US20010027242A1 - Low monomer content NCO prepolymers based on - Google Patents
Low monomer content NCO prepolymers based on Download PDFInfo
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- US20010027242A1 US20010027242A1 US09/819,662 US81966201A US2001027242A1 US 20010027242 A1 US20010027242 A1 US 20010027242A1 US 81966201 A US81966201 A US 81966201A US 2001027242 A1 US2001027242 A1 US 2001027242A1
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- Prior art keywords
- prepolymer
- nco
- diisocyanate
- monomer content
- catalyst
- Prior art date
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- Granted
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- 239000000178 monomer Substances 0.000 title claims abstract description 26
- MZEGJNMYXWIQFF-UHFFFAOYSA-N 2,5-diisocyanato-1,1,3-trimethylcyclohexane Chemical compound CC1CC(N=C=O)CC(C)(C)C1N=C=O MZEGJNMYXWIQFF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 5
- 229920005862 polyol Polymers 0.000 claims description 14
- 150000003077 polyols Chemical class 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 125000005442 diisocyanate group Chemical group 0.000 claims description 12
- -1 2-methylpentamethylene Chemical group 0.000 claims description 7
- 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 7
- 239000000203 mixture Substances 0.000 claims description 7
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 239000004970 Chain extender Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 150000001414 amino alcohols Chemical class 0.000 claims description 3
- 239000002981 blocking agent Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 238000013008 moisture curing Methods 0.000 claims description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 150000003623 transition metal compounds Chemical class 0.000 claims description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 claims description 2
- AZAATSCSAHQERB-UHFFFAOYSA-N 3,5-dimethylpyrazole Chemical compound CC1=CC(C)=N[N]1 AZAATSCSAHQERB-UHFFFAOYSA-N 0.000 claims 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002917 oxazolidines Chemical class 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000526 short-path distillation Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- C08G18/28—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
- C08G18/08—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
- C08G18/70—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
Definitions
- the invention relates to low-monomer containing, NCO-containing prepolymers (hereinafter NCO prepolymers) based on 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), to a process for their preparation, and to their use.
- NCO prepolymers low-monomer containing, NCO-containing prepolymers based on 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI)
- Aliphatic and cycloaliphatic diisocyanates are widely employed in high-grade light-and weather-stable polyurethane coatings.
- Isophorone diisocyanate (IPDI) is selective owing to the different steric environment of the two isocyanate groups, but prepolymerization under identical conditions leads to relatively low monomer contents. In both cases, the monomer content may be lowered by means of a technically complex short-path (flash) distillation.
- the object was to find NCO prepolymers having a very low monomer content and being suitable, moreover, for use directly, without a distillation process for the purpose of removing the monomers.
- TCDI 1,4-diisocyanato-2,2,6-trimethylcyclohexane
- the invention provides for a low-monomer containing, NCO-containing prepolymer based on 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI) and polyol, having a residual monomer content of less than 1.0% by weight, obtainable by reacting a diisocyanate component comprising 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI) and at least one at least difunctional polyol in an NCO/OH ratio of 2-1.5:1 in the presence of at least one catalyst at 20-100° C.
- TMCDI 1,4-diisocyanato-2,2,6-trimethylcyclohexane
- the invention likewise provides a process for preparing NCO-containing prepolymers based on TMCDI and polyols, having a residual monomer content of less than 1.0% by weight, by reacting TMCDI and at least one polyol in an NCO/OH ratio of 2-1.5:1 in the presence of at least one catalyst at 20-100° C.
- TMCDI Trimethacrylate-maleic acid copolymer
- TMCDI Trimethacrylate-maleic anhydride copolymer
- the monomer content of the prepolymer prepared in this way is below 1.0% by weight, usually below 0.5% by weight, and therefore does not require labeling as hazardous to health.
- the residual monomer content of the prepolymer describes the content of diisocyanate monomer.
- TMCDI may be used alone as the isocyanate component or in combination with other diisocyanates.
- diisocyanates suitable for mixing with TMCDI are hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4′-methylenebis(cyclohexyl isocyanate) (HMDI), 2-methylpentamethylene 1,5-diisocyanate (MPDI), trimethylhexamethylene 1,6-diisocyanate (TMDI), or m-tetramethylxylylene diisocyanate (TMXDI).
