WO1992016574A1

WO1992016574A1 - Water blown foam

Info

Publication number: WO1992016574A1
Application number: PCT/US1991/002799
Authority: WO
Inventors: Ralph Colafati
Original assignee: Material Technologies & Sciences, Inc.
Priority date: 1991-03-25
Filing date: 1991-04-19
Publication date: 1992-10-01
Also published as: BR9107331A; EP0615526A1; AU7858991A; MY106388A; CA2119882A1; EP0615526A4; HUT68199A; HU9400541D0

Abstract

The subject invention provides a urethane foam which does not require chlorofluorocarbons to manufacture and which conforms to the Montreal Protocol. The compositions of the subject invention are usable in a spray and a pourable form, and may be used in a variety of applications such as in the production of siding, shingles, building panels, marine floatation, and roofing materials.

Description

WATER BLOWN FOAM

Background of the Invention

This patent application is a continuation-in-part of U.S. Serial No. 471,857, filed January 29, 1990, the contents of which are hereby incorporated by reference.

Urethane foam is used in architectural building panels, siding, shingles, marine floatation, εprayed-on roof materials, and as insulation for the tops of buildings both to prevent leaking and to provide insulation.

The Montreal Protocol, an agreement signed by most of the world's developed nations in 1987, pledges to cut the use of chlorofluorocarbons in the production of urethane foam in half by 1998. It is anticipated that this summer the agreement will be strengthened to totally ban the use of chlorfluorocarbons by the year 2000. In addition, Congress has recently increased taxes on chlorofluoroσarbon products. Therefore, alternative sources of foam producing material must be employed. Current replacements for chlorofluorocarbons increase the cost of producing urethane foams. Accordingly, a need currently exists for a low cost method of producing these foams.

The subject invention provides a composition which produces a rigid foam when combined with diphenyl ethane diisocyanate. The subject invention provides a water blown foam having a commercially valuable density of from, for example, about 0.3 lb/ft³ to about 5 lb/ t³ or more. In summary, the subject invention offers a low cost, environmentally safe alternative to conventional urethane foams.

^«.n^*πτma v of the Invention

The subject invention provides a urethane foam which does not require chlorofluorocarbons to manufacture. Two embodiments of this invention are disclosed.

The first embodiment is a composition useful for producing a foam which comprises: (a) an oxyalkylated polyol having a hydroxyl number of from about 28 to about 800, (b) a rigid polyether polyol, a polyester polyol or an oxyalkylated bisphenol A, (c) an organic surfactant, (d) an amine catalyst, (e) a polyisocyanate catalyst, and (f) a quaternary ammonium salt or a triazine.

The second embodiment is a composition useful for producing a foam which comprises: (a) an oxyalkylated polyol having a hydroxyl number of from about 28 to about 800, (b) a rigid polyether polyol, a polyester polyol or oxyalkylated bisphenol A, (c) a polyalkyleneoxidemethylsiloxane copolymer, (d) an amine catalyst, (e) a polyisocyanurate catalyst, and (f) a quaternary ammonium salt or a triazine.

Detailed Description of the Invention

The compositions of the subject invention produce a foam when mixed with polymeric MDI or other suitable isocyanates known to those skilled in the art such as, for example, hexamethylene diisocyanate, phenylene diisocyanate, toluene diisocyanate, and 4,4'-diphenyl methane diisocyanate, and 2,4- and 2,6-toluene diisocyanates individually or together as their commercially available mixtures. Other suitable mixtures of diisocyanates are those known commercially as "crude MDI", also known as PAPI, which contain about 60% of 4,4'-diphenylmethane diisocyanate along with other iso eric and analogous higher polyisocyanates. Also suitable are "prepolymers" of these polyisocyanates comprising a partially pre-reacted mixture of polyisocyanates and polyether or polyester polyol.

