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US-12624150-B2 - Surfactant-free filled polyurethane foam and method of making same

US12624150B2US 12624150 B2US12624150 B2US 12624150B2US-12624150-B2

Abstract

Polyurethane foams and methods of manufacturing are described herein. The foam can include (a) a polyurethane formed by the reaction of (i) one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, and (ii) one or more polyols; and (b) a filler. The amount of filler in the foam can be from 50 to 90% by weight, based on the total weight of the foam. The filler can include a plurality of fibers and/or a particulate filler. The polyurethane foams described herein are made without adding a surfactant to the reaction mixture. The density of the polyurethane foam can be at least 5 lb/ft 3 .

Inventors

  • Hamed Lakrout
  • Russ Majors
  • Brian Shaw
  • Guy Crocco
  • Li Ai
  • Amitabha Kumar
  • Russell Hill

Assignees

  • Westlake Royal Building Products Inc.

Dates

Publication Date
20260512
Application Date
20240524

Claims (18)

  1. 1 . A filled polyurethane foam comprising: a polyurethane; and an inorganic particulate filler comprising calcium carbonate and fly ash; wherein the inorganic particulate filler has a multimodal particle size distribution having a first mode with a first median particle diameter and a second mode with a second median particle diameter different than the first median particle diameter, wherein the calcium carbonate has the first median particle diameter, and wherein the first median particle diameter is from 30 microns to 40 microns; and wherein the filled polyurethane foam has a flexural strength of 400 psi or greater, a density of at least 10 lb/ft 3 , or both a flexural strength of 400 psi or greater and a density of at least 10 lb/ft 3 .
  2. 2 . The filled polyurethane foam of claim 1 , wherein the fly ash has the second median particle diameter, and the second median particle diameter is less than 30 microns.
  3. 3 . The filled polyurethane foam of claim 1 , wherein the fly ash has the second median particle diameter, and the second median particle diameter is from 5 microns to 15 microns.
  4. 4 . The filled polyurethane foam of claim 1 , wherein the filled polyurethane foam comprises from 0.1% by weight to 15% by weight calcium carbonate, based on a total weight of the filled polyurethane foam.
  5. 5 . The filled polyurethane foam of claim 1 , wherein the filled polyurethane foam comprises from 50% by weight to 80% by weight fly ash, based on a total weight of the filled polyurethane foam.
  6. 6 . The filled polyurethane foam of claim 1 , wherein the fly ash comprises Class C fly ash, Class F fly ash, or a mixture of Class C fly ash and Class F fly ash.
  7. 7 . The filled polyurethane foam of claim 1 , wherein the inorganic particulate filler is coated with a sizing agent.
  8. 8 . The filled polyurethane foam of claim 1 , further comprising 3% by weight to 5% by weight of a plurality of fibers, based on a total weight of the filled polyurethane foam.
  9. 9 . The filled polyurethane foam of claim 1 , wherein the filled polyurethane foam comprises from 70% by weight to 80% by weight of the inorganic particulate filler, based on a total weight of the filled polyurethane foam.
  10. 10 . The filled polyurethane foam of claim 1 , wherein the filled polyurethane foam has a compressive strength of 100 psi or greater.
  11. 11 . The filled polyurethane foam of claim 1 , wherein a thickness of the filled polyurethane foam is 0.125 inch to 2 inches.
  12. 12 . A filled polyurethane foam comprising: a polyurethane; and an inorganic particulate filler comprising a first filler comprising calcium carbonate and a second filler; wherein the inorganic particulate filler has a multimodal particle size distribution having at least two modes including a first mode with a first median particle diameter and a second mode with a second median particle diameter different than the first median particle diameter, wherein the calcium carbonate has the first median particle diameter, and wherein the first median particle diameter is from 30 microns to 40 microns; and wherein the filled polyurethane foam has a flexural strength of 400 psi or greater, a density of at least 10 lb/ft 3 , or both a flexural strength of 400 psi or greater and a density of at least 10 lb/ft 3 .
  13. 13 . The filled polyurethane foam of claim 12 , wherein the second filler is selected from the group consisting of ash, ground/recycled glass, milled glass, glass spheres, glass flakes, activated carbon, calcium carbonate, aluminum trihydrate, silica, sand, ground sand, silica fume, slate dust, crusher fines, red mud, amorphous carbon, clays, mica, talc, wollastonite, alumina, feldspar, bentonite, quartz, garnet, saponite, beidellite, granite, slag, calcium oxide, calcium hydroxide, antimony trioxide, barium sulfate, magnesium oxide, titanium dioxide, zinc carbonate, zinc oxide, nepheline syenite, perlite, diatomite, pyrophillite, flue gas desulfurization material, soda ash, trona, expanded clay, expanded shale, expanded perlite, vermiculite, volcanic tuff, pumice, hollow ceramic spheres, hollow plastic spheres, expanded plastic beads, ground tire rubber, and combinations thereof.
  14. 14 . The filled polyurethane foam of claim 12 , wherein the second filler comprises fly ash.
  15. 15 . The filled polyurethane foam of claim 12 , wherein the second filler has the second median particle diameter, and the second median particle diameter is less than 30 microns.
