TWI775882B - Polyurethane foams and process for forming the same - Google Patents

Abstract

This invention provides polyurethane foams containing a brominated flame retardant. Also provided are formulations and methods for preparing polyurethane foams containing a brominated flame retardant.

Description

Polyurethane foam and method of forming the same

The present invention relates to a brominated short chain alcohol suitable as a flame retardant in flexible and rigid polyurethane foams.

Fire resistance is an important characteristic of polyurethane foam. Various compounds or mixtures thereof have been used to effectively meet applicable fire safety standards. Reference (1-chloro-2-propyl) phosphate (TCPP) is a flame retardant widely used in polyurethane foams. However, TCPP is a non-reactive compound in polyurethane foam formation and thus can leach or migrate out of the foam. This leads to health and environmental problems.

Brominated isocyanate-reactive compounds that have been disclosed as flame retardants are 2,3-dibromobutene-1,4-diol (eg, US Pat. No. 4,002,580). However, 2,3-dibromobutene-1,4-diol (DBBD) is a solid with a high melting point and requires an additional step of pre-dissolution in order to make it suitable for use in polyurethane foam applications.

Therefore, there would be a need for flame retardants that are liquid under processing conditions and have a low viscosity to allow easy processing (mixing and pumping). In addition to their effectiveness as flame retardants, there is a need to provide compounds that are compatible with the polyurethane foam manufacturing process and that do not migrate out of the polyurethane foam over time, This reduces health and environmental impacts.

The present invention provides formulations and methods for making flame retardant polyurethane foams. More particularly, the present invention provides an isocyanate-reactive brominated flame retardant compound suitable for use in a polyurethane form. In particular, the present invention relates to 2,3-dibromo-2-propen-1-ol (2,3-dibromoallyl alcohol or DBAA) in polyurethane foams, including open-cell spray foams, Applications in closed cell spray foam, rigid panel foam and flexible foam.

One embodiment of the present invention is a polyurethane foam formed from a composition comprising DBAA.

Formulations useful for making flame retardant polyurethane foams are also provided.

Other embodiments of the present invention include methods of forming polyurethane foams.

As used throughout this document, the phrase "reactive brominated flame retardant" has the meaning equivalent to "isocyanate-reactive brominated flame retardant."

Polyurethane foams are typically prepared by contacting the two main liquid components, namely the polyisocyanate (Part A) and the polyol (Part B). Part B, here the formulation of the invention, containing all components except the polyisocyanate, needs to be in liquid form. As used herein, the term "liquid" means that the formulation is in a liquid state under the conditions of use of the Part B formulation. For more information on forming polyurethane foams, see, eg, US Patent Nos. 3,954,684; 4,209,609; 5,356,943; 5,563,180; and 6,121,338.

The present invention relates to polyurethane foams which are flame retardant using dibromoallyl alcohol (DBAA). These foams are formed from formulations comprising DBAA, at least one polyol, at least one blowing agent, at least one catalyst, and at least one surfactant, which formulations are contacted with a polyisocyanate.

Isocyanate-reactive brominated flame retardants contain at least one functional group that is available and capable of reacting with another polyurethane-forming component during polyurethane formation, so that the resulting polyurethane has a Chemically bound forms contain reactive brominated flame retardants. It is believed that the functional groups of reactive brominated flame retardants react with isocyanate groups during the preparation of polyurethane foam; typically, the functional (reactive) groups in reactive brominated flame retardants are hydroxyl groups.

The isocyanate-reactive brominated flame retardant used in the practice of this invention is a known molecule, 2,3-dibromo-prop-2-en-1-ol (also referred to herein as dibromoallyl alcohol or DBAA), It has ^CAS® Registry No. 7228-11-7 (Chemical Abstracts Service). DBAA is not commercially available, but the synthesis of DBAA from propargyl alcohol ( ₂ -propyn-l-ol) and elemental bromine (Br2) in solvent at room temperature is known. In the past, DBAA has been used as an intermediate for the preparation of phosphorus compounds (see US Patent No. 3,950,457).

