Polyoxyalkylene polyol or monool and polyurethane resin

Patent metadata

Field	Value
Publication number	US-9388271-B2
Application number	US-201013259367-A
Country	US
Kind code	B2
Filing date	Mar 24, 2010
Priority date	Mar 30, 2009
Publication date	Jul 12, 2016
Grant date	Jul 12, 2016

Abstract

There is provided a polyoxyalkylene polyol or monool (S) represented by formula (2). In the formula (2), R 2 represents an m-valent group in which m active hydrogens are removed from the active hydrogen-containing compound (H); Z is an alkylene group or a cycloalkylene group, and these groups are unsubstituted or substituted with a halogen atom or an aryl group. A hydroxyl value x, total degree of unsaturation y and the content of ethylene oxide z satisfy mathematical expression (3). In mathematical expression (3), x represents 5 to 280 mgKOH/g, y represents total degree of unsaturation represented by a unit meq/g, and z is from 0 to 50.

R 2 —[—(ZO) p -(AO) q -(CH 2 CH 2 O) r -H]  (2)

y≦ 18.9× x −2 ×(100− z )/100  (3)

First claim

The invention claimed is:

1. A polyoxyalkylene polyol or monool (S), which is an alkylene oxide adduct of an active hydrogen-containing compound (H), wherein 40% or more of hydroxyl groups located at the terminal are primary hydroxyl group-containing groups represented by formula (1);
wherein the polyoxyalkylene polyol or monool (S) is represented by formula (2);

wherein in the formula (1), R 1 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or a phenyl group, and these groups are unsubstituted or substituted with a halogen atom or an aryl group,
R 2 —[—(ZO) p -(AO) q -(CH 2 CH 2 O) r -H] m   (2)

wherein in the formula (2), R 2 represents an m-valent group in which m active hydrogens are removed from the active hydrogen-containing compound (H); Z is a group represented by the formula (3) or (4) shown below; A is a group represented by the formula (5) or (6) shown below in which 40% or more of the structure of A located at the terminal among the moiety of (AO)q in the formula (2) is a structure represented by the formula (6) and, when a plurality of Zs or As are present, each be the same or different; m is 1 (when (S) is a monool) or an integer of 2 to 100 (when (S) is a polyol); p is 0 or an integer of 1 to 200; q is an integer of 1 to 200; and r is 0 or an integer of 1 to 200,

wherein in the formulas (3) and (4), R 3 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or a phenyl group and these groups are unsubstituted or substituted with a halogen atom or an aryl group and, in the formulas (5) and (6), R 4 is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or a phenyl group and these groups are unsubstituted or substituted with a halogen atom or an aryl group,
wherein a hydroxyl value x, the total degree of unsaturation y and the content of ethylene oxide z satisfy a relationship of the mathematical expression (3),
y≦ 18.9× x −2 ×(100− z )/100  (3)

in the mathematical expression (3), x represents 5 to 280 mgKOH/g, y represents the total degree of unsaturation represented by a unit meq/g, and z is the content (% by weight) of ethylene oxide based on the weight of (S) and is from 0 to 50,
wherein the moiety of -(AO)q- in the formula (2) is obtained by ring-opening addition polymerization of an alkylene oxide having 3 to 12 carbon atoms in the presence of at least one catalyst (C) selected from the group consisting of a compound represented by the formula (7-1) shown below, a compound represented by the formula (7-2) shown below and a compound represented by the formula (7-3) shown below

in the formula (7-1), (7-2) or (7-3), respectively, X represents a boron atom or an aluminum atom; F is a fluorine atom; and R 5 represents a substituted or unsubstituted phenyl group represented by the formula (8) shown below or a tertiary alkyl group represented by the formula (9) shown below, and each be the same or different,

in the formula (8), Y represents an alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group or a cyano group; and k represents the number of 0 to 5 and, when k is 2 to 5 a plurality of Ys being respectively the same or different,

in the formula (9), R 6 , R 7 or R 8 each independently represents an alkyl group having 1 to 4 carbon atom.

2. The polyoxyalkylene polyol or monool according to claim 1 , wherein r is 0 in the formula (2).

3. The polyoxyalkylene polyol or monool according to claim 1 , wherein the total content of zinc, iron, cobalt, chromium and manganese is 2 ppm or less in the polyoxyalkylene polyol or monool (S).

4. The polyoxyalkylene polyol or monool according to claim 1 , wherein the hydroxyl value x is from 10 to 115 mgKOH/g.

5. The polyoxyalkylene polyol or monool according to claim 1 , wherein 60% or more of the hydroxyl group-containing groups located at the terminal are primary hydroxyl group-containing groups represented by the formula (1).

6. A method for producing a polyoxyalkylene polyol or monool, comprising:
carrying out addition polymerization of an active hydrogen compound (H) with an alkylene oxide in the presence of a catalyst (C) in a reaction vessel ( 1 ) while removing a low boiling point compound (t) as a by-product having a boiling point of 150° C. or lower under a pressure of 0.1 MPa, continuously or intermittently, out of the system,
wherein the catalyst (C) is represented by one of formulae (7-1) to (7-3) below

in the formula (7-1), (7-2) or (7-3), respectively, X represents a boron atom or an aluminum atom; F is a fluorine atom; and R 5 represents a substituted or unsubstituted phenyl group represented by the formula (8) shown below or a tertiary alkyl group represented by the formula (9) shown below, and each be the same or different,

in the formula (8), Y represents an alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group or a cyano group; and k represents the number of 0 to 5 and, when k is 2 to 5, a plurality of Ys being respectively the same or different,

in the formula (9), R 6 , R 7 or R 8 each independently represents an alkyl group having 1 to 4 carbon atom.

7. The method according to claim 6 , wherein the low boiling point compound (t) is selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, allyl alcohol, and a compound formed by adding less than 2 mol of alkylene oxide to allyl alcohol.

8. A foamed or non-foamed polyurethane resin obtained by reacting a polyol component with an organic polyisocyanate component (V), wherein the polyoxyalkylene polyol or monool according to claim 1 is used as at least a part of the polyol component.

Assignees

• Nakaminami Hiromichi
• Sugahara Shogo
• Yasuhara Shu
• Murata Kouichi
• Sanyo Chemical Ind Ltd

Inventors

• Nakaminami Hiromichi
• Sugahara Shogo
• Yasuhara Shu
• Murata Kouichi

Classifications

• C08G18/6674

  with compounds of group C08G18/3203 · CPC title

• C08G18/283

  Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds · CPC title

• C08G18/14

  Manufacture of cellular products · CPC title

• C08G65/2609

  containing aliphatic hydroxyl groups · CPC title

• C08G18/4825

  Polyethers containing two hydroxy groups (C08G18/4833 - C08G18/5096 take precedence) · CPC title