Highly filled polyurethane composites

• US 9,988,512 B2
• Filed: 01/22/2015
• Issued: 06/05/2018
• Est. Priority Date: 01/22/2015
• Status: Active Grant

• Current Assignee: Westlake Royal Building Products Incorporated
• Original Assignee: Boral Ip Holdings (Australia) Pty Limited (Seven Group Holdings Limited)
• Inventors: Crocco, Guy, Zhang, Ying, Ai, Li
• Primary Examiner(s): Rodd, Christopher M
• Application Number:
  US14/784,196
• Publication Number:
  US 20160369080A1
• Time in Patent Office: 1,230 Days
• Field of Search: None
• CPC Class Codes: C08G 18/1816 having carbocyclic groups
• CPC Class Codes: C08G 18/4018 Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• CPC Class Codes: C08G 18/4208 containing aromatic groups
• CPC Class Codes: C08G 18/4804 Two or more polyethers of different physical or chemical nature
• CPC Class Codes: C08G 18/4808 Mixtures of two or more polyetherdiols
• CPC Class Codes: C08G 18/4816 mixtures of two or more polyetherpolyols having at least three hydroxy groups
• CPC Class Codes: C08G 18/482 Mixtures of polyethers containing at least one polyether containing nitrogen
• CPC Class Codes: C08G 18/5021 having nitrogen
• CPC Class Codes: C08G 18/7664 containing alkylene polyphenyl groups
• CPC Class Codes: C08G 2101/00 Manufacture of cellular products
• CPC Class Codes: C08G 2110/0008 flexible
• CPC Class Codes: C08G 2110/0016 semi-rigid
• CPC Class Codes: C08G 2110/0025 rigid
• CPC Class Codes: C08G 2110/0033 having integral skins
• CPC Class Codes: C08G 2110/0083 prepared using water as the sole blowing agent
• CPC Class Codes: C08K 11/005 Waste materials, e.g. treated or untreated sewage sludge
• CPC Class Codes: C08K 3/013 Fillers, pigments or reinforcing additives
• CPC Class Codes: C08L 75/04 Polyurethanes

Abstract

Composite materials and methods for their preparation are described herein. The composite materials can comprise (a) a polyurethane and (b) from 35% to 90% by weight, based on the total weight of the composite, of a particulate filler dispersed in the polyurethane. The polyurethane can be 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. The one or more polyols that form the polyurethane comprise a high hydroxyl number polyol having a hydroxyl number of at least 250 mg KOH/g. In some cases, the one or more polyols that form the polyurethane can have a weight average equivalent weight of from 200 to 1100 amu. In some cases, the one or more polyols that form the polyurethane can include less than 5% by weight, based on the total weight of the one or more polyols that form the polyurethane, of one or more flexible polyols having a hydroxyl number of less than 150 mg KOH/g and a functionality of less than 3.

Claims

1. A composite comprising:

(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,

wherein the one or more polyols comprise at least 95% by weight, based on the total weight of the one or more polyols, of one or more high hydroxyl number polyols having a hydroxyl number of at least 250 mg KOH/g, and

wherein the one or more polyols have a weight average equivalent weight of from 200 amu to 250 amu; and

(b) from 35% by weight to 90% by weight, based on the total weight of the composite, of a particulate filler,

wherein the particulate filler has at least one of;

(a) a loss-on-ignition at 750°

C. of 0.10% to 5.0% when determined in accordance with ASTM C618-12a;

or (b) a ratio of BET surface area to loss-on-ignition of 1.5 to 5.5, wherein BET surface area is measured in m²/g and loss-on-ignition is measured in percent, wherein BET surface area is determined in accordance with ASTM C1069-09, and wherein loss-on-ignition is determined in accordance with ASTM C618-12a.

2. The composite of claim 1, wherein the one or more polyols satisfy Eq. 1 below

(2.1)(F)+(0.3)(EW)−

(0.0036)(F)(EW)>

12 

 

Eq. 1

wherein

F is the weight average functionality of the one or more polyols; and

EW is the weight average equivalent weight of the one or more polyols.

