WO2001051552A2

WO2001051552A2 - Blowing agent blends

Info

Publication number: WO2001051552A2
Application number: PCT/US2001/000186
Authority: WO
Inventors: Mary Charlotte Bogdan; David John Williams; Peter Brian Logsdon; Leslie Bruce Bemont
Original assignee: Honeywell International Inc.
Priority date: 2000-01-07
Filing date: 2001-01-03
Publication date: 2001-07-19
Also published as: AU2626901A; WO2001051552A3

Abstract

The invention relates to polyurethane and polyisocyanurate closed-cell foams. More particularly, the invention relates to polyurethane and polyisocyanurate closed-cell foams prepared with a blowing agent comprising 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124) and 1,1-dichloro-1-fluoroethane (HCFC-141b) or a C2-C6 hydrocarbon. Foams prepared with the blowing agent of the invention possess improved thermal performance.

Description

BLOWING AGENT BLENDS

Field of the Invention

The invention relates to polyurethane and polyisocyanurate closed-cell foams. More particularly, the invention relates to polyurethane and polyisocyanurate closed- cell foams prepared with a blowing agent comprising 1-chloro- 1,2,2,2- tetrafluoroethane (HCFC-124) and 1,1-dichloro-l-fluoroethane (HCFC-141b) or a hydrocarbon. Foams prepared with the blowing agent of the invention possess improved cell nucleation and thermal performance.

Background of the Invention

The class of foams known as low density rigid polyurethane or polyisocyanurate foam has utility in a wide variety of insulation applications including roofing systems, building panels, refrigerators and freezers. A critical factor in the large-scale commercial acceptance of rigid polyurethane foams in the building insulation industry has been their ability to provide a good balance of properties. Rigid polyurethane and polyisocyanurate foams are known to provide outstanding thermal insulation, excellent fire properties and superior structural properties at reasonably low densities.

The methods of producing polyurethane and polyisocyanurate foams are generally known and consist in general of the reaction of an organic polyisocyanurate (including diisocyanate) and a polyol or mixture of polyols in the presence of a volatile blowing agent, which is caused to vaporize by the heat liberated during the reaction of isocyanate and polyol. This reaction can be enhanced through the use of amine and/or other catalysts as well as surfactants. The catalysts ensure adequate curing of the foam, while the surfactants regulate and control cell size. Flame- retardants are traditionally added to rigid polyurethane or polyisocyanurate foam to reduce its flammability.

The foam industry has historically used liquid fluorocarbon blowing agents such as trichlorofluoromethane (CFC-1 1) and 1,1-dichloro-l-fluoroethane (HCFC-141b) because of their ease of use in processing conditions. Fluorocarbons act not only as blowing agents by virtue of their volatility, but also are encapsulated or entrained in the closed cell structure of the rigid foam and are the major contributor to the low thermal conductivity properties of rigid urethane foams.

The use of a fluorocarbon as the preferred commercial expansion or blowing agent in insulating foam applications is based in part on the resulting k-factor associated with the foam produced. K-factor is defined as the rate of transfer of heat energy by conduction through one square foot of one inch thick homogenous material in one hour where there is a difference of one degree Fahrenheit perpendicularly across the two surfaces of the material. Since the utility of closed-cell polyurethane- type foams is based, in part, upon their thermal insulation properties, it would be advantageous to identify materials that produce lower k-factor foams.

l-chloro-l,2,2,2-tetrafluoroethane (HCFC-124) is a known blowing agent. It has now been discovered that the use of HCFC-124 as a co-blowing agent for 1,1- dichloro-l-fluoroethane HCFC-141b unexpectedly results in foams having superior thermal performance to foam produced with HCFC-141b. The results are unexpected since one would anticipate on the basis of vapor thermal conductivity that the addition of HCFC-124 to HCFC-141b systems would elevate the k-factor of the foam produced. It has also been discovered that that polyurethane and polyisocyanurate closed cell foams prepared in the presence of a blowing agent composition comprising HCFC-124 and at least one hydrocarbon exhibit better than expected thermal and physical properties.