DBAA can be used to form both flexible and rigid polyurethane foams. DBAA is a reactive component that becomes part of the polyurethane foam. This provides the advantage that DBAA does not migrate out of the foam. Another advantage is that DBAA has a high bromine content (74 wt%). Other flame retardants that can be included with DBAA in polyurethane foam include tetrabromophthalic anhydride mixed esters with diethylene glycol and propylene glycol, paras(1-chloro-2-propyl)phosphoric acid Esters or both sine (1-chloro-2-propyl) phosphate and mixed esters of tetrabromophthalic anhydride and diethylene glycol and propylene glycol.

Formulations of the present invention that can be used as part B in a process for forming polyurethane foams include DBAA, polyol, blowing agent, catalyst, and surfactant.

In forming the polyurethane foam of the present invention, a flame retardant amount of DBAA is used. The flame retardant amount means the amount of DBAA required to obtain the desired level of flame retardancy. The flame retardant amount typically ranges from about 1 wt% to about 25 wt%, preferably from about 3 wt% to about 20 wt%, more preferably from about 3 wt% to about 18 wt%, based on the total weight of the formulation (Part B component).

The polyol used to form the polyurethane foam in the practice of the present invention can be any polyol typically used to make flexible polyurethane foam or rigid polyurethane foam. Often, mixtures of polyols are used, and specific polyols are selected for their effect on the properties of the polyurethane foam formed.

When forming flexible polyurethane foams, the polyols typically have a hydroxyl number of up to about 150 mg KOH/g, preferably from about 5 mg KOH/g to about 150 mg KOH/g, more preferably from about 10 to about 100 mg KOH/g g. Even more preferably a polyol or mixture of polyols in the range of about 20 mg KOH/g to about 75 mg KOH/g. When polymeric polyols are used, they typically have molecular weights in the range of about 2,000 to about 10,000, preferably about 3,000 to about 8,000.

When forming rigid polyurethane foams, the polyol is typically a polyol or mixture of polyols having a hydroxyl number in the range of about 100 to about 850 mg KOH/g, preferably in the range of about 110 to about 600 mg KOH/g . When polymeric polyols are used, they typically have molecular weights in the range of about 250 to about 5000, often 400 to about 3000.

Polyols suitable for use in forming polyurethane foams include polyether polyols, polyester polyols, aliphatic polyols, and polyoxyalkylene glycols. Mixtures of two or more polyols can be used. Preferred polyols for forming rigid polyurethane foams include polyester polyols.

Useful polyoxyalkylene diols include polyoxyethylene diols, polyoxypropylene diols, and block and hybrid polyoxyethylene-polyoxypropylene diols.

Aliphatic polyols typically contain up to about 18 carbon atoms per molecule. Suitable aliphatic polyols include ethylene glycol, propylene glycol, isobutanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, triethylene glycol, glycerol, trimethylol Ethane, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, tetraethylene glycol, dipentaerythritol, sorbitol, sucrose and alpha-methyl glycoside.

Polyether polyols are prepared by reacting one or more alkylene oxides having 2 to about 8 carbons in the alkylene group with an initiator molecule containing two or more hydroxyl groups. Suitable polyether polyols include sucrose/glycerol polyether polyols; sucrose polyether polyols based on glycerol, propylene oxide and ethylene oxide; glycerol initiated polyether polyols such as glycerol/propylene oxide polyether polyols alcohol; and a mannich-based polyether polyol.

Polyester polyols are prepared by polymerizing polycarboxylic acids or derivatives thereof (eg, acid chlorides or anhydrides thereof) with polyols. Suitable polyester polyols include aromatic polyester polyols and diethylene glycol-phthalic anhydride polyester polyols.

