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EP-4739489-A1 - COMPOSITES FORMED USING LEWIS-ACID POLYMERIZED POLYOLS AND METHODS OF PREPARING SAME

EP4739489A1EP 4739489 A1EP4739489 A1EP 4739489A1EP-4739489-A1

Abstract

Methods may include preparing a reacting mixture by combining: an isocyanate component; and an isocyanate-reactive component that includes at least one Lewis acid catalyzed polyether polyol having a percent by weight (wt%) of 90 wt%or more polypropylene oxide, a primary hydroxy concentration of at least 30 wt%, a functionality of at least 2, an OH number in the range of 100 mg KOH/g to 800 mg KOH/g, and an average acetal content of at least 0.05 wt%; and combining the reacting mixture with one or more reinforcing materials.

Inventors

  • DHYANI, Abhishek
  • KEATON, An Nguyen
  • WILLUMSTAD, THOMAS
  • SUZUKI, MASAYUKI
  • WANG, YUN
  • HAN, Hongjie
  • SUN, GANG
  • BAGGIO, Enrico
  • BRAMANTE, GUIDO

Assignees

  • Dow Global Technologies LLC

Dates

Publication Date
20260513
Application Date
20230706

Claims (10)

  1. A method of forming a composite comprising: preparing a reacting mixture by combining: an isocyanate component; and an isocyanate-reactive component that includes at least one Lewis acid catalyzed polyether polyol having a percent by weight (wt%) of 90 wt%or more polypropylene oxide, a primary hydroxy concentration of at least 30 wt%, a functionality of at least 2, an OH number in the range of 100 mg KOH/g to 800 mg KOH/g, and an average acetal content of at least 0.05 wt%; and combining the reacting mixture with one or more reinforcing materials.
  2. The method of claim 1, wherein the isocyanate-reactive component includes at least 10 wt%of the polyether polyol.
  3. The method of claim 1, wherein the polyether polyol is a polypropylene oxide polyol.
  4. The method of claim 1, wherein the composite has a density higher than 0.850 g/mL.
  5. The method of claim 1, wherein the polyether polyol has a weight average molecular weight from 200 Da to 1,000 Da, and a functionality of 2 to 4.
  6. The method of claim 1, wherein the Lewis acid catalyst used to generate the polyether polyol has a general formula M (R 1 ) 1 (R 2 ) 1 (R 3 ) 1 (R 4 ) 0 or 1 , whereas M is boron, aluminum, indium, bismuth or erbium, R 1 , R 2 , R 3 , and R 4 are each independent, R 1 includes a first fluoro/chloro or fluoroalkyl-substituted phenyl group, R 2 includes a second fluoro/chloro or fluoroalkyl-substituted phenyl group, R 3 includes a third fluoro/chloro or fluoroalkyl-substituted phenyl group or a first functional group or functional polymer group, optional R 4 is a second functional group or functional polymer group.
  7. The method of claim 1, wherein the isocyanate-reactive component further comprises a hydroxy (meth) acrylate monomer, prepolymer, or polymer.
  8. The method of claim 1, wherein the isocyanate component is present at a percent by weight (wt%) ranging from 35 wt%to 65 wt%of the reacting mixture.
  9. The method of claim 1, wherein the method for forming the composite comprises pultrusion, infusion, or filament winding.
  10. A composite prepared by the method of claim 1.

Description

COMPOSITES FORMED USING LEWIS-ACID POLYMERIZED POLYOLS AND METHODS OF PREPARING SAME Field Embodiments relate to polyurethane and polyurethane/ (methacrylate) hybrid compositions used in the fabrication of polyurethane composites and reinforced materials having improved mechanical properties. INTRODUCTION Polyurethane (PU) formulations may be manufactured into reinforced composites by a variety of fabrication processes, which include processes such as pultrusion, infusion and filament winding. Pultrusion is a continuous manufacturing process to make fiber reinforced polymer composite profiles with constant cross-sectional area, which are often used in structural applications. Infusion is a process where the PU resin is brought into contact with and impregnated into fibers by application of vacuum, and it is applied for manufacturing articles such as wind blades. Filament winding is instead typically applied to manufacturing items such as pipes or closed end structures (pressure vessels or tanks) in a process that involves winding filaments, pre-impregnated with resin, over a rotating mandrel. As with most fabrication technologies, the reduction of demolding time with maintained or improved product quality results in increased productivity. To reduce demolding time, higher loadings of catalysts or polyols containing higher concentrations of reactive primary hydroxyl groups (e.g., ethylene oxide (EO) derivatives) can be used. However, the use of polyurethane catalysts can be prohibitively expensive, and can increase volatility and shorten the cure time of the formulation during processing. Polyols containing high concentrations of primary hydroxy groups may be obtained using EO as the alkoxylation reagent, which result in higher hygroscopicity, and can lead to accumulation of water in the formulation when exposed to the atmosphere. The increased polarity of EO-containing polyols can also lead to issues with compatibility with nonpolar formulation components and the generation of haze and turbidity. SUMMARY In an aspect, embodiments of the present disclosure include methods of forming a composite comprising: preparing a reacting mixture by combining: an isocyanate  component; and an isocyanate-reactive component that includes at least one Lewis acid catalyzed polyether polyol having a percent by weight (wt%) of 90 wt%or more polypropylene oxide, a primary hydroxy concentration of at least 30 wt%, a functionality of at least 2, an OH number in the range of 100 mg KOH/g to 800 mg KOH/g, and an average acetal content of at least 0.05 wt%; and combining the reacting mixture with one or more reinforcing materials. DETAILED DESCRIPTION Embodiments relate to two component polyurethane and polyurethane/ (meth) acrylate hybrid compositions for use in composite manufacture that include Lewis acid catalyzed polyether polyols produced by polymerization in the presence of a perfluoroalkyl-substituted arylborane catalyst. Polymer-forming composition include an isocyanate component and an isocyanate reactive component that includes at least Lewis acid catalyzed polyether polyol. Lewis acid catalyzed polyether polyols disclosed herein may have a percent by weight (wt%) of 90 wt%or more polypropylene oxide, a primary hydroxy concentration of at least 30 wt%, a functionality of at least 2, an OH number in the range of 100 mg KOH/g to 800 mg KOH/g, and an average acetal content of at least 0.05 wt%. Methods also include the formation of a composite that include combining the components in the presence of a reinforcement material using a suitable process such as infusion, pultrusion, or filament winding. The use of a Lewis acid polymerization catalyst (e.g., perfluoroalkyl-substituted arylborane catalysts) to produce polyether polyols may improve polyol reactivity with the isocyanate component, particularly for polypropylene oxide based (or containing) polyether polyols, by increasing the percentage of primary hydroxyl groups. Increased concentrations of primary hydroxyl groups are associated with faster cure times and improved appearance of the final product. Comparative formulations that include concentrations of polyethylene oxide to increase the percentage of primary OH terminal functional groups, producing some decrease in demold time during manufacture. However, the presence of polyethylene oxide also leads to decreased compatibility with nonpolar polymer phases and layers such as PVC skin layers, production of an open cell structure prone to discoloration by oxidative gases, and high reactivity-related scorching. On the other hand, polypropylene oxide-based polyether polyols show good  compatibility with nonpolar phases, but preparation of polyether polyols by standard KOH alkoxylation catalysis from monomers having carbon numbers greater than two (i.e., propylene oxide, butylene oxide) produces products having ＞ 95 %secondary OH groups. PU compositions and composites disclosed herein include polyether po