In the preferred embodiment, the compositions of the subject invention are mixed in a ratio of about 1:1 with polymeric MDI, and may be present in substoichiometric amounts. MDI is diphenylmethane diisocyanate which is known in the art to produce modifiers and polyol. At 1:1 MDI is present in substoichiometric amounts. A mixture of MDI and a composition of the subject invention may be obtained using standard equipment known to persons skilled in the art.

The subject invention provides a composition useful for producing a foam which comprises: (a) an oxyalkylated polyol having a hydroxyl number of from about 28 to about 800, (b) a rigid polyether polyol, preferably with a functionality greater than 3.0 and most preferably with a functionality greater than

3.8, a polyester polyol, or an oxyalkylated bisphenol A, (c) an organic surfactant, (d) an amine catalyst, (e) a polyisocyanate catalyst, and (f) a quaternary ammonium salt or a triazine.

Preferably, the oxyalklylated polyol has a functionality of from about 2 to about 4 and is most preferably oxyalkylated glycerine.

The above composition is to be mixed with water, and the components are preferably present in amounts effective to produce a foam when mixed with diphenylmethane diisocyanate or other suitable isocyanate.

In preferred embodiments, the compounds are present in the amounts stated below:

The oxyalkylated polyol having a hydroxyl number of from about 28 to about 800 is present in the range of from about 1% to about 80% by weight of the composition. The oxyalkylated polyol is a viscosity modifier. The most preferred compound of this type is LHT-240 which is produced by Union Carbide.

A rigid polyether polyol, a polyester polyol or an oxyalklated bisphenol A must be present. If a rigid polyether polyol is used, the rigid polyether polyol the range of from about 20% to about 70% by weight of the composition. Preferably, the rigid polyether polyol has a functionality greater than 3.0 and most preferably greater than 3.8. 35OX is the preferred compound and is produced by Arco Chemical. This compound is a rigid polyol, and is useful for producing the cross-linking required to manufacture rigid foams.

If a polyester polyol is used, the polyester polyol is present in the range of from about 5% to about 80% by weight of the composition. Most preferred, are polyester polyols based on terephthalate, such as polyethylene terephthalate and dimethyl terephthalate. Sources of these terephthal tes include bottle scrap and fiber scrap. Dimethyl terephthalate is most preferable TERATE-203 manufactured by Cape Industries and CHARDONAL-570 manufactured by Oxid Chemicals, Inc. Polyester polyols may also include those produced by reacting a dicarboxylic acid with an excess of a diol for example, adipic acid with ethylene glycol or butanediol, or by reacting a lactone with an excess of a diol such as caprolactone and propylene glycol.

Polyester polyols generally have hydroxyl numbers ranging from about 100 to about 700, preferably from about 100 to about 400, and have an average functionality of from about 1 to 8, and more preferably from about 2 to 3.

If an oxyalkylated bisphenol A is used, the oxyalkylated bisphenol A is present in the range of from about 50% to 95% by weight of the composition. The use of oxylalkylated bisphenol A renders the final foam stable at temperatures greater than 350*F.

Accordingly, the use of an oxyalkylated bisphenol A produces foam suitable for use at high temperatures.

The organic surfactant is present in the range of from about 0.5% to about 4.0% by weight of the composition. Organic surfactants are well known to those skilled in the art and are readily deter inable. Both silicone and non-silicone organic surfactants may be utilized. However, non-silicone organic surfactants are preferred. The most preferred compound is LK-443 which is manufactured by Air Products. A surfactant is utilized for stabilizing and forming cell structure.

The amine catalyst is present in the range of from about 0.1% to about 10.0% by weight of the composition. N,N- dimethylcyclohexyla ine is the preferred amine catalyst. N,N- dimethylcyclohexylamine is available as polycat-8, referred to in the trade as PC-8, which is produced by Air Products. The amine catalyst initiates the reaction between the above- identified composition and the isocyanate. Tertiary and delayed action amines, such as triethylene diamine and triethanol amine may also be employed.