For forming both flexible and rigid polyurethane foams, the amount of polyol is typically about 40 wt% to about 80 wt% and often about 50 wt% to about 80 wt% based on the total weight of the Part B component (formulation) within the range of 70wt%. When more than one polyol is present, these equivalent amounts refer to the total amount of polyols in the formulation.

Blowing agents that can be used in the present invention to form flexible and rigid polyurethane foams include water; volatile hydrocarbons; hydrocarbons such as n-pentane, isopentane, cyclopentane; halocarbons (fully halogenated); chlorofluorocarbons), specifically trichlorofluoromethane (CFC-11); and halogenated hydrocarbons (hydrogen-containing chlorofluorocarbons, or HCFCs), such as 1,1-dichloro-1-fluoroethane (HCFC-141b), 1-chloro-1,1-difluoroethane (HCFC-142b), chlorodifluoromethane (HCFC-22). Mixtures of any two or more blowing agents can be used. In some cases, DBAAs allow water to be the only blowing agent in the formulation.

Other suitable blowing agents when forming flexible polyurethane foams in the practice of the present invention include methylene chloride (methylene chloride) and acetone. A preferred blowing agent for flexible polyurethane foams includes water. The amount of blowing agent used to form the flexible foam can range from about 0.5 wt % to about 20 wt %, preferably from about 2.5 wt % to about 15 wt %, based on the total weight of the Part B component (formulation).

For forming rigid polyurethane foams, blowing agents useful in the practice of this invention include partially fluorinated hydrocarbons (HFCs). Suitable blowing agents for rigid foams include trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)), 1,1,1,3,3-pentafluoropropane (HFC-245fa) ), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3 , 3-hexafluoropropane (HFC-236ea), 1,1,1,4,4,4-hexafluorobutane (HFC-356mffm) and 1,2-bis(trifluoromethyl)ethylene; Hydrocarbons of pentane, isopentane and cyclopentane. Mixtures of any two or more blowing agents can be used.

When forming rigid foams, preferred blowing agents include water, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, 1,2-bis( trifluoromethyl)ethylene and water with 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene or 1,2-bis(trifluoromethyl) A mixture of ethylene. In some cases, 2,3-dibromoallyl alcohol allows water to be the only blowing agent in the formulation. The amount of blowing agent used to form the rigid foam can range from about 0.5 wt % to about 20 wt %, preferably from about 2.5 wt % to about 15 wt %, based on the total weight of the Part B components.

Various types of catalysts useful in the practice of this invention when forming flexible or rigid polyurethane foams include tertiary amines, tin catalysts (typically organotin compounds), bismuth catalysts, other organometallic catalysts, and organocarboxylic acids the potassium salt. Mixtures of catalysts of the same type and/or different types can be used in the practice of the present invention.

In the amine catalyst, the groups on the amine are preferably alkyl groups; more preferably, these groups are oxygen-containing groups such as ether groups or saturated alcohol groups. Suitable amine catalysts include dimethylethylamine, triethylenediamine, dimethylethylamine, dimethylcyclohexylamine, dimethylbenzylamine, tetramethyldipropylenetriamine, pentamethylamine Diethylenetriamine, gins(dimethylaminopropyl)-hydrotriazine, 1-methyl-4-(2-dimethylaminoethyl)piperazine, 1,4-diazepine ( 2,2,2) Bicyclooctane, 3-methoxy-N,N-dimethylpropylamine, N-methylmorpholine, N-ethylmorpholine, N-cocomorpholine, bis( Dimethylaminoethyl) ether and ethanolamine catalysts such as dimethylethanolamine, 2-(2-dimethylaminoethoxy)ethanol, and N,N,N'-trimethylaminoethyl-ethanolamine. For flexible foams, preferred catalysts include 2-(2-dimethylaminoethoxy)ethanol. For rigid polyurethane foams, the amine catalyst is preferably a tertiary amine.