- HDI hexamethylene diisocyanate
- IPDI isophorone diisocyanate
- HMDI 4,4′-methylenebis(cyclohexyl isocyanate)
- MPDI 2-methylpentamethylene 1,5-diisocyanate
- TMDI trimethylhexamethylene 1,6-diisocyanate
- TMXDI
- the polyols used for preparing the prepolymers of the invention are preferably polyesters, polyethers, polyacrylates, polycaprolactones, polycarbonates or polyurethanes or mixtures thereof having a preferred OH functionality of 2-6.
- Catalysts that are suitable for the reaction are customary in commerce and are based, generally, on metal compounds or transition metal compounds based on aluminum, tin, zinc, titanium, manganese, bismuth, or zirconium, such as dibutyltin dilaurate, zinc octoate, titanium tetrabutylate or zirconium octoate, for example, or else tertiary amines such as 1,4diazobicylo[2.2.2]octane, for example.
- the prepolymers of the invention may also comprise chain extenders, such as low molecular mass polyhydric alcohols or amino alcohols, for example.
- the NCO-containing prepolymers of the invention may also be blocked using conventional blocking agents such as methyl ethyl ketoxime, e-caprolactam, diethyl malonate, ethyl acetoacetate, b 3 , 5 -dimethylpyrazole, and diisopropyl-amine, for example, and used in heat-curing one-component formulations.
- conventional blocking agents such as methyl ethyl ketoxime, e-caprolactam, diethyl malonate, ethyl acetoacetate, b 3 , 5 -dimethylpyrazole, and diisopropyl-amine, for example, and used in heat-curing one-component formulations.
- the invention additionally provides a process for preparing NCO-containing prepolymers based on TMCDI and polyols, having a residual monomer content of less than 1.0% by weight, by reacting TMCDI and at least one at least difunctional polyol in an NCO/OH ratio of 2-1.5:1 in the presence of at least one catalyst at 20-100° C.
- the invention also provides for the use of the prepolymers in moisture-curing coating systems.
- the low-monomer NCO prepolymers of the invention may be cured with moisture at room temperature, either directly or, for the purpose of increasing the reaction rate, with the addition of polyketimines or oxazolidines.
- Curing may be accelerated using the catalysts known in the chemistry of isocyanates, examples being tertiary amines, such as 1,4-diazabicyclo[2.2.2]octane, triethylamine, etc., and/or metal salts such as zinc chloride, dibutyltin dilaurate, etc.
- tertiary amines such as 1,4-diazabicyclo[2.2.2]octane, triethylamine, etc.
- metal salts such as zinc chloride, dibutyltin dilaurate, etc.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Low-monomer, NCO-containing prepolymers based on 1,4-diisocyanato-2,2,6-trimethylcyclohexane, a process for their preparation, and their use.
Description
- 1. Field of the Invention
- The invention relates to low-monomer containing, NCO-containing prepolymers (hereinafter NCO prepolymers) based on 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), to a process for their preparation, and to their use.
- 2. Discussion of the Background
- Aliphatic and cycloaliphatic diisocyanates are widely employed in high-grade light-and weather-stable polyurethane coatings. For many applications, such as for prepolymer formation, it is advantageous if the two isocyanate groups have different reactivities. This so-called selectivity reduces the proportion of unwanted monomers, and the resulting products have lower viscosities and improved technical processability.
- Hexamethylene diisocyanate (HDI) exhibits no selectivity whatsoever and so the corresponding NCO prepolymers have a high proportion of unwanted, toxicologically objectionable monomers. Isophorone diisocyanate (IPDI), on the other hand, is selective owing to the different steric environment of the two isocyanate groups, but prepolymerization under identical conditions leads to relatively low monomer contents. In both cases, the monomer content may be lowered by means of a technically complex short-path (flash) distillation.
- The object was to find NCO prepolymers having a very low monomer content and being suitable, moreover, for use directly, without a distillation process for the purpose of removing the monomers.
- It has surprisingly been found that 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), a readily available cycloaliphatic diisocyanate (J. Appl. Polym. Sci. 1994, 54(2), 207-218; EP 0945427 A1) is particularly suitable for use in NCO prepolymers. Without any complex short-path distillation, the residual monomer content is distinctly lower than in the case of prepolymers based on IPDI.
- The invention provides for a low-monomer containing, NCO-containing prepolymer based on 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI) and polyol, having a residual monomer content of less than 1.0% by weight, obtainable by reacting a diisocyanate component comprising 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI) and at least one at least difunctional polyol in an NCO/OH ratio of 2-1.5:1 in the presence of at least one catalyst at 20-100° C.