The polyisocyanate catalyst employed may be any known in the art. It is preferred, however, that the isocyanate catalyst is lead, present in the form of 24% lead naphthanate which is present in the range of from about 0.1% to about 5.0% by weight of the composition. Other heavy metal catalysts, tin catalysts, and potassium catalysts may also be employed.

Water is present in the range of from about 0.4% to about 80% by weight of the composition.

The quaternary ammonium salt and/or triazine is the key component to provide a stable low density, water blown foam. It is preferred that the quaternary ammonium salt is TMR, however, other compounds such as Polycat 41, Polycat 43, or Dabco HB may be used.

In the preferred embodiments, TMR, which is a quaternary ammonium salt of a carboxylic acid, is present in the range of from about 0.1% to about 3% by weight of the composition. TMR is manufactured by Air Products. TMR is a trimerization catalyst and is available as TMR 1, TMR 2, TMR 3, and TMR 4. The lower the number which follows TMR, the slower the reaction time.

The most preferred embodiment is sprayable foam which comprises about 47.50% by weight of LHT-240; about 47.25% by weight of 350X; about 1.00% by weight of LK-443; about 0.25% by weight of PC-8; about 0.20% by weight of 24% lead naphthanate; about 2.80% by weight of water; and about 1.00% by weight of TMR.

The first embodiment may also contain one or more fire retardants. Various fire retardants (this term is to include smoke suppressers, intumescent compositions and coatings, anti- dripping agents, etc.) may be added including, but not limited to, ammonium phosphate, such as ammonium polyphosphate and monoammonium phosphate, melamine, tetrakis (2-chloroethyl) ethylene phosphonate, pentabromodiphenyl oxide, tris (1,3- dichloropropyl) phosphate, tris(beta-chloroethyl) phosphate, molybdenum trioxide , ammonium molybdatate , pentabromodiphenyloxide , tricresyl phosphate, 2,3- d i b romop rop anol , hexabromocyc lododecane , dibro oethyldibromocyclohexame, tris (2 , 3-dibromopropyl) phosphate, tris (beta-chloropropyl) phosphate, a halogenated hydrocarbon, such as chlorowax 70, dicyandiamide, oxamide and biuret. Most preferably, the fire retardant is monoammonium phosphate. Monoammonium phosphate offers the advantage of low cost and usability, even in "fertilizer" grades.

A second composition useful for producing foam is also provided which comprises: (a) an oxyalkylated polyol, preferably having a hydroxyl number of from about 28 to about 800, (b) a rigid polyether polyol, preferably with a functionality greater than 3.0, and most preferably with a functionality greater than 3.8 and a hydroxyl number of from about 250 to about 800, a polyester polyol or an oxyalkylated bisphenol A, (c) a polyalkyleneoxide ethylsiloxane copolymer, (d) an amine catalyst, (e) a polyisocyanurate catalyst, and (f) a quaternary ammonium salt or a triazine. Preferably the oxyalkylated polyol has a functionality of from about 2 to about 4, and is most preferably oxyalkylated glycerine. The above composition is to be mixed with water, and the components are preferably present in amounts effective to produce a foam when mixed with diphenylmethane diisocyanate or other suitable isocyanate.

In the preferred second embodiment the compounds are present in the amounts stated below:

The oxyalkylated polyol having a hydroxyl number of from about 28 to about 800 is present in the range of from about 1% to about 80% by weight of the composition.

