 19
- 229920000768 polyamine Polymers 0.000 claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 33
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 28
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 28
- -1 hydrocarbon diol Chemical class 0.000 claims description 26
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 18
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 17
- WJIOHMVWGVGWJW-UHFFFAOYSA-N 3-methyl-n-[4-[(3-methylpyrazole-1-carbonyl)amino]butyl]pyrazole-1-carboxamide Chemical compound N1=C(C)C=CN1C(=O)NCCCCNC(=O)N1N=C(C)C=C1 WJIOHMVWGVGWJW-UHFFFAOYSA-N 0.000 claims description 15
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims description 5
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 5
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 5
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 claims description 5
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 5
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 5
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 3
- FEUISMYEFPANSS-UHFFFAOYSA-N 2-methylcyclohexan-1-amine Chemical compound CC1CCCCC1N FEUISMYEFPANSS-UHFFFAOYSA-N 0.000 claims description 3
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 claims description 3
- HGINADPHJQTSKN-UHFFFAOYSA-M 3-ethoxy-3-oxopropanoate Chemical compound CCOC(=O)CC([O-])=O HGINADPHJQTSKN-UHFFFAOYSA-M 0.000 claims description 3
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 claims description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 3
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 claims description 3
- QRVSDVDFJFKYKA-UHFFFAOYSA-N dipropan-2-yl propanedioate Chemical compound CC(C)OC(=O)CC(=O)OC(C)C QRVSDVDFJFKYKA-UHFFFAOYSA-N 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 22
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000903 blocking effect Effects 0.000 description 12
- 239000012948 isocyanate Substances 0.000 description 11
- 150000002513 isocyanates Chemical class 0.000 description 11
- 150000002690 malonic acid derivatives Chemical class 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 6
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 238000004049 embossing Methods 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000582 polyisocyanurate Polymers 0.000 description 3
- 239000011495 polyisocyanurate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-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
- 229920000742 Cotton Polymers 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-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
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001621 bismuth Chemical class 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002433 hydrophilic molecules Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 239000006223 plastic coating Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000004729 acetoacetic acid derivatives Chemical class 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000005535 neodecanoate group Chemical class 0.000 description 1
