DE2708611A1 - Blocked carboxy gp. contg. polyurethane prepolymer prepn. - by reacting a poly:isocyanate, a hydroxy acid and a blocking agent - Google Patents
Blocked carboxy gp. contg. polyurethane prepolymer prepn. - by reacting a poly:isocyanate, a hydroxy acid and a blocking agentInfo
- Publication number
- DE2708611A1 DE2708611A1 DE19772708611 DE2708611A DE2708611A1 DE 2708611 A1 DE2708611 A1 DE 2708611A1 DE 19772708611 DE19772708611 DE 19772708611 DE 2708611 A DE2708611 A DE 2708611A DE 2708611 A1 DE2708611 A1 DE 2708611A1
- Authority
- DE
- Germany
- Prior art keywords
- water
- parts
- isocyanate
- groups
- prepolymer
- 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 33
- 229920001730 Moisture cure polyurethane Polymers 0.000 title claims abstract description 21
- 239000012948 isocyanate Substances 0.000 title claims abstract description 14
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 14
- 150000001261 hydroxy acids Chemical class 0.000 title description 2
- 239000002981 blocking agent Substances 0.000 title 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 239000003973 paint Substances 0.000 claims abstract description 14
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 229920002635 polyurethane Polymers 0.000 claims abstract description 6
- 239000004814 polyurethane Substances 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000004922 lacquer Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- -1 glycol ethers Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 150000001414 amino alcohols Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims 2
- 239000012895 dilution Substances 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 16
- 239000006185 dispersion Substances 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 13
- 239000004925 Acrylic resin Substances 0.000 description 8
- 229920000178 Acrylic resin Polymers 0.000 description 8
- 229920001225 polyester resin Polymers 0.000 description 8
- 239000004645 polyester resin Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229920006389 polyphenyl polymer Polymers 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- VLNDSAWYJSNKOU-UHFFFAOYSA-N 1-isocyanato-4-[(4-isocyanato-3-methylcyclohexyl)methyl]-2-methylcyclohexane Chemical compound C1CC(N=C=O)C(C)CC1CC1CC(C)C(N=C=O)CC1 VLNDSAWYJSNKOU-UHFFFAOYSA-N 0.000 description 1
- LYDHLGJJJAWBDY-UHFFFAOYSA-N 1-isocyanato-4-[2-(4-isocyanatocyclohexyl)propan-2-yl]cyclohexane Chemical compound C1CC(N=C=O)CCC1C(C)(C)C1CCC(N=C=O)CC1 LYDHLGJJJAWBDY-UHFFFAOYSA-N 0.000 description 1
- HODFXOIYAQPWHD-UHFFFAOYSA-N 2,4-bis(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC=C(O)C(CC(C)C)=C1 HODFXOIYAQPWHD-UHFFFAOYSA-N 0.000 description 1
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- VKOUCJUTMGHNOR-UHFFFAOYSA-N Diphenolic acid Chemical compound C=1C=C(O)C=CC=1C(CCC(O)=O)(C)C1=CC=C(O)C=C1 VKOUCJUTMGHNOR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 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 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N mandelic acid Chemical compound OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000008096 xylene Substances 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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
-
- 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
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
Verfahren zur Herstellung von carboxylgruppenhaltigen Poly-Process for the production of carboxyl-containing poly
urethan-PrSpolymeren mit verkappten Isocyanatgruppen.urethane prepolymers with blocked isocyanate groups.
Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Herstellen von carboxylgruppenhaltigen Polyurethan-Präpoly meren mit verkappten Isocyanatgruppen, die bei erhUhter Temperatur mit Hydroxy- oder Epoxyverbindungen zu Polyurethanen umgesetzt werden können.The present invention relates to a method of production of carboxyl-containing polyurethane prepolymers with blocked isocyanate groups, those at elevated temperature with hydroxyl or epoxy compounds to form polyurethanes can be implemented.
In der deutschen Patentschrift 895 527 ist ein Verfahren zur Herstellung von Urethan- und gegebenenfalls CarbonsSureestergruppen enthaltenden Bindemitteln beschrieben, die ausser mit Isocyanatgruppen reaktionsfAhigen Wasserstoffatomen verkappte Isocyanatgruppen enthalten. Zum Verkappen der Isocyanatgruppen werden Alkohole, insbesondere verzweigte Alkohole, Phenole, Malonester und Acetessigesterverwendet. Die Produkte sind insbesondere als Lackbindemittel geeignet, und werden, soweit sie als solche verwendet werden, ausschliesslich aus LMsungen aufgetragen. Beim Erhitzen daraus hergestellter Lackfilme wird das Isocyanatverkappungsmittel, also z.B. der Alkohol, das Phenol usw., unter Ruckbildung freier Isocyanatgruppen abgespalten, und die so freigesetzten Isocyanatgruppen reagieren alsdann mit den reaktionsfähigen Wasserstoffatomen, wobei Vernetzung und damit Aushärtung der Lackfilme eintritt.In the German patent specification 895 527 is a method for production of binders containing urethane and optionally carboxylic acid ester groups described the hydrogen atoms which are reactive with isocyanate groups contain blocked isocyanate groups. Used to cap the isocyanate groups Alcohols, particularly branched alcohols, phenols, malonic esters and acetoacetic esters are used. The products are particularly suitable as paint binders and, if they are used as such, applied exclusively from solvent solutions. At the The isocyanate capping agent, ie E.g. the alcohol, the phenol, etc., are split off with reformation of free isocyanate groups, and the isocyanate groups released in this way then react with the reactive ones Hydrogen atoms, with crosslinking and thus hardening of the paint films.