The composition requires a polyether polyol, a polyester polyol or an oxyalkylated bisphenol A. If a rigid polyether polyol is used, the rigid polyether polyol is present in the range of from about 20% to about 70% by weight of the composition. Preferably, the rigid polyether polyol has a functionality of greater than 3.0 and most preferably greater than 3.8; typically, the hydroxyl number is from about 250 to about 800. Most preferably, this compound is 74-532 which is manufactured by Olin Corporation. If a polyester polyol is used, the polyester polyol is present in the range of from about 5% to about 80% by weight of the composition. Most preferred, are polyester polyols based on terephthalate, such as polyethylene terephthalate and dimethyl terephthalate. Sources of these terephthalates include bottle scrap and fiber scrap. Dimethyl terephthalate is most preferable TERATE-203 manufactured by Cape Industries and CHARDONAL-570 manufactured by Oxid Chemicals, Inc. Polyester polyols may also include those produced by reacting a dicarboxylic acid with an excess of a diol for example, adipic acid with ethylene glycol or butanediol, or by reacting a lactone with an excess of a diol such as caprolactone and propylene glycol.

If an oxyalkylated bisphenol A is used, the oxyalkylated bisphenol A is present in the range of from about 50% to 95% by weight of the composition. The use of oxylalkylated bisphenol A renders the final foam stable at temperatures greater than 350"F. Accordingly, the use of an oxyalkylated bisphenol A produces foam suitable for use at high temperatures. The polyalkylenoxidemethylsiloxane copolymer is present in the range of from about 0.5% to about 4.0% by weight of the composition. The most preferred compound is L-5420 which produced by Union Carbide. L-5420 functions to improve mixing and to form fine cell structure.

The amine catalyst is present in the range of from about 0.1% to about 10.0% by weight of the composition.

The polyisocyanurate catalyst is present in the range of from about 0.5% to about 1.5% by weight of the composition. Most preferably, the catalyst is Curithane 52 which is manufactured by Air Products. It is a final curative and functions to increase adhesion and thermal stability.

In the preferred embodiment, the quaternary ammonium salt is TMR, which is present in the range of from about 0.1% to about 3.0% by weight of the composition. As in the first composition, TMR may be present as TMR 1, TMR 2, TMR 3, or TMR 4.

The second embodiment may also contain one or more fire retardants. Various fire retardants (this term is to include smoke suppressers, intumescent compositions and coatings, anti- dripping agents, etc.) may be added including, but not limite to, ammonium phosphate, such as ammonium polyphosphate an monoammonium phosphate, melamine, tetrakis (2-chloroethyl ethylene phosphonate, pentabromodiphenyl oxide, tris (1,3 dichloropropyl) phosphate, tris(beta-chloroethyl) phosphate molybdenum trioxide , ammonium molybdatate pentabromodiphenyloxide , tricresyl phosphate, 2,3 d ib rom op rop an ol , hexabromocycl ododecane dibromoethyldibro ocyclohexame, tris (2 , 3-dibromopropyl) phosphate, tris (beta-chloropropyl) phosphate, a halogenate hydrocarbon, such as chlorowax 70, dicyandiamide, oxamide an biuret. Most preferably, the fire retardant is monoammoniu phosphate. Monoammonium phosphate offers the advantage of lo cost and usability, even in "fertilizer" grades.

The subject invention also provides foams comprising eithe of the two above-identified compositions and diphenylmethan diisocyanate or other suitable isocyanate. The first compositio is preferably a sprayable composition which is useful in th roofing and insulation industries. The second composition i preferably a pourable composition which is useful in producin blocks of foam for siding, shingles, insulation and marin floatation, among other things.

The subject invention also provides a process for producin a foam which comprises mixing the above-identified composition with diphenylmethane diisocyanate or other suitable isocyanate.

The following Experimental Detail Section is set forth to aid in the understanding of the subject invention and is not intended to limit or restrict the invention in any manner.

Experimental Detail

In conventional urethane foams, low density is produced through the use of chlorofluorocarbon blowing agents. Until now the use of water blown foams has been limited to higher density foams, i.e. about 10 lb/ft³ or greater. The reason for this is that an excess of isocynate has been used to react with the water thereby producing CO2. In contrast, the subject invention provides a low density foam, preferably, by using substoichiometric amounts of isocyanate.

An index of 100 indicates a 1:1 stoichiometric ratio. The urethane foams of the prior art have isocyanate indices of greater than 100. The higher the index, the greater the excess of the first component, i.e. isocyanate.

