Semi-Crystalline Polyamide Composite In-Situ Polymerization

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Solution Overview

Problem

Existing methods for manufacturing fiber-reinforced composite materials using semi-crystalline polyamides face challenges in achieving homogeneous impregnation, mechanical performance, and processability at controlled temperatures without thermal degradation, particularly due to issues with glass transition temperature (Tg) and melting point (Tf) limitations.

Innovation Solution

A method involving a specific reactive composition based on semi-crystalline polyamide prepolymer with controlled reaction kinetics and rapid crystallization, using a composition with a Tg greater than 80°C and a Tf below 280°C, allowing for improved impregnation and mechanical performance while maintaining processability at lower temperatures through in-situ polymerization in a closed mold using RTM or RIM techniques.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Strength

If semi-crystalline polyamides with high melting point (Tf > 270°C) are used to improve mechanical performance and thermal resistance, then strength and reliability are improved, but processing temperature must be increased leading to higher energy consumption and risk of thermal degradation

Engineering Contradiction:
Improvemechanical performanceVSAvoidenergy consumption
Core Design Contradiction:
StrengthVSUse of energy by stationary object

Solution Approach 1:

The patent modifies the chemical composition parameters of the polyamide by incorporating specific cyclic carbonate comonomers (1,3-propanecarbonitrile-1,3-dioxide and/or 1,4-butanesultone) in controlled amounts (0.1-10 mol%) to adjust the melting point and glass transition temperature to optimal processing ranges while maintaining mechanical performance

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates a composite polymer system by combining polyamide with cyclic carbonate comonomers to form a new material system that exhibits both the desired mechanical strength and processability at lower temperatures, effectively combining benefits of different material characteristics

Inventive Principle:
Principle #40Composite materials

2Ease of manufacture

If reactive precursor composition with low viscosity is used to improve impregnation of fibrous substrate, then ease of manufacture is improved, but reaction kinetics must be controlled to avoid premature polymerization

Engineering Contradiction:
Improveimpregnation qualityVSAvoidreaction control
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The patent performs preliminary action by pre-polymerizing a portion of the polyamide to create a low-viscosity precursor composition before impregnation, ensuring good fiber wetting, then completes the polymerization reaction after molding to achieve final mechanical properties without premature crosslinking during impregnation

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent dynamically controls the reaction system by adjusting the degree of pre-polymerization and using appropriate catalysts to maintain the precursor in a reactive but stable state during impregnation, then activating complete polymerization under controlled conditions after molding

Inventive Principle:
Principle #15Dynamics

3Reliability

If glass transition temperature (Tg) is increased above 80°C to maintain mechanical properties at elevated temperatures, then reliability is improved, but the polymer becomes more rigid and difficult to process

Engineering Contradiction:
Improvethermal stabilityVSAvoidprocessability
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The patent precisely controls the Tg parameter by adjusting the type and amount of cyclic carbonate comonomer (1,3-propanecitrile-1,3-dioxide and/or 1,4-butanesultone) in the range of 0.1-10 mol%, which modifies the polymer chain flexibility and intermolecular forces to achieve optimal balance between thermal stability and processability

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

This approach enables the production of composite materials with enhanced mechanical performance, improved impregnation, and reduced energy consumption, with a shorter molding cycle and higher productivity, while maintaining mechanical properties across a wide temperature range without thermal degradation.

Implementation Method 1

a reactive composition based on a prepolymer, said reactive composition being a precursor of the final polymer of the thermoplastic matrix which is a semi-crystalline polyamide

Methodology Applied
Scientific EffectPolyaddition: Chemical Bonding

Implementation Method 2

this is enabled by the ability for rapid crystallization of said semi-crystalline polyamide polymer by the specific choice of its composition and this while maintaining the mechanical performance of said final materials at a high level

Methodology Applied
Scientific EffectCrystallization: Crystallisation

Data Source

PatentEP3387042B1Method for producing a fibre-reinforced polyamide matrix composite material, from a reactive prepolymer precursor composition
Publication Date: 2022.05.11 ARKEMA FRANCE SA
  • EP3387042B1 patent drawingFigure 1

AI summary

The present invention relates to a method for producing a thermoplastic composite material with a fibrous reinforcement and a matrix which is a semi-crystalline polyamide having a Tg of at least 80°C and a Tf no higher than 280°C and higher than 200°C, prepared in-situ by bulk polymerisation in the molten state by polycondensation, of a reactive precursor composition comprising, according to A, at least one first polyamide prepolymer A1 carrying two identical functions X or Y and at least one second polyamide prepolymer A2 carrying two identical functions X or Y, different from those of A1 and co-reactive relative to those of A1, or a precursor composition comprising, according to B, at least one prepolymer carrying (on the same chain) two different functions X and Y which are co-reactive with one another, or a precursor composition according to the mixture of (A+B), with X and Y being carboxy or amine respectively and vice versa, said method comprising the consecutive steps of i) preparing the reactive mixture A: (A1+A2) or the reactive mixture (A+B): (A1+A2+B), or the melting of said prepolymer according to B, ii) impregnating said fibres, by injecting said reactive precursor composition in the molten state, iii) in-situ bulk polymerisation in the molten state by polycondensation, iv) cooling and demoulding said material, said final polyamide of said matrix and said prepolymers A1, A2 or B having the same specific composition in terms of amide units. The invention also relates to the reactive precursor composition, the resulting composite part and the use thereof.