- 125000005474 octanoate group Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8048—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8093—Compounds containing active methylene groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/82—Post-polymerisation treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
本发明涉及包含封闭型聚氨酯预聚物的单组分体系。本发明的主题是单组分体系,其包含a)至少一种聚氨酯预聚物,其基于至少一种二异氰酸酯和/或多异氰酸酯和至少一种二元醇和/或多元醇,其中至少一种二元醇或多元醇是具有900至2150g/mol的数均分子量的聚烷撑二醇,其中所有未转化的异氰酸酯基团用至少一种丙二酸酯封闭,和b)至少一种二胺和/或多胺;其生产方法、其用途和使用其生产人造皮革和(人造)皮革涂层的方法。
Description
技术领域
本发明涉及可用于生产人造皮革和(人造)皮革涂层的单组分体系及其生产方法。本发明进一步涉及所述单组分体系用于生产人造皮革或(人造)皮革涂层的用途,以及生产人造皮革或(人造)皮革涂层的方法。
背景技术
人造皮革是使用塑料生产的纺织品和其它柔性片状制品,其具有或不具有外层,其具有对应于使用目的的部分类似皮革的性质和/或表面构型(例如压花)。术语“人造皮革”在此特别应理解为是指包含至少一个载体层(例如由纸、棉或塑料,特别是聚酯制成)和至少一个平面附着(例如施加)的塑料涂层的皮革样材料。
相比之下,“(人造)皮革涂层”是可以施加到天然皮革或人造皮革上以实现人造皮革典型的特定性质的塑料涂层。
最近已经发现,基于与至少双官能醇和/或胺交联的聚氨酯预聚物的塑料实现由其制成的人造皮革和(人造)皮革涂层的特别有利的性质。聚氨酯预聚物在此应理解为是指具有至少一个氨基甲酸酯键并且可由不足的多元醇和过量的二异氰酸酯或多异氰酸酯生产的低聚或聚合的异氰酸酯封端反应产物。由于由二异氰酸酯或多异氰酸酯和多元醇组分生产的纯聚氨酯预聚物即使在室温下也会与所列举的交联剂反应,它们必须储存在分开的容器中。相关技术因此被称为双组分技术。
JP 2014-105250 A公开了一种氨基甲酸酯预聚物组合物,其含有由20-80重量%的羟基封端氨基甲酸酯预聚物和20-80重量%的无氨基甲酸酯基团的低聚物制成的含羟基的氨基甲酸酯预聚物。该组合物可用适当的交联剂作为双组分体系的成分加工产生人造皮革。
CN 102758359 A公开了一种基于双组分体系的生产聚氨酯泡沫涂层的方法,其中首先生产由聚氨酯组分A(多元醇或多胺)和聚氨酯组分B(基于二异氰酸酯的异氰酸酯单体或异氰酸酯和多元醇的预聚物)制成的下部泡沫层,随后在上部用含有水性聚氨酯和交联剂(脂族环氧树脂或多异氰酸酯)的水性聚氨酯组合物进行涂覆。该聚氨酯泡沫涂层可用作合成皮革。
JP 2006-316127 A公开了一种可固化的无溶剂氨基甲酸酯树脂组合物,其含有具有活性氢原子的化合物和多异氰酸酯,其中后者是二醇和二异氰酸酯的加合物。该组合物可用于生产人造皮革。
EP 3 514 189 A1公开了一种适用于生产人造皮革的双组分体系。多元醇组分基于二异氰酸酯和异氰脲酸酯与多元醇组分的反应产物。
由于双组分体系具有反应迅速的缺点,必须将两种组分分开储存。在一些情况下,设备中的固化可能也以不想要的方式发生。因此,开发出单组分体系,其中以化学可逆的方式封闭聚氨酯预聚物的异氰酸酯基团,以避免在室温下在加入交联剂时就已反应。用肟或内酰胺封闭异氰酸酯基团是现有技术中常规的。
例如,JP 2006-070059 A公开了一种由聚碳酸酯二醇和有机二异氰酸酯制成的聚氨酯预聚物,其适用于单组分体系并且随后封闭其异氰酸酯基团。该预聚物优选用酮肟或内酰胺封闭。
但是,用酮肟和内酰胺封闭的缺点尤其包括在解封闭过程中消去有毒副产物。
现有技术教导了替代性地用丙二酸酯封闭预聚物以解决这个问题。
DE 196 22 136 A1公开了一种用丙二酸酯封闭异氰酸酯-多元醇预聚物的方法。
DE 11 2005 001 991 T5公开了一种基于TDI和二醇的预聚物,其用丙二酸二乙酯封闭。
US 4,240,943 A公开了一种基于六亚甲基二异氰酸酯和聚酯二醇的氨基甲酸酯预聚物,其随后用丙二酸二乙酯封闭。
WO 2014/039306 A1公开了丙二酸二乙酯封闭的H12MDI-聚THF预聚物的生产。
EP 3 712 188 A1公开了多异氰酸酯组合物,其包含至少一种二异氰酸酯、数均分子量为400-5000且平均羟基数为3至8的多元醇,其可以已与可为丙二酸酯的封闭剂反应。
US 5,863,983公开了一种方法,其中(尤其磺酸酯封闭的多元醇)与异氰酸酯反应,随后用丙二酸酯进行封闭。
现有技术进一步教导了丙二酸酯封闭的预聚物与二元醇或多元醇的反应。
US 4,518,522 A公开了例如尤其由具有不同数均分子量的聚烷撑二醇和不同二异氰酸酯制成的预聚物。
DE 25 50 156 A1公开了可由分子量为62至大约300g的多羟基化合物和异氰酸酯并随后用例如丙二酸二乙酯封闭生产的封闭型多异氰酸酯的混合物。它们用于烘烤漆料并在此与具有至少两个对于异氰酸酯基团呈反应性的氢原子和大约400至大约50000g/mol的分子量的化合物反应。
EP 3 689 936 A1公开了可包含封闭型多异氰酸酯和多羟基化合物的涂料。封闭型多异氰酸酯可具有通过与亲水化合物反应形成的氨基甲酸酯单元。该亲水化合物可以是基于环氧乙烷的聚醚多元醇,其优选包含不多于30个环氧乙烷单元。
EP 53 766 A1公开了包含异氰酸酯和多元醇的预聚物的组合物,其用丙二酸酯封闭并用多元醇固化。其中描述的体系用于生产涂料。用胺固化在其中被认为是不利的。
现有技术进一步描述了用胺固化丙二酸酯封闭的预聚物。用胺固化在此具有可更快速和/或不用催化剂进行的优点。此外,适用于固化的典型二元醇和多元醇具有吸湿的缺点。