- The invention likewise provides a process for preparing NCO-containing prepolymers based on TMCDI and polyols, having a residual monomer content of less than 1.0% by weight, by reacting TMCDI and at least one polyol in an NCO/OH ratio of 2-1.5:1 in the presence of at least one catalyst at 20-100° C.
- For the preparation of the low-monomer content, NCO prepolymers of the invention, TMCDI may be introduced as an initial charge, alone or in a mixture with other aliphatic or cycloaliphatic diisocyanates, and an at least difunctional polyol is added. The NCO/OH ratio is between 2:1 and 1.5:1. Generally, the reaction takes place in the presence of a catalyst at 20-100°C. In addition to the polymeric polyols, it is also possible to use chain extenders, such as low molecular weight polyhydric alcohols or amino alcohols, for example. The monomer content of the prepolymer prepared in this way is below 1.0% by weight, usually below 0.5% by weight, and therefore does not require labeling as hazardous to health. Within the context of the present invention, the residual monomer content of the prepolymer describes the content of diisocyanate monomer.
- TMCDI may be used alone as the isocyanate component or in combination with other diisocyanates. Examples of diisocyanates suitable for mixing with TMCDI are hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4′-methylenebis(cyclohexyl isocyanate) (HMDI), 2-methylpentamethylene 1,5-diisocyanate (MPDI), trimethylhexamethylene 1,6-diisocyanate (TMDI), or m-tetramethylxylylene diisocyanate (TMXDI). Preferably TMCDI comprises >25 wt %, more preferably >50 wt %, even more preferably >75 wt % of the isocyanate component.
- The polyols used for preparing the prepolymers of the invention are preferably polyesters, polyethers, polyacrylates, polycaprolactones, polycarbonates or polyurethanes or mixtures thereof having a preferred OH functionality of 2-6.
- Catalysts that are suitable for the reaction are customary in commerce and are based, generally, on metal compounds or transition metal compounds based on aluminum, tin, zinc, titanium, manganese, bismuth, or zirconium, such as dibutyltin dilaurate, zinc octoate, titanium tetrabutylate or zirconium octoate, for example, or else tertiary amines such as 1,4diazobicylo[2.2.2]octane, for example.
- The prepolymers of the invention may also comprise chain extenders, such as low molecular mass polyhydric alcohols or amino alcohols, for example.
- Moreover, the NCO-containing prepolymers of the invention may also be blocked using conventional blocking agents such as methyl ethyl ketoxime, e-caprolactam, diethyl malonate, ethyl acetoacetate, b 3,5-dimethylpyrazole, and diisopropyl-amine, for example, and used in heat-curing one-component formulations.
- The invention additionally provides a process for preparing NCO-containing prepolymers based on TMCDI and polyols, having a residual monomer content of less than 1.0% by weight, by reacting TMCDI and at least one at least difunctional polyol in an NCO/OH ratio of 2-1.5:1 in the presence of at least one catalyst at 20-100° C.
- The invention also provides for the use of the prepolymers in moisture-curing coating systems.
- The low-monomer NCO prepolymers of the invention may be cured with moisture at room temperature, either directly or, for the purpose of increasing the reaction rate, with the addition of polyketimines or oxazolidines.
- Curing may be accelerated using the catalysts known in the chemistry of isocyanates, examples being tertiary amines, such as 1,4-diazabicyclo[2.2.2]octane, triethylamine, etc., and/or metal salts such as zinc chloride, dibutyltin dilaurate, etc.
- Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified. The example which follows is intended to illustrate, but not restrict, the invention:
- 281 g (1.35 mol) of 1,4-diisocyanato-2,2,6-trimethylcyclohexane and 0.1 g of DBTL were introduced into a reaction vessel and heated to 40° C. At this temperature, 719 g of a polytetramethylene glycol (TERATHANE 1000, OHN: 116, Du Pont) were added dropwise with stirring and under inert gas (NCO/OH=1.8:1). Three hours after dropwise addition, the NCO content was 5.03% (theoretical: 5.04%). The viscosity was 15 Pas and the monomer content was 0.13% by weight (GC).