Detailed Description of the Invention

The invention relates to blowing agent compositions comprising 1 -chloro- 1,2,2,2-tetrafluoroethane and at least one co-blowing agent selected from the group consisting of 1,1-dichloro-l-fluoroethane and C₄-C₆ hydrocarbons.

In one embodiment, the invention relates to a blowing agent composition comprising l-chloro-l,2,2,2-tetrafluoroethane and 1,1-dichloro-l-fluoroethane. The preferred compositions of the invention are reported in the Table below. The ranges reported in the table are in weight percent based on the total amount of blowing agent composition and are understood to be prefaced by "about".

% HCFC-141b in blowing | % HCFC-124

In another embodiment, blowing agent compositions comprising 1 -chloro- 2,2,2,2-tetrafluoroethane and a C₄-C₆ hydrocarbon. Suitable C₄-C₆ hydrocarbons are n-butane, isobutane, n-pentane, isopentane, cyclopentane, hexane, isohexane and mixtures thereof. Cyclopentane, isopentane and n-pentane are preferred.

Preferably, this embodiment of the invention provides a blowing agent composition comprising from about 50 to about 99 weight percent of 1-chloro- 1,2,2,2-tetrafluoroethane and from about 1 to about 50 weight percent of at least one hydrocarbon selected from the group consisting of n-pentane, isopentane, cyclopentane and mixtures thereof.

More preferably, this embodiment provides a blowing agent composition comprising from about 66 to about 99 weight percent of 1-chloro- 1,2,2,2- tetrafluoroethane and from about 1 to about 33 weight percent of at least one hydrocarbon selected from the group consisting of n-pentane, isopentane, cyclopentane and mixtures thereof.

Most preferably, this embodiment provides a blowing agent composition comprising from about 90 to about 99 weight percent of 1-chloro- 1,2,2,2- tetrafluoroethane and from about 1 to about 10 weight percent of at least one hydrocarbon selected from the group consisting of n-butane, isobutane, n-pentane, isopentane, cyclopentane, hexane, isohexane and mixtures thereof. The most preferred compositions of this embodiment of the invention advantageously do not have a flash point at -25°F according to ASTM 3828-87.

In another embodiment of the invention, there is provided a method of preparing foam compositions based on isocyanate which comprises reacting and foaming a mixture of ingredients which will react to form polyurethane or polyisocyanurate foams in the presence of the blowing agent composition of the invention.

In yet another embodiment, the invention provides a closed cell foam prepared from a polymer foam formulation containing the blowing agent composition of the invention.

In still another embodiment, the invention provides a polyol premix composition comprising a polyol and the blowing agent composition of the invention.

With respect to the preparation of rigid or flexible polyurethane or polyisocyanurate foams using hydrocarbons as the blowing agent, any of the methods well known in the art can be employed. See Saunders and Frisch, Volumes I and II Polyurethanes Chemistry and Technology (1962). In general, polyurethane or polyisocyanurate foams are prepared by combining an isocyanate, a polyol or mixture of polyols, a blowing agent or mixture of blowing agents, and other materials such as catalysts, surfactants, and optionally, flame retardants, colorants, or other additives.

