Novel amphiphilic block acrylic resin retanning agent and preparation method thereof

Abstract

The invention relates to a novel amphiphilic block acrylic resin retanning agent and a preparation method thereof. The invention is characterized in that the preparation method comprises the following steps: 1. (methyl) acrylic acid reversible addition-fragmentation chain transfer free-radical polymerization; and 2. synthesis of amphiphilic block acrylic resin retanning agent. The amphiphilic block acrylic resin retanning agent is a milk white thick liquid in appearance, the pH value is 3.0, and the effective substance content is 20-30 wt%. The product has the advantages of favorable acid-resistant stability, favorable alkali-resistant stability and favorable storage stability, enhances the absorption of the wet blue leather for the chrome tanning agent, enables the crust leather grain surface to be fine, compact and full, and obviously enhances the tearing strength of the crust leather.

Description

technical field

[0001] The invention relates to the technical field of leather retanning technology, in particular to a novel amphiphilic block acrylic resin retanning agent and a preparation method thereof. Background technique

[0002] In the leather industry, the retanning process is very important because it can make up for many defects of chrome tanning. Among the many types of retanning agents, the retanning agents based on acrylic monomers have been widely studied and applied. For decades, acrylic resin retanning agents can endow chrome tanned leather with various value-added properties, such as fullness, elasticity, and grain fullness; in recent years, amphiphilic acrylic resins with retanning and fatliquoring functions Tanning agents have attracted widespread attention; amphiphilic acrylic resin retanning agents are usually composed of hydrophilic and hydrophobic two parts, wherein the hydrophilic group (such as carboxyl) reacts with trivalent chromium in wet blue l...

Examples

Embodiment 1

[0016] 1. Reversible addition-fragmentation chain transfer radical polymerization of acrylic acid: 90 parts of acrylic acid, 4.5 parts of RAFT reagent, 0.9 part of 4,4'-azobis(4-cyanovaleric acid) (V501), 0.5 part of carbonic acid Add sodium hydrogen, 256.7 parts of deionized water and 5 parts of mixed emulsifier into the reaction kettle, heat up to 80°C, and react for 3 hours to obtain polyacrylic acid macromolecule RAFT reagent; 2. Synthesis of amphiphilic block acrylic resin retanning agent: Continue to add 0.45 parts of 4,4'-azobis(4-cyanovaleric acid) (V501) to the reactor, add 10 parts of lauryl acrylate dropwise into the reactor within 2 hours, and continue the reaction after the addition is complete After 4 hours, after the reaction was completed, an amphiphilic block acrylic resin retanning agent was obtained.

Embodiment 2

[0018] 1. Reversible addition-fragmentation chain transfer radical polymerization of acrylic acid: 90 parts of acrylic acid, 4.5 parts of RAFT reagent, 0.9 part of 4,4'-azobis(4-cyanovaleric acid) (V501), 0.5 part of carbonic acid Add sodium hydrogen, 256.7 parts of deionized water and 5 parts of mixed emulsifier into the reaction kettle, heat up to 80°C, and react for 3 hours to obtain polyacrylic acid macromolecule RAFT reagent; 2. Synthesis of amphiphilic block acrylic resin retanning agent: Continue to add 0.45 parts of 4,4'-azobis(4-cyanovaleric acid) (V501) to the reactor, and add 10 parts of lauryl methacrylate dropwise into the reactor within 2 hours. The reaction was continued for 4 hours, and after the reaction was completed, an amphiphilic block acrylic resin retanning agent was obtained.