EP 3 348 593 A1公开了由二异氰酸酯和丙二酸酯制成的封闭型多异氰酸酯。多异氰酸酯可通过二异氰酸酯与二元至六元醇(例如三羟甲基丙烷)的反应生产。该说明书公开了所述封闭型多异氰酸酯在还可包含多胺的1K组合物中的用途。
US 5,071,937 A公开了包含异氰酸酯和分子量为400-10000g/mol的多元醇的丙二酸酯封闭型异氰酸酯预聚物和空间位阻芳族多胺的涂料组合物。还公开了它们与用于制备它们的多元醇一起用于生产可用于不同目的的涂料组合物的用途。但是,芳胺的使用是不利的--不仅考虑到潜在的健康危害,而且由于涂料的所得不利性质。
现有技术进一步公开了用胺固化基于聚醚和异氰酸酯的丙二酸酯封闭型预聚物。
US 4,439,593 A和US 4,677,180 A公开了包含异氰酸酯和多元醇的丙二酸酯封闭型预聚物的涂料组合物。多元醇是具有100-10000g/mol,优选400-8000g/mol或800-8000g/mol的数均分子量的化合物。该化合物优选是聚醚。该涂料组合物可进一步含有二胺,并用于各种目的。可用的胺尤其包括异佛尔酮二胺和4,4‘-二氨基二环己基甲烷。
EP 0 034 272公开了一种生产具有丝绒样表面的片状制品的方法,其使用包含封闭型NCO预聚物和多胺的涂料浆。该NCO预聚物可由分子量为500-10000,优选1000-6000的含羟基化合物和各种二异氰酸酯生产。优选使用平均分子量为1000-6000g/mol的聚环氧丙烷聚醚。也可以尤其用丙二酸酯进行封闭,但丁酮肟是优选的。
WO 2017/107064 A1公开了一种适用于生产或涂覆尤其皮革制品的组合物,其包含至少一种封闭型异氰酸酯封端的预聚物(由多元醇组分和异氰酸酯组分生产)和至少一种多胺。多元醇组分优选具有2000-8000g/mol,更优选2500-7000g/mol,非常特别优选3000-6500g/mol的数均分子量。其可以是聚醚多元醇。异氰酸酯组分可以是脂族或芳族多异氰酸酯。该预聚物尤其可以用丙二酸酯封闭。
但是,现有技术中描述的1K组合物无法生产具有足够好的性质的人造皮革和(人造)皮革涂层。迄今已知的1K组合物尤其无法与良好的弹性模量值一起实现足够好的拉伸强度和伸长率值。理想的是17-23N/mm2的拉伸强度、600-900重量%的伸长率值和在100%下2-4.5MPa、在200%下4-7MPA和在300%下5.5-10MPa的弹性模量值(所有值根据DIN ENISO 527测量)。
发明内容
因此本发明的目的是避免现有技术的缺点。本发明的目的尤其是提供单组分组合物,其在固化过程中没有消去有毒副产物,并且可用于生产具有良好性质的人造皮革和(人造)皮革涂层,特别是在上述参数如拉伸强度、伸长率和弹性模量方面。
通过根据本发明的单组分体系实现这一目的,其包含
a)至少一种聚氨酯预聚物,其基于至少一种二异氰酸酯和/或多异氰酸酯和至少一种二元醇和/或多元醇,其中至少一种二元醇或多元醇是具有900-2150g/mol的数均分子量的聚烷撑二醇,其中所述聚氨酯预聚物的所有未转化的异氰酸酯基团用至少一种丙二酸酯封闭,和
b)至少一种二胺和/或多胺。
a)聚氨酯预聚物
“基于”至少一种二异氰酸酯和/或多异氰酸酯和至少一种二元醇和/或多元醇的聚氨酯预聚物在此被理解为是指可由不足的至少一种二醇和/或至少一种多元醇和过量的至少一种二异氰酸酯和/或至少一种多异氰酸酯生产并具有至少两个氨基甲酸酯键(通过所述至少一种二元醇或多元醇的各自羟基与二异氰酸酯或多异氰酸酯的各自异氰酸酯基团的反应形成)的低聚或聚合的异氰酸酯封端反应产物,随后封闭其未转化的末端异氰酸酯基团。用所述至少一种丙二酸酯封闭(一个或多个)未转化的异氰酸酯基团通过使丙二酸酯的CH-酸性α位碳原子键合到所述(一个或多个)异氰酸酯基团的亲电碳原子上而进行。
二异氰酸酯/多异氰酸酯
该预聚物原则上基于一种或多种二异氰酸酯和/或多异氰酸酯。但是,当其基于一种二异氰酸酯或多异氰酸酯时,实现特别好的性质。术语“多异氰酸酯”在此被理解为是指具有至少三个异氰酸酯基团的化合物。
该预聚物原则上可基于至少一种二异氰酸酯和/或多异氰酸酯。但是,用至少一种二异氰酸酯或至少一种多异氰酸酯实现特别好的性质。该预聚物更优选基于一种二异氰酸酯或一种多异氰酸酯。其更优选基于一种二异氰酸酯。
该预聚物优选基于至少一种(环)脂族二异氰酸酯,即至少一种具有环状和/或脂族键合的异氰酸酯基团的二异氰酸酯。该预聚物更优选基于(环)脂族二异氰酸酯。基于芳族化合物(即非(环)脂族化合物)的体系导致不利的性质,尤其是在黄化方面。
更优选的是,所述至少一种二异氰酸酯选自HDI(六亚甲基二异氰酸酯)、TMDI(2,2,4-和2,4,4-三甲基六亚甲基二异氰酸酯的混合物)、H12MDI(4,4’-亚甲基-双-(环己基异氰酸酯))、IPDI(异佛尔酮二异氰酸酯)、TMXDI(邻四甲基苯二亚甲基二异氰酸酯、间四甲基苯二亚甲基二异氰酸酯、对四甲基苯二亚甲基二异氰酸酯或其混合物)、XDI(邻苯二亚甲基二异氰酸酯、间苯二亚甲基二异氰酸酯、对苯二亚甲基二异氰酸酯或其混合物)、MDI(2,2’-二苯甲烷二异氰酸酯、2,4’-二苯甲烷二异氰酸酯、4,4’-二苯甲烷二异氰酸酯或其混合物)、TDI(2,4-甲苯二异氰酸酯),再更优选的是,所述至少一种二异氰酸酯选自HDI、TMDI、H12MDI和IPDI。当所述二异氰酸酯选自HDI、TMDI、H1 2MDI、IPDI、TMXDI、XDI、MDI和TDI时,实现特别好的结果。当所述二异氰酸酯选自HDI、TMDI、H12MDI和IPDI(异佛尔酮二异氰酸酯)时,实现尤其好的结果。当二异氰酸酯是IPDI时,实现最佳结果。
该预聚物可基于至少一种多异氰酸酯。进一步优选的是,该预聚物基于至少一种,优选一种二异氰酸酯和至少一种,更优选一种多异氰酸酯。多异氰酸酯特别优选是衍生自IPDI、HDI、H12MDI或TDI的多异氰酸酯。特别优选的多异氰酸酯是相应的异氰脲酸酯,非常特别优选是IPDI和HDI的异氰脲酸酯。
基于二异氰酸酯和多异氰酸酯的总质量计,该预聚物优选基于0-40重量%,更优选0-30重量%,再更优选0-20重量%的多异氰酸酯。
二元醇/多元醇
该预聚物原则上基于一种二元醇或多种二元醇和/或一种多元醇或多种多元醇。但是,当其基于一种二元醇或多元醇或总共两种二元醇或多元醇时,实现特别好的性质。术语“多元醇”在此被理解为是指具有至少三个羟基的化合物。用至少一种二元醇实现特别好的性质。更优选的是,该预聚物基于一种或两种,更优选两种二元醇。再更优选的是,其基于80-100重量%的第一二元醇和0-20重量%的第二二元醇,其中重量数据基于二元醇的总质量计。该预聚物非常特别优选基于两种二元醇。再更优选的是,其基于80-99重量%,再更优选80-95重量%的第一二元醇和0.1-20重量%,再更优选5-20重量%的第二二元醇,其中重量数据基于二元醇的总质量计。
