A kind of formaldehyde-free amino resin retanning agent

A formaldehyde amino and retanning agent technology, which is applied in the field of retanning agents, can solve the problems of lowering the performance of finished leather, unstable methylene ether bonds, and ineffective removal of aldehydes, and achieve low production costs, low prices, Effect of improving leather feel

Active Publication Date: 2017-02-15
四川德赛尔新材料科技有限公司 +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For example, the formaldehyde in the methyl etherified amino resin product can be removed by vacuum dehydration, methanol removal and formaldehyde in the later stage of the reaction (Yan Xinning, Wang Guanzhong, Shi Qingxue, etc. A kind of low free formaldehyde methyl etherified melamine formaldehyde resin crosslinking agent Synthetic method [P].CN101817914A, 2010-09-01), but the effect of removing aldehyde is not obvious; Adding formaldehyde scavenger in the later stage of reaction is an effective and direct method, but commercially available formaldehyde scavenger is generally more expensive, And the use of formaldehyde scavenger will reduce the use performance of finished leather, so the use of formaldehyde scavenger is subject to certain restrictions
In addition, although the low-formaldehyde amino resin retanning agent product has undergone formaldehyde removal treatment, formaldehyde is used as the starting material in the synthesis process, and the methylene ether bond formed by the condensation of formaldehyde is unstable, so it will continue to be released during use. Free formaldehyde (Gu Jiyou. Adhesives and coatings [M]. Beijing: China Forestry Press, 1999),

Method used

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  • A kind of formaldehyde-free amino resin retanning agent
  • A kind of formaldehyde-free amino resin retanning agent
  • A kind of formaldehyde-free amino resin retanning agent

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] (1) First add 130kg of melamine, 600kg of glutaraldehyde, and 450kg of pure water into the reaction kettle and stir evenly, then adjust the pH of the reaction system to 7.5 with 5kg of 10% sodium hydroxide solution, and slowly heat to 60~65℃ and keep it at this temperature Incubate for 1.0 hour to obtain a hydroxylated melamine prepolymer.

[0034] (2) Add 150kg of water and 85kg of sodium bisulfite to the prepolymer, increase the temperature to 85°C, and keep the temperature for 2.0h.

[0035] (3) Cool down to 60°C, add 100kg of hydrolyzed collagen with a molecular weight of about 5000 and 200kg of pure water, adjust the pH to 5.5, keep the temperature for 2.0 hours and then lower the temperature to below 45°C, and adjust the pH to neutral to obtain the product.

Embodiment 2

[0037] (1) First add 85kg of dicyandiamide, 400kg of glutaraldehyde, and 250kg of pure water into the reaction kettle and stir evenly, then use 4kg of 10% potassium hydroxide solution to adjust the pH of the reaction system to 8.5, slowly heat to 60~65℃ and The temperature was kept for 2.0 hours to obtain a hydroxylated melamine prepolymer.

[0038] (2) Add 200kg water and 55kg sodium metabisulfite to the prepolymer, heat up to 80℃ and keep for 3.0h

[0039] (3) Cooling down to 60°C, adding 150kg of hydrolyzed collagen with a molecular weight of 20,000 to 40,000 and 180kg of pure water, adjusting the pH to 4.5, keeping the temperature for 1.0 hour and then cooling to below 45°C and adjusting the pH to neutral to obtain the product.

Embodiment 3

[0041] (1) First add 130 kg of melamine, 500 kg of glutaraldehyde, and 300 kg of pure water into the reactor and stir evenly, then add 10 kg of 20% sodium carbonate solution to adjust the pH of the reaction system to 8.0, slowly heat to 60~65℃ and keep it at this temperature Keep the temperature for 1.5 hours to obtain a hydroxylated melamine prepolymer.

[0042] (2) Add 175kg water and 65kg sodium bisulfite to the prepolymer, heat up to 90℃ and keep for 1.5h

[0043] (3) Cool down to 60°C, add 130kg of hydrolyzed collagen with a molecular weight of about 10000-15000 and 175kg of pure water, adjust the pH to 6.5, keep the temperature to below 45°C for 3.0 hours and adjust the pH to neutral to obtain the product.

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Abstract

The invention discloses a formaldehyde-free amino resin retanning agent. The formaldehyde-free amino resin retanning agent is characterized by being formed as follows: firstly, obtaining an intermediate containing hydroxyl and aldehyde group residue in molecule by using an amino monomer and glutaraldehyde through nucleophilic addition; then, obtaining the formaldehyde-free amino resin retanning agent by a series of reactions such as sulfonation, hydrolyzed collagen end-blocking, condensation and etherification. The formaldehyde-free amino resin retanning agent provided by the invention is an amino resin condensation product containing an aldehyde group, has retanning performance comparable with that of the conventional amino resin retanning agent, has an aldehyde group capable of performing covalent cross-linking reaction with the amino on collagenous fiber in molecule, and can be used for improving the humidity and heat-resistant stability of finished leather. Formaldehyde is not used in a preparation process of the formaldehyde-free amino resin retanning agent, so that harms of formaldehyde in the finished leather can be greatly lowered.

Description

Technical field [0001] The invention belongs to the technical field of retanning agents for tanning leather and fur, and specifically relates to a new formaldehyde-free amino resin retanning agent. Background technique [0002] Amino resins are widely used in the leather industry due to their good leather filling properties and better dyeing properties. Amino resins are usually the condensation products of melamine, dicyandiamide, urea and other amino-containing monomers with aldehydes (mainly formaldehyde). Since the reaction between amino-containing monomers and formaldehyde under alkaline conditions is reversible, a certain amount of free formaldehyde will inevitably exist in such products or during product use, and the presence of formaldehyde will seriously harm people's health. With the continuous improvement of people's living standards and the need for environmental protection, more stringent limits have been put forward for the content of formaldehyde in leather. Common...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C14C3/22C08G12/40
Inventor 孙青永彭章义丁学斌石碧谢衡廖学品
Owner 四川德赛尔新材料科技有限公司
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