Liquid Difunctional Bio-Benzoxazine Compounds for Faster Curing

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Solution Overview

Problem

Conventional benzoxazine resins are solid, toxic, and require energy-intensive processes, leading to high viscosity and slow gel times, making them difficult to process and inefficient for matrix or coating applications.

Innovation Solution

A new class of difunctional benzoxazine compounds derived from furfuraldehyde, which are liquid at standard conditions, providing comparable thermoset properties with improved gel times and bio-carbon content, eliminating the need for formaldehyde and reducing processing challenges.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Strength

If conventional benzoxazine resins are used, then high molecular weight thermoset polymers with good cross-linkage are obtained, but the resins are solid with high viscosity making them difficult to process

Engineering Contradiction:
Improvecross-linkage qualityVSAvoidprocessability
Core Design Contradiction:
StrengthVSEase of operation

Solution Approach 1:

The invention changes the physical state parameter of benzoxazine resins from solid to liquid by modifying the chemical structure (using furfuraldehyde-derived compounds with specific molecular weights and functional groups). This parameter change enables the resin to remain liquid at processing temperatures, dramatically improving processability while maintaining the ability to form high molecular weight cross-linked thermoset polymers upon curing

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention creates a composite chemical structure combining furfuraldehyde-derived benzoxazine rings with specific linker groups (L1, L2) that provide both liquid state at room temperature and reactivity for cross-linking. The composite molecular architecture achieves the dual goal of low viscosity for processing and high cross-linkage density for strength

Inventive Principle:
Principle #40Composite materials

2Reliability

If conventional benzoxazine resins are used, then thermoset polymers are formed, but the gel times are slow reducing process efficiency

Engineering Contradiction:
Improvethermoset formationVSAvoidgel time
Core Design Contradiction:
ReliabilityVSProductivity

Solution Approach 1:

The invention modifies the chemical composition parameters of the benzoxazine resin by incorporating furfuraldehyde-derived structures with specific functional groups that increase reactivity. This changes the curing kinetics parameter, reducing gel time from hours to minutes while still forming complete thermoset polymers, thereby improving productivity without sacrificing reliability

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The liquid state of the resin at room temperature serves as a preliminary action that enables better penetration and distribution into substrates before curing occurs. This preliminary wetting action, combined with the modified chemical structure, allows the resin to maintain reliability of thermoset formation while significantly accelerating the overall process through reduced gel time

Inventive Principle:
Principle #10Preliminary action

3Ease of manufacture

If formaldehyde is used in benzoxazine synthesis, then conventional benzoxazine resins are produced, but the process is energy-intensive and produces toxic byproducts

Engineering Contradiction:
Improveresin productionVSAvoidtoxicity and energy consumption
Core Design Contradiction:
Ease of manufactureVSObject-affected harmful factors

Solution Approach 1:

The invention converts the harmful formaldehyde synthesis route into a beneficial furfuraldehyde-based process. Furfuraldehyde, derived from renewable lignocellulosic biomass, replaces formaldehyde to produce benzoxazine resins that are less toxic and can be synthesized under milder, more energy-efficient conditions. The furfuraldehyde structure inherently provides the necessary reactivity for benzoxazine formation without the carcinogenic properties of formaldehyde

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

Solution Approach 2:

The invention uses furfuraldehyde, a cheaper and more environmentally benign alternative to formaldehyde, as the carbonyl component in the Mannich reaction. This substitution reduces both the energy intensity and toxicity of the manufacturing process while maintaining ease of resin production, effectively replacing a harmful chemical pathway with a greener alternative

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

4Reliability

If conventional benzoxazine resins are used, then polymers with good physical electrical performance are obtained, but the resins require high processing temperatures increasing energy consumption

Engineering Contradiction:
Improvephysical electrical performanceVSAvoidprocessing temperature
Core Design Contradiction:
ReliabilityVSUse of energy by moving object

Solution Approach 1:

The invention changes the thermal processing parameters by modifying the resin chemistry to enable curing at lower temperatures. The furfuraldehyde-derived benzoxazine structure, with its specific functional groups and molecular weight, allows the polymerization reaction to proceed efficiently at reduced temperatures while still achieving complete cure and maintaining the physical electrical performance characteristics of the thermoset polymer

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 liquid benzoxazine compounds offer enhanced handling and application properties, allowing for efficient curing at lower temperatures without premature polymerization, resulting in high molecular weight thermoset polymers with superior cross-linkage and bio-carbon content.

Implementation Method 1

Benzoxazines are capable of undergoing ring opening on heating without the need of catalysts and without emitting volatiles, leading to self-polymerisation

Methodology Applied
Scientific EffectSelf-polymerisation: Chemical Bonding

Implementation Method 2

The process to synthesise the benzoxazine structure is a Mannich reaction between the primary amine and the aldehyde liberating water to form an iminium ion, followed by cyclisation with the phenolic compound

Methodology Applied
Scientific EffectMannich reaction: Chemical Bonding

Data Source

PatentEP4396184B1Difunctional bio-benzoxazine compounds, preparation methods and uses thereof
Publication Date: 2025.09.17 JONES PAUL
  • EP4396184B1 patent drawingFigure 1~2
  • EP4396184B1 patent drawingFigure 3~4
  • EP4396184B1 patent drawingFigure 5~6

AI summary

The invention relates to a class of difunctional benzoxazine compounds useful as curatives, as well as methods of preparation, and uses thereof. The difunctional benzoxazine compounds comprise two benzoxazine rings, each disubstituted with two furfuryl groups. The two benzoxazine rings may be attached via a hydrocarbyl linker or two benzoxazine moieties may share a common benzene group. The difunctional benzoxazine compounds are capable of self-polymerisation via a ring opening reaction which allows them to act as a curative. In one aspect, the present invention provides a compound of formula (I) below. (I)