根据本发明,至少一种二元醇和/或多元醇是具有900至2150g/mol的数均分子量的聚烷撑二醇,其中通过根据DIN EN ISO 13885-1使用THF作为洗脱剂的GPC测定数均分子量。如果使用仅一种二元醇和/或多元醇,该预聚物因此仅基于具有900至2150g/mol的数均分子量的聚烷撑二醇作为二元醇或多元醇。
如果使用多于一种二元醇或多元醇,在聚氨酯预聚物的生产过程中,基于存在的其它二元醇和/或多元醇的总质量计,聚烷撑二醇的比例优选为至少50重量%,更优选至少60重量%,再更优选至少70重量%。优选的是,聚烷撑二醇是第一二元醇。
当聚烷撑二醇是聚四亚甲基醚二醇(聚THF)时,实现特别好的结果。再更优选的是,第一二元醇是聚四亚甲基醚二醇。
当聚四亚甲基醚二醇具有950-2100g/mol的数均分子量时,实现最佳结果。相应的优选商品是polyTHF1000、polyTHF1800和polyTHF2000(BASF)。数均分子量非常特别优选为950-1200g/mol。相应的非常特别优选的商品是polyTHF1000(BASF)。
如果该预聚物基于多于仅一种二元醇/多元醇,该预聚物的生产不仅使用聚烷撑二醇,而且还使用至少一种附加的,优选第二,二元醇或多元醇。该预聚物优选基于聚烷撑二醇和附加二元醇或多元醇。该预聚物再更优选基于聚烷撑二醇和第二二元醇。
为了实现良好性质,附加或第二二元醇选自
-羟基封端的聚酯二醇,特别是己二酸酯二醇、琥珀酸酯二醇和邻苯二甲酸酯二醇,优选具有500-3000g/mol,特别优选1000-2000g/mol的数均分子量,
-羟基封端的聚碳酸酯二醇,优选具有500-3000,更优选1000-2000g/mol的数均分子量,
-羟基封端的聚己内酯二醇,优选具有500-3000,更优选1000-2000g/mol的数均分子量和
-具有2至10个碳原子的烃二醇。
非常特别优选的是,该附加或第二二元醇是具有2至10个碳原子的烃二醇。更优选的是,该预聚物基于选自乙二醇、正丙二醇、异丙二醇、2-甲基-1,3-丙二醇、正丁二醇和正戊二醇、正己二醇、二乙二醇、1,4-环己烷二甲醇、三丙二醇和1,10-癸二醇的烃二醇。再更优选的是,该预聚物基于选自乙二醇、正丙二醇、异丙二醇、2-甲基-1,3-丙二醇、正丁二醇和正戊二醇、正己二醇的烃二醇。该预聚物特别优选基于正丁二醇。
该预聚物特别优选基于具有950-1200g/mol的数均分子量的聚四亚甲基醚二醇和正丁二醇。
丙二酸酯
由于在聚氨酯预聚物的生产中使用不足的二元醇或多元醇,所得中间体具有未转化的异氰酸酯基团。这些在聚氨酯预聚物的生产中用至少一种丙二酸酯封闭。在此,先前游离的异氰酸酯基团可以用丙二酸单烷基酯和丙二酸二烷基酯封闭。封闭优选用丙二酸酯进行。再更优选用选自丙二酸二甲酯、丙二酸二乙酯、丙二酸二异丙酯和丙二酸单乙酯的丙二酸酯进行封闭。非常特别优选的是,用丙二酸二乙酯进行封闭。
生产预聚物的方法
下面描述单组分体系中包含的聚氨酯预聚物的生产。其中a)使至少一种二元醇和/或多元醇与过量的至少一种二异氰酸酯和/或多异氰酸酯反应,和随后b)用至少一种丙二酸酯封闭未转化的异氰酸酯基团。
原则上可以使用一种或多种二异氰酸酯和/或多异氰酸酯。但是,当使用一种二异氰酸酯或多异氰酸酯时,实现特别好的性质。术语“多异氰酸酯”在此被理解为是指具有至少三个异氰酸酯基团的化合物。
原则上可以使用至少一种二异氰酸酯和/或多异氰酸酯。但是,用至少一种二异氰酸酯或至少一种多异氰酸酯实现特别好的性质。再更优选使用一种二异氰酸酯或多异氰酸酯。再更优选使用一种二异氰酸酯。
非常特别优选使用至少一种(环)脂族二异氰酸酯,即至少一种具有环状和/或脂族键合的异氰酸酯基团的二异氰酸酯。再更优选使用(环)脂族二异氰酸酯。基于芳族化合物的聚合物具有不利的性质,特别是在其后续应用中的黄化方面。
再更优选的是,所述至少一种二异氰酸酯选自HDI(六亚甲基二异氰酸酯)、TMDI(2,2,4-和2,4,4-三甲基六亚甲基二异氰酸酯的混合物)、H12MDI(4,4’-亚甲基-双-(环己基异氰酸酯))、IPDI(异佛尔酮二异氰酸酯)、TMXDI(邻四甲基苯二亚甲基二异氰酸酯、间四甲基苯二亚甲基二异氰酸酯、对四甲基苯二亚甲基二异氰酸酯或其混合物)、XDI(邻苯二亚甲基二异氰酸酯、间苯二亚甲基二异氰酸酯、对苯二亚甲基二异氰酸酯或其混合物)、MDI(2,2’-二苯甲烷二异氰酸酯、2,4’-二苯甲烷二异氰酸酯、4,4’-二苯甲烷二异氰酸酯或其混合物)、TDI(2,4-甲苯二异氰酸酯)。再更优选的是,所述至少一种二异氰酸酯选自HDI、TMDI、H12MDI和IPDI。当所述二异氰酸酯选自HDI、TMDI、H12MDI、IPDI、TMXDI、XDI、MDI和TDI时,实现特别好的结果。当所述二异氰酸酯选自HDI、TMDI、HMDI和IPDI时,实现非常特别好的结果。当二异氰酸酯是IPDI时,实现最佳结果。
该方法中也可使用至少一种多异氰酸酯。更优选的是,根据本发明的方法中使用至少一种,优选一种二异氰酸酯和至少一种,更优选一种多异氰酸酯。特别优选使用衍生自IPDI、HDI、H12MDI或TDI的多异氰酸酯。特别优选的多异氰酸酯是相应的异氰脲酸酯,非常特别优选是IPDI和HDI的异氰脲酸酯。
该方法优选使用基于二异氰酸酯和多异氰酸酯的总质量计0-40重量%,更优选0-30重量%,再更优选0-20重量%的多异氰酸酯。
除了所述至少一种二异氰酸酯和/或多异氰酸酯外,该方法还使用至少一种或多种二元醇和/或一种或多种多元醇。但是,当使用一种二元醇或多元醇或总共两种二醇或多元醇或二醇和多元醇的混合物时,实现特别好的性质。术语“多元醇”在此被理解为是指具有至少三个羟基的化合物。用至少一种二元醇实现特别好的性质。更优选使用一种至两种二元醇。非常特别优选使用两种二元醇。再更优选使用80-100重量%的第一二元醇和0-20重量%的第二二元醇,其中重量数据基于二元醇的总质量计。该预聚物非常特别优选基于两种二元醇。再更优选使用80-99.9重量%,再更优选80-95重量%的第一二元醇和0.1-20重量%,再更优选5-20重量%的第二二元醇,其中重量数据基于二元醇的总质量计。
至少一种二元醇和/或多元醇是具有900至2150g/mol的数均分子量的聚烷撑二醇,其中通过根据DIN EN ISO 13885-1使用THF作为洗脱剂的GPC测定数均分子量。
如果使用多于一种二元醇或多元醇,在聚氨酯预聚物的生产过程中,基于存在的其它二元醇和/或多元醇的总质量计,聚烷撑二醇的比例优选为至少50重量%,更优选至少60重量%,再更优选至少70重量%。
当聚烷撑二醇是聚四亚甲基醚二醇(聚THF)时,实现特别好的结果。聚四亚甲基醚二醇是更优选的。