It is convenient in many applications to provide the components for polyurethane or polyisocyanurate foams in pre-blended foam formulations. Most typically, the foam formulation is pre-blended into two components. The isocyanate or polyisocyanate composition comprises the first component, commonly referred to as the "A" component. The polyol or polyol mixture, surfactant, catalysts, blowing agents, flame retardant, and other isocyanate reactive components comprise the second component, commonly referred to as the "B" component. While the surfactant, catalyst(s) and blowing agent are usually placed on the polyol side, they may be placed on either side, or partly on one side and partly on the other side. Accordingly, polyurethane or polyisocyanurate foams are readily prepared by bringing together the A and B side components either by hand mix, for small preparations, or preferably machine mix techniques to form blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, froths, and the like. Optionally, other ingredients such as fire retardant, colorants, auxiliary blowing agents, water, and even other polyols can be added as a third stream to the mix head or reaction site. Most conveniently, however, they are all incorporated into one B component. Any organic polyisocyanate can be employed in polyurethane or polyisocyanurate foam synthesis inclusive of aliphatic and aromatic polyisocyanates. Preferred, as a class is the aromatic polyisocyanates. Preferred polyisocyanates for rigid polyurethane or polyisocyanurate foam synthesis are the polymethylene polyphenyl isocyanates, particularly the mixtures containing from about 30 to about 85 percent by weight of methyl enebis(phenyl isocyanate) with the remainder of the mixture comprising the polymethylene polyphenyl polyisocyanates of functionality higher than 2. Preferred polyisocyanates for flexible polyurethane foam synthesis are toluene diisocyanates including, without limitation, 2,4-toluene diisocyanate, 2,6- toluene diisocyanate, and mixtures thereof.

Typical polyols used in the manufacture of rigid polyurethane foams include, but are not limited to, aromatic amino-based polyether polyols such as those based on mixtures of 2,4- and 2,6-toluenediamine condensed with ethyl ene oxide and/or propylene oxide. These polyols find utility in pour-in-place molded foams. Another example is aromatic alkylamino-based polyether polyols such as those based on ethoxylated and/or propoxylated aminoethylated nonylphenol derivatives. These polyols generally find utility in spray applied polyurethane foams. Another example is sucrose-based polyols such as those based on sucrose derivatives and/or mixtures of sucrose and glycerine derivatives condensed with ethylene oxide and/or propylene oxide. These polyols generally find utility in pour-in-place molded foams.

Typical polyols used in the manufacture of flexible polyurethane foams include, but are not limited to, those based on glycerol, ethylene glycol, trimethylolpropane, ethylene diamine, pentaerythritol, and the like condensed with ethylene oxide, propylene oxide, butylene oxide, and the like. These are generally referred to as "polyether polyols". Another example is the graft copolymer polyols, which include, but are not limited to, conventional polyether polyols with vinyl polymer grafted to the polyether polyol chain. Yet another example is polyurea modified polyols which consist of conventional polyether polyols with polyurea particles dispersed in the polyol.

Examples of polyols used in polyurethane modified polyisocyanurate foams include, but are not limited to, aromatic polyester polyols such as those based on complex mixtures of phthalate-type or terephthalate-type esters formed from polyols such as ethylene glycol, diethylene glycol, or propylene glycol. These polyols are used in rigid laminated boardstock, and may be blended with other types of polyols such as sucrose-based polyols, and used in polyurethane foam applications.

Catalysts used in the manufacture of polyurethane foams are typically tertiary amines including, but not limited to, N-alkylmorpholines, N-alkylalkanolamines, N,N-dialkylcyclohexylamines, and alkylamines where the alkyl groups are methyl, ethyl, propyl, butyl and the like and isomeric forms thereof, as well as heterocyclic amines. Typical, but not limiting, examples are triethylenediamine, tetramethylethylenediamine, bis(2-dimethylaminoethyl)ether, triethylamine, tripropylamine, tributylamine, triamylamine, pyridine, quinoline, dimethylpiperazine, piperazine, N,N-dimethylcyclohexylamine, N-ethylmorpholine, 2-methylpiperazine, N,N-dimethylethanolamine, tetramethylpropanediamine. methyltriethylenediamine, and mixtures thereof.

Optionally, non-amine polyurethane catalysts are used. Typical of such catalysts are organometallic compounds of lead, tin, titanium, antimony, cobalt, aluminum, mercury, zinc, nickel, copper, manganese, zirconium, and mixtures thereof. Exemplary catalysts include, without limitation, lead 2-ethylhexoate, lead benzoate, ferric chloride, antimony trichloride, and antimony glycolate. A preferred organo-tin class includes the stannous salts of carboxylic acids such as stannous octoate, stannous 2-ethylhexoate, stannous laurate, and the like, as well as dialkyl tin salts of carboxylic acids such as dibutyl tin diacetate, dibutyl tin dilaurate, dioctyl tin diacetate, and the like.

