Rigid polyurethane foams suitable for use as panel insulation

• US 10,640,600 B2
• Filed: 04/24/2018
• Issued: 05/05/2020
• Est. Priority Date: 04/24/2018
• Status: Active Grant

• Current Assignee: Covestro LLC (Covestro AG)
• Original Assignee: Covestro LLC (Covestro AG)
• Inventors: Rider, Shawn G., Sounik, David F.
• Primary Examiner(s): Rioja, Melissa A
• Application Number:
  US15/961,328
• Publication Number:
  US 20190322791A1
• Time in Patent Office: 742 Days
• CPC Class Codes: B32B 2250/03 3 layers
• CPC Class Codes: B32B 2260/023 Two or more layers
• CPC Class Codes: B32B 2262/101 Glass fibres
• CPC Class Codes: B32B 2266/0278 Polyurethane
• CPC Class Codes: B32B 2305/022 Foam
• CPC Class Codes: B32B 2307/304 Insulating
• CPC Class Codes: B32B 2323/10 Polypropylene
• CPC Class Codes: B32B 2367/00 Polyesters, e.g. PET, i.e. polyethylene terephthalate
• CPC Class Codes: B32B 5/245 another layer next to it being a foam layer
• CPC Class Codes: C08G 18/1808 having alkylene polyamine groups
• CPC Class Codes: C08G 18/1816 having carbocyclic groups
• CPC Class Codes: C08G 18/2018 having one nitrogen atom in the ring
• CPC Class Codes: C08G 18/2027 having two nitrogen atoms in the ring
• CPC Class Codes: C08G 18/4244 containing oxygen in the form of ether groups
• 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 18/4825 Polyethers containing two hydroxy groups C08G18/4833 - C08G18/5096 take precedence
• CPC Class Codes: C08G 18/4829 Polyethers containing at least three hydroxy groups C08G18/4833 - C08G18/5096 take precedence
• CPC Class Codes: C08G 18/4883 containing cyclic groups having at least one oxygen atom in the ring
• CPC Class Codes: C08G 18/5021 having nitrogen
• CPC Class Codes: C08G 18/5024 : containing primary and/or secondary amino groups
• CPC Class Codes: C08G 18/7664 : containing alkylene polyphenyl groups
• CPC Class Codes: C08G 18/7671 : containing only one alkylene bisphenyl group
• CPC Class Codes: C08G 2110/0025 : rigid
• CPC Class Codes: C08J 2205/10 : Rigid foams
• CPC Class Codes: C08J 2375/08 : from polyethers
• CPC Class Codes: C08J 9/0038 : containing phosphorus
• CPC Class Codes: C08J 9/144 : containing carbon, halogen and hydrogen only

Abstract

Disclosed are polyurethane-foam forming compositions, rigid polyurethane foams and methods for their production, as well as to composite articles comprising such foams sandwiched between facer substrates, including use of such composite elements for side-wall and/or roof insulating elements for refrigerated tractor trailers. The rigid polyurethane foams are produced from an isocyanate-reactive component comprising: (1) a polyol blend; (2) a halogenated hydroolefin; (3) a surfactant; (4) water; and (5) a tertiary amine catalyst composition.

Claims

1. A rigid polyurethane foam-forming composition comprising:

(a) a diisocyanate and/or polyisocyanate; and

(b) an isocyanate-reactive component comprising;

(1) a polyol blend comprising;

(i) 60 to 98% by weight, based on the total weight of the polyol blend, of a saccharide-initiated polyether polyol having an OH number of from 200 to 600 mg KOH/g and a functionality of 4 to 6;

(ii) 1 to 20% by weight, based on the total weight of the polyol blend, of an aliphatic triol-initiated polyether polyol having an OH number of 100 to 500 mg KOH/g and a functionality of from greater than 2 to 4; and

(iii) 1 to 20% by weight, based on the total weight of the polyol blend, of an aliphatic amine-initiated polyether polyol having an OH number of from 20 to 120 mg KOH/g and a functionality of 3 to 6;

(2) a halogenated olefin;

(3) a surfactant;

(4) water; and

(5) a tertiary amine catalyst composition comprising;

(i) 80 to 99% by weight, based on the total weight of the tertiary amine catalyst composition, of a morpholine compound; and

(ii) 1 to 20% by weight, based on the total weight of the tertiary amine catalyst composition, of an imidazole compound.

2. The rigid polyurethane foam-forming composition of claim 1, wherein:

(A) the saccharide-initiated polyether polyol has an OH number of from 300 to 550 mg KOH/g and a functionality of 4.0 to 4.5;

(B) the aliphatic triol-initiated polyether polyol has an OH number of 200 to 250 mg KOH/g and a functionality of 2.5 to 3.5; and

(C) the aliphatic amine-initiated polyether polyol has an OH number of from 50 to 70 mg KOH/g and a functionality of 3.5 to 4.5.

3. The rigid polyurethane foam-forming composition of claim 1, wherein the saccharide-initiated polyether polyol and the aliphatic triol-initiated polyether polyol are present in the polyol blend in a weight ratio of 3:

1 to 30;

1.

4. The rigid polyurethane foam-forming composition of claim 1, wherein the saccharide-initiated polyether polyol and the aliphatic triol-initiated polyether polyol are present in the polyol blend in a weight ratio of 5:

1 to 15;

1.

5. The rigid polyurethane foam-forming composition of claim 1, wherein:

(A) the saccharide-initiated polyether polyol and the aliphatic amine-initiated polyether polyol are present in the polyol blend in a weight ratio of 5;

1 to 20;

1; and

(B) the aliphatic triol-initiated polyether polyol and the aliphatic amine-initiated polyether polyol are present in the polyol blend in a weight ratio of at least 0.3;

1.

