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-9856343-B2
Publication Date
2018-01-02
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 that serve as low viscosity cross-linkers for thermoset vinyl ester resins. These monomers are partially to fully bio-based and can produce materials having properties that meet or exceed those of similar petroleum-derived vinyl ester resins. The invention addresses the preparation and use of these monomers in resin systems, enabling new vinyl ester resins with reduced viscosity and improved characteristics.
The problem being solved arises from the use of petroleum-based vinyl ester resins which are typically high molecular weight species with very high viscosities, requiring hazardous reactive diluents like styrene to reduce viscosity. These diluents are regulated due to their environmental hazards. Additionally, there is a need to reduce dependence on petroleum due to its price volatility and environmental cost. Bio-based options previously have relied on styrene and still face challenges in toughness and processability.
The invention specifically solves these issues by providing anhydrosugar-based monomers with relatively low molecular weight due to their bicyclic core structure from natural sugars. This low molecular weight reduces the viscosity of vinyl ester resins, thus allowing for reduced use of reactive diluents without compromising toughness or processability. The monomers can serve as vinyl ester cross-linkers, viscosity modulators, and glass transition temperature (Tg) enhancers within vinyl ester resin systems. They can be polymerized alone or mixed with petroleum-based resins and reactive diluents to tailor properties such as viscosity, Tg, and toughness for various applications.
Claims Coverage
The patent contains two independent claims defining polymerizable monomers and copolymers formed by curing compositions including these monomers. The main inventive features focus on the chemical nature of the monomers, their polymerization, and use in resin compositions blending bio-based monomers with vinyl ester and polyester monomers and reactive diluents.
Polymerizable anhydrosugar-based monomers
The polymerizable monomer is selected from a group of monomers derived from anhydrosugars such as isosorbide, isomannide, or isoidide functionalized with (meth)acrylate groups or derivatives, capable of free radical polymerization.
Copolymers formed by curing bio-based monomers with free-radical initiators
Copolymer compositions include at least one polymerizable monomer from the group of anhydrosugar-based monomers, cured using a free-radical initiator to form materials with properties comparable to petroleum-based resins.
Vinyl ester and unsaturated polyester monomer incorporation
The curable compositions comprise vinyl ester resin monomers and/or unsaturated polyester monomers alongside the bio-based monomers, forming cross-linked copolymers with specific weight percentages of bio-based monomers, vinyl ester or polyester monomers, and reactive diluents.
Use of reactive diluents in formulation
The curable compositions further include reactive diluents that may be petroleum- or bio-based such as styrene, furfuryl methacrylate, methacrylated lauric acid, or others, enabling viscosity adjustment and processability.
Selection of particular vinyl ester resin types
The vinyl ester resin monomers are selected from methacrylated or acrylated glycidyl ethers of bisphenols, ethoxylated bisphenols, novolac vinyl esters, and related bisphenol types including bisphenol A, F, E, among others.
Specified compositional ratios
The compositions specify weight percentage ranges for the anhydrosugar-based monomers (1-99% or 5-95%), vinyl ester or polyester monomers (1-70% or 10-55%), and reactive diluents (0-60% or 0-50%), allowing tailored resin systems with controlled viscosity and mechanical properties.
The inventive features cover polymerizable monomers derived from renewable anhydrosugars and their use in forming thermoset copolymers with vinyl ester and unsaturated polyester monomers. The claims emphasize the bio-based composition, inclusion of reactive diluents, specific compositional weight ranges, and selection of vinyl ester types, enabling resin systems with improved viscosity, toughness, and Tg properties while reducing petroleum dependency.
Stated Advantages
Reduces resin viscosity allowing lower use of hazardous reactive diluents, improving environmental and processing profiles.
Provides bio-based vinyl ester resins with physical properties that meet or exceed petroleum-derived equivalents.
Enables modulation of glass transition temperature (Tg) to desired levels without increasing viscosity.
Reduces dependence on petroleum feedstocks and hazardous air pollutants while maintaining resin toughness and processability.
Offers resins with viscosities suitable for liquid molding, composite layups, and vacuum assisted resin transfer molding (VARTM).
Documented Applications
Use as vinyl ester cross-linkers in thermosetting resin systems replacing petroleum-based cross-linkers.
Production of polymer matrix composites for military, automotive, recreational, and marine applications such as vehicle body panels, armor, composite hoods, and boat hull structures.
Use as biosensors, rheology modifiers, biomaterials, and polymerizable surfactants for media encapsulation.
Gel coating materials providing protective coatings for composites and other surfaces.
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