Foam examples produced by mixing various ratios of polymeric MDI (A side) and the preferred spray foam composition of the subject invention (B side) . The foams produced the various ratios were then tested for resistance to cold and heat. The B side of the subject invention consisted of:

As a control, a B side was prepared which did not contain a quaternary ammonium salt or a triazine, i.e. the above-identified B side without TMR-3. This control B side, although not known in the prior art, represents a typical water blown foam.

The following ratios of A:B were tested:

A B Isoc anate

Foams were made at each of the above indices and were allowed to cure for 24 hours at 72"F, in an atmosphere of 50% relative humidity. Two sets of foam were tested, one using the preferred sprayable foam composition of the subject invention, the second using the same composition without TMR-3.

Samples were cut into 2 inch square cubes and subjected to temperatures of 20°F. A second set of samples were subjected to temperatures of 250*F.

The following table summarizes the results obtained:

Table 1

Time Until the

Ratio of Isocyanate Amount of Shrinkage Onset of Shrinkage A/B Index 20*F 250'F w/TMR w/o TMR w/TMR w/o MTR

None*I < 1 hour

None*j < 1 hour

None*j < 6 hours

None*j Minimal*

None*j None*

*After 18 days, conclusion of the experiment.

The above experiment demonstrates that conventional water blown foams are not useful at isocyanate indices below 100, whereas, the compositions of the subject invention provide lighter, commercially useful, foams using substoichiometric amounts of isocyanate. The pourable foam composition of the subject invention demonstrated similar results when tested under like conditions.

Although the subject invention has been described in considerable detail with reference to certain preferred versions, other versions are possible. Therefore, the spirit and scope of the appended claims should not be limited to preferred embodiments contained herein and should only be limited in scope by the claims and their equivilents.

Claims

What is claimed is:

1. A composition useful for producing foam which comprises:

(a) an oxyalkylated polyol having hydroxyl number of from about 28 to about 800;

(b) a rigid polyether polyol, a polyester polyol or an oxyalkylated bisphenol A;

(c) an organic surfactant;

(d) an amine catalyst;

(e) a polyisocyanate catalyst; and

(f) a quaternary ammonium salt or a triazine.

2. A composition of claim 1, wherein the rigid polyether polyol, polyester polyol or oxyalkylated bisphenol A, surfactant, amine catalyst, polyisocyanate catalyst, and quaternary ammonium salt or triazine, are present in amounts effective to produce a foam when mixed with diphenylmethane diisocyanate.

3. A composition of claim 1, wherein the oxyalkylated polyol is present in the range of from about 1% to about 80% by weight of the composition.

4. A composition of claim 1, wherein composition contains a rigid polyether polyol present in the range of from about 20% to about 70% by weight of the composition.

5. A composition of claim 1, wherein the composition contains a polyester polyol present in the range of from about 5% to about 80% by weight of the composition.

6. A composition of claim 1, wherein the composition contains an oxyalkylated bisphenol A present in the range of from about 50% to about 95% by weight of the composition.

7. A composition of claim 1, wherein the organic surfactant is present in the range of from about 0.5% to about 4.0% by weight of the composition.

8. A composition of claim 1, wherein the amine catalyst is present in the range of from about 0.1% to about 10.0% by weight of the composition.

9. A composition of claim 1, wherein the isocyanate catalyst is 24% lead naphthanate which is present in the range of from about 0.1% to about 5.0% by weight of the composition.

10 A composition of claim 1 further comprising water.

11. A composition of claim 10, wherein water is present in the range of from about 0.4% to about 80% by weight of the composition.

