2-Bromo-2,2-difluoroacetone acetone fork protection monoglyceride, water-based polyurethane and preparation method
A technology of acetonylidene acetate and difluoroacetate, applied in the field of printing and dyeing auxiliaries, can solve the problems of easy water absorption, poor flame retardancy, yellowing of textiles, etc.
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[0029] The present invention provides a preparation method for 2-bromo-2,2-difluoroacetate protected acetonylidene monoglyceride described in the scheme, comprising the following steps: condensing 2-bromo-2,2-difluoroacetate, Glycerol and a basic catalyst are mixed for transesterification to obtain 2-bromo-2,2-difluoroacetate acetonylidene-protected monoglycerides having the structure described in formula I;
[0030] The molar ratio of the 2-bromo-2,2-difluoroacetate to acetonide is 1:1-5.
[0031] In the present invention, unless otherwise specified, the raw materials used are commercially available products well known in the art.
[0032] In the present invention, the 2-bromo-2,2-difluoroacetate is preferably methyl 2-bromo-2,2-difluoroacetate or ethyl 2-bromo-2,2-difluoroacetate. The basic catalyst preferably includes one or more of hydroxide, carbonate, bicarbonate, sodium hydride and sodium alkoxide, more preferably includes alkali metal hydroxide, alkali metal carbonate...
Embodiment 1
[0070] Add 203 grams of ethyl 2-bromo-2,2-difluoroacetate, 260 grams of acetonide, and 3.2 grams of sodium methoxide to a 1L reaction vessel equipped with a thermometer, a reflux condenser, a water separator, and a stirrer at 115 After reacting at ℃ for 12 hours, the resulting reaction product was subjected to vacuum distillation to collect fractions under the condition of 104-106℃ / 25mmHg to obtain 2-bromo-2,2-difluoroacetate-protected acetonylidene monoglycerol with the structure shown in formula I The ester was 285.5 grams, the yield was 98.8%, and the purity was 99.5%.
[0071]
[0072] Carry out NMR analysis to the 2-bromo-2,2-difluoroacetate acetonylidene protected monoglycerides prepared in Example 1, the results are as follows Figure 1 ~ Figure 2 shown, where figure 1 is the H NMR spectrum, figure 2 It is NMR fluorine spectrum. Depend on Figure 1 ~ Figure 2 It can be seen that the acetonylidene-protected 2-bromo-2,2-difluoroacetate monoglyceride prepared in Ex...
Embodiment 2
[0077] Add 189 grams of 2-bromo-2,2-methyl difluoroacetate, 260 grams of acetonide, and 1.89 grams of potassium hydroxide in a 1L reaction vessel equipped with a thermometer, reflux condenser, water separator and stirrer. Reaction at 125°C for 8 hours, and then the obtained reaction product was subjected to vacuum distillation to collect fractions under the condition of 104-106°C / 25mmHg to obtain 283.3 grams of 2-bromo-2,2-difluoroacetonylidene-protected monoglyceride. The yield is 98.0%, and the purity is 99.5%.
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