Types of tin compounds useful as catalysts include dialkyl(dialkylthio)stannanes, stannous(II) salts of organic carboxylic acids, and dialkyltin(IV) salts of carboxylic acids. Tin catalysts suitable in the practice of this invention include dibutylbis(dodecylthio)stannane, stannous (II) octoate, stannous (II) acetate, dibutyltin dilaurate, and dioctyl diacetate tin.

Another type of catalyst is one or more potassium salts of organic carboxylic acids. Suitable potassium salts include potassium acetate and potassium caprylate.

For both flexible and rigid polyurethane foams, the catalyst is typically present in a total of about 0.25 wt % to about 10 wt %, preferably about 1 wt % to about 8 wt %, based on the total weight of the formulation (Part B component) amount used. When more than one catalyst is present, these equivalent amounts refer to the total amount of catalyst in the formulation.

The preparation of polyurethane foams often requires surfactants, and surfactants are generally used when forming both flexible and rigid polyurethane foams.

For both flexible and rigid polyurethane foams, suitable polysiloxane surfactants include polysiloxane glycols, polysiloxane glycol copolymers, polyether-modified polysiloxanes, polyether Modified dimethylpolysiloxanes (such as polyether polydimethylsiloxane copolymers), polysiloxane polyoxyethylene copolymers, polysiloxane polyoxyethylene copolymers, polysiloxane copolymers substances and the like. Polysiloxane surfactants are the preferred type of surfactant for forming both flexible and rigid polyurethane foams. Polyether-modified dimethylpolysiloxane and polysiloxane copolymers are preferred polysiloxane surfactants.

Cell openers, typically polyoxyalkylenes, are the preferred type of surfactant for flexible foams. Suitable polyoxyalkylene cell openers in the practice of this invention include polyethylene glycol monoallyl ether, polyethylene glycol allyl methyl diether, polyethylene glycol monoallyl ether acetate, polyethylene glycol Glycol Monomethyl Ether, Polyethylene Glycol Glyceryl Ether, Polyethylene Glycol-Polypropylene Glycol Monoallyl Ether, Polyethylene Glycol-Polypropylene Glycol Monoallyl Monomethyl Dieter and Polyethylene Glycol-Polypropylene Glycol Propyl ether acetate.

Other surfactants that can be used when forming rigid polyurethane foams include emulsifiers such as castor oil sulfate or sodium salts of fatty acids; amine-containing fatty acid salts such as diethylamine oleate and diethanolamine hard Fatty acid esters; salts of sulfonic acids such as dodecylbenzenedisulfonic acid and ricinoleic acid such as alkali metal or ammonium salts; ethoxylated alkylphenols, ethoxylated fatty alcohols; etheramine tetra Grade amine compound; 2-hydroxypropyltrimethylammonium formate; hydroxy-nonylphenyl-N-methylglycine sodium (N-((2-hydroxy-5-nonylphenyl)methyl)-N-methyl - the sodium salt of glycine) and castor oil.

For forming both flexible and rigid polyurethane foams, typically from about 0.1 wt % to about 5 wt %, preferably from about 0.5 wt % to about 5 wt %, based on the total weight of the Part B component (formulation) Amount of surfactant used. When more than one surfactant is present, these equivalent amounts refer to the total amount of surfactants in the formulation.

One or more optional additives that may be included in the formulations of the present invention when forming flexible or rigid polyurethane foams include antioxidants, diluents, chain extenders or crosslinkers, synergists ( Preferred are melamine), stabilizers, fungistatic agents, pigments, dyes, fillers, antistatic agents and plasticizers.

The components of the formulation can be combined in any order; preferably, the blowing agent is the last ingredient added. More preferably, DBAA is combined with a polyol, followed by a surfactant, catalyst, and any optional ingredients, followed by a blowing agent.

The isocyanate or polyisocyanate (Part A component) used to form the polyurethane foam in the practice of the present invention may be used to prepare a flexible polyurethane foam or a rigid polyurethane, as appropriate Any isocyanate or polyisocyanate of foam. When a polymeric polyisocyanate is used, it preferably has an isocyanate (NCO) content of about 25 wt% to about 50 wt%, preferably about 25 wt% to about 40 wt%.

