Cellulose Formate Filament Esterification Without Cellulose Degradation

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Solution Overview

Problem

Existing methods for chemically modifying cellulose to improve solubility and processing properties are hindered by strong acidity causing degradation, leading to low-strength renewable materials, and high molecular weight cellulose remains difficult to esterify homogeneously.

Innovation Solution

An esterification method using a mixture of formic acid, zinc chloride, and water at specific molar ratios, conducted at room temperature, followed by filamentation, coagulation, and drying to produce a cellulose formate filament material with high strength.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Stability of the object's composition

If concentrated formic acid solution (99 wt%) is used for esterification, then dissolution of cellulose is achieved, but the process takes more than 24 hours and cannot dissolve high molecular weight cellulose

Engineering Contradiction:
Improvedissolution of celluloseVSAvoidesterification time
Core Design Contradiction:
Stability of the object's compositionVSLoss of time

Solution Approach 1:

The patent changes the chemical parameters of the esterification system by using formic acid combined with zinc chloride and water in specific molar ratios (2-4):1:(1-2), rather than pure concentrated formic acid. This parameter modification enables rapid esterification of high molecular weight cellulose within 1-12 hours while achieving complete dissolution and homogeneous substitution.

Inventive Principle:
Principle #35Parameter changes

2Productivity

If temperature is increased or strong acid catalysts (sulfuric acid, hydrochloric acid, phosphoric acid) are added to accelerate esterification, then reaction speed increases, but cellulose degradation occurs and homogeneous esterification of high molecular weight cellulose cannot be achieved

Engineering Contradiction:
Improveesterification rateVSAvoidcellulose strength
Core Design Contradiction:
ProductivityVSStrength

Solution Approach 1:

The patent replaces traditional strong acid catalysts with a zinc chloride-based system combined with formic acid and water. This chemical parameter change enables rapid esterification at room temperature without causing cellulose degradation, achieving both high productivity and preservation of cellulose strength.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

Zinc chloride acts as an intermediary catalyst in the esterification system, mediating between formic acid and cellulose to achieve rapid reaction without the harsh conditions required by traditional strong acids. The zinc chloride-water-formic acid complex provides a milder yet effective catalytic environment that prevents degradation.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Stability of the object's composition

If degree of substitution of formyl exceeds 1.3, then cellulose dissolution is achieved, but the process cannot be completed in reasonable time and high molecular weight cellulose cannot be dissolved

Engineering Contradiction:
Improvecellulose dissolutionVSAvoidesterification efficiency
Core Design Contradiction:
Stability of the object's compositionVSProductivity

Solution Approach 1:

The patent modifies the esterification system parameters by incorporating zinc chloride and water with formic acid in specific molar ratios. This enables achievement of degree of substitution exceeding 1.3 with complete dissolution of high molecular weight cellulose within 1-12 hours, simultaneously improving both dissolution completeness and reaction efficiency.

Inventive Principle:
Principle #35Parameter changes

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The method achieves homogeneous esterification of cellulose, resulting in a cellulose formate filament material with a tensile strength of not less than 1 GPa, overcoming the limitations of prior art.

Implementation Method 1

a strong acidity of the mixed solvent causes the degradation of a cellulose macromolecular structure... hydrogen bonding interaction investigation

Methodology Applied
Scientific EffectHydrogen bonding:

Implementation Method 2

Cellulose can undergo esterification when being mixed with a concentrated formic acid solution (99 wt%)... cellulose can be dissolved

Methodology Applied
Scientific EffectEsterification:

Implementation Method 3

subjecting the reaction solution to filamentation, followed by coagulation, washing, and drying in sequence

Methodology Applied
Scientific EffectCoagulation: Coagulation

Data Source

PatentEP4578880B1Esterification method of cellulose and preparation method of cellulose formate filament material
Publication Date: 2026.04.29 NORTHEAST FORESTRY UNIV
  • EP4578880B1 patent drawingFigure 1~2
  • EP4578880B1 patent drawingFigure 3~4
  • EP4578880B1 patent drawingFigure 5

AI summary

An esterification method of cellulose and a preparation method of a cellulose formate filament material are provided, belonging to the technical field of cellulose renewable materials. The esterification method of cellulose includes the following steps: mixing cellulose with an esterification system to obtain a mixture, and subjecting the mixture to esterification, where the esterification system includes formic acid, zinc chloride, and water at a molar ratio of (2-4): 1: (1-2). An esterification system with a specific molar ratio can homogeneously esterify cellulose macromolecules at room temperature. Cellulose formate samples in examples all show a degree of substitution of not less than 0.6, thereby promoting the preparation of a high-strength cellulose formate filament material.