In der deutschen Offenlegungsschrift 2 047 718 sind Urethan-und gegebenenfalls Carbonsäureestergruppen enthaltende Lackbindemittel beschrieben, die ausser mit Isocyanatgruppen reaktionsfShigen Wasserstoffatomen mit E-Caprolactam verkappte Isocyanatgruppen enthalten und die durch Erhitzen:auf Temperaturen oberhalb etwa 1400C, vorzugsweise.1700C bis 2100C vernetzen.In the German Offenlegungsschrift 2 047 718 are urethane and optionally Lacquer binders containing carboxylic acid ester groups described, except with Isocyanate groups blocked hydrogen atoms with E-caprolactam Contain isocyanate groups and that by heating: to temperatures above about 1400C, preferably 1700C to 2100C.
Die beschriebenen Lackbindemittel beziehen sich Jedoch nur auf Systeme, die als Pulverlacke Verwendung finden.However, the paint binders described only relate to systems which are used as powder coatings.
Demgegenüber sind die nach dem erfindungsgemässen Verfahren erhältlichen carboxylgruppenhaltigen Polyurethan-P'rffpolymere auch und insbesondere zur Verwendung in wasserlöslichen, wasserdispergierbaren bzw. in organischen Lösungsmitteln löslichen, wärmevernetzenden Lacken geeignet.In contrast, those obtainable by the process according to the invention are available carboxyl group-containing polyurethane prepolymers also and in particular for use in water-soluble, water-dispersible or soluble in organic solvents, suitable for heat-curing lacquers.
Das erfindungsgemässe Verfahren zum Herstellen von carboxylgruppenhaltigen Polyurethan-Präpolymeren mit verkappten Isocyanatgruppen, die bei erhöhter Temperatur mit Hydroxy- oder Epoxyverbindungen zu Polyurethanen umgesetzt werden können, ist dadurch gekennzeichnet, dass man ein mindestens difunktionelles Isocyanat mit einer Hydroxycarbonsäure und einer weiteren aktiven Wasserstoff enthaltenden und zur Umsetzung mit einer Isocyanatgruppe befähigten Verbindung umsetzt nach dem Schema: (MCONH)x-R1-(NHCOO)y-R2-(COOH)n wobei M-H eine aktiven Wasserstoff enthaltende, zur Reaktion mit einem Isocyanat befllhigte Verbindung ist, R1 und R2 gleiche oder verschiedene aliphatische, cycloaliphatische oder aromatische Reste sind und x, y und n gleiche oder verschiedene ganze,Zahlen sind.The inventive method for producing carboxyl-containing polyurethane prepolymers with blocked isocyanate groups, which can be reacted at elevated temperature with hydroxyl or epoxy compounds to form polyurethanes, is characterized in that an at least difunctional isocyanate with a hydroxycarboxylic acid and a further active hydrogen-containing and for Reaction with a compound capable of isocyanate reacts according to the scheme: (MCONH) x-R1- (NHCOO) y-R2- (COOH) n where MH is an active hydrogen-containing compound capable of reacting with an isocyanate, R1 and R2 are identical or different aliphatic, cycloaliphatic or aromatic radicals and x, y and n are the same or different integers, numbers.
Die Herstellung von carboxylgruppenhaltigen Polyurethan-Prä polymeren mit verkappten Isocyanatgruppen bietet die Möglichkeit, feste und flUssige Polymere zu erhalten, deren Carboxylgruppen mit Epoxygruppen reagieren können und deren Isocyanatgruppen nach der Abspaltung des Verkappungsmittels mit den Hydroxylgruppen, die nach der Reaktion der Carboxyle mit Epoxygruppen frei werden, oder mit anderen hydroxylhaltigen Verbindungen reagieren können.The production of carboxyl-containing polyurethane prepolymers with blocked isocyanate groups offers the possibility of solid and liquid polymers to obtain whose carboxyl groups can react with epoxy groups and whose isocyanate groups after the cleavage of the capping agent with the hydroxyl groups, which after the Reaction of the carboxyls with epoxy groups becomes free, or with other hydroxyl-containing groups Connections can react.
Eine andere besondere Eigenschaft dieser PrSpolymere ist, dass die Carboxylgruppen mit aminhaltigen Basen neutralisiert werden kennen, so dass man wasserlösliche oder wasserdispergierbare Produkte erheilt, diemit anderen hydroxylhaltigen, wasserlffslichen oder wasserdispergierbaren Produkten nach der Verdunstung der Amine und nach Abspalt des Verkappungsmittels reagieren kbnnen.Another special property of these polymers is that the Carboxyl groups can be neutralized with amine-containing bases, so that one can water-soluble or water-dispersible products, which are mixed with other hydroxyl-containing, water-soluble or water-dispersible products after evaporation of the amines and can react after the capping agent has been split off.
