Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
2001-09-17
2002-12-17
Barts, Samuel (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C564S360000, C564S361000, C564S384000, C564S389000, C521S163000, C521S164000, C521S167000
Reexamination Certificate
active
06495722
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to foamed products produced by admixture of an isocyanate with a polyol which is a Mannich condensate. More particularly, the invention relates to Mannich condensates useful for producing foams, wherein the Mannich condensates possess physical properties which render them useful in conventional spray equipment, and which properties yield foam products which are physically useful in applications where analogous foams made with prior art Mannich condensate polyols fail.
BACKGROUND INFORMATION
When it is desired to prepare polyurethane foams which are blown using water only as a blowing agent, or mixtures of water and auxiliary blowing agents, it is found that the Mannich polyols available in the prior art are either too viscous to be used in spray equipment or do not provide foams with good physical properties.
WO 00/156690 discloses Mannich polyols with viscosities of 300-3500 cps. The technology therein uses a mixture of ethylene oxide and propylene oxide as alkoxylating agent. U.S. Pat. No. 6,281,393 is similar to WO 00/156690. Japan Kokai 173826 (1992) Mannich polyols with a hydroxyl number in the range of between 350-500. The technology therein uses a mole ratio of phenolic to formaldehyde of 1:2.1-3 and 20-50% (wt.) ethylene oxide. U.S. Pat. No. 4,383,102 provides low viscosity Mannich polyols using a mixture of ethylene oxide and propylene oxide (as alkoxylating agent). The entire contents of each of these patents and publications are herein incorporated by reference thereto.
SUMMARY OF THE INVENTION
The present invention relates to a foamed product which is formed from the admixture of: a first component comprising an organic isocyanate and a second component comprising a Mannich polyol. The Mannich polyol has a hydroxy number in the range of 250-340 and a viscosity of 3500 cps or less. The Mannich polyol is derived from nonylphenol, formaldehyde, an alkanolamine, and propylene oxide as the sole alkoxylating agent. The invention also relates to the Mannich polyols which are disclosed.
The Mannich condensate polyol product useful according to the invention comprises a mixture of:
, said mixture being derived from:
a) nonylphenol,
b) formaldehyde,
c) an alkanolamine selected from the group consisting of: diethanolamine, or mixtures of diethanolamine with monoethanolamine; and
d) propylene oxide as the sole alkoxylating agent, wherein said mixture has a hydroxy number in the range of 250-340 and a viscosity of 3500 cps or less. Preferably, the ratio of MONO/DI in the above mixture is any ratio in the range of between 10/90 to 70/30.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides Mannich polyols prepared from nonylphenol, formaldehyde, ethanolamines, and propylene oxide as the sole alkoxylating agent. The Mannich polyols of the invention have a hydroxy number in the range of 250-340 and a viscosity of 3500 cps or less. The invention also relates to polyurethane spray foams prepared from these polyols and an organic isocyanate such as MDI, TDI, aliphatic isocyanates, or polymeric forms of any of these.
The polyols of this invention are useful in preparing rigid spray urethane foams. The polyols of this invention allow for good water blown or partially water blown spray foams to be prepared. They also have improved hydrocarbon solubility and HCFC solubility thus allowing for wide formulating parameters. Prior art polyols suffer from high viscosity, and produce foams having poor properties.
The lower viscosity of the polyols of this invention enable preparation of components having suitable viscosities for forming end use products using spray techniques, i.e., spray foams. If the viscosity is too high, the pumps used in association with the spraying can cavitate or poor mixing of the A-component (isocyanate) and B-component occurs, thus forming inferior or unusable products. The polyols of this invention also give improved solubility of auxiliary blowing agents like 134a and isopentane. Finally the foams produced from these polyols have superior physical properties, i.e. dimensional stabilities and inter laminar adhesion. Both of these are unexpected, especially the inter laminar adhesion.
This invention is concerned with Mannich condensate polyols having a relatively low hydroxyl number and relatively low viscosity which are made using propylene oxide as the sole alkoxylating agent, and not a mix of propylene oxide and ethylene oxide as taught in the prior art. The invention is also concerned with the use of such Mannich condensate polyols in all-water blown or partially water blown rigid polyurethane foams. The Mannich condensate polyols of the invention are prepared from nonylphenol, formaldehyde, an alkanolamine (which may be neat diethanolamine, or a mixture of diethanolamine with monoethanolamine), and propylene oxide. The procedure for preparing a Mannich condensate polyol according to the invention is set forth in the examples. The preferred hydroxyl number range for a Mannich condensate polyol prepared according to the invention is 250-340, with the most preferred being in the range of 290-330. The viscosity of a Mannich condensate polyol according to the invention is less than 3500 cps with the preferred range being any value in the range of 1500 to 3000 cps.
The rigid urethane foams are ones that are either “all water blown”, or use water as the primary blowing agent, which in the former case means that all of, and in the latter case means that at least 50% of the gas used in generating the foam cells is derived from carbon dioxide that is generated from the reaction of isocyanate with water that is present in the formulation.
The polyols made using propylene oxide as the sole alkoxylating agent according to the invention provide all water blown foams that were dimensionally stable, while prior art polyols that used both ethylene oxide and propylene oxide do not possess good dimensional stability. Further, the all water blown foams resulting from the use of the polyols of this invention gave extremely good inter laminar adhesion (adhesion between separate foam layers).
REFERENCES:
patent: 4383102 (1983-05-01), McDaniel et al.
patent: 6281393 (2001-08-01), Molina et al.
patent: 0 398 147 (1994-11-01), None
patent: 173826 (1990-11-01), None
patent: WO 0015690 (1999-09-01), None
Devine Marshall P.
Weaver Patrick L.
Zimmerman Robert L.
Barts Samuel
Brown Ron D.
Huntsman Petrochemical Corporation
Stolle Russ R.
Whewell Christopher J.
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