When forming flexible polyurethane foams, the isocyanate typically has at least two isocyanate groups. Isocyanates can be aliphatic or aromatic. When forming rigid polyurethane foams, polyisocyanates are used, and the polyisocyanates may be aromatic or aliphatic. Suitable polyisocyanates for both flexible and rigid polyurethane foams in the practice of the present invention include, but are not limited to, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate methyl ester, 2-methyl-1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HMDI), 1,7-heptamethylene diisocyanate, 1,10-decamethylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate (IPDI), 4,4'-methylene dicyclohexyl diisocyanate (H12MDI) ), hexahydrotoluene diisocyanate and its isomers, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 4 ,4'-methylenebis(cyclohexyl isocyanate), phenylene diisocyanate, toluene diisocyanate (TDI), xylene diisocyanate, other alkylated benzene diisocyanates, toluene diisocyanate, 1,5- Naphthalene diisocyanate, diphenylmethane diisocyanate (MDI, sometimes called methylene diisocyanate), 1-methoxyphenyl-2,4-diisocyanate, 4,4'-diphenylmethane Diisocyanate, 2,4'-diphenylmethane diisocyanate, mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate, 4,4'-diisocyanate Biphenylate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4',4"-triphenylmethane triisocyanate, toluene 2,4,6-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, Polymeric polyisocyanates such as polyisocyanatopolymethylenepolyphenylene and mixtures of any two or more of the foregoing.

Polyisocyanates useful in forming both the flexible and rigid polyurethane foams of the present invention include those commonly known as polymeric methylene diisocyanate (MDI), polyisocyanate-based prepolymers and its mixtures. Polymeric MDI contains varying amounts of isomeric diphenylmethane diisocyanate and tricyclic, tetracyclic and greater than tetracyclic oligomers. In general, any commercial polymeric MDI with an isocyanate content of about 25 wt% or more can be used. The preferred polymeric MDI has an isocyanate content of about 30 wt% or more. Other isocyanates may be present with the polymeric MDI in minor amounts as long as the polyisocyanate mixture as a whole remains liquid. Preferably, the polyisocyanate is polymeric MDI.

The polyurethane foam compositions of the present invention are formed from the components of Part A and Part B, wherein Part A is one or more isocyanates or polyisocyanates as described above, and Part B comprises the formulation of the present invention. The polyurethane forming reaction generally proceeds readily at room temperature; typically, Parts A and B begin to react with each other upon contact, and continue to react (cure) to form a polyurethane foam. Often, a mixture of Parts A and B is sprayed or cast to form a polyurethane foam.

In the method of the present invention for forming polyurethane foam, A) at least one isocyanate and/or polyisocyanate and B) are made of 2,3-dibromoallyl alcohol, at least one polyol, at least one A formulation formed by a blowing agent, at least one catalyst, and at least one surfactant is contacted to form a mixture; and the mixture is allowed to cure to form a polyurethane foam.

The amount of isocyanate and/or polyisocyanate can be defined by the isocyanate index.

The theoretical equivalent of isocyanate is equal to one equivalent of isocyanate per equivalent of reactive hydrogen from Part B. In the method of the present invention, the isocyanate index value typically ranges from 80 to 200 or from about 90 to about 150. Rigid polyurethane foams are typically prepared by combining polyisocyanates with isocyanate-reactive hydrogens in amounts such that the isocyanate index is in the range of about 85 to about 1000, preferably about 95 to about 400, more preferably about 95 to about 200 Compounds of atoms (eg, hydroxyl groups) come together to form.