Embodiment 3

[0020] 1. Reversible addition-fragmentation chain transfer radical polymerization of methacrylic acid: 80 parts of methacrylic acid, 4 parts of RAFT reagent, 0.8 part of 4,4'-azobis(4-cyanovaleric acid) (V501) , 0.5 parts of sodium bicarbonate, 255.5 parts of deionized water and 5 parts of mixed emulsifier were added to the reaction kettle, the temperature was raised to 80°C, and the reaction was carried out for 3 hours to obtain a polymethacrylic acid macromolecule RAFT reagent; 2. Amphiphilic block acrylic resin Synthesis of retanning agent: continue to add 0.4 parts of 4,4'-azobis(4-cyanovaleric acid) (V501) to the reaction kettle, and drop 20 parts of lauryl acrylate into the reaction kettle dropwise within 2 hours After the addition, the reaction was continued for 4 hours. After the reaction was completed, an amphiphilic block acrylic resin retanning agent was obtained.

technical field

[0001] The invention relates to the technical field of leather retanning technology, in particular to a novel amphiphilic block acrylic resin retanning agent and a preparation method thereof. Background technique

[0002] In the leather industry, the retanning process is very important because it can make up for many defects of chrome tanning. Among the many types of retanning agents, the retanning agents based on acrylic monomers have been widely studied and applied. For decades, acrylic resin retanning agents can endow chrome tanned leather with various value-added properties, such as fullness, elasticity, and grain fullness; in recent years, amphiphilic acrylic resins with retanning and fatliquoring functions Tanning agents have attracted widespread attention; amphiphilic acrylic resin retanning agents are usually composed of hydrophilic and hydrophobic two parts, wherein the hydrophilic group (such as carboxyl) reacts with trivalent chromium in wet blue l...

Examples

Embodiment 1

[0016] 1. Reversible addition-fragmentation chain transfer radical polymerization of acrylic acid: 90 parts of acrylic acid, 4.5 parts of RAFT reagent, 0.9 part of 4,4'-azobis(4-cyanovaleric acid) (V501), 0.5 part of carbonic acid Add sodium hydrogen, 256.7 parts of deionized water and 5 parts of mixed emulsifier into the reaction kettle, heat up to 80°C, and react for 3 hours to obtain polyacrylic acid macromolecule RAFT reagent; 2. Synthesis of amphiphilic block acrylic resin retanning agent: Continue to add 0.45 parts of 4,4'-azobis(4-cyanovaleric acid) (V501) to the reactor, add 10 parts of lauryl acrylate dropwise into the reactor within 2 hours, and continue the reaction after the addition is complete After 4 hours, after the reaction was completed, an amphiphilic block acrylic resin retanning agent was obtained.

Embodiment 2

[0018] 1. Reversible addition-fragmentation chain transfer radical polymerization of acrylic acid: 90 parts of acrylic acid, 4.5 parts of RAFT reagent, 0.9 part of 4,4'-azobis(4-cyanovaleric acid) (V501), 0.5 part of carbonic acid Add sodium hydrogen, 256.7 parts of deionized water and 5 parts of mixed emulsifier into the reaction kettle, heat up to 80°C, and react for 3 hours to obtain polyacrylic acid macromolecule RAFT reagent; 2. Synthesis of amphiphilic block acrylic resin retanning agent: Continue to add 0.45 parts of 4,4'-azobis(4-cyanovaleric acid) (V501) to the reactor, and add 10 parts of lauryl methacrylate dropwise into the reactor within 2 hours. The reaction was continued for 4 hours, and after the reaction was completed, an amphiphilic block acrylic resin retanning agent was obtained.

Embodiment 3

[0020] 1. Reversible addition-fragmentation chain transfer radical polymerization of methacrylic acid: 80 parts of methacrylic acid, 4 parts of RAFT reagent, 0.8 part of 4,4'-azobis(4-cyanovaleric acid) (V501) , 0.5 parts of sodium bicarbonate, 255.5 parts of deionized water and 5 parts of mixed emulsifier were added to the reaction kettle, the temperature was raised to 80°C, and the reaction was carried out for 3 hours to obtain a polymethacrylic acid macromolecule RAFT reagent; 2. Amphiphilic block acrylic resin Synthesis of retanning agent: continue to add 0.4 parts of 4,4'-azobis(4-cyanovaleric acid) (V501) to the reaction kettle, and drop 20 parts of lauryl acrylate into the reaction kettle dropwise within 2 hours After the addition, the reaction was continued for 4 hours. After the reaction was completed, an amphiphilic block acrylic resin retanning agent was obtained.

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