Perfluoralkylene-containing allyloxy ethyl carbamate and preparation method and application thereof

Abstract

The invention discloses a novel polymer monomer perfluoralkylene-containing allyloxy ethyl carbamate and a preparation method and application thereof. The preparation method comprises the following steps: (1) taking toluene-2,4-diisocyanate shown in a formula (II) as a raw material to perform first-step addition reaction with glycol monoene oxybispropanol shown in a formula (III) by taking organic tin as a catalyst in a polar aprotic solvent, and reacting until the raw material II basically disappears to obtain reaction liquid A of an intermediate shown in a formula (IV); and (2) directly adding the reaction liquid A to 2-methoxyl-3-perfluorenoxy diol shown in a formula (V) to perform second-step addition reaction, obtaining reaction liquid B after the reaction is over, and performing solvent removal and column chromatography on the reaction liquid B to obtain the polymer monomer perfluoralkylene-containing allyloxy ethyl carbamate shown in a formula (I). The invention provides the brand-new polymer monomer capable of being prepared into a surfactant; and the synthesis method is simple, and convenient to operate.

Description

(1) Technical field

[0001] The invention relates to a new type of allyloxyethyl carbamate containing a perfluoroalkene group in a polymer monomer and a preparation method and application thereof. (2) Background technology

[0002] Fluorocarbon surfactant is a special surfactant, and its performance can be summarized as: "three highs" and "two phobias". "Three highs": high surface activity - the mass fraction of 0.005% to 0.1% can reduce the surface tension of water to 2.0×10 -2 N·m -1 Below; high heat resistance - can be used above 300 °C; high chemical stability - still has high surface activity in strong alkali and strong acid solutions. "Two hates": Fluorine-containing hydrocarbon groups are both water-repellent and oil-repellent [Fluorosurfactants, China Light Industry Press, 1998]. Another superior performance of fluorocarbon surfactants is that it has a higher ability to reduce surface tension when compounded with hydrocarbon surfactants. Some people measure the sur...

Examples

Embodiment 1

[0028] Add 50mL of 1,2-dichloroethane, 17.4g (0.1mol) of toluene-2,4-diisocyanate, 1.9g (0.008mol) of tetraethyltin, and 0.5g of hydroquinone into a 250mL four-necked flask. Polymerizing agent, stirred, heated up to 75°C, 10.2g (0.1mol) of ethylene glycol monoallyl ether was added dropwise, after the dropwise addition was completed, TLC was detected, and the reaction process was tracked, and the temperature was kept stirring for 4h. 53.6 g (0.1 mol) of 2-methoxy-3-perfluorononenyloxypropanol was added dropwise. After the dropwise addition was completed, TLC detection was carried out to track the reaction progress, and the reaction was carried out while maintaining the temperature and stirring for 5 h. Reaction is completed, and solvent extraction is separated by silica gel column chromatography (V 环己烷 :V 乙酸乙酯 =7:3), after removing the solvent, yellow viscous paste I was obtained 1 (n=9), the perfluoroalkenyl-containing acrylate represented by formula (I), the yield is 66.8%,...

Embodiment 2

[0033] React according to the method of Example 1, but 2-methoxyl-3-perfluorononenyloxypropanol is changed to 2-methoxyl-3-perfluorohexenyloxypropanol 38.6g (0.1mol), Other reaction conditions are identical with embodiment 1, obtain pale yellow paste I 2 (n=6), yield 61.0%, purity 99.3%.

[0034] 19 F NMRδ(CDCl 3 ): -129.4(t, 3F), -127.4(s, 3F), -121.6(m, 2F), -83.3(s, 2F), -78.1(t, 1F).