To form polyurethane foams, the functionality (i.e., the average number of hydroxyl groups per molecule) of the formulation (Part B) typically provided by the polyol or polyol mixture is typically about 2 or more, compared to Preferably it is about 2 to about 8; more preferably about 3 or more, especially about 3 to about 8, more especially about 3 to about 7. As a monool, DBAA has a functionality of one (ie, one hydroxyl group in the molecule), it is chain terminated, so at least a portion of the polyols in the formulation have three or more hydroxyl groups per molecule to form polyamines Carbamate foam. DBAA is included in the calculation of the average functionality of Part B.

In the polyurethane foam, the 2,3-dibromoallyl alcohol is typically about 0.5 wt% to about 12.5 wt%, preferably about 1.5 wt%, based on the total weight of the polyurethane foam From about 10 wt%, more preferably from about 1.5 wt% to about 9%. The polyol is typically in the range of about 20 wt % to about 40 wt % and often about 25 wt % to about 35 wt %, based on the total weight of the polyurethane foam. The surfactant is present in an amount of about 0.05 wt % to about 2.5 wt %, preferably about 0.25 wt % to about 2.5 wt %, based on the total weight of the polyurethane foam. The catalyst is present in a total amount of about 0.125 wt % to about 5 wt %, preferably about 0.5 wt % to about 4 wt %, based on the total weight of the polyurethane foam. When more than one ingredient of that type is present, these equivalent amounts refer to the total amount of ingredients of each type in the foam.

The rigid polyurethane foams formed in the present invention have a density range that varies with the end application. For open cell insulating foams, the density typically ranges from about 0.4 lb/ft ³ to about 1.2 lb/ft ³ (6.3 kg/m ³ to 18.9 kg/m ³ ). For closed cell insulating foams, the density typically ranges from about 1.6 lb/ft ³ to about 3.5 lb/ft ³ (25.6 kg/m ³ to 56.1 kg/m ³ ). For molded architectural foams, the density typically ranges from about 4.0 lb/ft ³ to about 31 lb/ft ³ (64.0 kg/m ³ to 497 kg/m ³ ).

The flexible polyurethane foams formed in the present invention have densities ranging from about 0.5 to about 1.0 lb/ft ³ (8 to 16 kg/m ³ ). Flexible polyurethane foam is typically used to form articles such as molded foam, slabstock foam, and can be used in furniture and car seating, as a cushioning material in mattresses, as carpet backing, in diapers As hydrophilic foam and as packaging foam.

The following examples are presented for illustrative purposes and are not intended to limit the scope of the invention. All percentages in the following examples are by weight unless otherwise indicated.

Example - General

In the examples, some of the substances used are mentioned by their trade names. More specifically.

DBAA: 2,3-dibromoallyl alcohol

Saytex® RB-79: Mixed ester of tetrabromophthalic anhydride with diethylene glycol and propylene glycol (Albemarle ^Corporation ).

TCPP: cf. (1-chloro-2-propyl) phosphate.

DE: diethylene glycol monoethyl ether.

Voranol ^® 280: a polyether polyol with a functionality of about 7.0, a hydroxyl number of about 280 and an average molecular weight of about 1400; Voranol ^® 370: a sucrose/glycerol polyether polyol with a functionality of 7.0; Voranol ^® 490: the functionality Sucrose/glycerol polyether polyol of 4.3 (all Voranol ^® materials are products of The Dow Chemical Company).

Vorasurf ^® 504 is a non-silicone organic surfactant (Dow Chemical Company).

Terate ^® HT 5503: Aromatic polyester polyol with a hydroxyl number in the range of 225 to 245, a functionality of 2 and an equivalent weight of 239; Terate ^® HT 5349: an aromatic polyester polyol with a functionality of about 2.45 and a hydroxyl number of 295 to 315 family of polyester polyols (all Terate ^® materials are products of Invista Corporation).

Stepanpol® PS-3152 ^is a diethylene glycol-phthalic anhydride polyester polyol with a functionality of 2 and a hydroxyl number of 315 (Stepan Chemical Company).