12. A composition of claim 1 further comprising a fire retardant.

13. A composition of claim 12, wherein the fire retardant is selected from the group consisting of ammonium phosphate, melamine, tetrakis (2-chloroethyl) ethylene phosphonate, pentabromodiphenyl oxide, tris ( 1 , 3-dichloropropyl) phosphate, tris(beta-chloroethyl) phosphate, molybedenum trioxide, ammonium molybdatate, pentabromodiphenyloxide, tricresyl phosphate, 2 , 3 - d ib romop r op an o 1 , hexabro ocyclododecane, dibromoethyldibromocyclohexane, tris(2,3-dibromopropyl) phosphate, tris(beta-chloropropyl) phosphate, a halogenated hydrocarbon, dicyandiamide, oxamide and biuret.

14. A composition of claim 13, wherein the fire retardant is ammonium phosphate.

15. A composition useful for producing foam which comprises:

(a) an oxyalkylated polyol having a hydroxyl number of from about 28 to about 800;

(c) a polyalkyleneoxidemethylsiloxane copolymer; (d) an amine catalyst;

(e) a polyisocyanurate catalyst; and

(f) a quaternary ammonium salt or a triazine.

16. A composition of claim 15, wherein the oxyalkylated polyol, polyether polyol, polyester polyol or an oxyalkylated bisphenol A, polyalkyleneoxidemethylsiloxane copolymer, amine catalyst, polyisocyanurate catalyst, and quaternary ammonium salt or triazine, are present in amounts effective to produce a foam when mixed with diphenylmethane diisocyanate.

17. A composition of claim 15, wherein the oxyalkylated polyol is present in the range of from about 1% to about 80% by weight of the composition.

18. A composition of claim 15, wherein the composition contains a polyether polyol present in the range of from about 20% to about 70% by weight of the composition.

19. A composition of claim 15, wherein the composition contains a polyester polyol present in the range of from about 5% to about 80% by weight of the composition.

20. A composition of claim 15, wherein the composition contains an oxyalkylated bisphenol A present in the range of from about 50% to about 95% by weight of the composition.

21. A composition of claim 15, wherein the polyalkyleneoxide- methy1siloxane copolymer is present in the range of from about 0.5% to about 4.0% by weight of the composition.

22. A composition of claim 15, wherein the amine catalyst is present in the range of from about 0.1% to about 10.0% by weight of the composition.

23. A composition of claim 15, wherein the polyisocyanurate catalyst is present in the range of from about 0.5% to about 1.5% by weight of the composition.

24. A composition of claim 15 further comprising water.

25. A composition of claim 24, wherein water is present in the range of from about 0.4% to about 80% by weight of the composition.

26. A composition of claim 15 further comprising a fire retardant.

27. A composition of claim 15, wherein the fire retardant is selected from the group consisting of ammonium phosphate, melamine, tetrakis (2-chloroethyl) ethylene phosphonate, pentabromodiphenyl oxide, tris (1, 3-dichloropropyl) phosphate, tris(beta-chloroethyl) phosphate, molybedenum trioxide, ammonium molybdatate, pentabromodiphenyloxide, tricresyl phosphate, 2 , 3 -d ibromopropano1 , hexabro ocyclododecane, dibromoethyldibromocyclohexane, tris(2,3-dibromopropyl) phosphate, tris(beta-chloropropyl) phosphate, a halogenated hydrocarbon, dicyandiamide, oxamide and biuret.

28. A composition of claim 15, wherein the fire retardant is ammonium phosphate.

29. A foam comprising the composition of claim 1 and diphenylmethane diisocyanate.

30. A foam comprising the composition of claim 15 and diphenylmethane diisocyanate.

31. A process for producing a foam which comprises mixing the composition of claim 1 with diphenylmethane diisocyanate.

32. A process of claim 31, wherein the diphenylmethane diisocyanate is present in substoichiometric amounts.

33. A process for producing a foam which comprises mixing the composition of claim 15 with diphenylmethane diisocyanate.

34. A process of claim 33, wherein the diphenylmethane diisocyanate is present in substoichiometric amounts.

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35. A foam of claim 29 which is sprayable.

36. A foam of claim 30 which is pourable.