- b 294 g (1.32 mol) of isophorone diisocyanate (VESTANAT IPDI, Degussa-Hüls AG) and 0.1 g of DBTL were introduced into a reaction vessel and heated to 40° C. At this temperature, 706 g of a polytetramethylene glycol (TERATHANE 1000, OHN: 116, Du Pont) were added dropwise with stirring and under inert gas (NCO/OH=1.8:1). Three hours after dropwise addition, the NCO content was 4.70% (theoretical: 4.90%). The viscosity was 33 Pas and the monomer content was 2.3% by weight (GC).
- This application is based on German patent application 10015891.9 filed in the German Patent Office on Mar. 20, 2000, the entire contents of which are hereby incorporated by reference.
Claims (14)
1. An NCO-containing prepolymer obtained by reacting a diisocyanate component comprising 1,4-diisocyanato-2,2,6-trimethylcyclohexane and at least one at least difunctional polyol in an NCO/OH ratio of 2-1.5:1 in the presence of at least one catalyst at 20-100° C., wherein said prepolymer has a residual monomer content of less than 1.0% by weight.
2. The prepolymer of , wherein said residual monomer content is less than 0.5% by weight.
claim 1
3. The prepolymer of , wherein said diisocyanate component further comprises a diisocyanate selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, trimethylhexamethylene 1,6-diisocyanate, m-tetramethylxylylene diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 2-methylpentamethylene 1,5-diisocyanate and a mixture thereof.
claim 1
4. The prepolymer of , wherein said polyol is selected from the group consisting of polyesters, polyethers, polycaprolactones, polyacrylates, polycarbonates, polyurethanes and a mixture thereof.
claim 1
5. The prepolymer of , wherein said catalyst is selected from the group consisting of tertiary amines, metal compounds and transition metal compounds based on aluminum, tin, zinc, titanium, manganese, bismuth, or zirconium.
claim 1
6. The prepolymer of , wherein said catalyst is selected from the group consisting of dibutyltin dilaurate, zinc octoate, titanium tetrabutylate, zirconium octoate, 1,4-diazabicyclo[2.2.2]octane and a mixture thereof.
claim 1
7. The prepolymer of , which further comprises chain extenders.
claim 1
8. The prepolymer of , wherein said chain extenders present comprise low molecular mass polyhydric alcohols or amino alcohols.
claim 7
9. The prepolymer of , obtained by further reacting a blocking agent.
claim 1
10. The prepolymer of , wherein said blocking agent is selected from the group consisting of MEK oxime, ε-caprolactam, diethyl malonate, ethyl acetoacetate, 1,2,4-triazole,3,5-dimethylpyrazole, diisopropylamine and a mixture thereof.
claim 9
11. A process for preparing an NCO-containing prepolymer comprising reacting 1,4-diisocyanato-2,2,6-trimethylcyclohexane and at least one at least difunctional polyol in an NCO/OH ratio of 2-1.5:1 in the presence of at least one catalyst at 20-100° C., wherein said prepolymer has a residual monomer content of less than 1.0% by weight.
12. The process of , wherein said process does not comprise a distillation step of the said NCO-containing prepolymer.
claim 11
13. A moisture-curing coating system comprising an NCO-containing prepolymer obtained by reacting a diisocyanate component comprising 1,4-diisocyanato-2,2,6-trimethylcyclohexane and at least one at least difunctional polyol in an NCO/OH ratio of 2-1.5:1 in the presence of at least one catalyst at 20-100° C., wherein said prepolymer has a residual monomer content of less than 1.0% by weight.