当聚四亚甲基醚二醇具有950-2100g/mol的数均分子量时,实现最佳结果。相应的优选商品是polyTHF1000、polyTHF1800和polyTHF2000(BASF)。数均分子量非常特别优选为950-1200g/mol。相应的非常特别优选的商品是polyTHF1000(BASF)。
基于多于仅一种二元醇/多元醇的预聚物的生产不仅使用聚烷撑二醇,而且还使用至少一种附加的或第二二元醇或多元醇,优选附加的或第二二元醇。
为了实现所得预聚物的良好性质,附加或第二二元醇选自
-羟基封端的聚酯二醇,特别是己二酸酯二醇、琥珀酸酯二醇和邻苯二甲酸酯二醇,优选具有500-3000g/mol,特别优选1000-2000g/mol的数均分子量,
-羟基封端的聚碳酸酯二醇,优选具有500-3000,更优选1000-2000g/mol的数均分子量,
-羟基封端的聚己内酯二醇,优选具有500-3000,更优选1000-2000g/mol的数均分子量,
-具有2至10个碳原子的烃二醇。
该方法中特别优选使用具有2至10个碳原子的烃二醇作为附加或第二二元醇。
更优选使用选自乙二醇、正丙二醇、异丙二醇、2-甲基-1,3-丙二醇、正丁二醇和正戊二醇、正己二醇、二乙二醇、1,4-环己烷二甲醇、三丙二醇和1,10-癸二醇的烃二醇。再更优选使用选自乙二醇、正丙二醇、异丙二醇、2-甲基-1,3-丙二醇、正丁二醇和正戊二醇、正己二醇的烃二醇。特别优选使用正丁二醇。
该方法中特别优选使用两种二元醇,更确切地说具有800-1200g/mol的数均分子量的聚四亚甲基醚二醇和正丁二醇。
反应步骤a)可以优选在不存在溶剂的情况下和在40-80℃,优选50-70℃的温度下进行。更优选的是,反应步骤a)在催化剂存在下进行,因为这使得能够实现更快的反应时间和更低的粘度。优选的催化剂可以选自任选烷基取代的有机酸锡盐、锌盐和铋盐。非常特别优选的盐是锡、锌和铋的任选烷基取代的乙酸盐、月桂酸盐和硬脂酸盐。非常特别优选用二月桂酸二丁基锡或辛酸锌进行根据本发明的方法的反应步骤a)。
聚氨酯预聚物的生产中使用过量的二异氰酸酯或多异氰酸酯。所得中间体因此包含未转化的异氰酸酯基团。它们现在在反应步骤b)中用至少一种丙二酸酯封闭。先前游离的异氰酸酯基团在此既可以用丙二酸单烷基酯和丙二酸二烷基酯封闭。封闭优选用丙二酸酯进行。再更优选用选自丙二酸二甲酯、丙二酸二乙酯、丙二酸二异丙酯和丙二酸单乙酯的丙二酸酯进行封闭。非常特别优选的是,用丙二酸二乙酯进行封闭。
反应步骤b)可以优选在不存在溶剂的情况下和在60-100℃,优选70-90℃的温度下进行。更优选在催化剂存在下进行反应步骤b)。优选的催化剂可以选自任选烷基取代的有机酸锡盐、锌盐和铋盐。非常特别优选的盐是锡、锌和铋的任选烷基取代的乙酸盐、月桂酸盐、硬脂酸盐、辛酸盐、新癸酸盐、乙酰乙酸盐、草酸盐、己二酸盐和葡糖酸盐。非常特别优选用二月桂酸二丁基锡或辛酸锌进行根据本发明的方法的反应步骤a)。
步骤a)和b)中所用的催化剂可以相同或不同。步骤a)和b)优选使用相同的催化剂。
催化剂量优选为基于所有组分的总质量计0.1-10%,优选0.1-7%。
步骤a)中的反应非常特别优选在50-70℃的温度下在一小时内进行。非常特别优选进行步骤b)中的反应以在70-90℃下在最多一小时的窗口内加入丙二酸酯。典型反应时间为5-10小时。
特别优选的是,在根据本发明的方法中,在步骤a)中使由以下组分组成的混合物反应
5-50重量%的IPDI、H12MDI、TMDI或HDI,
0-30重量%的选自IPDI、H12MDI、TMDI或HDI的聚异氰脲酸酯,
5-90重量%的具有1000、1800或2000g/mol的数均分子量的聚四亚甲基醚二醇(对应于商品PolyTHF 100、PolyTHF1800和PolyTHF2000),
0-50重量%的丁二醇和
0.1-10重量%的辛酸锌。
在此,百分比数据基于组合物的总质量计。随后,优选地,可以加入
5-50重量%的丙二酸二乙酯(基于该组合物和丙二酸二乙酯的总质量计)
并进行步骤b)。
非常特别优选的是,在根据本发明的方法中,在步骤a)中使由以下组分组成的混合物反应
10-30重量%的IPDI、H12MDI、TMDI或HDI,
0-5重量%的选自IPDI、H12MDI、TMDI或HDI的聚异氰脲酸酯,
20-80重量%的具有1000、1800或2000g/mol的数均分子量的聚四亚甲基醚二醇,
0-20重量%的丁二醇和
0.1-7重量%的辛酸锌。
在此,百分比数据基于组合物的总质量计。随后,优选地,可以加入
5-25重量%的丙二酸二乙酯(基于该组合物和丙二酸二乙酯的总质量计)
并进行步骤b)。
再更优选的是,在根据本发明的方法中,在步骤a)中使由以下组分组成的混合物反应
10-30重量%的IPDI、H12MDI、TMDI或HDI,
1-5重量%的选自IPDI、H12MDI、TMDI或HDI的聚异氰脲酸酯,
20-80重量%的具有1000、1800或2000g/mol的数均分子量的聚四亚甲基醚二醇,
0-20重量%的丁二醇和
0.1-7重量%的辛酸锌。
在此,百分比数据基于组合物的总质量计。随后,优选地,可以加入
5-25重量%的丙二酸二乙酯(基于该组合物和丙二酸二乙酯的总质量计)
并进行步骤b)。
本发明的主题因此还是套装,其包含通过任一上述方法可获得的预聚物。
b)二胺/多胺
单组分体系包含至少一种二胺和/或多胺。二胺具有两个氨基。多胺具有三个或更多个氨基。其优选包含至少一种二胺。其非常特别优选包含一种二胺。再更优选的是,该二胺是(环)脂族胺或聚醚胺。
二胺优选选自异佛尔酮二胺(IPD)、4,4’-二氨基二环己基甲烷(PACM)、4,4’-亚甲基双(2-甲基环己胺)(DMDC)、2,2,4-和2,4,4-三甲基六亚甲基二胺(TMD)的混合物、己二胺(HDA)、1,3-双(氨基甲基)环己烷(1,3-BAC)和聚氧丙烯二胺。聚氧丙烯二胺优选是被称为D-230的聚氧丙烯二胺。该二胺因此可以优选选自异佛尔酮二胺(IPD)、4,4’-二氨基二环己基甲烷(PACM)、4,4’-亚甲基双(2-甲基环己胺)(DMDC)、2,2,4-和2,4,4-三甲基六亚甲基二胺(TMD)的混合物、己二胺(HDA)、1,3-双(氨基甲基)环己烷(1,3-BAC)和被称为D-230的聚氧丙烯二胺。
本发明的主题进一步是生产单组分体系的方法,其中相互混合至少一种聚氨酯预聚物和至少一种二胺和/或多胺,所述聚氨酯预聚物基于具有900至2150g/mol的数均分子量的聚烷撑二醇和任选附加二元醇和/或多元醇,其中所述聚氨酯预聚物的所有未转化的异氰酸酯基团用至少一种丙二酸酯封闭。
本发明的主题进一步是根据本发明的聚氨酯预聚物用于生产人造皮革或(人造)皮革涂层的用途。