In the preparation of polyisocyanurate foams, trimerization catalysts are used for the purpose of converting the blends in conjunction with excess A component to polyisocyanurate-polyurethane foams. The trimerization catalysts employed can be any catalyst known to one skilled in the art including, but not limited to, glycine salts and tertiary amine trimerization catalysts, alkali metal carboxylic acid salts, and mixtures thereof. Preferred species within the classes are potassium acetate, potassium octoate, and N-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate.

Dispersing agents, cell stabilizers, and surfactants may be incorporated into the blowing agent mixture. Surfactants, better known as silicone oils, are added to serve as cell stabilizers. Some representative materials are sold under the names of DC- 193. B-8404, and L-5340 which are, generally, polysiloxane polyoxyalkylene block co- polymers such as those disclosed in U.S. Patent Nos. 2,834,748, 2,917,480, and 2,846,458.

Other optional additives for the blowing agent mixture may include flame retardants such as tris(2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (1,3-dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like. Other optional ingredients may include from 0 to about 3 percent water, which chemically reacts with the isocyanate to produce carbon dioxide. The carbon dioxide acts as an auxiliary-blowing agent.

Also included in the mixture are blowing agents. HCFC-124 and HCFC-141b are known blowing agents that are commercially available from Honeywell International Inc. Hydrocarbons such as n-butane, isobutane, n-pentane, isopentane, cyclopentane, hexane and isohexane are known blowing agents that are also commercially available.

Generally speaking, the amount of blowing agent present in the blended mixture is dictated by the desired foam densities of the final polyurethane or polyisocyanurate foams products. The polyurethane foams produced can vary in density from about 0.5 pound per cubic foot to about 40 pounds per cubic foot, preferably from about 1.0 to about 20.0 pounds per cubic foot, and most preferably from about 1.5 to about 6.0 pounds per cubic foot for rigid polyurethane foams and from about 1.0 to about 4.0 pounds per cubic foot for flexible foams. The density obtained is a function of how much of the blowing agent, or blowing agent mixture, is present in the A and/or B components, or that is added at the time the foam is prepared.

Example

The invention is further illustrated by the following examples, in which parts or percentages are by weight unless otherwise specified. The following materials were used in the examples. Polyol Blend: A polyester polyol with an OH number of 240 containing a compatibilizer to aid miscibility. It is a commercially available from KOSA

HCFC-124: 1-chloro- 1,2,2,2-tetrafluoroethane commercially available from Honeywell International Inc.

HCFC-141b: 1,1-dichloro-l-fluoroethane commercially available from

Honeywell International Inc.

Cyclopentane: commercially available from Phillips 66 Company.

Surfactant A: A polysiloxane polyether copolymer, which is commercially available from Goldschmidt.

Catalyst A: An inorganic potassium based amine, which is commercially available from Air Products.

Catalyst B: A trimerization catalyst which is commercially available from Air Products.

Example 1

In this example, rigid polyisocyanurate foams were prepared using the formulation shown in Table 1.

The foams were prepared by a general procedure commonly referred to as "handmixing". For each blowing agent or blowing agent pair, a premix of polyol, surfactant, and catalysts was prepared in the same proportions displayed in Table 1. About 100 grams of each formulation was blended. The premix was blended in a 32oz paint can, and stirred at about 1500 rpm with a Conn 2" diameter ITC mixer until a homogeneous blend was achieved. When mixing was complete, the can was covered and placed in a refrigerator controlled at 32°F. The foam blowing agent or pre-blended pair of blowing agents was also stored in pressure bottles at 32°F. The A- component was kept in sealed containers at 70°F.

The pre-cooled blowing agent was added in the required amount to the premix.

