WO2009089400A1

WO2009089400A1 - Compositions and use of 2-chloro-3,3,3-trifluoropropene foam-forming composition in the preparation of polyisocyanate-based foams

Info

Publication number: WO2009089400A1
Application number: PCT/US2009/030514
Authority: WO
Inventors: Gary Loh; Joseph Anthony Creazzo
Original assignee: E. I. Du Pont De Nemours And Company
Priority date: 2008-01-11
Filing date: 2009-01-09
Publication date: 2009-07-16

Abstract

A foam-forming composition is disclosed which includes both 2-chloro-3,3,3-trifluoropropene and an active hydrogen-containing compound having two or more active hydrogens. Also disclosed is a closed-cell polyurethane or polyisocyanurate polymer foam prepared from reaction of effective amounts of the foam-forming composition and a suitable polyisocyanate. Also disclosed is a process for producing a closed-cell polyurethane or polyisocyanurate polymer foam by reacting an effective amount of the foam-forming composition with a suitable polyisocyanate.

Description

TITLE

COMPOSITIONS AND USE OF 2-CHLORO-3,3,3- TRIFLUOROPROPENE FOAM-FORMING COMPOSITION IN THE

PREPARATION OF POLYISOCYANATE-BASED FOAMS

This application claims priority of U.S. Patent Application 61/020465 filed January 11 , 2008 and U.S. Patent Application 61/107679 filed October 23, 2008.

FIELD OF THE INVENTION

The disclosure herein relates to foam-forming compositions comprising a chlorofluoroolefin blowing agent and an active hydrogen- containing compounds, and using such compositions for producing polyurethane and polyisocyanurate foams. More particularly, the disclosure herein relates to foam-forming compositions comprising 2- chloro-3,3,3-trifluoropropene and an active hydrogen-containing compound having two or more active hydrogens, and using such compositions for producing polyurethane and polyisocyanurate foams.

BACKGROUND OF THE INVENTION Closed-cell polyisocyanate-based foams are widely used for insulation purposes, for example, in building construction and in the manufacture of energy efficient electrical appliances. In the construction industry, polyurethane/polyisocyanurate board stock is used in roofing and siding for its insulation and load-carrying capabilities. Poured and sprayed polyurethane foams are widely used for a variety of applications including insulating roofs, insulating large structures such as storage tanks, insulating appliances such as refrigerators and freezers, insulating refrigerated trucks and railcars, etc.

All of these various types of polyurethane/polyisocyanurate foams require blowing agents (also known as foam expansion agents or foam expansion compositions) for their manufacture. Insulating foams depend on the use of halocarbon blowing agents, not only to foam the polymer, but primarily for their low vapor thermal conductivity, a very important characteristic for insulation value. For example, hydrofluorocarbons (HFCs) have been employed as blowing agents for polyurethane foams. An example of an HFC employed in this application is HFC-245fa (1 ,1 ,1 ,3,3-pentafluoropropane). However, the HFCs are of concern due to their contribution to the "greenhouse effect", i.e., they contribute to global warming. As a result of their contribution to global warming, the HFCs have come under scrutiny, and their widespread use may also be limited in the future. Hydrocarbons have also been proposed as foam blowing agents.

However, these compounds are flammable, and many are photochemical Iy reactive, and as a result contribute to the production of ground level ozone (i.e., smog). Such compounds are typically referred to as volatile organic compounds (VOCs), and are subject to environmental regulations.

There is need for producing foams that provide low flammability, good thermal insulation and high dimensional stability by using a blowing agent that has low global warming potential (GWP). 2-chloro-3,3,3- trifluoropropene is one of the good candidates. There is need for producing polyurethane/polyisocyanurate foams by using 2-chloro-3,3,3-trifluoropropene as the blowing agent together with active hydrogen-containing compounds having two or more active hydrogens.