Embodiment 3

[0036] Add 50mL of N,N-dimethylacetamide, 17.4g (0.1mol) of 2,4-TDI, 4.27g (0.01mol) of tetraphenyltin into a 250mL four-necked flask, and 0.8 p-hydroxyanisole as a polymerization inhibitor , stirred, the temperature was raised to 100°C, and 15.3 g (0.15 mol) of ethylene glycol monoallyl ether was added dropwise. After the completion of the dropwise addition, TLC was detected to track the reaction process, and the temperature was kept to stir for 4 hours. 80.4 g (0.15 mol) of 2-methoxy-3-perfluorononenyloxypropanol was added dropwise. After the dropwise addition was completed, TLC detection was carried out to track the reaction progress, and the reaction was carried out while maintaining the temperature and stirring for 5 h. After completion of the reaction, desolvation, silica gel column chromatography

[0037] (V 环己烷 :V 乙酸乙酯 = 7: 3), the yellow paste I was obtained after removing the solvent 1 (n=9), yield 69.2%, purity 99.7%.

(1) Technical field

[0001] The invention relates to a new type of allyloxyethyl carbamate containing a perfluoroalkene group in a polymer monomer and a preparation method and application thereof. (2) Background technology

[0002] Fluorocarbon surfactant is a special surfactant, and its performance can be summarized as: "three highs" and "two phobias". "Three highs": high surface activity - the mass fraction of 0.005% to 0.1% can reduce the surface tension of water to 2.0×10 -2 N·m -1 Below; high heat resistance - can be used above 300 °C; high chemical stability - still has high surface activity in strong alkali and strong acid solutions. "Two hates": Fluorine-containing hydrocarbon groups are both water-repellent and oil-repellent [Fluorosurfactants, China Light Industry Press, 1998]. Another superior performance of fluorocarbon surfactants is that it has a higher ability to reduce surface tension when compounded with hydrocarbon surfactants. Some people measure the sur...

Examples

Embodiment 1

[0028] Add 50mL of 1,2-dichloroethane, 17.4g (0.1mol) of toluene-2,4-diisocyanate, 1.9g (0.008mol) of tetraethyltin, and 0.5g of hydroquinone into a 250mL four-necked flask. Polymerizing agent, stirred, heated up to 75°C, 10.2g (0.1mol) of ethylene glycol monoallyl ether was added dropwise, after the dropwise addition was completed, TLC was detected, and the reaction process was tracked, and the temperature was kept stirring for 4h. 53.6 g (0.1 mol) of 2-methoxy-3-perfluorononenyloxypropanol was added dropwise. After the dropwise addition was completed, TLC detection was carried out to track the reaction progress, and the reaction was carried out while maintaining the temperature and stirring for 5 h. Reaction is completed, and solvent extraction is separated by silica gel column chromatography (V 环己烷 :V 乙酸乙酯 =7:3), after removing the solvent, yellow viscous paste I was obtained 1 (n=9), the perfluoroalkenyl-containing acrylate represented by formula (I), the yield is 66.8%,...

Embodiment 2

[0033] React according to the method of Example 1, but 2-methoxyl-3-perfluorononenyloxypropanol is changed to 2-methoxyl-3-perfluorohexenyloxypropanol 38.6g (0.1mol), Other reaction conditions are identical with embodiment 1, obtain pale yellow paste I 2 (n=6), yield 61.0%, purity 99.3%.

[0034] 19 F NMRδ(CDCl 3 ): -129.4(t, 3F), -127.4(s, 3F), -121.6(m, 2F), -83.3(s, 2F), -78.1(t, 1F).

Embodiment 3

[0036] Add 50mL of N,N-dimethylacetamide, 17.4g (0.1mol) of 2,4-TDI, 4.27g (0.01mol) of tetraphenyltin into a 250mL four-necked flask, and 0.8 p-hydroxyanisole as a polymerization inhibitor , stirred, the temperature was raised to 100°C, and 15.3 g (0.15 mol) of ethylene glycol monoallyl ether was added dropwise. After the completion of the dropwise addition, TLC was detected to track the reaction process, and the temperature was kept to stir for 4 hours. 80.4 g (0.15 mol) of 2-methoxy-3-perfluorononenyloxypropanol was added dropwise. After the dropwise addition was completed, TLC detection was carried out to track the reaction progress, and the reaction was carried out while maintaining the temperature and stirring for 5 h. After completion of the reaction, desolvation, silica gel column chromatography

[0037] (V 环己烷 :V 乙酸乙酯 = 7: 3), the yellow paste I was obtained after removing the solvent 1 (n=9), yield 69.2%, purity 99.7%.

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