Preparation method of fluorine-containing acrylate terpolymer emulsion

Abstract

The invention relates to a preparation method of a fluorine-containing acrylate terpolymer emulsion, which comprises the following steps: by taking perfluorohexyl ethyl (methyl) acrylate, high fatty alcohol (methyl) acrylate and a crosslinking monomer as main raw materials, taking persulfate as initiator and using composite emulsifier and a proper amount of co-emulsifier, chain transfer agent and deionized water, performing high-speed shearing at 40 DEG C for 0.5-2 hours, and then performing ultrasonic emulsification for 20-60 minutes to obtain a stable pre-emulsion; and taking part of the pre-emulsion, adding part of the initiator, heating to 50-90 DEG C, reacting for 0.5-1 hours, dropwisely adding the residual pre-emulsion and residual initiator, reacting for 3-6 hours while keeping the temperature, cooling, and regulating the pH value. The prepared emulsion is uniform and stable in particle size and does not contain harmful ingredients such as PFOS / PFOA and the like; and a coated film formed by the emulsion has favorable water repellency and oil repellency.

Description

technical field

[0001] The invention relates to a method for preparing a fluorine-containing acrylate terpolymer emulsion, and belongs to the technical field of fluorine-containing acrylate polymer preparation. Background technique

[0002] Fluorine is the most electronegative element in the periodic table. After the hydrogen in the carbon chain is replaced by a fluorine atom, the bond energy increases and the polarity increases. Fluorocarbon polymers have strong stability and extremely low surface energy. Fluorine-containing acrylate polymers are mainly used in water and oil repellent finishing of fabrics.

[0003] At present, the fluorine-containing acrylate polymers used for fabric finishing are mainly composed of fluorine-containing (meth)acrylates, non-fluorine-containing (meth)acrylates and cross-linking monomers, and are mainly prepared by emulsion polymerization. Fluorine-containing (meth)acrylates provide water and oil repellency, non-fluorine-containing monomers c...

Examples

Embodiment 1

[0047] (1) Add 35ml of deionized water, 10ml of acetone, 4.55g of perfluorohexyl ethyl acrylate, 9.30g of stearyl acrylate, 2-((2-hydroxyethyl)sulfonyl)ethyl acrylate into a 100ml reaction bottle Esters 1.20g, OP-10 (non-ionic surfactant) 0.46g, anionic surfactant sodium dodecyl sulfate 0.25g, dodecyl mercaptan 0.10g, high-speed shearing at 40°C for 1h, then ultrasonic emulsification After 0.5h, a milky white pre-emulsion was obtained.

[0048] Take 0.11 g of the initiator ammonium persulfate, dissolve it in 10 ml of deionized water, and prepare a solution for later use.

[0049] (2) In a 100ml reaction vessel equipped with stirring, reflux condenser, thermometer, and constant pressure dropping funnel, pass nitrogen protection, add 1 / 2 mass of pre-emulsion prepared in step (1) and 1 / 3 mass The initiator was heated to 80°C to react, and blue fluorescence appeared after 1 hour of reaction, then the remaining pre-emulsion and initiator were added dropwise, and the addition was c...

Embodiment 2

[0051] (1) Add 35ml of deionized water, 10ml of acetone, 6.07g of perfluorohexyl ethyl acrylate, 7.67g of lauryl acrylate, and 2-((2-hydroxyethyl)sulfonyl)ethyl acrylate into a 100ml reaction bottle in sequence 1.36g, OP-100.46g, anionic surfactant sodium lauryl sulfate 0.26g, dodecyl mercaptan 0.072g, high-speed shearing at 40°C for 1h, and ultrasonic emulsification for 30min to obtain a milky white pre-emulsion.

[0052] Take 0.11 g of the initiator ammonium persulfate, dissolve it in 10 ml of deionized water, and prepare a solution for later use.

[0053] (2) The heating reaction temperature is 83° C., and other conditions are the same as (2) in Example 1.