6. The rigid polyurethane foam-forming composition of claim 1, wherein:

(A) the saccharide-initiated polyether polyol and the aliphatic amine-initiated polyether polyol are present in the polyol blend in a weight ratio of 5;

1 to 15;

1; and

(B) the aliphatic triol-initiated polyether polyol and the aliphatic amine-initiated polyether polyol are present in the polyol blend in a weight ratio of 0.5;

1 to 1.5;

1.

7. The rigid polyurethane foam-forming composition of claim 1, wherein the halogenated olefin comprises trans-1,1,1-trifluoro-3-chloropropene.

8. The rigid polyurethane foam-forming composition of claim 1, wherein the morpholine compound comprises:

(A) 40 to 80% by weight, based on the total weight of the morpholine compound, of dimorpholinodiethylether; and

(B) 20 to 60% by weight, based on the total weight of the morpholine compound, of N-methylmorpholine.

9. A method of making a rigid polyurethane foam, comprising reacting a polyol blend with an organic polyisocyanate in the presence of a halogenated olefin, water, a tertiary amine catalyst composition, and a surfactant, wherein:

(1) the polyol blend comprises;

(i) 60 to 98% by weight, based on the total weight of the polyol blend, of a saccharide-initiated polyether polyol having an OH number of from 200 to 600 mg KOH/g and a functionality of 4 to 6;

(ii) 1 to 20% by weight, based on the total weight of the polyol blend, of an aliphatic triol-initiated polyether polyol having an OH number of 100 to 500 mg KOH/g and a functionality of from greater than 2 to 4; and

(iii) 1 to 20% by weight, based on the total weight of the polyol blend, of an aliphatic amine-initiated polyether polyol having an OH number of from 20 to 120 mg KOH/g and a functionality of 3 to 6; and

(2) the tertiary amine catalyst composition comprises;

(i) 80 to 99% by weight, based on the total weight of the tertiary amine catalyst composition, of a morpholine compound; and

(ii) 1 to 20% by weight, based on the total weight of the tertiary amine catalyst composition, of an imidazole compound.

10. The method of claim 9, wherein:

(A) the saccharide-initiated polyether polyol has an OH number of from 300 to 550 mg KOH/g and a functionality of 4.0 to 4.5;

(B) the aliphatic triol-initiated polyether polyol has an OH number of 200 to 250 mg KOH/g and a functionality of 2.5 to 3.5; and

(C) the aliphatic amine-initiated polyether polyol has an OH number of from 50 to 70 mg KOH/g and a functionality of 3.5 to 4.5.

11. The method of claim 9, wherein the saccharide-initiated polyether polyol and the aliphatic triol-initiated polyether polyol are present in the polyol blend in a weight ratio of 3:

1 to 30;

1.

12. The method of claim 9, wherein the saccharide-initiated polyether polyol and the aliphatic triol-initiated polyether polyol are present in the polyol blend in a weight ratio of 5:

1 to 15;

1.

13. The method of claim 9, wherein:

(A) the saccharide-initiated polyether polyol and the aliphatic amine-initiated polyether polyol are present in the polyol blend in a weight ratio of 5;

1 to 20;

1; and

(B) the aliphatic triol-initiated polyether polyol and the aliphatic amine-initiated polyether polyol are present in the polyol blend in a weight ratio of at least 0.3;

1.

14. The method of claim 9, wherein:

(A) the saccharide-initiated polyether polyol and the aliphatic amine-initiated polyether polyol are present in the polyol blend in a weight ratio of 5;

1 to 15;

1; and

(B) the aliphatic triol-initiated polyether polyol and the aliphatic amine-initiated polyether polyol are present in the polyol blend in a weight ratio of 0.5;

1 to 1.5;

1.

15. The method of claim 9, wherein the halogenated olefin comprises trans-1,1,1-trifluoro-3-chloropropene.

16. The method of claim 9, wherein the morpholine compound comprises:

(A) 40 to 80% by weight, based on the total weight of the morpholine, of dimorpholinodiethylether; and

(B) 20 to 60% by weight, based on the total weight of the morpholine, of N-methylmorpholine.

17. A composite article comprising a rigid polyurethane foam sandwiched between facer substrates, wherein the rigid polyurethane foam comprises the reaction product of:

(a) a diisocyanate and/or polyisocyanate; and

(b) a polyol blend comprising;

(i) 60 to 98% by weight, based on the total weight of the polyol blend, of a saccharide-initiated polyether polyol having an OH number of from 200 to 600 mg KOH/g and a functionality of 4 to 6;

(ii) 1 to 20% by weight, based on the total weight of the polyol blend, of an aliphatic triol-initiated polyether polyol having an OH number of 100 to 500 mg KOH/g and a functionality of from greater than 2 to 4; and

(iii) 1 to 20% by weight, based on the total weight of the polyol blend, of an aliphatic amine-initiated polyether polyol having an OH number of from 20 to 120 mg KOH/g and a functionality of 3 to 6;

in the presence of

(c) a halogenated olefin;

(d) a surfactant;

(e) water; and

(f) a tertiary amine catalyst composition comprising;

(i) 80 to 99% by weight, based on the total weight of the tertiary amine catalyst composition, of a morpholine compound; and

(ii) 1 to 20% by weight, based on the total weight of the tertiary amine catalyst composition, of an imidazole compound.

18. The composite article of claim 17 wherein the facer substrates comprise a polypropylene resin reinforced with continuous bi-directional glass fibers and/or a fiberglass reinforced polyester copolymer.

19. The composite article of claim 17, wherein the composite article is embodied in a refrigerated tractor trailer side-wall and/or roof.