Renewable bio-based (meth)acrylated monomers as vinyl ester cross-linkers
Inventors
Palmese, Giuseppe R. • La Scala, John Joseph • Sadler, Joshua Matthew • Lam, Anh-Phuong Thy
Assignees
Drexel University • United States Department of the Army
Publication Number
US-9644059-B2
Publication Date
2017-05-09
Expiration Date
2032-08-10
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Abstract
Anhydrosugar-based monomers prepared from isosorbide, isomannide, and isoidide and resin systems containing these anhydrosugar-based monomers that are partially to fully bio-based, which may produce materials having properties that meet or exceed the properties of similar petroleum derived vinyl ester resins.
Core Innovation
The invention relates to novel anhydrosugar-based monomers derived from isosorbide, isomannide, or isoidide, which are used for producing renewable vinyl ester resin systems. These monomers serve as low viscosity cross-linkers and enable the production of neat polymers for vinyl ester resins. The monomers are partially to fully bio-based and can yield materials with properties that meet or exceed those of similar petroleum-derived vinyl ester resins.
The problem being addressed is the current reliance on petroleum-based vinyl ester resins that require hazardous reactive diluents such as styrene to reduce viscosity. These diluents are regulated due to their classification as Hazardous Air Pollutants (HAPs) and Volatile Organic Compounds (VOCs). Additionally, petroleum products have high environmental costs and price volatility. Existing bio-based vinyl ester resins still depend on reactive diluents and often suffer from low toughness and processability when the styrene content is reduced. Therefore, there is a need for bio-based vinyl ester resins that provide excellent processability, acceptable toughness, and reduced dependency on reactive diluents.
The invention provides anhydrosugar-based monomers that have low molecular weight due to their confined bicyclic core structure derived from naturally occurring sugars. This low molecular weight allows these monomers to reduce the overall viscosity of vinyl ester resins, enabling a decrease in reactive diluent concentration while maintaining suitable toughness and processability. These monomers can function as viscosity modulators, Tg (glass transition temperature) enhancers, and vinyl ester cross-linkers for producing bio-based thermosetting polymer systems that can replace petroleum-based counterparts.
Claims Coverage
The patent includes nine main inventive features derived from independent claims covering polymerizable monomers, their methods of preparation, and copolymers formed therefrom with specific components and compositions.
Polymerizable anhydrosugar-based monomer
The invention encompasses monomers selected from those derived from isosorbide, isomannide, and isoidide, functionalized to be polymerizable with (meth)acrylate groups capable of free radical polymerization.
Method for acylating anhydrosugars
A method of producing polymerizable monomers by acylating one or more hydroxyl groups of anhydrosugars using acrylic or methacrylic anhydride with a base catalyst in an aprotic solvent, specifically targeting anhydrosugars including isosorbide, isomannide, and isoidide.
Copolymer formed by curing compositions including anhydrosugar monomers
Formation of copolymers by curing compositions comprising at least one polymerizable anhydrosugar monomer using a free-radical initiator, optionally including vinyl ester resin monomers, unsaturated polyester monomers, and reactive diluents.
Compositional ranges in curable compositions
Employing specific weight percentages in curable compositions containing polymerizable anhydrosugar monomers, vinyl ester and/or unsaturated polyester monomers, and reactive diluents, with ranges for monomers from 1-99%, vinyl ester/polyester monomers from 1-70%, and reactive diluents from 0-60% by weight.
Use of vinyl ester resin monomers
Inclusion of vinyl ester monomers selected from (meth)acrylated glycidyl ethers of bisphenols, (meth)acrylated ethoxylated bisphenols, and novolac vinyl esters, specifically from bisphenol types such as bisphenol A and its variations.
Reactive diluents in curable compositions
The curable compositions may include reactive diluents such as styrene, 2-hydroxymethacrylate, methyl methacrylate, methyl acrylate, furfuryl methacrylate, methacrylated lauric acid, and methacrylated fatty acids to aid in processing and polymerization.
Use of unsaturated polyester monomers
Compositions can include unsaturated polyester monomers made from components such as phthalic acid, terephthalic acid, m-phthalic acid, suberic acid, adipic acid, succinic acid, maleic acid, fumaric acid, butylene glycol, propylene glycol, and ethylene glycol, combined with anhydrosugar monomers and reactive diluents.
Polymerizable monomers with specific structural formulas
Monomers of the invention include those having particular structural formulas designated as formula 2 and 2a, which relate to methacrylated derivatives of the anhydrosugars.
Curing with free-radical initiators
The invention covers curing the anhydrosugar-based monomer compositions with free-radical initiators forming copolymers with mechanical properties and Tg comparable to petroleum-based vinyl ester resins.
The claims cover polymerizable anhydrosugar-based monomers derived from renewable sources, their synthetic methods through acylation, and curable compositions including these monomers combined with vinyl ester or unsaturated polyester resins and reactive diluents. The invention emphasizes compositions with specific weight ratios and curing methods to produce bio-based vinyl ester copolymers with desired mechanical and thermal properties.
Stated Advantages
The anhydrosugar-based monomers enable the production of vinyl ester resins with lower viscosity, allowing for reduced use of hazardous reactive diluents like styrene.
The monomers possess low volatility, multiple polymerizable sites, and low cost, improving processability and sustainability.
Use of these monomers results in vinyl ester resins with acceptable toughness and elevated glass transition temperatures (Tg), enhancing performance compared to bio-based reactive diluents alone.
They allow tailoring of resin viscosity and Tg over a wide range to suit specific applications, thus enabling improved resin flow characteristics and performance.
The resultant polymers have stiffness and toughness comparable to petroleum-derived vinyl ester resins, supporting their use as replacements.
Documented Applications
Production of thermosetting vinyl ester resins for use as adhesives and resin matrices for fiber reinforced composites in military and commercial applications.
Use as viscosity modulators and Tg enhancers in vinyl ester resin formulations to reduce hazardous diluent content while maintaining material properties.
Manufacture of polymer matrix composites applicable in vehicle armor, body panels, composite hoods, boat hull structures, and other structural composites.
Use as gel coating materials to provide protective coatings for composites and various surfaces in automotive, recreational, and marine uses.
Applications in biosensors, rheology modifiers, biomaterials, and polymerizable surfactants for media encapsulation due to the polymerizability and structural features of the monomers.
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