3. The composite of claim 1, wherein the one or more polyols satisfy Eq. 2 below

(2.1)(F)+(0.3)(EW)−

(0.0036)(F)(EW)>

15 

 

Eq. 2

wherein

F is the weight average functionality of the one or more polyols; and

EW is the weight average equivalent weight of the one or more polyols.

4. The composite of claim 1, wherein the particulate filler comprises an inorganic filler fly ash.

5. The composite of claim 1, wherein the composite comprises from 45% by weight to 70% by weight, based on the total weight of the composite, of the particulate filler.

13. The composite of claim 1, wherein the composite has a normalized flexural strength of 20 to 50.

15. The composite of claim 1, wherein the one or more polyols comprise at least 99.9% by weight, based on the total weight of the one or more polyols, of one or more high hydroxyl number polyols having a hydroxyl number of at least 250 mg KOH/g.

6. A composite comprising:

(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,

wherein the one or more polyols include at least 95% by weight, based on the total weight of the one or more polyols, of one or more rigid polyols having a hydroxyl number of at least 250 mg KOH/g, and

wherein the one or more polyols include less than 5% by weight, based on the total weight of the one or more polyols, of one or more flexible polyols having a hydroxyl number of less than 150 mg KOH/g and a functionality of less than 3; and

wherein the one or more polyols have a weight average equivalent weight of from 200 amu to 250 amu; and

(b) from 35% by weight to 90% by weight, based on the total weight of the composite, of a particulate filler,

wherein the particulate filler has at least one of;

(a) a loss-on-ignition at 750°

C. of 0.10% to 5.0% when determined in accordance with ASTM 0618-12a;

or (b) a ratio of BET surface area to loss-on-ignition of 1.5 to 5.5, wherein BET surface area is measured in m²/g and loss-on-ignition is measured in percent, wherein BET surface area is determined in accordance with ASTM C1069-09, and wherein loss-on-ignition is determined in accordance with ASTM 0618-12a.

8. The composite of claim 6, wherein the one or more polyols satisfy Eq. 1 below

(2.1)(F)+(0.3)(EW)−

(0.0036)(F)(EW)>

12 

 

Eq. 1

wherein

F is the weight average functionality of the one or more polyols; and

EW is the weight average equivalent weight of the one or more polyols.

9. The composite of claim 6, wherein the one or more polyols satisfy Eq. 2 below

(2.1)(F)+(0.3)(EW)−

(0.0036)(F)(EW)>

15 

 

Eq. 2

wherein

F is the weight average functionality of the one or more polyols; and

EW is the weight average equivalent weight of the one or more polyols.

10. The composite of claim 6, wherein the particulate filler comprises an inorganic filler fly ash.

11. The composite of claim 6, wherein the composite comprises from 45% to 70% by weight, based on the total weight of the composite, of the particulate filler.

14. The composite of claim 6, wherein the composite has a normalized flexural strength of 20 to 50.

7. The composite of 17, wherein the one or more polyols include less than 1% by weight, based on the total weight of the one or more polyols, of one or more flexible polyols having a hydroxyl number of less than 150 mg KOH/g and a functionality of less than 3.

12. A method of preparing a composite material, comprising:

mixing (1) a particulate filler;

(2) at least one isocyanate selected from the group consisting of diisocyanates, polyisocyanates, and combinations thereof;

(3) one or more polyols, wherein the one or more polyols comprise at least 95% by weight, based on the total weight of the polyols, a high hydroxyl number polyol having a hydroxyl number of at least 250 mg KOH/g, and wherein the one or more polyols have a weight average equivalent weight of from 200 amu to 250 amu; and

(4) a catalyst; and

allowing the at least one isocyanate and the one or more polyols to react in the presence of the particulate filler and the catalyst to form the composite material;

from 35% by weight to 90% by weight, based on the total weight of the composite, of a particulate filler,

wherein the particulate filler has at least one of;

(a) a loss-on-ignition at 750°

C. of 0.10% to 5.0% when determined in accordance with ASTM 0618-12a;

or (b) a ratio of BET surface area to loss-on-ignition of 1.5 to 5.5, wherein BET surface area is measured in m²/g and loss-on-ignition is measured in percent, wherein BET surface area is determined in accordance with ASTM C1069-09, and wherein loss-on-ignition is determined in accordance with ASTM 0618-12a.