本发明的主题进一步是生产人造皮革或(人造)皮革涂层的方法,其中使用根据本发明的单组分体系。该方法中特别优选使用含有正好一种二胺或多胺的单组分体系。非常特别优选使用含有一种二胺的体系。非常特别优选使用含有一种聚氨酯预聚物和一种二胺的体系。
优选进行生产人造皮革的方法,以将所述单组分体系施加到载体上并热固化。也可以在热固化过程中或之后提供用于表面构型的压花步骤。载体优选是纤维状载体,优选包含天然或人造纤维的载体。载体更优选是纸、棉或聚酯。
优选进行生产(人造)皮革涂层的方法,以将所述单组分体系施加到人造皮革或皮革块上并热固化。也可以在热固化过程中或之后提供用于表面构型的压花步骤。
由于聚氨酯预聚物在室温下不与单组分体系中的所述至少一种二胺和/或多胺反应,该体系可以储存。
具体实施方式
实施例:
1.预聚物的生产
最初用表1中示出的初始重量通过在0.1重量%DBTL存在下在60℃下在一小时内反应而生产异佛尔酮二异氰酸酯和聚THF的预聚物。
随后用表1中示出的丙二酸二乙酯(本发明的实施例)或己内酰胺/MEK肟(对比例)的初始重量通过在2.0重量%辛酸锌存在下在80℃下在8小时内反应而生产二异氰酸酯预聚物。
2.人造皮革生产
为了生产(人造)皮革涂层,将所得封闭型预聚物与二胺(PACM或异佛尔酮二胺)和附加组分以根据表1的初始重量在实验室混合装置中在40℃的温度和1200rpm的混合速度下混合。
用层施涂器将该物料施加到离型基底上,并在120℃至150℃的温度下固化,以提供(人造)皮革涂层。
所得涂层的试验结果概括在表2中。考虑到所实现的拉伸强度、伸长率和弹性模量的值,只有丙二酸酯封闭的预聚物产生最佳涂层。
表1
*=非本发明的对比例
IPDI:异佛尔酮二异氰酸酯,Evonik Industries AG
PolyTHF 1000:PolyTHF(摩尔质量1000g/mol),BASF
PolyTHF 650:PolyTHF(摩尔质量650g/mol),BASF
PolyTHF 3000:PolyTHF(摩尔质量3000g/mol),BASF
PACM:4,4’-二氨基二环己基甲烷,Evonik Industries AG
IPDA:异佛尔酮二胺,Evonik Industries AG
丙二酸二乙酯:Merck
MEK肟和乙酰丙酮:Merck
ε-己内酰胺:BASF
TIB Kat 218:TIB Chemicals
Coscat 83:
Borchikat 22和0761:Borchers
Tegoglide B1484:Evonik Industries AG
表2
测量参数 | 单位 | 1 | 2 | 3 | 4 | 5 | 6 | 7* | 8* | 9* |
层障度 | μm | 173 | 144 | 180 | 166 | 167 | 146 | 377 | 246 | 158 |
拉伸强度 | N/mm2 | 20.4 | 19.7 | 21.1 | 21.3 | 20.4 | 16.1 | 3.1 | 36.1 | 30.7 |
伸长率 | % | 879 | 751 | 884 | 593 | 409 | 1900 | 206 | 863 | 792 |
弹性模量100% | Mpa | 2.7 | 2.8 | 2.8 | 4.4 | 7.3 | 0.7 | 2.5 | 7.6 | 7.6 |
弹性模量200% | Mpa | 4.2 | 4.6 | 4.1 | 6.5 | 11.1 | 1.1 | 3.2 | 9.7 | 9.6 |
弹性模量300% | Mpa | 5.7 | 6.4 | 5.4 | 9.1 | 15.6 | 1.3 | 0.0 | 12.4 | 12.1 |
测量方法:
层厚度:DIN EN ISO 2360
拉伸强度、伸长率、弹性模量100%、弹性模量200%、弹性模量300%:DIN EN ISO527。
Claims (18)
1.单组分体系,其包含
a)至少一种聚氨酯预聚物,其基于至少一种二异氰酸酯和/或多异氰酸酯和至少一种二元醇和/或多元醇,
其中至少一种二元醇或多元醇是具有900至2150g/mol的数均分子量的聚烷撑二醇,其中所有未转化的异氰酸酯基团用至少一种丙二酸酯封闭,和
b)至少一种二胺和/或多胺。
2.根据权利要求1的单组分体系,
其特征在于
所述预聚物基于二异氰酸酯。
3.根据权利要求1或2的单组分体系,
其特征在于
所述二异氰酸酯或所述至少一种二异氰酸酯是(环)脂族二异氰酸酯。
4.根据前述权利要求任一项的单组分体系,
其特征在于
所述二异氰酸酯或所述至少一种二异氰酸酯选自HDI、TMDI、H12MDI、IPDI、TMXDI、XDI、MDI和TDI。
5.根据权利要求4的单组分体系,
其特征在于
所述二异氰酸酯或所述至少一种二异氰酸酯是IPDI。
6.根据前述权利要求任一项的单组分体系,
其特征在于
所述预聚物基于一种或两种,优选两种二元醇。
7.根据权利要求6的单组分体系,
其特征在于
所述预聚物基于80-100重量%的第一二元醇和0-20重量%的第二二元醇,其中重量数据基于二元醇的总质量计。
8.根据前述权利要求任一项的单组分体系,
其特征在于
所述聚烷撑二醇是聚四亚甲基醚二醇。
9.根据权利要求8的单组分体系
其特征在于
聚四亚甲基醚二醇的数均分子量为950-1200g/mol。
10.根据权利要求7-9任一项的单组分体系,
其特征在于
第二二元醇是具有2至10个碳原子的烃二醇。
11.根据权利要求10的单组分体系,
其特征在于
所述烃二醇选自乙二醇、正丙二醇、异丙二醇、2-甲基-1,3-丙二醇、正丁二醇、正戊二醇、正己二醇、二乙二醇、1,4-环己烷二甲醇、三丙二醇和1,10-癸二醇。
12.根据前述权利要求任一项的单组分体系,
其特征在于
所述至少一种丙二酸酯选自丙二酸二甲酯、丙二酸二乙酯、丙二酸二异丙酯和丙二酸单乙酯。
13.根据权利要求12的单组分体系,
其特征在于
所述丙二酸酯是丙二酸二乙酯。
14.根据前述权利要求任一项的单组分体系,
其特征在于
所述二胺/多胺是二胺并选自异佛尔酮二胺、4,4’-二氨基二环己基甲烷、4,4’-亚甲基双(2-甲基环己胺)、2,2,4-和2,4,4-三甲基六亚甲基二胺的混合物、己二胺、1,3-双(氨基甲基)环己烷和聚氧丙烯二胺。
15.根据前述权利要求任一项的单组分体系用于生产人造皮革或(人造)皮革涂层的用途。
16.生产根据权利要求1-14任一项的单组分体系的方法,其包括相互混合至少一种聚氨酯预聚物和至少一种二胺和/或多胺,所述聚氨酯预聚物基于具有900至2150g/mol的数均分子量的聚烷撑二醇和任选附加二元醇和/或多元醇,其中所述聚氨酯预聚物的所有未转化的异氰酸酯基团用至少一种丙二酸酯封闭。
17.生产人造皮革的方法,其中将根据权利要求1-14任一项的单组分体系施加到载体上并热固化。