SUMMARY OF THE INVENTION

This disclosure provides a foam-forming composition comprising 2- chloro-3,3,3-trifluoropropene and an active hydrogen-containing compound having two or more active hydrogens.

This disclosure also provides a closed-cell polyurethane or polyisocyanurate polymer foam prepared from reaction of effective amounts of the foam-forming composition and a suitable polyisocyanate.

This disclosure also provides a method for producing a closed-cell polyurethane or polyisocyanurate polymer foam. The method comprises reacting an effective amount of the foam-forming composition and a suitable polyisocyanate.

DETAILED DESCRIPTION The composition of this disclosure is a foam-forming composition comprising 2-chloro-3,3,3-thfluoropropene (HCFC-1233xf) and an active hydrogen-containing compound having two or more active hydrogens, in the form of hydroxyl groups. In this disclosure, HCFC-1233xf is used as a blowing agent. HCFC-1233xf is a known compound which is available from

SynQuest Laboratories, Inc. in Alachua, FL.

By "cream time", it is meant to refer to the time period starting from the mixing of the active hydrogen-containing compound with polyisocyanate, and ending at when the foaming starts to occur and color of the mixture starts to change.

By "rise time", it is meant to refer to the time period starting from the mixing of the active hydrogen-containing compound with polyisocyanate, and ending at when the foam rising stops.

By "tack free time", it is meant to refer to the time period starting from the mixing of the active hydrogen-containing compound with polyisocyanate, and ending at when the surface of the foam is no longer tacky.

By "initial R-value", it is meant to refer to the polymer foam's insulation value (thermal resistance) measured at a mean temperature of 75 ⁰F within 24 hours after the foam is formed and becomes tack free.

The active hydrogen-containing compounds of this invention can comprise compounds having two or more groups that contain an active hydrogen atom reactive with an isocyanate group, such as described in U.S. Patent No. 4,394,491 ; hereby incorporated by reference. Examples of such compounds have at least two hydroxyl groups per molecule, and more specifically comprise polyols, such as polyether or polyester polyols. Examples of such polyols are those which have an equivalent weight of about 50 to about 700, normally of about 70 to about 300, more typically of about 90 to about 270, and carry at least 2 hydroxyl groups, usually 3 to 8 such groups.

Examples of suitable polyols comprise polyester polyols such as aromatic polyester polyols, e.g., those made by transesterifying polyethylene terephthalate (PET) scrap with a glycol such as diethylene glycol, or made by reacting phthalic anhydride with a glycol. The resulting polyester polyols may be reacted further with ethylene - and/or propylene oxide - to form an extended polyester polyol containing additional internal alkyleneoxy groups. Examples of suitable polyols also comprise polyether polyols such as polyethylene oxides, polypropylene oxides, mixed polyethylene- propylene oxides with terminal hydroxyl groups, among others. Other suitable polyols can be prepared by reacting ethylene and/or propylene oxide with an initiator having 2 to 16, generally 3 to 8 hydroxyl groups as present, for example, in glycerol, pentaerythhtol and carbohydrates such as sorbitol, glucose, sucrose and the like polyhydroxy compounds. Suitable polyether polyols can also include alaphatic or aromatic amine- based polyols.

The present invention also relates to processes for producing a closed-cell polyurethane or polyisocyanurate polymer foam by reacting an effective amount of the foam-forming compositions with a suitable polyisocyanate.

Typically, before reacting with a suitable polyisocyanate, the active hydrogen-containing compound described hereinabove and optionally other additives are mixed with the blowing agent HCFC-1233xf to form a foam-forming composition. Such foam-forming composition is typically known in the art as an isocyanate-reactive preblend, or B-side composition. The foam-forming composition of this invention can be prepared in any manner convenient to one skilled in this art, including simply weighing desired quantities of each component and, thereafter, combining them in an appropriate container at appropriate temperatures and pressures.