Mit den nach dem erfindungsgemffssen Verfahren herstellbaren Prffpolymèren kann man unter Verwertung der Reaktivität der Carboxyl- und der Isocyanatgruppen, wärmevernetzende Lacke in Wasserlösung oder Wasserdispersion, in LUsung mit organischen VerdUnnungsmitteln und in festem Zustand formulieren. Im wasserlöslichen oder wasserverdUnnbaren Zustand und in festem Zustand setzen diese Produkte das Problem der Umweltverschmutzung deutlich herab. -- F(ir die Herstellung von carboxylgruppenhaltigen Polyurethan-Prflpolymeren mit verkappten Isocyanatgruppen kann man Di- und Polyisocyanate verwenden, wie z.B.: Toluylendiisocyanat (TDI); Xylylendiisocyanat (XDI); Diphenylmethyl-4,4'-Diisocyanat; Trysphenylmethyl-4,4',4''-Triisocyanat; Polyphenyl-Polymethylisocyanat; Isophorondiisocyanat (IPDI); Hexamethylendiisocyanat (HMDI); 2,2,4 (2,4,4)-Trismethylendiisocyanat (TMDI); Methylcyclohexyldiisocyanat; Dicyclohexylmethyldiisocyanat; Bis-(3-methyl-4-isocyanat-cyclohexyl)-methan; 2,2-bis-(4-isocyanatcyclohexyl)-propan; Hexamethylendiisocyanat-Biuret; sowie andere Verbindungen mit mindestens 2 NCO-Gruppen pro Molekül.With the test polymers which can be produced by the process according to the invention one can utilize the reactivity of the carboxyl and isocyanate groups, heat-crosslinking lacquers in water solution or water dispersion, in LUsung with organic Formulate thinners and as a solid. In the water-soluble or water-dilutable State and in solid state, these products pose the problem of environmental pollution clearly down. - For the production of carboxyl group-containing Polyurethane test polymers with blocked isocyanate groups can be di- and polyisocyanates use such as: tolylene diisocyanate (TDI); Xylylene diisocyanate (XDI); Diphenylmethyl 4,4'-diisocyanate; Trysphenylmethyl-4,4 ', 4 "-triisocyanate; Polyphenyl polymethyl isocyanate; Isophorone diisocyanate (IPDI); Hexamethylene diisocyanate (HMDI); 2,2,4 (2,4,4) trismethylene diisocyanate (TMDI); Methylcyclohexyl diisocyanate; Dicyclohexylmethyl diisocyanate; Bis (3-methyl-4-isocyanato-cyclohexyl) methane; 2,2-bis (4-isocyanatocyclohexyl) propane; Hexamethylene diisocyanate biuret; as well as others Compounds with at least 2 NCO groups per molecule.
Als Carboxylgruppen-Baustein verwendet man Hydroxysäuren oder andere Verbindungen; die mindestens eine -OH und eine -COOH-Gruppe pro Molekül enthalten, wie z.B. GlykolsSure; Salizylscf,tire; WeinsLture; p-HydroxybenzoesSure; Dimethylolpropionsäure; Aepfelsäure; Rizinolsure; Pheny"lglykolsäure, 4,4-Bis-(4-hydroxyphenyl)-Pentansäure und andere.Hydroxy acids or others are used as carboxyl group building blocks Links; which contain at least one -OH and one -COOH group per molecule, such as glycolic acid; Salicylic scf, tire; WeinsLture; p-hydroxybenzoic acid; Dimethylol propionic acid; Malic acid; Ricinoleic acid; Phenylglycolic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid and other.
Um die carboxylgruppenhaltigen Präpolymere zu verkappen, verwendet man ein aktives WasserNtoffatom enthaltende Verbindungen wie Phenol; 2,4-Diisobutylphenol; Kresol; Isooctylphenol; ptert-Butylphenol; Phenylphenol oder Verbindungen mit einer NOH-Gruppe wie Methyläthylketoxim; Azetonoxim, Pyruvaldehyd-l-O, oder cyclische Verbindungen mit einer -CO-NH-Gruppe wie Pyrrolidon,Piperidon-2, E-Caprolactam usw.Used to cap the prepolymers containing carboxyl groups compounds containing an active hydrogen atom such as phenol; 2,4-diisobutylphenol; Cresol; Isooctylphenol; ptert-butylphenol; Phenylphenol or compounds with a NOH group such as methyl ethyl ketoxime; Acetone oxime, pyruvaldehyde-l-O, or cyclic Compounds with a -CO-NH group such as pyrrolidone, piperidone-2, E-caprolactam, etc.
Die nachfolgenden Beispiele sollen zur weiteren Erläuterung der Erfindung dienen, ohne sie in irgendeiner Weise zu beschrän ken.The following examples are intended to further illustrate the invention serve without restricting them in any way.
Beispiel 1 In einen 1,5 Liter Dreihals-Glaskolben mit RUhrer,.Thermometer und RUckflusskUhler werden 540 Teile Isophorondiisocyanat (IPDI) und 183 Teile Weinsäure eingewogen: Der Ansatz wird auf 700C geheizt. Dann werden 277 Teile -Caprolactam portionsweise zugegeben und die Temperatur stufenweise bis 140°C erhöht.Example 1 In a 1.5 liter three-necked glass flask with a stirrer, thermometer and reflux cooler, 540 parts of isophorone diisocyanate (IPDI) and 183 parts of tartaric acid are used weighed in: The batch is heated to 700C. Then 277 parts are -Caprolactam Added in portions and the temperature increased gradually to 140 ° C.
Au-+ diese Weise erhält man ein carboxylgruppenhaltiges PolyurethanPrIpolymer mit verkappten Isocyanatgruppen mit <0,5% freie -NCO, 10,2% verkapptem -NCO, einer Säurezahl von ca.In this way, a carboxyl group-containing polyurethane prime polymer is obtained with blocked isocyanate groups with <0.5% free -NCO, 10.2% blocked -NCO, an acid number of approx.
135 und dem Erweichungspunkt von ca. 870C.135 and the softening point of approx. 870C.
Dieses Präpolymer, verdUnnt mit kleinen Mengen von. Glykoläthern oder Mischungen aus Glykoläthern und Alkoholen und mit Ammoniak, Aminen, Amino-Alkoholen oder mit anderen stickstoffhaltigen Basen neutralisiert bis zum pH-Wert von 7,5-8,5 ist in jedem Verhältnis mit Wasser verdUnnbar.This prepolymer, diluted with small amounts of. Glycol ethers or Mixtures of glycol ethers and alcohols and with ammonia, amines, amino alcohols or neutralized with other nitrogenous bases up to pH 7.5-8.5 can be diluted with water in any ratio.