The contents were stirred for two minutes with a Conn 2" ITC mixing blade turning at

1000 rpm. Following this, the mixing vessel and contents were re- weighed. If there was a weight loss, the blowing agent or the blend was added to the solution to make up any weight loss. The can is than covered and replaced in the refrigerator.

After the contents have cooled again to 32°F, approximately 10 minutes, the mixing vessel was removed from refrigerator and taken to the mixing station. A pre- weighted portion of A-component, isocyanurate, was added quickly to the B- component, the ingredients mixed for 10 seconds using a Conn 2" diameter ITC mixing blade at 3000 rpm and poured into a 8"x 8"x 4"cardboard cake box and allowed to rise. Cream, initiation, gel and tack free times were recorded for the individual polyurethane foam samples.

The foams were allowed to cure in the boxes at room temperature for at least 24 hours. After curing, the blocks were trimmed to a uniform size and densities measured. Any foams that did not meet the density specification 1.9 + .1 lb/ft³ were discarded and new foams were prepared.

After ensuring that all the foams meet the density specifications, the foams were tested for k-factor according to ASTM C518. The k-factor results are listed in Table 1

Table 1

The foams co-blown with HCFC-124 and HCFC-141b have surprisingly better k-factors than foams produced with HCFC-124 or HCFC-141b alone at low temperatures. At room temperature the k-factors are equivalent. These results are contrary to expectation since the vapor thermal conductivity of HCFC-124 (0.08496 @ 70°F) is higher than that of HCFC-141b (0.0696 @ 70°F), and one would expect the addition of HCFC-124 to HCFC-141b to result in a foam having an elevated k-factor.

Example 2

In this example, rigid polyisocyanurate were prepared in a lab using the formulation shown in Table 2. Four experiments were conducted. Experiment 1 used HCFC-124 as a blowing agent. The second and third experiment were conducted using cyclopentane as a blowing agent with HCFC-124 as a co-blowing agent. The fourth experiment was conducted using cyclopentane as the blowing agent.

The foams were prepared by a general procedure commonly referred to as

"handmixing". For each blowing agent or blowing agent pair, a premix of polyol, surfactant, and catalysts was prepared in the same proportions displayed in Table 2. About 100 grams of each formulation was blended. The premix was blended in a 32oz paint can, and stirred at about 1500 rpm with a Conn 2" diameter ITC mixer until a homogeneous blend was achieved. When mixing was complete, the can was covered and placed in a refrigerator controlled at 32°F. The foam blowing agent or pre-blended pair of blowing agents was also stored in pressure bottles at 32°F. The A-component was kept in sealed containers at 70°F.

The pre-cooled blowing agent was added in the required amount to the premix.

The contents were stirred for two minutes with a Conn 2" ITC mixing blade turning at 1000 rpm. Following this, the mixing vessel and contents were re- weighed. If there was a weight loss, the blowing agent or the blend was added to the solution to make up any weight loss. The can is then covered and replaced in the refrigerator.

After the contents have cooled again to 32°F, approximately 10 minutes, the mixing vessel was removed from refrigerator and taken to the mixing station. A pre- weighted portion of A-component, isocyanurate, was added quickly to the B-component, the ingredients mixed for 10 seconds using a Conn 2" diameter ITC mixing blade at 3000 rpm and poured into a 8"x 8"x 4"cardboard cake box and allowed to rise. Cream, initiation, gel and tack free times were recorded for the individual polyurethane foam samples.

The foams were allowed to cure in the boxes at room temperature for at least 24 hours. After curing, the blocks were trimmed to a uniform size and densities measured. Any foams that did not meet the density specification 1.85 + .1 lb/ft³ were discarded and new foams were prepared.

After ensuring that all the foams meet the density specifications, the foams were tested for k-factor according to ASTM C518. The k-factor results are listed in Table 2.

Table 2

The foams co-blown with HFC- 124 and cyclopentane have surprisingly better k-factors than foams produced with HFC- 124 or cyclopentane alone. Figure 1 further illustrates the unexpectedly non-linear relationship between k-factor and cyclopentane concentration. Example 3

In this example, rigid polyisocyanurate were prepared and tested as in Example 2 except that n-pentane was the hydrocarbon species. The foam formulations and k-factor results are listed in Table 3.