When preparing polyisocyanate-based foams, the polyisocyanate reactant is normally selected in such proportion relative to that of the active hydrogen-containing compound that the ratio of the equivalents of isocyanate groups to the equivalents of active hydrogen groups, i.e., the foam index, is from about 0.9 to about 10 and in most cases from about 1 to about 4. While any suitable polyisocyanate can be employed in the instant process, examples of suitable polyisocyanates useful for making polyisocyanate-based foam comprise at least one of aromatic, aliphatic and cycloaliphatic polyisocyanates, among others. Representative members of these compounds comprise diisocyanates such as meta- or paraphenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6- diisocyanate, hexamethylene-1 ,6-diisocyanate, tetramethylene-1 ,4- diisocyanate, cyclohexane-1 ,4-diisocyanate, hexahydrotoluene diisocyanate (and isomers), napthylene-1 ,5-diisocyanate, 1-methylphenyl- 2,4-phenyldiisocyanate, diphenylmethane-4,4-diisocyanate, diphenylmethane-2,4-diissocyanate, 4,4 -biphenylenediisocyanate and 3,3-dimethyoxy-4,4 biphenylenediisocyanate and 3,3- dimethyldiphenylpropane-4,4-diisocyanate; thisocyanates such as toluene- 2,4,6-thisocyanate and polyisocyanates such as 4,4 - dimethyldiphenylmethane-2,2,5,5-tetraisocyanate and the diverse polymethylenepoly-phenylopolyisocyanates, mixtures thereof, among others.

A crude polyisocyanate may also be used in the practice of this invention, such as the crude toluene diisocyanate obtained by the phosgenating a mixture comprising toluene diamines, or the crude diphenylmethane diisocyanate obtained by the phosgenating crude diphenylmethanediamine. Specific examples of such compounds comprise methylene-bhdged polyphenylpolyisocyanat.es, due to their ability to crosslink the polyurethane.

It is often desirable to employ minor amounts of additives in preparing polyisocyanate-based foams. Among these additives comprise one or more members from the group consisting of catalysts, surfactants, flame retardants, preservatives, colorants, antioxidants, reinforcing agents, filler, antistatic agents, among others well known in this art. Depending upon the composition, a surfactant can be employed to stabilize the foaming reaction mixture while curing. Such surfactants normally comprise a liquid or solid organosilicone compound. The surfactants are employed in amounts sufficient to stabilize the foaming reaction mixture against collapse and to prevent the formation of large, uneven cells. In one embodiment of this invention, about 0.1 % to about 5% by weight of surfactant based on the total weight of all foaming ingredients (i.e. blowing agents + active hydrogen-containing compounds + polyisocyanates + additives) are used. In another embodiment of this invention, about 1.5% to about 3% by weight of surfactant based on the total weight of all foaming ingredients are used.

One or more catalysts for the reaction of the active hydrogen- containing compounds, e.g. polyols, with the polyisocyanate may be also employed. While any suitable urethane catalyst may be employed, specific catalyst comprise tertiary amine compounds and organometallic compounds. Exemplary such catalysts are disclosed, for example, in U.S. Patent No. 5,164,419, which disclosure is incorporated herein by reference. For example, a catalyst for the thmerization of polyisocyanates, such as an alkali metal alkoxide, alkali metal carboxylate, or quaternary amine compound, may also optionally be employed herein. Such catalysts are used in an amount which measurably increases the rate of reaction of the polyisocyanate. Typical amounts of catalysts are about 0.1 % to about 5% by weight based on the total weight of all foaming ingredients. In the process of the invention for making a polyisocyanate-based foam, the active hydrogen-containing compound (e.g. polyol), polyisocyanate and other components are contacted, thoroughly mixed, and permitted to expand and cure into a cellular polymer. The mixing apparatus is not critical, and various conventional types of mixing head and spray apparatus are used. By conventional apparatus is meant apparatus, equipment, and procedures conventionally employed in the preparation of isocyanate-based foams in which conventional isocyanate- based foam blowing agents, such as fluorothchloromethane (CCI3F, CFC- 11 ), are employed. Such conventional apparatus are discussed by: H. Boden et al. in chapter 4 of the Polyurethane Handbook, edited by G. Oertel, Hanser Publishers, New York, 1985; a paper by H. Grunbauer et al. titled "Fine Celled CFC-Free Rigid Foam - New Machinery with Low Boiling Blowing Agents" published in Polyurethanes 92 from the Proceedings of the SPI 34th Annual Technical/Marketing Conference, October 21 -October 24, 1992, New Orleans, Louisiana; and a paper by M. Taverna et al. titled "Soluble or Insoluble Alternative Blowing Agents? Processing Technologies for Both Alternatives, Presented by the Equipment Manufacturer", published in Polyurethanes World Congress 1991 from the Proceedings of the SPI/ISOPA September 24-26, 1991 , Acropolis, Nice, France. These disclosures are hereby incorporated by reference.

