Hexafluoropropylene-oligomer-containing polymer monomer as well as synthesizing method and application thereof

Abstract

The invention mainly discloses a hexafluoropropylene-oligomer-containing polymer monomer as well as a preparation method and an application thereof. The preparation method comprises the following steps of: (1) carrying out primary addition reaction in a polar aprotic solvent by taking methylbenzene-2,4-diisocyanate shown by a formula (II) as raw material and glycol monoene oxybispropanol shown bya formula (III) and taking organotin as catalyst, and obtaining reaction liquid A of an intermediate shown by a formula (IV) after the reaction is finished; and (2) directly adding the reaction liquid A into N-methyl-N-hydroxyethyl-p-perfluor vinoxyl benzylamine shown by a formula (V) to realize secondary addition reaction, obtaining reaction liquid B after the reaction is finished, and obtainingthe hexafluoropropylene-oligomer-containing polymer monomer shown by a formula (I) after the reaction liquid B carries out by desolventizing and column chromatography separation. The invention has the advantage that an absolutely-new hexafluoropropylene-oligomer-containing polymer monomer (I) which can be used for preparing waterproof and grease-proof primer is provided; in addition, the synthesizing method is simple, and the operation thereof is convenient.

Description

(1) Technical field

[0001] The invention relates to a polymerization monomer containing hexafluoropropylene oligomer, its synthesis method and application. (2) Background technology

[0002] The research and development of environmentally friendly fluoropolymers, especially the synthesis and application of fluoropolymer emulsions is an inevitable trend in the development of organic fluorine materials. The fluorine-containing polymer emulsion uses water as the dispersion medium, avoids the pollution of the environment caused by the volatilization of the organic solvent, and protects the environment while reducing the product cost. Therefore, fluorine-containing polymer emulsions have broad application prospects in super weather-resistant exterior wall coatings and functional coatings [Surface Coatings International, 1996 (7): 312]. Composition and structure are decisive factors in the performance of fluoropolymers. Therefore, among numerous polymerizable monomers, it is ver...

Examples

Embodiment 1

[0027] Add 15 mL of 1,2-dichloroethane, 1.74 g (10 mmol) of toluene-2,4-diisocyanate, 0.19 g (0.8 mmol) of tetraethyltin, and 0.05 g of p-hydroxyanisole into a 50 mL four-necked flask. Polymerizing agent, stirred, heated up to 75°C, added dropwise 1.02g (10mmol) of ethylene glycol monoallyl ether, after the dropwise addition, TLC detection, followed the reaction process, kept the temperature and stirred for 4h. 6.11 g (10 mmol) of N-methyl-N-hydroxyethyl-4-perfluorononenyloxybenzylamine was added dropwise. After the dropwise addition was completed, TLC was detected to track the reaction progress, and the reaction was carried out while maintaining the temperature and stirring for 5 hours. Reaction is completed, and solvent extraction is separated by silica gel column chromatography (V 二氯甲烷 :V 乙酸乙酯 :V 环己烷 =5:4:1), the light yellow paste I was obtained after removing the solvent 1 (n=9), the polymerized monomer containing hexafluoropropylene oligomer represented by formula (I)...

Embodiment 2

[0032] Carry out the reaction according to the method of Example 1, but N-methyl-N-hydroxyethyl-4-perfluorononenyloxybenzylamine is changed to N-methyl-N-hydroxyethyl-4-perfluorohexene Base oxybenzylamine 4.61g (10mmol), other operation is as embodiment 1, obtains the light yellow paste of polymerized monomer containing hexafluoropropylene oligomer shown in formula (I), I 2 (n=6), yield 66.3%, purity 99.3%.

[0033] 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

[0035] Add 15mL of N,N-dimethylformamide (DMF), 1.74g (10mmol) of 2,4-TDI, 0.23g (1mmol) of tetraethyltin, and 0.08g of hydroquinone into a 250mL four-necked flask as a polymerization inhibitor 1.53 g (15 mmol) of ethylene glycol monoallyl ether was added dropwise. After the addition was completed, TLC was used to detect the reaction progress, and the temperature was kept and stirred for 4 hours. 9.17 g (15 mmol) of N-methyl-N-hydroxyethyl-4-perfluorononenyloxybenzylamine was added dropwise. After the dropwise addition was completed, TLC was detected to track the reaction progress, and the temperature was kept stirring for 5 hours. 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, a light yellow paste I was obtained 1 (n=9), yield 68.9%, purity 99.7%.

(1) Technical field

[0001] The invention relates to a polymerization monomer containing hexafluoropropylene oligomer, its synthesis method and application. (2) Background technology

[0002] The research and development of environmentally friendly fluoropolymers, especially the synthesis and application of fluoropolymer emulsions is an inevitable trend in the development of organic fluorine materials. The fluorine-containing polymer emulsion uses water as the dispersion medium, avoids the pollution of the environment caused by the volatilization of the organic solvent, and protects the environment while reducing the product cost. Therefore, fluorine-containing polymer emulsions have broad application prospects in super weather-resistant exterior wall coatings and functional coatings [Surface Coatings International, 1996 (7): 312]. Composition and structure are decisive factors in the performance of fluoropolymers. Therefore, among numerous polymerizable monomers, it is ver...

Examples

Embodiment 1

[0027] Add 15 mL of 1,2-dichloroethane, 1.74 g (10 mmol) of toluene-2,4-diisocyanate, 0.19 g (0.8 mmol) of tetraethyltin, and 0.05 g of p-hydroxyanisole into a 50 mL four-necked flask. Polymerizing agent, stirred, heated up to 75°C, added dropwise 1.02g (10mmol) of ethylene glycol monoallyl ether, after the dropwise addition, TLC detection, followed the reaction process, kept the temperature and stirred for 4h. 6.11 g (10 mmol) of N-methyl-N-hydroxyethyl-4-perfluorononenyloxybenzylamine was added dropwise. After the dropwise addition was completed, TLC was detected to track the reaction progress, and the reaction was carried out while maintaining the temperature and stirring for 5 hours. Reaction is completed, and solvent extraction is separated by silica gel column chromatography (V 二氯甲烷 :V 乙酸乙酯 :V 环己烷 =5:4:1), the light yellow paste I was obtained after removing the solvent 1 (n=9), the polymerized monomer containing hexafluoropropylene oligomer represented by formula (I)...

Embodiment 2

[0032] Carry out the reaction according to the method of Example 1, but N-methyl-N-hydroxyethyl-4-perfluorononenyloxybenzylamine is changed to N-methyl-N-hydroxyethyl-4-perfluorohexene Base oxybenzylamine 4.61g (10mmol), other operation is as embodiment 1, obtains the light yellow paste of polymerized monomer containing hexafluoropropylene oligomer shown in formula (I), I 2 (n=6), yield 66.3%, purity 99.3%.

[0033] 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

[0035] Add 15mL of N,N-dimethylformamide (DMF), 1.74g (10mmol) of 2,4-TDI, 0.23g (1mmol) of tetraethyltin, and 0.08g of hydroquinone into a 250mL four-necked flask as a polymerization inhibitor 1.53 g (15 mmol) of ethylene glycol monoallyl ether was added dropwise. After the addition was completed, TLC was used to detect the reaction progress, and the temperature was kept and stirred for 4 hours. 9.17 g (15 mmol) of N-methyl-N-hydroxyethyl-4-perfluorononenyloxybenzylamine was added dropwise. After the dropwise addition was completed, TLC was detected to track the reaction progress, and the temperature was kept stirring for 5 hours. 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, a light yellow paste I was obtained 1 (n=9), yield 68.9%, purity 99.7%.

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