Table 3

The foams co-blown with HFC- 124 and n-pentane have suφrisingly better k-factors than one would anticipate in comparison to the k-factors for foams produced with either HFC- 124 or n-pentane alone. Figure 1 further illustrates the unexpectedly non-linear relationship between k-factor and n-pentane concentration.

Example 4

In this example, rigid polyisocyanurate were prepared and tested as in Example 2 except that isopentane was the hydrocarbon species. The foam formulations and k-factor results are listed in Table 4. Table 4

The foams co-blown with HFC- 124 and isopentane have suφrisingly better k-factors than one would anticipate in comparison to the k-factors for foams produced with either HFC- 124 or isopentane alone. Figure 1 further illustrates the unexpectedly non-linear relationship between k-factor and isopentane concentration.

Example 5

In this example, rigid polyisocyanurate were prepared and tested as in Example 2 except that hexane was the hydrocarbon species. The foam formulations and k-factor results are listed in Table 5.

Table 5

The foams co-blown with HCFC-124 and hexane have suφrisingly better k-factors than one would anticipate in comparison to the k-factors for foams produced with either HCFC-124 or hexane alone. Figure 1 further illustrates the unexpectedly non-linear relationship between k-factor and hexane concentration.

Example 6

This example shows that certain blowing agent compositions of the invention have the additional advantage of being non-flammable. Blends of the hydrocarbon and HCFC-124 are tested via ASTM 3828-87 seta flash point at-25°F. Samples of the HCFC-124/hydrocarbon are prepared prior to placement in the seta test chamber. The blend is prepared in a Fischer porter tube. The appropriate weight of hydrocarbon material is charged to the Fischer porter tube. The tube and its contents are placed in a liquid nitrogen bath and frozen. The tube is then attached to a gas rack and evacuated. The appropriate weight of HCFC-124 is transferred into the Fischer porter tube through the gas rack. The Fischer porter tube is warmed and the contents are thoroughly mixed. Results of the flashpoint testing are shown in Table 6. Table 6

Claims

What is claimed is:

1. A blowing agent composition comprising l-chloro-l,2,2,2-tetrafluoroethane and at least one co-blowing agent selected from the group consisting of 1.1-dichloro-l- fluoroethane and C₄-C₆ hydrocarbon.

2. The blowing agent composition of claim 1 wherein the co-blowing agent is 1,1- dichloro- 1 -fluoroethane.

3. The blowing agent of claim 2 wherein the 1 , 1 ,-dichloro- 1 -fluoroethane is present in an amount of from 50 to 99 weight percent.

4. The blowing agent composition of claim 1 wherein the co-blowing agent is C₄-C₆ hydrocarbon.

5. The blowing agent composition of claim 1 wherein the C₄-C₆ hydrocarbon is selected from the group consisting of n-butane, isobutane, n-pentane, isopentane, cyclopentane, hexane, isohexane and mixtures thereof.

6. The blowing agent composition of claim 1 , 4 or 5 wherein the C₄-C₆ hydrocarbon is present in an amount of from 1 to 50 weight percent.

7. The blowing agent composition of claim 1, 4, 5 or 6 wherein the C₄-C₆ hydrocarbon is present in an amount of from 1 to 10 weight percent.

8. A method of preparing polyurethane and polyisocyanurate foam compositions comprising reacting and foaming a mixture of ingredients which react to form polyurethane or polyisocyanurate foams in the presence of the blowing agent of claim 1, 2, 3, 4, 5, 6 or 7.

9. A closed cell foam composition prepared from a polymer foam formulation containing the blowing agent of claim 1, 2, 3, 4, 5, 6 or 7.

10. A premix of a polyol and a blowing agent wherein the blowing agent comprises the blowing agent composition of claim 1, 2, 3, 4, 5, 6 or 7.