  16. 16 . The filled polyurethane foam of claim 12 , wherein the filled polyurethane foam comprises from 0.1% by weight to 15% by weight calcium carbonate, based on a total weight of the filled polyurethane foam.
  17. 17 . The filled polyurethane foam of claim 12 , further comprising from 3% by weight to 5% by weight of a plurality of fibers, based on a total weight of the filled polyurethane foam.
  18. 18 . The filled polyurethane foam of claim 12 , wherein a thickness of the filled polyurethane foam is 0.125 inch to 2 inches.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. application Ser. No. 17/523,639, filed on Nov. 10, 2021, which is a continuation of U.S. application Ser. No. 16/302,450, filed on Nov. 16, 2018, now U.S. Pat. No. 11,198,753, which is the U.S. national stage entry under 35 U.S.C. § 371 of International Application No. PCT/US2016/033756, filed on May 23, 2016, all of which are incorporated by reference herein in their entireties. FIELD OF THE DISCLOSURE This disclosure relates generally to polyurethane foams, more particularly, to surfactant-free highly filled polyurethane foams. BACKGROUND OF THE DISCLOSURE Polymeric composites that contain organic and/or inorganic filler materials have become desirable for a variety of uses because of their excellent mechanical properties and weathering stability. In general, the superior properties of the organic-inorganic composites are achieved through use of the organic as a matrix material that acts as a glue with enhanced flexural properties or as a fibrous component providing reinforcement and improved tensile properties. The inorganic material imparts various properties of rigidity, toughness, hardness, optical appearance, interaction with electromagnetic radiation, density, and many other physical and chemical attributes. The use of polyurethane compositions has grown due to their superior tensile strength, impact resistance, and abrasion resistance compared to, for example, unsaturated polyester and vinyl ester-based composites. Processes for preparing polyurethane foamed compositions are known and have significant commercial success. In particular, it is known in the art to produce polyurethane foams by reacting a polyisocyanate with a polyol in the presence of a blowing agent, a catalyst, a surfactant, and optionally other ingredients. Although these formulations can produce suitable polyurethane foams, there is a need for alternate formulations for forming polyurethane foams. The compositions and methods described herein address these and other needs. SUMMARY OF THE DISCLOSURE Polyurethane foam and methods of manufacturing are described herein. In some embodiments, the foam can include (a) a polyurethane formed by the reaction of (i) one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, and (ii) one or more polyols; and (b) a filler in an amount of from greater than 50% to 90% by weight, based on the total weight of the polyurethane composite. The polyurethane foams described herein are made without adding a surfactant during the reaction of the one or more isocyanates and the one or more polyols. The density of the polyurethane foam can be at least 5 lb/ft3. In some cases, the density of the foam can be from 10 lb/ft3 to 35 lb/ft3, from 10 lb/ft3 to 30 lb/ft3 or from 15 lb/ft3 to 25 lb/ft3. The amount of polyurethane in the foam can be from 10% to 50% by weight, for example, 15% to 45% by weight, based on the total weight of the foam. In some embodiments, the one or more polyols can have an average hydroxyl number of from 100 to 700 mg KOH/g, from 100 to 500 mg KOH/g, or from 200 to 400 mg KOH/g. The one or more polyols can have an average molecular weight of from 250 to 1500 g/mol or from 500 to 1000 g/mol. The average functionality of the one or more polyols can be from 2.5 to 5.5, from 3 to 5.5, or from 3 to 4. In some embodiments, the average functionality of the one or more first polyols can be 2 or more. The one or more first polyols can have an average viscosity of 150 to 5000 cPs or from 150 to 2500 cPs at 25° C. In some cases, a blend of the one or more polyols and the one or more isocyanates used in the foams can have an average viscosity of from 100 to 6000 cPs, from 100 to 2500 cPs, or from 100 to 1400 cPs at 25° C. As described above, the polyurethane foam can include a filler. The filler can have an average aspect ratio of length to diameter of from 1:1 to 10,000:1 or from 1:1 to 6000:1. The filler can include a particulate filler and/or a plurality of fibers. The particulate filler in the foam can include coal ash such as fly ash. In certain embodiments, the particulate filler can have a median particle size of less than 50 microns or less than 25 microns. In some embodiments, the particulate filler has a particle size distribution having at least two modes. The amount of particulate filler in the foam can be from 50 to 85% by weight, based on the total weight of the foam. For example, the particulate filler can be present in an amount from 50% to 80% or from 60% to 85% by weight, based on the total weight of the foam. The plurality of fibers can be present in the foam can be from 0.25% to 10% by weight, based on the total weight of the foam. In some examples, the fibers can be present in an amount from 0.25% to 8%, from 0.25% to 6%, from 0.5% to 6%, or from 0.5% to 5% by weight, based on the total weight of the foam. The fibers can have an average as