Die mit diesem Präpolymer kombinierbaren Produkte werden Ublicherweise als Vernetzungspartner fur Lackbindemittelsysteme verwendet. Es kennen gesättigte Polyester-, Acryl-, bzw. Epoxyharze o.a. mit einer Hydroxylzahl von 35 bis 200 und einer Säurezahl von 3 bis 150 sein.The products which can be combined with this prepolymer are customarily used used as a crosslinking partner for paint binder systems. Saturated people know it Polyester, acrylic or epoxy resins or others with a hydroxyl number of 35 to 200 and an acid number from 3 to 150.
Wenn die Säurezahl Uber 30 liegt, sind diese Polykondensate und Polymere nach Neutralisation mit geeigneten Basen vollkommen wasserlöslich oder wasserdispergierbar. Diese Verbindungen sind mit der im vorstehenden Beispiel 1 beschriebenen carboxylgruppenhaltigen Polyuretan-Präpolymer zur Herstellung wasserlöslicher oder wasserdispergierbarer Lacke besonders geeignet.If the acid number is above 30, these are polycondensates and polymers completely water-soluble or water-dispersible after neutralization with suitable bases. These compounds are similar to that described in Example 1 above containing carboxyl groups Polyurethane prepolymer for the production of water-soluble or water-dispersible Lacquers are particularly suitable.
Wenn die Säurezahl niedriger als 30 ist, erhält man normalerweise Polykondensate und Polymere, die in Kombination mit den im vorstehenden Beispiel 1 beschriebenen carboxylgruppenhaltigen Polyurethan -Präpolymeren zur Herstellung von lösungsmittel haltigen oder pulverförmigen Lacken geeignet sind. Im letzteren Falle muss der Erweichungspunkt des Polymers oderPolykondensates über 750C liegen um das Blockieren der Pulverlacke zu vermeiden.If the acid number is lower than 30, one usually obtains Polycondensates and polymers in combination with those in the previous example 1 described carboxyl group-containing polyurethane prepolymers for production of solvent-based or powder-form paints are suitable. In the latter In this case, the softening point of the polymer or polycondensate must be above 750C to avoid blocking the powder coatings.
Die gesättigten Polyesterharze werden Ublicherweise durch Veresterung bzw. Umesterung, eventuell in Anwesenheit von Katalysatoren, produziert.The saturated polyester resins are usually made by esterification or transesterification, possibly in the presence of catalysts.
Die Acrylharze werden durch Polymerisation in Lösungsmitteln oder in wässriger Dispersion produziert.The acrylic resins are made by polymerization in solvents or produced in aqueous dispersion.
Nachstehend einige Herstellbeispiele von Polykondensaten und Polymeren a) Man stellt aus 73 Teilen Dimethylterephthalat, 15 Teilen Aethylenglykol und 12 Teilen Glyzerin ein wasserlösliches Polyesterharz her und erhält ein Produkt mit einer Hydroxylzahl von 55-60 und einer Säurezahl von 50-55, welches unter Mitverwendung von Aethylglykolacetat und nach Neutralisation mit ausgewählen Basen vollkommen wasserlUslich ist. Dieses Produkt kann als Vernetzungspartner für wasserlösliche oder wasserdispergierbare Lackbindemittelsysteme in Konibination m t dem in Beispiel 1 beschriebenen carboxylgruppenhaltigen Polyurethan-Präpolimer in folgenden Zusammensetzungen verwendet werden: System A: 73 Teile Polyesterharz- 27 Teile Präpolymer (Fest auf Fest) System B: 51 Teile Polyesterharz - 39 Teile Präpolymer -10 Teile Epoxyharz (mit Epoxyäquivalent 190).Below are some examples of the preparation of polycondensates and polymers a) It is made from 73 parts of dimethyl terephthalate, 15 parts of ethylene glycol and 12 Share glycerine a water-soluble polyester resin and get a product with a hydroxyl number of 55-60 and an acid number of 50-55, which is also used of ethyl glycol acetate and after neutralization with selected bases completely is water soluble. This product can be used as a crosslinking partner for water-soluble or water dispersible Varnish binder systems in combination With the carboxyl-containing polyurethane prepolymer described in Example 1 can be used in the following compositions: System A: 73 parts polyester resin 27 parts prepolymer (solid on solid) System B: 51 parts polyester resin - 39 parts Prepolymer -10 parts epoxy resin (with epoxy equivalent 190).
b) Ein anderes Polyesterharz in Pulverform oder in Ltssungsmitteln angelöst kann aus 41 Teilen Neopentylglykol und 59 Teilen Terephthalsäure hergestellt werden. Dabei erhält man ein Produkt mit Hydroxylzahl von 45-50 und Säurezahl 10.b) Another polyester resin in powder form or in solvents partially dissolved can be made from 41 parts of neopentyl glycol and 59 parts of terephthalic acid will. This gives a product with a hydroxyl number of 45-50 and an acid number of 10.
Dieses Produkt wird in Aethylglykolacetat und Xylol angelöst und in Kombination mit dem in Beispiel 1 beschriebenen carboxylgruppenhaltigen Polyurethan-PrKpolymer in folgenden Zusammensetzungen verwendet: System C: 75 Teile Polyesterharz - 25 TeilePrSpolymer (Fest auf Fest) System D: 55 Teile Polyesterharz - 35 Teile Präpolymer -10 Teile Epoxyharz (mit Epoxyäquivalent 190). This product is dissolved in ethyl glycol acetate and xylene and in combination with the carboxyl group-containing polyurethane prepolymer described in Example 1 used in the following compositions: System C: 75 parts polyester resin - 25 Parts of PrSpolymer (solid on solid) System D: 55 parts of polyester resin - 35 parts of prepolymer -10 parts epoxy resin (with epoxy equivalent 190).
