Free-Radically Polymerizable Crosslinker for Structural Adhesives
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Solution Overview
Problem
Existing structural adhesives with rigid bonds exhibit poor impact resistance and are prone to bond failure due to high and uneven stress distribution, leading to distortion and bond-line read through, especially when bonding larger parts, and the incorporation of elastomeric materials can increase viscosity and reduce oxidation resistance.
Innovation Solution
A free-radically polymerizable crosslinker is developed, comprising divalent segments bonded to secondary and tertiary nitrogen atoms, which, when combined with monofunctional monomers and free-radical initiators, forms a curable composition that achieves high adhesion, elongation, and impact resistance without the need for liquid rubber materials, allowing for flexible bonding without surface treatment.
Engineering Contradictions & Design Principles
Engineering Contradiction Analysis
1Strength
If elastomeric materials are incorporated into structural adhesives to improve impact resistance and flexibility, then elongation and impact resistance are improved, but viscosity increases and oxidation resistance decreases
Solution Approach 1:
The patent changes the chemical parameters by using free-radically polymerizable crosslinkers with specific nitrogen atom configurations (secondary and tertiary N atoms in defined ratios) instead of traditional elastomeric materials. This chemical parameter change achieves flexibility and impact resistance through polymer chain structure rather than rubber particle reinforcement, avoiding the viscosity increase associated with elastomer incorporation.
Solution Approach 2:
The patent introduces local quality by creating specific molecular environments with secondary and tertiary nitrogen atoms positioned at defined distances from polymerizable groups. This localized chemical structure provides flexibility and adhesion at the molecular level without requiring bulk elastomeric materials, thus maintaining low viscosity while achieving high impact resistance.
2Strength
If rigid bonds are used in structural adhesives to achieve high adhesion strength, then bond strength is improved, but stress distribution becomes uneven leading to bond failure and distortion
Solution Approach 1:
The patent applies dynamics by creating a polymer network with mobile secondary and tertiary nitrogen atoms that can dynamically adjust to stress distributions. The free-radically polymerizable groups form crosslinks that maintain structural integrity while the nitrogen-containing segments provide dynamic flexibility, allowing the bond to redistribute stresses uniformly rather than concentrating them at rigid interfaces.
Solution Approach 2:
The patent creates a composite molecular structure combining polymerizable groups (for crosslinking and strength) with nitrogen-containing segments (for flexibility and stress distribution). This molecular composite achieves both high adhesion strength and uniform stress distribution, preventing bond failure and distortion while maintaining reliability.
3Strength
If surface treatment is applied to substrates to improve adhesion, then adhesion strength is improved, but manufacturing complexity and processing time increase
Solution Approach 1:
The patent applies self-service by designing a crosslinker that inherently provides adhesion promotion through its molecular structure (secondary and tertiary nitrogen atoms with polymerizable groups). The adhesive composition itself contains the adhesion-promoting functionality, eliminating the need for external surface treatments. The nitrogen-containing segments self-assemble at interfaces to provide strong bonding without requiring substrate modification.
Solution Approach 2:
The patent achieves universality by creating a multi-functional crosslinker that simultaneously provides crosslinking (for strength), adhesion promotion (through nitrogen segments), and flexibility (through molecular structure). This single compound performs multiple functions that traditionally required separate surface treatments and adhesive formulations, simplifying the overall manufacturing process while maintaining high adhesion strength.
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 curable composition provides bonded constructions with high adhesion (>1000 psi), elongation (>50%), and impact resistance (>2 J) without surface treatment, minimizing bond-line read through and resisting hydrolysis, while maintaining flexibility and reworkability.
Implementation Method 1
at least one free-radical initiator; and at least one free-radically polymerizable crosslinker
Data Source
AI summary
A free-radically polymerizable crosslinker comprising divalent segments Z represented by the formula (I). Each divalent segment Z is respectively directly bonded to i) two secondary N atoms, each further directly bonded to a divalent segment Z or an X group; ii) two tertiary N atoms, each further directly bonded to p additional divalent segments Z and (2-p) X groups, wherein p is 0, 1, or 2; or iii) a secondary N atom further directly bonded to one additional divalent segment Z or an X group, and a tertiary N atom further directly bonded to p additional divalent segments Z and (2-p) X groups. R1 represents an alkylene group having from 1 to 4 carbon atoms, n represents a positive integer. X is represented by the formula: (II) L represents a covalent bond, O, S, NR1, or a divalent linking group having from 2 to 8 carbon atoms and up to 3 oxygen atoms. R2 is a free-radically polymerizable group selected from vinyloxy, allyloxy, methacryloxy, vinylaryl having from 8 to 12 carbon atoms, and 2-propenylaryl having from 9 to 13 carbon atoms. No two of O, S, or N atoms in the X group are adjacent. A curable composition comprises a monofunctional free-radically polymerizable monomer, a free-radical initiator, and the free-radically polymerizable crosslinker. At least partially cured reaction products are also disclosed.


