Acrylic Ether-Ester Monomers for Low-Shrinkage Coatings

Resolve Bottlenecks,
Find Innovative Solutions
Generate Solutions

Solution Overview

Problem

Existing multifunctional acrylic monomers used in coatings suffer from poor flexibility and adhesion due to high crosslinking density, leading to a compromise in hardness and flexibility, and rely on expensive and difficult-to-access polyols, with alkoxylation reducing reactivity.

Innovation Solution

A novel acrylic product is developed using a mixture of linear and branched oligo(ether-ester)s derived from common polyols and acrylic acid in the presence of cyclic carboxylic anhydride or its polyacid form, controlling crosslinking density and reactivity without using expensive materials, achieving a balance between hardness and flexibility.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Strength

If existing multifunctional acrylic monomers are used to increase crosslinking density, then hardness and chemical resistance are improved, but flexibility and adhesion deteriorate

Engineering Contradiction:
ImprovehardnessVSAvoidflexibility
Core Design Contradiction:
StrengthVSEase of operation

Solution Approach 1:

The patent modifies the molecular structure parameters of acrylic monomers by introducing specific ether-ester linkages and controlling the distribution of acrylic groups. This changes the physical and chemical properties of the polymer network, achieving both high hardness and flexibility simultaneously by optimizing the balance between crosslinking density and chain mobility.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention creates a composite molecular structure combining rigid aromatic components for hardness with flexible aliphatic ether-ester segments for flexibility. This composite approach at the molecular level allows the material to exhibit both high strength and good flexibility, resolving the traditional trade-off between these properties.

Inventive Principle:
Principle #40Composite materials

2Reliability

If existing multifunctional acrylic monomers are used to increase crosslinking density, then chemical resistance is improved, but adhesion to substrates deteriorates

Engineering Contradiction:
Improvechemical resistanceVSAvoidadhesion
Core Design Contradiction:
ReliabilityVSEase of operation

Solution Approach 1:

The patent applies local quality by creating regions of high crosslinking density for chemical resistance while maintaining regions of lower crosslinking with flexible linkages for adhesion. The molecular structure contains localized rigid segments for durability and flexible segments for substrate bonding, allowing both properties to coexist.

Inventive Principle:
Principle #3Local quality

3Ease of operation

If alkoxylation of starting polyols is performed to reduce crosslinking density, then flexibility is improved, but reactivity deteriorates

Engineering Contradiction:
ImproveflexibilityVSAvoidreactivity
Core Design Contradiction:
Ease of operationVSSpeed

Solution Approach 1:

The invention segments the polyol structure into distinct functional regions: reactive segments containing hydroxyl groups for high reactivity, and flexible segments containing ether linkages for flexibility. This segmentation allows the molecule to simultaneously exhibit both high reactivity and flexibility without the trade-off observed in conventional alkoxylated polyols.

Inventive Principle:
Principle #1Segmentation

4Quantity of substance

If expensive multifunctional polyols such as ditrimethylol propane or dipentaerythritol are used, then high functionality is achieved, but manufacturing cost increases significantly

Engineering Contradiction:
ImprovefunctionalityVSAvoidmanufacturing cost
Core Design Contradiction:
Quantity of substanceVSEase of manufacture

Solution Approach 1:

The patent replaces expensive, difficult-to-access multifunctional polyols with cheaper, readily available alternatives. By using conventional polyols combined with multifunctional acrylic monomers, the invention achieves the same high functionality at significantly lower cost, making the manufacturing process more economically viable.

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

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 solution provides high functionality with controlled crosslinking density, low shrinkage, and improved adhesion and flexibility, maintaining high reactivity and hardness without the need for aromatic structures like bisphenol A, and simplifies the synthesis process while reducing environmental impact.

Implementation Method 1

the product of reaction of a polyol or of a mixture of polyols, and of acrylic acid in the presence of at least one cyclic carboxylic anhydride or of its polycarboxylic acid form

Methodology Applied
Scientific EffectEsterification: Chemical Bonding

Implementation Method 2

Multifunctional acrylic monomers of high functionality... in terms of acrylic groups... for increasing the crosslinking density

Methodology Applied
Scientific EffectPolymerization crosslinking: Chemical Bonding

Data Source

PatentUS10501402B2Multifunctional acrylic ether-ester products modified with carboxylic anhydride or its polyacid form, process for preparing same and associated crosslinkable compositions
Publication Date: 2019.12.10 ARKEMA FRANCE SA

AI summary

The invention relates to a multifunctional acrylic product having a number-average functionality f of acrylate groups greater than 2.1, which is the product of reaction by esterification and by etherification, via Michael addition reaction, between a) a polyol or a mixture of polyols R(OH)m having a functionality m of at least 3 for a polyol alone or having an average functionality greater than 2.1 for a mixture of polyols, and b) the acrylic acid (R1OH) in the presence of c) at least one cyclic polycarboxylic anhydride or of its polyacid form having a carboxy functionality z of at least 2 and up to 4, the ratio r1 of number of carboxy groups of said anhydride or polyacid c) with respect to those of the acrylic acid b) r1=CO2Hc/CO2Hb being from 0.01 to 0.4 with overall r=CO2H/OH<1, said acrylic product comprising in its composition both:units A) of oligoether-ester acrylate that are derived from a) and b) andunits B) of oligoester acrylate that are derived from c),said acrylic product being a mixture of acrylic products comprising at least one acrylic product p1 chemically linking, in its molecular structure, the two types of units A) and B) as defined above.The invention also relates to a process for preparing said product, to crosslinkable compositions comprising same and to the use thereof in coatings, sealing, moulding or composite compositions, chemical sealing compositions, 3D printing compositions or compositions for 3D objects produced layer-by-layer. One particular advantage of these compositions is their low shrinkage despite their high functionality.