Dieselben Lackbindemittelsysteme können selbstverständlich auch als Trockensubstanz zur Herstellung von Pulverlacken verwendet werden. The same paint binder systems can of course also be used as Dry substance can be used for the production of powder coatings.
c) Man stellt aus 10 - 12 Teilen Methacrylsäure' 16 - 20 Teilen Glycidylversatat, 20 - 25 Teilen Styrol und 45 - 55 Teilen Butylacrylat in einer 70%igen Ablösung in Aethylglykolacetat, an wasserlösliches Acrylharz her. Man erhält ein Produkt mit Hydroxylzahl 50 - 65 und Säurezahl 45 -.55, das nach Neutralisation mit geeigneten Basen vollkommen wasserlöslich ist.c) 16-20 parts of glycidyl versatate are made from 10-12 parts of methacrylic acid, 20-25 parts of styrene and 45-55 parts of butyl acrylate in a 70% release in ethyl glycol acetate, on water-soluble acrylic resin. A product is obtained with hydroxyl number 50 - 65 and acid number 45 -.55, which after neutralization with suitable Bases is completely soluble in water.
Dieses Produkt kann als Vernetzungspartner fUr wasserlosliche oder wasserdispergierbare Lackbindemittelsysteme in Kombination mit dem in Beispiel 1 beschriebenen carboxylgrupl haltigen Polyurethan-Präpolymer in folgenden Zusammensetzungen verwendet werden: System E: 70 Teile Acrylharz - 30 Teile Präpolymer (Fest auf Fest) System F: 50 Teile Acrylharz - 40 Teile Präpolymer - 10 Teile Epoxyharz (mit Epoxyäquivalent'190). This product can be used as a crosslinking partner for water-soluble or water-dispersible paint binder systems in combination with that in Example 1 carboxyl group-containing polyurethane prepolymer described in the following compositions are used: System E: 70 parts acrylic resin - 30 parts prepolymer (solid on solid) System F: 50 parts acrylic resin - 40 parts prepolymer - 10 parts epoxy resin (with epoxy equivalent of 190).
d) Aehnlichstellt man aus 8 - 10 Teilen Butylacrylat, 20 - 25 Teilen Styrol, 20 - 25 Teilen Aethylacrylat, 20 - 25 Teilen Methylmethacrylat, 15 - 20 Teilen Hydroxypropylmethacrylat und 2 - 5 Methacrylsäure ein in organischen Lösungsmitteln ungelöstes Acrylharz her.d) A similar preparation is made from 8-10 parts of butyl acrylate and 20-25 parts Styrene, 20-25 parts of ethyl acrylate, 20-25 parts of methyl methacrylate, 15-20 Part hydroxypropyl methacrylate and 2-5 methacrylic acid in organic solvents undissolved acrylic resin.
Man erhält ein Produkt mit HydrQylzahl 50 - 7Q und SSurezahl 10 - 15. Dieses Produkt kann als Vernetzungspartner fUr lösungsmittelhaltige Lackbindemittelsysteme in Kombination mit dem in Beispiel 1 beschriebenen carboxylgruppenhaltigen Polyurethan-Präpolymer in folgenden Zusammensetzungen verwendet werden: System G: 66 Teile Acrylharz - 34 Teile Präpolymer (Fest auf Fest) System H: 45 Teile Acrylharz - 45 Teile Präpolymer -10 Teile Epoxyharz (mit Epoxyäquivalent 190). A product is obtained with a hydrodynamic number 50 - 7Q and an acid number 10 - 15. This product can be used as a networking partner for solvent-based Varnish binder systems in combination with that described in Example 1 containing carboxyl groups Polyurethane prepolymer can be used in the following compositions: System G: 66 parts acrylic resin - 34 parts prepolymer (solid on solid) System H: 45 parts acrylic resin 45 parts prepolymer -10 parts epoxy resin (with epoxy equivalent 190).
Dieselben Lackbindemittelsysteme können in einigen Fällen auch als Trockensubstanz zur Herstellung von Pulverlacken verwendet werden. The same paint binder systems can in some cases also be used as Dry substance can be used for the production of powder coatings.
Vor Verwendung in flUssigen Lackbindemittelsystemen muss das carboxylhaltige Polyurethan-Präpolymer in Aethylglykolacetat angelöst werden.Before using in liquid paint binder systems, the carboxyl-containing Polyurethane prepolymer are dissolved in ethyl glycol acetate.
In Kombination mit hvdroxylgruppenhaltigen, wasserverdtlnnbaren oder wasserdispergierbaren Polymeren oder Polykondensaten erhält man Bindemittelsysteme fUr Wasserlössliche Lacke, die beim Einbrennen (30 Min.) bei 1800 harte, glänzende, flexible Filme ergeben.In combination with hydroxyl-containing, water-dilutable or Binder systems are obtained from water-dispersible polymers or polycondensates For water-soluble lacquers that are hard, glossy, flexible films result.
Aehnlich kann man das Präpolymer mit organischen Ltssungsmitteln verdUnnen, mit lösungsmittelverdUnnbaren, hydroxylgruppenhaltigen oder epoxydgruppenhaltigen Polymeren und Polykondensaten kombinieren und erhält Bindemittelsysteme fUr konventionelle Lacke, die sich beim Einbrennen (30 Min.) bei 180°C vernetzen.Similarly, the prepolymer can be diluted with organic solvents, with solvent-thinnable, hydroxyl-containing or epoxy-containing Polymers and polycondensates combine and obtain binder systems for conventional ones Lacquers that cross-link when stoving (30 min.) At 180 ° C.
