A kind of preparation method and application of 10-hydroxyl-1,8-diazabicycloundeca-7-ene
A diazabicyclo, hydroxyl technology, applied in the field of polyurethane, can solve the problems of no catalytic gel, high-efficiency catalyst, low activity, etc.
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Embodiment 1
[0080] Carrier 1: Preparation of Mn-ZSM-5 molecular sieve
[0081] Weigh 40g of dried ZSM-5 molecular sieve (silicon-aluminum ratio 30-40); weigh 1.2g of manganese sulfate, dissolve it in 60ml of pure water, and prepare a manganese sulfate solution, and pour the solution into the above-mentioned ZSM-5 molecular sieve , after stirring evenly, let stand for 12h, dry at 120°C, and activate at 550°C for 4h to obtain the modified Mn-ZSM-5 molecular sieve.
[0082] Step 1: Heat 60g caprolactam, 2g potassium ethoxide and 100ml ethanol to boiling, add 50ml epichlorohydrin dropwise within 30min, reflux for 1h, cool to room temperature, add 6ml6N sulfuric acid to acidify, filter, evaporate ethanol, and then The fraction at 201-205°C was collected under reduced pressure (7mmHg), which was N-(3-chloro-2-hydroxypropyl)caprolactam, and the yield was 89.2% according to gas chromatography. The product was qualitatively analyzed by mass spectrometry and NMR. Figure see Figure 2-4 .
[0083...
Embodiment 2
[0085] Carrier one: with reference to embodiment 1
[0086] Step 1: Heat 60g of caprolactam, 4g of potassium ethylate and 100ml of isopropanol to boiling, add 50ml of epichlorohydrin dropwise within 30min, reflux for 2.5h, cool to room temperature, add 6ml of 6N sulfuric acid to acidify, filter, and evaporate the isopropanol After alcohol, the fraction at 201-205°C was collected under reduced pressure (7mmHg), which was N-(3-chloro-2-hydroxypropyl)caprolactam, with a yield of 90.9%.
[0087] Step 2: Add 35g of N-(3-chloro-2-hydroxypropyl) caprolactam and 1.75g of the ZSM-5 molecular sieve prepared above into the reaction kettle, after nitrogen replacement, add 100ml of dioxane containing 47g of liquid ammonia The temperature of the solution was raised to 80°C, and after stirring for 1.5 hours, nitrogen gas was blown into it to purge for 30 minutes, and the catalyst was filtered out. Then add 500ml of water, filter, dry, and collect fractions at 145-150°C under a pressure of...
Embodiment 3
[0089] Carrier one: with reference to embodiment 1
[0090] Step 1: Heat 60g caprolactam, 0.3g potassium ethoxide and 100ml isopropanol to boiling, add 50ml epichlorohydrin dropwise within 30min, reflux for 1h, cool to room temperature, add 6ml6N sulfuric acid to acidify, filter, and evaporate ethanol , and then collect the fraction at 201-205° C. under reduced pressure (7 mmHg), which is N-(3-chloro-2-hydroxypropyl) caprolactam, with a yield of 83%.
[0091] Step 2: Add 20g of N-(3-chloro-2-hydroxypropyl)caprolactam and 1.75g of the ZSM-5 molecular sieve prepared above into the reaction kettle, after nitrogen replacement, add 100ml of liquid ammonia, heat up to 80°C, and stir After 1.5h, the pressure was released, and ethanol was added to filter out the catalyst. After the ethanol was distilled off, the fraction collected at 145-150°C under a pressure of 7 mmHg was 10-hydroxy-1,8-diazabicycloundec-7-ene with a yield of 92.1%.
[0092] The raw materials that comparative ex...
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