18.生产(人造)皮革涂层的方法,其中将根据权利要求1-14任一项的单组分体系施加到人造皮革或皮革块上并热固化。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP22177717 | 2022-06-08 | ||
EP22177717.0 | 2022-06-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117186352A true CN117186352A (zh) | 2023-12-08 |
Family
ID=81984559
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310664545.1A Pending CN117186352A (zh) | 2022-06-08 | 2023-06-06 | 包含封闭型聚氨酯预聚物的单组分体系 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20230399539A1 (zh) |
EP (1) | EP4289878A1 (zh) |
JP (1) | JP2023180243A (zh) |
KR (1) | KR20230168980A (zh) |
CN (1) | CN117186352A (zh) |
TW (1) | TW202413471A (zh) |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2550156C2 (de) | 1975-11-07 | 1983-12-15 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Polyisocyanatgemischen mit blockierten Isocyanatgruppen und ihre Verwendung in Polyuretan-Einbrennlacken |
US4240943A (en) | 1978-02-27 | 1980-12-23 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Textile finishing composition |
DE3004327C2 (de) | 1980-02-06 | 1982-06-03 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Velourleder-Imitaten im Umkehrverfahren |
DE3046409A1 (de) | 1980-12-10 | 1982-07-15 | Bayer Ag, 5090 Leverkusen | Beschichtungsmittel und ein verfahren zur herstellung von ueberzuegen |
US4439593A (en) | 1983-05-26 | 1984-03-27 | Mobay Chemical Corporation | Polyurethane compositions with improved storage stability |
US4518522A (en) | 1983-09-19 | 1985-05-21 | Mobay Chemical Corporation | Blocked polyisocyanates with improved storage stability |
US4677180A (en) | 1986-07-16 | 1987-06-30 | Mobay Corporation | Polyurethane compositions with improved storage stability |
US5071937A (en) | 1987-12-22 | 1991-12-10 | Mobay Corporation | Coating compositions based on blocked polyisocyanates and sterically hindered aromatic polyamines |
US5789518A (en) | 1996-05-16 | 1998-08-04 | China Textile Institute | Method for aqueous polyurethane blocking reaction |
US5863983A (en) | 1997-08-25 | 1999-01-26 | China Textile Institute | Manufacturing method for blocked aqueous dispersion of polyurethanes |
JP4736378B2 (ja) | 2004-08-31 | 2011-07-27 | Dic株式会社 | 人工皮革または合成皮革 |
HU227574B1 (hu) | 2004-09-02 | 2011-08-29 | Polinvent Kft | Eljárás poliizocianát/polikovasav alapú poliaddíciós és hibrid mûgyanták elõállítására blokkolt poliizocianátok felhasználásával és az eljárásban felhasználható blokkolt poliizocianátok |
JP2006316127A (ja) | 2005-05-11 | 2006-11-24 | Achilles Corp | 無溶剤型硬化性ウレタン樹脂組成物及び該組成物を用いて得られるシート状物。 |
CN102758359B (zh) | 2012-07-06 | 2014-05-14 | 河南永合塑胶有限公司 | 一种基于直接涂层法的聚氨酯合成革清洁生产工艺 |
JP6302472B2 (ja) | 2012-09-07 | 2018-03-28 | ルブリゾル アドバンスド マテリアルズ, インコーポレイテッド | デジタルプリントのための布の前処理 |
JP5989518B2 (ja) | 2012-11-26 | 2016-09-07 | 大日精化工業株式会社 | 2液型塗工剤および合成擬革 |