Beispiel 2 In einem 1,5-Liter Glaskolben werden 579 Teile Isophorondiisocyanat und 195 Teile Weinsäure eingewogen. Der Ansatz wird auf 700C geheizt. Dann wird durch einen Fülltrichter portionsweise 226 Teile Methyläthylketoxim zugegeben und die Temperatur auf 1200C gesteigert.Example 2 579 parts of isophorone diisocyanate are placed in a 1.5 liter glass flask and 195 parts of tartaric acid are weighed out. The batch is heated to 700C. Then it will be 226 parts of methyl ethyl ketoxime were added in portions through a funnel and the temperature increased to 1200C.
Auf diese Weise erhält man ein carboxylgruppenhaltiges Polyurethan-Präpolymer mit verkappten Isocyanatgruppen, mit0,5% freiem -NCO, 10,9% verkapptem -NCO, Säurezahl ca. 140 und Erweichungspunkt ca. .750C.In this way, a carboxyl-containing polyurethane prepolymer is obtained with blocked isocyanate groups, with 0.5% free -NCO, 10.9% blocked -NCO, acid number approx. 140 and softening point approx. 750C.
Mit diesem Präpolymer, verdünnt und neutralisiert wie in Beispiel 1 beschrieben, kann man wasserverdünnbare, wärmehärtende Lacke zum Einbrennen (30 Min.) bei 1500C erhalten..With this prepolymer, diluted and neutralized as in the example 1, you can use water-thinnable, thermosetting varnishes for stoving (30 Min.) At 1500C ..
Aehnlich kann man das Präpolymer mit organischen Lösungsmitteln verdUnnen und lösungsmittelverdUnnbare, bei 1500C härtbare Lack erhalten.Similarly, the prepolymer can be diluted with organic solvents and solvent-thinnable varnish that can be hardened at 1500C.
In festem Zustand kann das Präpolymer in Kombination mit festen hydroxylgruppenhaltigen oder epoxydgruppenhaltigen Polymeren oder Polykondensaten fUr die Herstellung von Pulverlacken verwendet werden, die beim Einbrennen (30 Min.) bei 1500C harte, glänzende, flexible Filme mit besonderem Runzeleffekt ergeben.In the solid state, the prepolymer can be used in combination with solid hydroxyl groups or polymers containing epoxy groups or polycondensates for the production of Powder coatings are used that produce hard, shiny, result in flexible films with a special wrinkle effect.
Beispiel 3 Nach dem in Beispiel 1 angegebenen Verfahren lässt sich aus 589 Teilen Polymethylpolyphenylisocyanat mit einem NCO-Anteil von 30-32%, 97 Teilen Dimethylolpropionsäure und 317 Teilen rolactam ein carboxylgruppenhaltiges Polyurethan-Präpolymer mit verkappten Isocyanatgruppen herstellen.Example 3 Following the procedure given in Example 1, the end 589 parts of polymethyl polyphenyl isocyanate with an NCO content of 30-32%, 97 parts of dimethylolpropionic acid and 317 parts of rolactam contain a carboxyl group Manufacture polyurethane prepolymer with blocked isocyanate groups.
Dieses Präpolymer enthält weniger als 0,56 freies -NCO, 11,8% verkapptes -NCO und hat eine Säurezahl von ca. 40.This prepolymer contains less than 0.56 free -NCO, 11.8% capped -NCO and has an acid number of approx. 40.
In Analogie zu den Angaben in Beispiel 1 kann man dieses Präpolymer fUr die Herstellung von wasserldslichen oder lösungsmittelhaltigen, bei 30 Min./1800C härtbaren Lacken verwenden.In analogy to the information in Example 1, this prepolymer can be used For the production of water-soluble or solvent-based, at 30 min./1800C Use curable paints.
Beispiel 4 Nach dem in Beispiel angegebenen Verfahren lässt sich aus 640 Teilen Polymethylpolyphenylisocyanat mit einem -NCO-Anteil von 30-32, 101 Teilen Dimethylolpropionsäure und 259 Teilen wasserfreiem Pyrrolidon ein carboxylgruppenhaltiges Polyurethan-Präpolymer mit verkappten Isocyanatgruppen herwtellen.Example 4 Following the procedure given in the example can be omitted 640 parts of polymethyl polyphenyl isocyanate with an -NCO content of 30-32, 101 parts Dimethylolpropionic acid and 259 parts of anhydrous pyrrolidone containing a carboxyl group Produce polyurethane prepolymer with blocked isocyanate groups.
Dieses Präpolymer hat einen Anteil von weniger als 0,5% an freiem zNCO, von 12,7% an verkapptem -NCO und eine Säurezahl von ca. 42.This prepolymer has a proportion of less than 0.5% free zNCO, of 12.7% of blocked -NCO and an acid number of approx. 42.
Gemäss den Angaben in Beispiel 2 kann dieses Präpolymer fUr die Herstellung von wasserlöslichen, ltssungsmittelhaltigen und festen Lacken verwendet werden, die beim Einbrennen (20 Min.) bei 2200C härtbar sind.According to the information in Example 2, this prepolymer can be used for production are used by water-soluble, solvent-based and solid paints, which are hardenable during baking (20 min.) at 2200C.
Beispiel 5 Nach dem in Beispiel 1 beschriebenen Verfahren lässt sich aus 605 Teilen Polymethylpolyphenylisocianat mit einem NCO-Anteil von 30-32%, 109 Teilen wasserfreier Glykolsäure und 286 Teilen Piperidon-2 ein carboxylgruppenhaltiges Polyurethan-Präpolymer mit verkappcen Isocyanatgruppen herstellen.Example 5 Following the procedure described in Example 1, from 605 parts of polymethyl polyphenyl isocyanate with an NCO content of 30-32%, 109 Parts of anhydrous glycolic acid and 286 parts of piperidone-2 containing a carboxyl group Manufacture polyurethane prepolymer with blocked isocyanate groups.
Dieses Präpolymer hat einen Anteil von weniger alls 0,4% an freiem -NCO, von 12% an verkapptem - NCO und eine Säurezahl von ca. 80.This prepolymer has a proportion of less than 0.4% of free -NCO, of 12% of capped -NCO and an acid number of approx. 80.
Aehnlich wie in Beispiel 2 beschrieben kann dieses Präpolymer fUr die Herstellung von wasserldslichen, lösungsmittelhaltigen und festen Lacken verwendet werden, die durch Einbrennen härtbar sind.Similar to that described in Example 2, this prepolymer can be used for used in the production of water-soluble, solvent-based and solid paints which can be hardened by baking.
Beispiel 6 In einen 1,5-Liter Dreihals-Glaskolben mit Rührer, Thermometer und RUckflusskUhler werden 650 Teile Glyzerin und 350 Teile Bernsteinsäureanhydrid eingewogen. Der Ansatz wird vorsichtig auf 130-1490C geheizt und die Temperatur gehalten bis sich eine Säurezahl von ca.Example 6 In a 1.5 liter three-necked glass flask equipped with a stirrer, thermometer and reflux cooler are 650 parts of glycerine and 350 parts of succinic anhydride weighed in. The batch is carefully heated to 130-1490C and the temperature held until an acid number of approx.
390 und eine Hydroxylzahl von ca. 780 eingestellt haben.390 and a hydroxyl number of approx. 780 have been set.
Nach dem in Beispiel 1 beschriebenen Verfahren lässt sich aus 199 Teilen des Produktes der oben erwähnten Reaktion, 486 Teilen Toluylendiisocyanat und 315 Teilen Cyclohexanonoxim ein carboxylgruppenhaltiges . Polyurethan-Präpolymer mit verkappten Isocyanatgruppen herstellen.Following the procedure described in Example 1 can be omitted 199 Parts of the product of the above mentioned reaction, 486 parts of tolylene diisocyanate and 315 parts of cyclohexanone oxime containing carboxyl groups. Polyurethane prepolymer with blocked isocyanate groups.
Dieses Präpolymer hat einen Anteil von weniger als 0,5% an freiem -NCO, von 11,7% an verkapptem -NCO, eine Säurezahl von ca. 78 und einen Erweichungspunkt von ca. 45°C.This prepolymer has a proportion of less than 0.5% free -NCO, of 11.7% of blocked -NCO, an acid number of about 78 and a softening point of approx. 45 ° C.
Es kann wie in den Beispielen 1 und 2 angeführt verwendet werden.It can be used as indicated in Examples 1 and 2.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2917976A IT1068004B (en) | 1976-11-09 | 1976-11-09 | PROCESS FOR THE MANUFACTURE OF CARBOSSILATED POLYURETHANE PREPOLYMERS CONTAINING BLOCKED ISOCYANIC GROUPS |
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| DE2708611A1 true DE2708611A1 (en) | 1978-05-11 |
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|---|---|---|---|
| DE19772708611 Pending DE2708611A1 (en) | 1976-11-09 | 1977-02-28 | Blocked carboxy gp. contg. polyurethane prepolymer prepn. - by reacting a poly:isocyanate, a hydroxy acid and a blocking agent |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4284544A (en) * | 1978-12-14 | 1981-08-18 | Bayer Aktiengesellschaft | Process for the preparation of water-dispersible or water-soluble blocked polyisocyanates, the blocked polyisocyanates obtainable by this process and lacquer binders containing these blocked polyisocyanates as isocyanate component |
| WO1981002894A1 (en) * | 1980-04-09 | 1981-10-15 | Textron Inc | Polymer compositions and manufacture |
| EP0056167A1 (en) * | 1981-01-08 | 1982-07-21 | Hoechst Aktiengesellschaft | Solid polymeric binder for thermosetting pulverulent coatings on the basis of polyurethane prepolymers containing carboxylic groups and having blocked isocyanate groups, pulverulent coatings containing the binder and coated metallic objects |
| GB2127829A (en) * | 1982-09-30 | 1984-04-18 | Mobay Chemical Corp | Aqueously dispersed coating compositions |
| US4452834A (en) * | 1981-09-23 | 1984-06-05 | Bayer Aktiengesellschaft | Process for the preparation of aqueous dispersions or solutions of polyurethane polyureas containing heat activated cross-linking agents, the dispersions or solutions obtainable by this process, and their use for the production of coatings |
| EP0104424A3 (en) * | 1982-09-01 | 1985-09-18 | Bayer Ag | Use of blocked polyisocyanates as curing agents for binders containing hydroxyl groups |
| US4608413A (en) * | 1983-12-15 | 1986-08-26 | Bayer Aktiengesellschaft | Aqueous polyurethane stoving lacquers and the use thereof for the production of lacquer films and coatings |
| EP0566953A1 (en) * | 1992-04-24 | 1993-10-27 | Bayer Ag | Aqueous coating compositions for elastic stoving lacquers |
| US5294665A (en) * | 1992-07-03 | 1994-03-15 | Bayer Aktiengesellschaft | Water soluble or water dispersible polyisocyanate mixtures and their use in stoving compositions |
| EP0698629A3 (en) * | 1994-08-26 | 1996-03-06 | Inventa Ag | |
| US6043301A (en) * | 1994-06-01 | 2000-03-28 | Hille; Hans-Dieter | Aqueous coating compositions |
| EP1193277A3 (en) * | 2000-09-27 | 2002-07-10 | Degussa AG | Water dispersable blocked polyisocyanate adducts in powder form, a process for their preparation and their use |
| US7049367B2 (en) | 2002-04-17 | 2006-05-23 | Bayer Aktiengesellschaft | Self-crosslinking PU dispersions |
| EP1669385A1 (en) * | 2004-12-08 | 2006-06-14 | Bayer MaterialScience LLC | Continuous method for manufacturing an acid functional blocked solid isocyanate |
| EP0998511B1 (en) * | 1997-07-30 | 2009-03-04 | Rhodia Chimie | Masked mixed isocyanate composition and its use in powder paint |
| CN102816294A (en) * | 2012-08-17 | 2012-12-12 | 浙江传化股份有限公司 | Preparation method of water-soluble blocked isocyanate crosslinking agent |
-
1976
- 1976-11-09 IT IT2917976A patent/IT1068004B/en active
-
1977
- 1977-02-28 DE DE19772708611 patent/DE2708611A1/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4284544A (en) * | 1978-12-14 | 1981-08-18 | Bayer Aktiengesellschaft | Process for the preparation of water-dispersible or water-soluble blocked polyisocyanates, the blocked polyisocyanates obtainable by this process and lacquer binders containing these blocked polyisocyanates as isocyanate component |
| WO1981002894A1 (en) * | 1980-04-09 | 1981-10-15 | Textron Inc | Polymer compositions and manufacture |
| EP0056167A1 (en) * | 1981-01-08 | 1982-07-21 | Hoechst Aktiengesellschaft | Solid polymeric binder for thermosetting pulverulent coatings on the basis of polyurethane prepolymers containing carboxylic groups and having blocked isocyanate groups, pulverulent coatings containing the binder and coated metallic objects |
| US4452834A (en) * | 1981-09-23 | 1984-06-05 | Bayer Aktiengesellschaft | Process for the preparation of aqueous dispersions or solutions of polyurethane polyureas containing heat activated cross-linking agents, the dispersions or solutions obtainable by this process, and their use for the production of coatings |
| EP0104424A3 (en) * | 1982-09-01 | 1985-09-18 | Bayer Ag | Use of blocked polyisocyanates as curing agents for binders containing hydroxyl groups |
| GB2127829A (en) * | 1982-09-30 | 1984-04-18 | Mobay Chemical Corp | Aqueously dispersed coating compositions |
| US4522851A (en) * | 1982-09-30 | 1985-06-11 | Mobay Chemical Corporation | Process for coating aqueous dispersion of epoxy resin and blocked polyisocyanate containing chemically incorporated anionic hydrophilic groups |
| EP0151661B1 (en) * | 1982-09-30 | 1987-11-11 | Mobay Corporation | Use of aqueously dispersed compositions as glass fiber sizing agent or for the manufacture of glass fiber sizing agents |
| US4608413A (en) * | 1983-12-15 | 1986-08-26 | Bayer Aktiengesellschaft | Aqueous polyurethane stoving lacquers and the use thereof for the production of lacquer films and coatings |
| US5455297A (en) * | 1992-04-24 | 1995-10-03 | Bayer Aktiengesellschaft | Water-based coating compositions and their use for the production of flexible coatings |
| EP0566953A1 (en) * | 1992-04-24 | 1993-10-27 | Bayer Ag | Aqueous coating compositions for elastic stoving lacquers |
| US5294665A (en) * | 1992-07-03 | 1994-03-15 | Bayer Aktiengesellschaft | Water soluble or water dispersible polyisocyanate mixtures and their use in stoving compositions |
| EP0576952A3 (en) * | 1992-07-03 | 1994-06-29 | Bayer Ag | Water-soluble dispersible polyisocyanate compositions and their use in storing lacquers |
| US6043301A (en) * | 1994-06-01 | 2000-03-28 | Hille; Hans-Dieter | Aqueous coating compositions |
| EP0698629A3 (en) * | 1994-08-26 | 1996-03-06 | Inventa Ag | |
| EP0998511B1 (en) * | 1997-07-30 | 2009-03-04 | Rhodia Chimie | Masked mixed isocyanate composition and its use in powder paint |
| EP1193277A3 (en) * | 2000-09-27 | 2002-07-10 | Degussa AG | Water dispersable blocked polyisocyanate adducts in powder form, a process for their preparation and their use |
| US7033522B2 (en) | 2000-09-27 | 2006-04-25 | Degussa Ag | Pulverulent, water-dispersible, blocked polyisocyanate adducts, a process for the preparation and their use |
| US7049367B2 (en) | 2002-04-17 | 2006-05-23 | Bayer Aktiengesellschaft | Self-crosslinking PU dispersions |
| EP1669385A1 (en) * | 2004-12-08 | 2006-06-14 | Bayer MaterialScience LLC | Continuous method for manufacturing an acid functional blocked solid isocyanate |
| CN102816294A (en) * | 2012-08-17 | 2012-12-12 | 浙江传化股份有限公司 | Preparation method of water-soluble blocked isocyanate crosslinking agent |
| CN102816294B (en) * | 2012-08-17 | 2014-06-18 | 浙江传化股份有限公司 | Preparation method of water-soluble blocked isocyanate crosslinking agent |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1068004B (en) | 1985-03-21 |
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