14. A method of coating comprising applying to a surface in need thereof, an NCO-containing prepolymer obtained by reacting a diisocyanate component comprising 1,4-diisocyanato-2,2,6-trimethylcyclohexane and at least one at least difunctional polyol in an NCO/OH ratio of 2-1.5:1 in the presence of at least one catalyst at 20-100° C., wherein said prepolymer has a residual monomer content of less than 1.0% by weight.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10015891.9 | 2000-03-30 | ||
| DE10015891 | 2000-03-30 | ||
| DE10015891A DE10015891A1 (en) | 2000-03-30 | 2000-03-30 | Low-monomer NCO-containing prepolymers based on 1,4-diisocyanato-2,2,6-trimethylcyclohexane, a process for their preparation, and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| US20010027242A1 true US20010027242A1 (en) | 2001-10-04 |
| US6417313B2 US6417313B2 (en) | 2002-07-09 |
Family
ID=7637019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/819,662 Expired - Fee Related US6417313B2 (en) | 2000-03-30 | 2001-03-29 | Low monomer content NCO prepolymers based on 1,4-diisocyanato-2,2,6-trimethylcyclohexane, a process for their preparation, and use |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6417313B2 (en) |
| EP (1) | EP1138707A1 (en) |
| JP (1) | JP2001278935A (en) |
| DE (1) | DE10015891A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030120019A1 (en) * | 2001-12-14 | 2003-06-26 | Steffen Hofacker | NCO prepolymers prepared from isophorone diisocyanate and having a low monomer content |
| US20050020798A1 (en) * | 2001-11-27 | 2005-01-27 | Thomas Bartz | Method for producing prepolymers containing isocyanate groups and urethane groups |
| CN112876646A (en) * | 2021-01-15 | 2021-06-01 | 华峰集团有限公司 | Modified chain extender and preparation method and application thereof |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1604926A (en) * | 2001-12-18 | 2005-04-06 | 汉高两合股份公司 | Method for producing polyurethane prepolymers having a low content of monomers |
| DE10163857A1 (en) * | 2001-12-22 | 2003-07-10 | Henkel Kgaa | Reactive polyurethanes with a low content of monomeric diisocyanates |
| DE102004048775A1 (en) * | 2004-10-07 | 2006-04-13 | Degussa Ag | Highly reactive uretdione group-containing polyurethane compositions |
| DE102005035000A1 (en) * | 2005-07-22 | 2007-01-25 | Basf Ag | Isocyanate group-containing prepolymers |
| US8147965B2 (en) | 2008-05-14 | 2012-04-03 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing thermoplastic polyurethane |
| US8889945B2 (en) | 2010-12-08 | 2014-11-18 | Kimberly-Clark Worldwide, Inc. | Elastic film containing a renewable starch polymer |
| US10695235B2 (en) | 2013-11-27 | 2020-06-30 | Kimberly-Clark Worldwide, Inc. | Printed 3D-elastic laminates |
| US9913764B2 (en) | 2013-12-18 | 2018-03-13 | Kimberly-Clark Worldwide, Inc. | Post-bonded grooved elastic materials |
| EP3401344B1 (en) | 2017-05-09 | 2020-04-08 | Evonik Operations GmbH | Method for the preparation of trimers and/or oligomers of diisocyanates |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2221756C3 (en) * | 1972-05-04 | 1980-06-26 | Bayer Ag, 5090 Leverkusen | Process for the production of solvent-resistant, lightfast, kink and friction-resistant polyurethane coatings on textile substrates, leather or synthetic leather or foils |
| DE3108953A1 (en) * | 1981-03-10 | 1982-09-30 | Herberts Gmbh, 5600 Wuppertal | HEAT-CURABLE COATING MEASURES, THEIR USE AND METHOD FOR COATING SUBSTRATES |
| DE3216567A1 (en) * | 1982-05-04 | 1983-11-10 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING AQUEOUS DISPERSIONS OF POLYURETHANES HAVING CHEMICAL FIXED CARBOXYLATE AND / OR SULFONATE GROUPS |
| DE19812613A1 (en) * | 1998-03-23 | 1999-09-30 | Bayer Ag | New cycloaliphatic polymer building blocks |
-
2000
- 2000-03-30 DE DE10015891A patent/DE10015891A1/en not_active Withdrawn
-
2001
- 2001-02-03 EP EP01102471A patent/EP1138707A1/en not_active Withdrawn
- 2001-03-27 JP JP2001090539A patent/JP2001278935A/en active Pending
- 2001-03-29 US US09/819,662 patent/US6417313B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050020798A1 (en) * | 2001-11-27 | 2005-01-27 | Thomas Bartz | Method for producing prepolymers containing isocyanate groups and urethane groups |
| US20030120019A1 (en) * | 2001-12-14 | 2003-06-26 | Steffen Hofacker | NCO prepolymers prepared from isophorone diisocyanate and having a low monomer content |
| US6825376B2 (en) | 2001-12-14 | 2004-11-30 | Bayer Aktiengesellschaft | NCO prepolymers prepared from isophorone diisocyanate and having a low monomer content |
| CN112876646A (en) * | 2021-01-15 | 2021-06-01 | 华峰集团有限公司 | Modified chain extender and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001278935A (en) | 2001-10-10 |
| DE10015891A1 (en) | 2001-10-11 |
| US6417313B2 (en) | 2002-07-09 |
| EP1138707A1 (en) | 2001-10-04 |
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