# Patent

## Title
Urethane composition

## Abstract

This is a divisional of copending application Ser. No. 07/829,866 filed on FEB. 3, 1992, U.S. Pat. No. 5,135,680 which in turn is a continuation-in-part of application Ser. No. 07/774,018, filed Oct. 9, 1991 (now abandoned).

## Background
This invention relates to novel compositions of hydrochlbrofluorocarbon ("HCFC") blowing agents such as 1,1-dichloro-1-fluoroethane ("141b") and stabilizing additives (or inhibitors) such as alpha-pinene oxide, more particularly to compositions of HCFC blowing agents which are stabilized against decomposition in polyol premix formulations or the corresponding polyurethane or polyisocyanurate foams made therefrom.

Polyurethane and polyisocyanurate foams are conventionally prepared by reacting an organic polyisocyanate including diisocyanate) "A-side" component with a "B-side" polyol premix component containing organic polyol, blowing agent, surfactant, catalyst, and possibly other additives such as flame retardants, antioxidants, and U.V. stabilizers. These A-side and B-side components may be purchased by the end-user in separate containers and stored for later use. Since decomposition of the HCFC blowing agent has been observed in the B-side premixes during storage and during the process of making the foam, HCFC compositions inhibited against such decompositions would be highly desirable. For example, the preferred 141b blowing agent has been observed to decompose during the foam-making process to up to about 1%, depending on the formulation and reaction conditions, of various decomposition products of which by far the predominant product is 1-chloro-1-fluoroethylene ("1131a"). Inhibition of such decomposition is desired both because of toxicity concerns and because the decomposition is accompanied by the formation of equivalent amounts of acid which in turn causes catalyst deactivation.

A composition is provided containing an HCFC blowing agent such as 141b and an inhibitor selected from 1,2-hexadecene oxide, alpha-pinene oxide, or limonene dioxide (preferably, alpha-pinene oxide or limonene dioxide). When incorporated in a premix, the composition may also contain a polyol and, optionally, other ingredients such as surfactants, catalysts, and flame retardants.

It has now been found that HCFC blowing agents such as 141b are stabilized against decomposition by the addition of a high boiling epoxide as an inhibitor, such as alpha-pinene oxide, limonene dioxide, or 1,2-hexadecene oxide (boiling points, in degrees C., of 177, 242, and 315, respectively). Low boiling epoxides, such as 1,2-epoxybutane, have been found to be ineffective.

While the examples illustrate the invention with the preferred 141b blowing agent, the invention is also applicable to other HCFCs such as 2,2-dichloro-1,1,1- trifluoroethane ("123") and 2-chloro-1,1,1,2-tetrafluoroethane ("124").

The inhibitor is present in an effective amount, typically from about 0.01 to about 2% by weight, based on the weight of the blowing agent(s), preferably 0.05 to 1%.

The compositions may also include a polyol or a fully formulated B-side formulation containing polyol, catalyst, surfactant, and, optionally, other additives. Typical polyols are, for example, Stepanol PS 2502A, an aromatic polyester polyol sold by the Stepan Company; Terate 203, an aromatic polyester polyol sold by Hercules, Inc.; Pluracol Polyol 975, a sucrose-based polyol sold by BASF; Poly-G 71-530, a polyether polyol sold by Olin; and Quadrol, an amine-based polyol supplied by BASF. Typical catalysts include Potassium HEX-CEM, a potassium octoate sold by Mooney Chemicals; Polycat 41, an N,N,N-tri(dimethylaminopropyl)cyclohexatriazine catalyst sold by Air Products; Polycat 8, an N,N-dimethylcyclohexylamine Dabco TMR-30, a 2,4,6-tri(dimethylaminomethyl)phenol supplied by Air Products; and Dabco K-15, a potassium 2-ethylhexoate in diethylene glycol supplied by Air Products. A typical surfactant is Dow Corning 193, a silicone polymer surfactant. A typical A-side component is Mondur E-489, an aromatic diisocyanate supplied by Mobay Chemical Co., or Lupranate M20S, a polymethylene diisocyanate supplied by BASF.

The invention was illustrated by first preparing a polyurethane foam with 141b in the absence of inhibitor by stirring a formulation containing polyol (100 g of Stepanol PS 2502A), 141b (25.8 g), surfactant (1.51 g of Dow Corning 193), catalyst (2.82 g of Potassium HEX-CEM and 0.7 g of Polycat 41), and diisocyanate (127.2 g of Mondur E-489). The contents were poured into a box and the resulting foam was left to cool to room temperature. After curing the foam at 250.degree. F. for 20 hours, the cell gas was analyzed by crushing a sample and injecting the released gas mixture directly to a gas chromatograph. The gas was found to contain 2180 ppm of 1131a, whereas the 141b starting material contained only 10 ppm of 1131a. Other minor components in the cell gas totalled only about 440 ppm, similar to the levels found in the 141b starting material. When 0.6 weight % of each of 1,2-hexadecene oxide and alpha-pinene oxide were dissolved in 141b, foams prepared as aforesaid contained only 1193 ppm and 510 ppm of 1131a, respectively.

The foregoing test was repeated using uninhibited 141b, 141b inhibited with 0.6 weight % of 1,2-hexadecene oxide, and 141b inhibited with 0.6 weight % of limonene dioxide. The prepared foams were found to contain 2590 ppm, 920 ppm, and 470 ppm of 1131a, respectively.

In another illustration, polyisocyanurate premixes containing 141b (uninhibited and inhibited with 0.6 weight % alpha-pinene oxide) were aged at 130 degrees F. The premixes contained a polyol (100g of Stepanol PS-2502A), 141b (37g), surfactant (3g of Dow Corning 193), and catalyst (2.8g of Dabco K-15 and 0.9g of Dabco TMR-30). The uninhibited premix was found to contain 100 ppm of 1131a, while the premix containing alpha-pinene oxide contained only 10 ppm of 1131a.

## Claims

1. A foamable composition comprising a polyol, a polyisocyanate, 1,1-dichloro-1-fluoroethane, and an inhibitor selected from alpha-pinene oxide, limonene dioxide, and 1,2-hexadecene oxide.

2. A foamable composition as in claim 1 wherein the inhibitor is alpha-pinene oxide.

3. A foamable composition as in claim 1 wherein the inhibitor is limonene dioxide.

4. A foamable composition as in claim 1 wherein the inhibitor is 1,2- hexadecene oxide.

5. A foam made from the composition of claim 1.