Polyester polyol and polyol blends and rigid polyurethane foam manufacturing

Patent metadata

Field	Value
Publication number	US-9758614-B2
Application number	US-201414914484-A
Country	US
Kind code	B2
Filing date	Sep 20, 2014
Priority date	Sep 30, 2013
Publication date	Sep 12, 2017
Grant date	Sep 12, 2017

Abstract

A polyester polyol is formed in a polycondensation reaction between an aromatic dicarboxylic acid, a polyol, and an epoxy compound having a straight chain alkyl or alkenyl group having at least six carbon atoms. The polyester polyol exhibits excellent compatibility with hydrocarbon blowing agents. As such, it is a useful component in rigid polyurethane foam formulations that are contain hydrocarbon blowing agents.

First claim

What is claimed is:

1. A polyol blend comprising
a) at least 40% by weight, based on the combined weights of all polyols in the polyol blend, of a polyether polyol having a hydroxyl functionality of greater than four and a hydroxyl equivalent weight of up to 250;
b) at least 10% by weight, based on the combined weights of all polyols in the polyol blend, of at least one polyether polyol having a hydroxyl functionality of 2 to 4 and a hydroxyl equivalent weight of up to 700; and
c) 8 to 30% by weight, based on the combined weights of all polyols in the polyol blend, of a polyester polyol formed by polycondensation of
(i) at least aromatic dicarboxylic acid, aromatic dicarboxylic anhydride or aromatic dicarboxylic acid diester;
(ii) a polyol having at least two hydroxyl groups per molecule, or a mixture of two or more such polyols; and
(iii) an epoxy compound having at least one oxirane group and at least one straight chain alkyl or alkenyl group having at least six carbon atoms;

until the carboxylic acid, anhydride or ester groups and the oxirane groups are essentially consumed, to produce a polyester polyol having an average hydroxyl functionality of at least 2 hydroxyl groups per molecule, a hydroxyl equivalent weight of 100 to 2000 and at least one straight chain alkyl or alkenyl group having at least six carbon atoms corresponding to the at least one straight chain alkyl or alkenyl group of the epoxy compound, wherein the polycondensation is performed in a two-step process by first reacting components (i) and (iii) such that only a portion of the carboxylic acid, anhydride or ester groups of component (i) are consumed to form a compound having an ester-containing intermediate containing an ester group and a new hydroxyl group, and then reacting the ester-containing intermediate with component (ii).

2. A polyol blend comprising
a) at least 40% by weight, based on the combined weights of all polyols in the polyol blend, of a polyether polyol having a hydroxyl functionality of greater than four and a hydroxyl equivalent weight of up to 250;
b) at least 10% by weight, based on the combined weights of all polyols in the polyol blend, of at least one polyether polyol having a hydroxyl functionality of 2 to 4 and a hydroxyl equivalent weight of up to 700; and
c) 8 to 30% by weight, based on the combined weights of all polyols in the polyol blend, of a polyester polyol formed by polycondensation of
(i) at least aromatic dicarboxylic acid, aromatic dicarboxylic anhydride or aromatic dicarboxylic acid diester;
(ii) a polyol having at least two hydroxyl groups per molecule, or a mixture of two or more such polyols; and
(iii) a glycidyl ether of a straight-chain alkanol having at least six carbon atoms;

until the carboxylic acid, anhydride or ester groups and the oxirane groups of the glycidyl ether are essentially consumed, to produce a polyester polyol having an average hydroxyl functionality of at least 2 hydroxyl groups per molecule, a hydroxyl equivalent weight of 100 to 2000 and at least one straight chain alkyl group having at least six carbon atoms corresponding to the group based on a straight-chain alkanol group having at least six carbon atoms of the glycidyl ether.

3. The polyol blend of claim 2 , wherein component (iii) is a glycidyl ether of a mixture of alkanols having 8 to 14 carbon atoms.

4. The polyol blend of claim 3 , wherein the mixture of alkanols having 8 to 14 carbon atoms is a mixture of dodecanol and tetradecanol.

5. The polyol blend of claim 1 , wherein component (i) is one or more of phthalic acid, phthalic anhydride, a dialkyl ester of phthalic acid, isophthalic acid, isophthalic anhydride, a dialkyl ester of isophthalic acid, terephthalic acid, terephthalic anhydride, a dialkyl ester of terephthalic acid, trimellitic acid and trimellitic anhydride.

6. The polyol blend of claim 1 , which has an average hydroxyl functionality of at least 2.5 and an average hydroxyl equivalent weight of 180 to 250.

7. A formulated polyol composition comprising 75 to 90% by weight of a polyol blend and 10 to 25% by weight of a hydrocarbon blowing agent, the weight percentages being based on the combined weight of the polyols in the formulated polyol composition and the hydrocarbon blowing agent; wherein the polyol blend comprises:
a) at least 40% by weight, based on the combined weights of all polyols in the polyol blend, of a polyether polyol having a hydroxyl functionality of greater than four and a hydroxyl equivalent weight of up to 250;
b) at least 10% by weight, based on the combined weights of all polyols in the polyol blend, of at least one polyether polyol having a hydroxyl functionality of 2 to 4 and a hydroxyl equivalent weight of up to 700; and
c) 8 to 30% by weight, based on the combined weights of all polyols in the polyol blend, of a polyester polyol formed by polycondensation of
(i) at least aromatic dicarboxylic acid, aromatic dicarboxylic anhydride or aromatic dicarboxylic acid diester;
(ii) a polyol having at least two hydroxyl groups per molecule, or a mixture of two or more such polyols; and
(iii) an epoxy compound having at least one oxirane group and at least one straight chain alkyl or alkenyl group having at least six carbon atoms;

until the carboxylic acid, anhydride or ester groups and the oxirane groups are essentially consumed, to produce a polyester polyol having an average hydroxyl functionality of at least 2 hydroxyl groups per molecule, a hydroxyl equivalent weight of 100 to 2000 and at least one straight chain alkyl or alkenyl group having at least six carbon atoms corresponding to the at least one straight chain alkyl or alkenyl group of the epoxy compound.

8. The formulated polyol composition of claim 7 , wherein the hydrocarbon blowing agent is one or more of isopentane, n-pentane, cyclopentane, cyclohexane, n-hexane and 2-methyl pentane.

9. The formulated polyol composition of claim 7 , wherein the hydrocarbon blowing agent includes cyclopentane.

10. A process for preparing a rigid polyurethane foam, comprising
A) mixing at least one polyisocyanate compound with the formulated polyol composition of claim 7 at an isocyanate index of 80 to 1000 to form a reactive mixture and
B) curing the reactive mixture to form a rigid polyurethane foam.

Assignees

• Dow Global Technologies Llc

Inventors

• Jimenez Jorge
• Lista Guiseppe
• Micheletti Davide

Classifications

• C08G63/58

  Cyclic ethers (C08G59/00 takes precedence); Cyclic carbonates; Cyclic sulfites {; Cyclic orthoesters} · CPC title

• C08G18/4883 Primary

  containing cyclic groups having at least one oxygen atom in the ring · CPC title

• C08G63/42

  Cyclic ethers (C08G59/00 takes precedence); Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters · CPC title

• C08G18/4208

  containing aromatic groups · CPC title

• C08G18/4294

  prepared from polyester forming components containing polyepoxy compounds (C08G18/4266 takes precedence) · CPC title