In one embodiment of this invention, a preblend of certain raw materials is prepared prior to reacting the polyisocyanate and active hydrogen-containing components. For example, it is often useful to blend the polyol(s), blowing agent, surfactant(s), catalysts(s) and other foaming ingredients, except for polyisocyanates, and then contact this blend with the polyisocyanate. Alternatively, all the foaming ingredients may be introduced individually to the mixing zone where the polyisocyanate and polyol(s) are contacted. It is also possible to pre-react all or a portion of the polyol(s) with the polyisocyanate to form a prepolymer.

The invention composition and processes are applicable to the production of all kinds of expanded polyurethane foams, including, for example, integral skin, RIM and flexible foams, and in particular rigid closed-cell polymer foams useful in spray insulation, as pour-in-place appliance foams, or as rigid insulating board stock and laminates.

The present invention also relates to the closed-cell polyurethane or polyisocyanurate polymer foams prepared from reaction of effective amounts of the foam-forming composition of this disclosure and a suitable polyisocyanate.

EXAMPLES

The present disclosure is further defined in the following Examples. It should be understood that these Examples, while indicating preferred embodiments, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the preferred features, and without departing from the spirit and scope thereof, can make various changes and modifications to adapt it to various uses and conditions.

Polyol A used in this Example is a sucrose/glycerine initiated polyether polyol (Voranol 360) purchased from Dow Chemicals Inc. at Midland, Ml, 49641 -1206. Polyol in this Example has viscosity of 3,600 centerpoise at 25⁰C. The content of hydroxyl groups in Polyol of this Example is equivalent to 360 mg KOH per gram of Polyol.

Polyol B is a toluene diamine (o-TDA) initiated aromatic polyether polyol (VORANOL 391 ) purchased from Dow Chemicals Inc. at Midland, Ml, 49641 -1206. Polyol B has viscosity of 4740 centerpoise at 25⁰C. The content of hydroxyl groups in Polyol B is equivalent to 391 mg KOH per gram of Polyol B.

Polyol C is an aromatic polyester polyol (Stepanpol PS2502-A) purchased from STEPAN Inc. at 22W Frontage Road, Northfield, IL 60093. Polyol C has viscosity of 3,000 centerpoise at 25⁰C. The content of hydroxyl groups in Polyol C is equivalent to 240 mg KOH per gram of Polyol C.

Silicon type surfactant A (Niax Silicone L-6900) and B (Niax Silicone L-5440) are mixtures of polyalkyleneoxidemethylsiloxane and polyalkylene oxide purchased from Momentive Performance Materials at 187 Danbury Road, Wilton, CT 06897 USA. Silicon type surfactant C is a polysiloxane (Dabco DC193) purchased from Air Products Inc. at 7201 Hamilton Blvd, Allentown PA 18195.

Amine catalyst A (Polycat 8) is N,N-dimethylcyclohexylamine purchased from Air Products Inc. at 7201 Hamilton Blvd, Allentown PA 18195.