EP3348593B1 (en) | 2015-09-11 | 2019-08-21 | Asahi Kasei Kabushiki Kaisha | Blocked polyisocyanate composition, one-component coating composition, coating film, and coated article |
CN108463521A (zh) | 2015-12-22 | 2018-08-28 | 科思创聚合物(中国)有限公司 | 用于纺织品的低溶剂涂料体系 |
US11661473B2 (en) | 2017-09-28 | 2023-05-30 | Asahi Kasei Kabushiki Kaisha | Blocked polyisocyanate composition and use thereof |
EP3514189B1 (de) | 2018-01-18 | 2023-07-26 | Evonik Operations GmbH | Lösemittel freies mehrkomponentensystem |
EP3712188B1 (en) | 2019-03-11 | 2022-05-11 | Asahi Kasei Kabushiki Kaisha | Polyisocyanate composition, blocked polyisocyanate composition, coating material composition, and coating film |
-
2023
- 2023-06-02 EP EP23177016.5A patent/EP4289878A1/de active Pending
- 2023-06-05 TW TW112120865A patent/TW202413471A/zh unknown
- 2023-06-06 CN CN202310664545.1A patent/CN117186352A/zh active Pending
- 2023-06-07 JP JP2023093764A patent/JP2023180243A/ja active Pending
- 2023-06-07 KR KR1020230072651A patent/KR20230168980A/ko unknown
- 2023-06-08 US US18/331,731 patent/US20230399539A1/en active Pending
Also Published As
Publication number | Publication date |
---|---|
TW202413471A (zh) | 2024-04-01 |
JP2023180243A (ja) | 2023-12-20 |
KR20230168980A (ko) | 2023-12-15 |
EP4289878A1 (de) | 2023-12-13 |
US20230399539A1 (en) | 2023-12-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10400144B2 (en) | Latent two-part polyurethane adhesives | |
US7691940B2 (en) | Aqueous polyurethane resin and method for producing aqueous polyurethane resin and film | |
CN1923804B (zh) | 含有异氰酸酯基团的加合物和在涂漆基材上具有有效粘合性的组合物 | |
CN101163728B (zh) | 异氰酸酯基封端的氨基甲酸酯预聚物、其制备方法和包括该氨基甲酸酯预聚物的粘合剂 | |
EP1578834B1 (en) | Polyurethane reactive composition | |
CN109476812B (zh) | 低硬度聚氨酯分散体 | |
US10745591B2 (en) | Method for adhesively bonding substrates using adhesives | |
US6515070B2 (en) | Low-temperature, heat-activated adhesives with high heat resistance properties | |
US5100995A (en) | Storage stable polyurethane adhesives | |
KR101116291B1 (ko) | 투습성이 우수한 무용제형 폴리우레탄 접착제의 제조방법 | |
KR101503098B1 (ko) | 수성 폴리우레탄 수지, 도막, 인공 또는 합성 피혁 | |
TW201920803A (zh) | 合成皮革之製造方法 | |
US11421129B2 (en) | Polyurethane urea-containing adipic acid dihydrazide coating where active hydrogens react with the glycidol epoxy group to form a diol | |
EP0745625A1 (en) | Aqueous polyurea dispersions with improved hardness and solvent resistance | |
CN117186352A (zh) | 包含封闭型聚氨酯预聚物的单组分体系 | |
JP4144245B2 (ja) | 湿気硬化型接着剤 | |
US20190359850A1 (en) | Low-solvent coating systems for textiles | |
EP1876197B1 (en) | Polyurethane reactive composition | |
JPH06145289A (ja) | 熱可塑性ポリウレタンポリ尿素及びその製造方法 | |
EP1632515A2 (en) | Polyurethane reactive composition | |
KR20240113226A (ko) | Uhmwpe 로프용 수계형 코팅수지 제조방법 | |
JP2021138937A (ja) | 印刷用プライマーおよび積層体 | |
US20140005329A1 (en) | Urethane Resin Adhesive Composition | |
JP4536249B2 (ja) | 熱硬化性ウレタン組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication |