| 摘要 |
<p>#CMT# #/CMT# Preparing alkylated aminoplast derivatives, comprises catalytic hydrogenation with hydrogen using a hydrogenation catalyst, and simultaneous catalytic alkylation with an alkylating substance of an aminoplast-formaldehyde resin using an alkylation catalyst. #CMT#USE : #/CMT# The alkylated aminoplast derivative is useful: as a co-monomer for a laminate coating or for polyurethane, a plasticizing substance, a flame retardant or for agrochemicals; and in a mixture comprising polyolefin, preferably polyethylene or polypropylene (all claimed). #CMT#ADVANTAGE : #/CMT# The process provides exclusively alkylated aminoplast derivatives without forming non-alkylated aminoplast derivatives. #CMT#INORGANIC CHEMISTRY : #/CMT# Preferred Components: The hydrogenation catalyst comprises a metal, a metal derivative and/or a metal alloy. The metal, metal derivative and/or metal alloy of the hydrogenation catalyst is/contains a metal of the group 8, 9 or 10 of the periodic system. The metal derivative of the hydrogenation catalyst is a phosphine, an oxide or a chloro compound of the metal. The hydrogenation catalyst comprises a neutral carrier material, preferably activated charcoal, a silicate, a phosphate, aluminum oxide and/or silicon dioxide. The alkylation catalyst comprises a metal and/or a metal oxide. The metal and/or metal derivative of the alkylation catalyst is/contains a metal of the group 8, 9 or 10 of the periodic system. The alkylation catalyst comprises an acid carrier material, preferably a zeolite, aluminum oxide and/or aluminosilicate. #CMT#[Image]#/CMT# #CMT#ORGANIC CHEMISTRY : #/CMT# Preferred Components: The alkylated aminoplast derivative comprises: alkylmelamine, N,N'-dialkylmelamine, N,N-dialkylmelamine, N,N',N"-trialkylmelamine, N,N,N'-trialkylmelamine, N,N,N',N'-tetraalkylmelamine or N,N,N',N''-tetraalkylmelamine; alkylbenzoguanamine, N,N'-dialkylbenzoguanamine, N,N-dialkylbenzoguanamine or N,N,N'-trialkylbenzoguanamine; alkylacetoguanamine, N,N'-dialkylacetoguanamine, N,N-dialkylacetoguanamine or N,N,N''-trialkylacetoguanamine; and alkylurea, N,N'-dialkylurea, N,N-dialkylurea or N,N,N'-trialkylurea. #CMT#POLYMERS : #/CMT# Preferred Process: The methylol group of the aminoplast-formaldehyde resin is completely etherified, partially etherified or unetherified. Preferred Components: The aminoplast-formaldehyde resin exhibits aminoplast-formaldehyde-ratio of 1:1.05-1:4, preferably 1:1.1-1:2, where in the aminoplast-formaldehyde-resin, at least one hydrogen atom is directly bounded at amino nitrogen atom of the aminoplast-formaldehyde-resin. The alkylating substance is an alcohol or an aminoplast-formaldehyde resin whose methylol group is at least partially etherified. The proportion of hydrogen in the total gas phase in the reaction mixture at room temperature is at least 80 vol.%, preferably at least 99 vol.%. The aminoplast-formaldehyde resin contains a substituted methyl-[1,3,5]triazin-2-yl-amine compound of formula (I) or substituted urea compound of formula (R9-N(R10)-C(=O)-N(R11)-CH 2-O-R12) (II). The alkylated aminoplast derivative contains a substituted methyl-[1,3,5]triazin-2-yl-amine compound of formula (III) or substituted urea compound of formula (R9-N(R10)-C(=O)-N(R11)-R12a) (IV). In formula (I) and (II): R1, R11 : H; R2, R12 : H or 1-20C-alkyl; R3 : Q1 or residue of formula (R5-N-R6), in which the central N atom is bounded at the triazine ring (I); Q1 : 1-30C-alkyl or 5-20C-cycloalkyl, 5-20C-aryl, 1-20C-alkyl substituted 5-20C-aryl or an imide of cyclic saturated carboxylic acid (all optionally substituted by one or more O, S, substituted N and/or optionally interrupted by one or more groups of -C(O)O-, -OC(O)- or -C(O)-); R4 : Q1 or residue of formula (R7-N-R8), in which the central N atom is bounded at the triazine ring (I); R5 : H, 1-20C-alkyl or CH 2-O-R5a; R6 : H, 1-20C-alkyl or CH 2-O-R6a; R7 : H, 1-20C-alkyl or CH 2-O-R7a; R8 : H, 1-20C-alkyl or CH 2-O-R8a; R9 : H, 1-20C-alkyl or CH 2-O-R9a; R10 : H, 1-20C-alkyl or CH 2-O-R10a; and R5a-R10a : H or 1-20C-alkyl. In formula (III) and (IV): R1, R11 : H; R2a, R12a : 1-20C-alkyl; R3 : Q1 or residue of formula (R5-N-R6), in which the central N atom is bounded at the triazine ring (I); Q1 : 1-30C-alkyl or 5-20C-cycloalkyl, 5-20C-aryl, 1-20C-alkyl substituted 5-20C-aryl or an imide of cyclic saturated carboxylic acid (all optionally substituted by one or more O, S, substituted N and/or optionally interrupted by one or more groups of -C(O)O-, -OC(O)- or -C(O)-); R4 : Q1 or residue of formula (R7-N-R8), in which the central N atom is bounded at the triazine ring (I); and R5-R10 : H or 1-20C-alkyl. #CMT#EXAMPLE : #/CMT# An autoclave was filled with 2 g of partially methanol etherified melamine-formaldehyde-resin with melamine-formaldehyde (M:F) ratio of 1:3 in 150 ml of dioxane, 70 ml of methanol, 2 mol.% of palladium (5% palladium on activated carbon) as hydrogenation catalyst and 0.6 g of palladium/mordenite as alkylation catalyst. The autoclave comprising the reaction mixture was flushed with nitrogen to displace the oxygenated air and subsequently filled with hydrogen gas (30 bar at room temperature) under continuous stirring. The autoclave was heated to 180[deg] C and stirred for 2 hours. After cooling down a repeated flushing with nitrogen was done to completely remove the residual hydrogen gas. The reaction solution was drained from the lower opening. The catalyst separation was performed by centrifugation. The solvent was evaporated and the product was dried in a vacuum oven at 30[deg] C. The product was composed of 1.4% hexamethylmelamine, 4.1% pentamethyl melamine, 1.5% N,N,N',N'-tetramethylmelamine, 9% N,N,N',N''-tetramethyl melamine, 8.9% N,N,N'-trimethylmelamine, 12.8% N,N',N''-trimethyl melamine, 2.7% N,N-dimethylmelamine, 23.4% N,N'-dimethylmelamine, 23.7% methyl melamine and 12.5% melamine.</p> |
