Anionic functionalized fluorine-containing polymer and preparation method thereof

Abstract

The invention discloses an anionic functionalized fluorine-containing polymer and a preparation method thereof. The functionalized fluorine-containing polymer is prepared through the following steps: subjecting a chlorine-containing monomer, a graftable active monomer and a hydrophilic functionalized monomer as copolymerization monomers to polymerization in an aqueous-phase dispersion system so as to obtain an active precursor polymer with a main chain containing an active side group for atom transfer radical polymerization, initiating an anionic functionalized polymer to interface atom transfer radical polymerization on a solid-liquid interface in an alkaline environment by utilizing the active side group so as to form the anionic functionalized fluorine-containing polymer containing an anionic type side chain. According to the invention, the anionic type side chain contains sulfonic groups and carboxylic groups and has strong electronegativity, so the polymer has strong hydrophilic performance and cation exchange adsorption performance, can be independently used for preparation or is mixed with other resins for preparation of highly-hydrophilic separating membrane products, gel electrolytes, adhesives, battery separators, cation exchange adsorption materials and flexible packaging materials, greatly broadens the application scope of vinyl chloride polymers, and has good application prospects.

Description

technical field

[0001] The invention belongs to the field of polymer materials, and in particular relates to an anion functionalized fluorine-containing polymer and a preparation method thereof. Background technique

[0002] Fluorine atoms have strong electronegativity, low polarizability, weak van der Waals force and high bond energy (485.3kJ / mol) of C-F bond, which makes fluoropolymers have outstanding heat resistance, solvent resistance, acid and alkali corrosion resistance, Excellent weather resistance, flame retardancy, and unique low surface energy, etc. Fluorine-containing polymers are mainly divided into fluorine-containing olefin polymers and fluorine-containing acrylate polymers.

[0003] Polyvinylidene fluoride (PVDF) is non-toxic and odorless, and its appearance is translucent or white powder or granules. Ultraviolet radiation and aging resistance; the molecular chains of PVDF are closely arranged, the crystallinity is high, the hydrophobicity is large, and the...

Examples

Embodiment 1

[0147] Synthesis of anion-functionalized fluoropolymer P1:

[0148]Add 2000ml deionized water, additive polyvinyl alcohol (PVA) 1.2g, additive hydroxypropyl methylcellulose (HPMC) 0.4g, initiator peroxydicarbonate bis(2-ethylhexyl) in the stainless steel reaction kettle (EHP) 1g, evacuated and filled with nitrogen repeatedly 3 times, then added 1500g of vinylidene fluoride, 27.19g of hydroxyethyl acrylate and 4.85g of allyl 2-bromo-2-methylpropionate, pre-dispersed and stirred at room temperature for 30 minute. The temperature was raised to a polymerization temperature of 47° C. to carry out a polymerization reaction. React for 12 hours, stop heating when the pressure drop in the kettle reaches 0.2MPa, let it volatilize naturally for 15 minutes, let air in for 5 minutes, vacuumize and fill with nitrogen three times, then add sodium bicarbonate until the pH is 8, add 22.03g of sodium acrylate , copper 5g, cuprous chloride 5g, 2,2'-bipyridine (bpy) 16g, then temperature contro...

Embodiment 2

[0167] Synthesis of anion-functionalized fluoropolymer P2:

[0168] P2 synthetic process with reference to embodiment 1. The formula is shown in Table 1 and the process parameters are shown in Table 2.

[0169] The P2 structure and performance characterization methods are the same as those described in Example 1. The general formula of the P2 structural formula is the same as that of P1, and the parameters in the general formula are shown in Table 3;

Embodiment 3

[0171] Synthesis of anion-functionalized fluoropolymer P3:

[0172] The synthesis process of P3 refers to Example 1. The formula is shown in Table 1 and the process parameters are shown in Table 2.

[0173] The P3 structure and performance characterization methods are the same as those described in Example 1. The general structure of P3 is the same as that of P1, and the parameters in the general formula are shown in Table 3; the molecular weight, molecular weight distribution and content of anion functionalized monomer components in the polymer of P3 are shown in Table 4.

technical field

[0001] The invention belongs to the field of polymer materials, and in particular relates to an anion functionalized fluorine-containing polymer and a preparation method thereof. Background technique

[0002] Fluorine atoms have strong electronegativity, low polarizability, weak van der Waals force and high bond energy (485.3kJ / mol) of C-F bond, which makes fluoropolymers have outstanding heat resistance, solvent resistance, acid and alkali corrosion resistance, Excellent weather resistance, flame retardancy, and unique low surface energy, etc. Fluorine-containing polymers are mainly divided into fluorine-containing olefin polymers and fluorine-containing acrylate polymers.

[0003] Polyvinylidene fluoride (PVDF) is non-toxic and odorless, and its appearance is translucent or white powder or granules. Ultraviolet radiation and aging resistance; the molecular chains of PVDF are closely arranged, the crystallinity is high, the hydrophobicity is large, and the...

Examples

Embodiment 1

[0147] Synthesis of anion-functionalized fluoropolymer P1:

[0148]Add 2000ml deionized water, additive polyvinyl alcohol (PVA) 1.2g, additive hydroxypropyl methylcellulose (HPMC) 0.4g, initiator peroxydicarbonate bis(2-ethylhexyl) in the stainless steel reaction kettle (EHP) 1g, evacuated and filled with nitrogen repeatedly 3 times, then added 1500g of vinylidene fluoride, 27.19g of hydroxyethyl acrylate and 4.85g of allyl 2-bromo-2-methylpropionate, pre-dispersed and stirred at room temperature for 30 minute. The temperature was raised to a polymerization temperature of 47° C. to carry out a polymerization reaction. React for 12 hours, stop heating when the pressure drop in the kettle reaches 0.2MPa, let it volatilize naturally for 15 minutes, let air in for 5 minutes, vacuumize and fill with nitrogen three times, then add sodium bicarbonate until the pH is 8, add 22.03g of sodium acrylate , copper 5g, cuprous chloride 5g, 2,2'-bipyridine (bpy) 16g, then temperature contro...

Embodiment 2

[0167] Synthesis of anion-functionalized fluoropolymer P2:

[0168] P2 synthetic process with reference to embodiment 1. The formula is shown in Table 1 and the process parameters are shown in Table 2.

[0169] The P2 structure and performance characterization methods are the same as those described in Example 1. The general formula of the P2 structural formula is the same as that of P1, and the parameters in the general formula are shown in Table 3;

Embodiment 3

[0171] Synthesis of anion-functionalized fluoropolymer P3:

[0172] The synthesis process of P3 refers to Example 1. The formula is shown in Table 1 and the process parameters are shown in Table 2.

[0173] The P3 structure and performance characterization methods are the same as those described in Example 1. The general structure of P3 is the same as that of P1, and the parameters in the general formula are shown in Table 3; the molecular weight, molecular weight distribution and content of anion functionalized monomer components in the polymer of P3 are shown in Table 4.

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