Amine catalyst B (Polycat 5) is Pentamethyldiethylenethamine purchased from Air Products Inc. at 7201 Hamilton Blvd, Allentown PA 18195. Co-catalyst (Curithane 52) is 2-methyl(n-nnethyl amino b-sodium acetate nonyl phenol) purchased from Air Products Inc. at 7201 Hamilton BI vd, Allentown PA 18195.

Potassium catalyst (Potassium HEX-CEM 977) contains 25 wt% diethylene glycol and 75 wt% potassium 2-ethylhexanoate, and is purchased from OMG Americas Inc. at 127 Public Square, 1500 Key Tower, Cleveland, OH 44114.

Amine catalyst C (Dabco TMR-30) is Tris-2,4,6- (dimethylaminomethyl)phenol purchased from Air Products Inc. at 7201 Hamilton Blvd, Allentown PA 18195.

Polymethylene polyphenyl isocyanate A (PAPI 27) and B (PAPI 580N) are purchased from Dow Chemicals, Inc. at Midland, Ml, 49641 - 1206.

EXAMPLE 1 (Polvol A) Polyol A, surfactant, catalysts, water and 2-chloro-3,3,3- thfluoropropene were pre-mixed by hand in a container with known volume. Polyisocyanate was added to the container to form the polyurethane foam. The foam was cut along the edge of the container to check the cell structure and density. The foam showed uniform cell structure. The formulation and properties of the foam are shown in Table 1 below. Table 1 Polyurethane foam formulation and properties - Polvol A

EXAMPLE 2 (Polvol A)

Polyol A, surfactant, catalysts, water and 2-chloro-3,3,3- trifluoropropene were pre-mixed by hand and then mixed with polyisocyanate. The resulting mixture was poured into a 8"x8"x2.5" paper box to form the polyurethane foam. The formulation and properties of the foam are shown in Tables 2 and 3 below.

Table 2 Polyurethane foam formulation - Polvol A

Table 3 Polyurethane foam properties - Polvol A

EXAMPLE 3 (Polvol B)

Polyol B, surfactant B, catalysts, water and 2-chloro-3,3,3- trifluoropropene were pre-mixed by hand and then mixed with polyisocyanate. The resulting mixture was poured into a 8"x8"x2.5" paper box to form the polyurethane foam. The formulation and properties of the foam are shown in Tables 4 and 5 below.

Table 4 Polyurethane foam formulation - Polyol B

Table 5 Polvurethane foam properties - Polvol B

EXAMPLE 4 (Polvol C)

Polyol C, surfactant C, catalysts, water and 2-chloro-3,3,3- trifluoropropene were pre-mixed by hand and then mixed with polyisocyanate. The resulting mixture was poured into a 8"x8"x2.5" paper box to form the polyurethane foam. The formulation and properties of the foam are shown in Tables 6 and 7 below. Table 6 Polyurethane foam formulation - Polyol C

Table 7 Polvurethane foam properties - Polvol C

Claims

Claims What is claimed is:

1. A foam-forming composition comprising 2-chloro-3,3,3- trifluoropropene and an active hydrogen-containing compound having two or more active hydrogens.

2. The foam-forming composition of claim 1 wherein said active hydrogen-containing compound is a polyether polyol.

3. The foam-forming composition of claim 1 wherein said active hydrogen-containing compound is a polyester polyol.

4. A closed-cell polyurethane or polyisocyanurate polymer foam prepared from reaction of effective amounts of the foam-forming composition of claim 1 , 2 or 3 and a suitable polyisocyanate.

5. The closed-cell polyurethane or polyisocyanurate polymer foam of claim 4 wherein said polymer foam has an initial R-value greater than 7.0 ft²-hr-°F/BTU-in.

6. A process for producing a closed-cell polyurethane or polyisocyanurate polymer foam comprising: reacting an effective amount of the foam-forming composition of claim 1 , 2 or 3 and a suitable polyisocyanate.