Embodiment 3

[0055] (1) Add 35ml of deionized water, 10ml of acetone, 4.55g of perfluorohexyl ethyl acrylate, 9.35g of stearyl acrylate, 2-((2-hydroxyethyl)sulfonyl) ethyl acrylate into a 100ml reaction bottle 1.44g of ester, 0.49g of NP-400, 0.30g of cationic surfactant cetyltrimethylammonium bromide, 0.062g of dodecyl mercaptan, high-speed shearing at 40°C for 1h, and ultrasonic emulsification for 35min to obtain milky white pre-emulsion.

[0056] Take 0.090 g of initiator ammonium persulfate, dissolve it in 10 ml of deionized water, and prepare a solution for later use.

[0057] (2) The reaction device, operation steps and other conditions are the same as (2) in Example 1.

technical field

[0001] The invention relates to a method for preparing a fluorine-containing acrylate terpolymer emulsion, and belongs to the technical field of fluorine-containing acrylate polymer preparation. Background technique

[0002] Fluorine is the most electronegative element in the periodic table. After the hydrogen in the carbon chain is replaced by a fluorine atom, the bond energy increases and the polarity increases. Fluorocarbon polymers have strong stability and extremely low surface energy. Fluorine-containing acrylate polymers are mainly used in water and oil repellent finishing of fabrics.

[0003] At present, the fluorine-containing acrylate polymers used for fabric finishing are mainly composed of fluorine-containing (meth)acrylates, non-fluorine-containing (meth)acrylates and cross-linking monomers, and are mainly prepared by emulsion polymerization. Fluorine-containing (meth)acrylates provide water and oil repellency, non-fluorine-containing monomers c...

Examples

Embodiment 1

[0047] (1) Add 35ml of deionized water, 10ml of acetone, 4.55g of perfluorohexyl ethyl acrylate, 9.30g of stearyl acrylate, 2-((2-hydroxyethyl)sulfonyl)ethyl acrylate into a 100ml reaction bottle Esters 1.20g, OP-10 (non-ionic surfactant) 0.46g, anionic surfactant sodium dodecyl sulfate 0.25g, dodecyl mercaptan 0.10g, high-speed shearing at 40°C for 1h, then ultrasonic emulsification After 0.5h, a milky white pre-emulsion was obtained.

[0048] Take 0.11 g of the initiator ammonium persulfate, dissolve it in 10 ml of deionized water, and prepare a solution for later use.

[0049] (2) In a 100ml reaction vessel equipped with stirring, reflux condenser, thermometer, and constant pressure dropping funnel, pass nitrogen protection, add 1 / 2 mass of pre-emulsion prepared in step (1) and 1 / 3 mass The initiator was heated to 80°C to react, and blue fluorescence appeared after 1 hour of reaction, then the remaining pre-emulsion and initiator were added dropwise, and the addition was c...

Embodiment 2

[0051] (1) Add 35ml of deionized water, 10ml of acetone, 6.07g of perfluorohexyl ethyl acrylate, 7.67g of lauryl acrylate, and 2-((2-hydroxyethyl)sulfonyl)ethyl acrylate into a 100ml reaction bottle in sequence 1.36g, OP-100.46g, anionic surfactant sodium lauryl sulfate 0.26g, dodecyl mercaptan 0.072g, high-speed shearing at 40°C for 1h, and ultrasonic emulsification for 30min to obtain a milky white pre-emulsion.

[0052] Take 0.11 g of the initiator ammonium persulfate, dissolve it in 10 ml of deionized water, and prepare a solution for later use.

[0053] (2) The heating reaction temperature is 83° C., and other conditions are the same as (2) in Example 1.

Embodiment 3

[0055] (1) Add 35ml of deionized water, 10ml of acetone, 4.55g of perfluorohexyl ethyl acrylate, 9.35g of stearyl acrylate, 2-((2-hydroxyethyl)sulfonyl) ethyl acrylate into a 100ml reaction bottle 1.44g of ester, 0.49g of NP-400, 0.30g of cationic surfactant cetyltrimethylammonium bromide, 0.062g of dodecyl mercaptan, high-speed shearing at 40°C for 1h, and ultrasonic emulsification for 35min to obtain milky white pre-emulsion.

[0056] Take 0.090 g of initiator ammonium persulfate, dissolve it in 10 ml of deionized water, and prepare a solution for later use.

[0057] (2) The reaction device, operation steps and other conditions are the same as (2) in Example 1.

Images