Carpol ^® GP-5171: a glycerol-initiated polyether polyol with a functionality of about 3, a hydroxyl number of 35, and an average molecular weight of about 5000; Carpol ^® GP-5015: a functionality of 3, a hydroxyl number of 34, and an average molecular weight of Glycerol-initiated polyether polyol of about 5000; Carpol ^® GP-1500: Glycerol-initiated polyether polyol of functionality of 3, hydroxyl number of 112 and average molecular weight of about 1500; Carpol ^® GSP-280: Functionality of 7. Sucrose polyether polyol based on glycerol, propylene oxide and ethylene oxide with a hydroxyl value of 280 and an average molecular weight of about 1400; Carpol ^® GSP-355: glycerol/sucrose with a functionality of 4.5 and a hydroxyl value of 355 Initiated polyether polyol; Carpol ^® MX-470: Mannich-based polyether polyol with a functionality of about 4, a hydroxyl number of 470 and an average molecular weight of 480; Carpol ^® GP-700: a functionality of 3, a hydroxyl group Glycerol and propylene oxide polyether polyol with a number of 240 and an average molecular weight of about 700 (all ^Carpol® materials are products of the Carpenter Company).

Terol ^® 250 is an aromatic polyester polyol (Huntsman Corporation) with a functionality of 2 and a hydroxyl number in the range of 235 to 255.

Dabco ^® DC193: polysiloxane diol surfactant; Dabco ^® T: amine with hydroxyl groups; Dabco ^® T-120: dibutylbis(dodecylthio)stannane; Dabco ^® PM-300: 2- Butoxy alcohol; Dabco ^® DC 5598: Polysiloxane glycol copolymer surfactant; Dabco ^® K-15: Potassium octanoate; Dabco ^® TMR: 2-hydroxypropyltrimethylammonium formate (all Dabco ^® materials are Air Products and Chemicals, Inc.).

Polycat® 204: Amine catalyst (Air ^Products and Chemicals, Inc).

Tomamine ^® Q17-2 PG is an etheramine quaternary amine surfactant (75%) in isopropanol (Air Products and Chemicals, Inc.).

Tegostab ^® B 8871: polysiloxane copolymer; Tegostab ^® B 8407: polyether polydimethylsiloxane copolymer (both products of Evonik Industries AG, Essen, Germany).

Jeffcat ^® ZR-70 is 2-(2-dimethylaminoethoxy)ethanol (an ethanolamine catalyst); Jeffcat ^® Z-110 is N,N,N'-trimethylaminoethyl-ethanolamine; Jeffcat ^® ZF -20 is bis(2-dimethylaminoethyl) ether (all ^Jeffcat® materials are products of Huntsman Corp., The Woodlands, TX).

Pel-cat 9506 is a mixture of potassium octanoate and potassium acetate; Pel-cat 9858-A is sodium hydroxy-nonylphenyl-N-methylglycine (both products of Elé Corporation).

Solstice® ^LBA : trans-1-chloro-3,3,3-trifluoropropene (Honeywell Inc.).

Genetron® ^245fa : 1,1,1,3,3-pentafluoropropane (Honeywell Inc.).

Opteon ^™ 1100: 1,2-bis(trifluoromethyl)ethylene; also known as ^Formacel® 1100 (The Chemours Company).

Papi® 27: Polymeric diphenylmethane diisocyanate (MDI) (Dow Chemical Company ⁾ with 31.4 wt% NCO, viscosity at 25°C of 150 to 225 cp and isocyanate equivalent weight of 134.

ASTM E-1354 Cone Calorimetry Measurements on Fire Test Technology Double Cone Calorimeter. For all examples, an incident heat ^flux of 40 kW/m was used for the expected smoke index calculation in the cone calorimetry test, and an expected flame was used for the cone calorimetry test using an incident heat ^flux of 100 kW/m Spread index calculation. The peak heat release rate (PHRR), which is the maximum amount of heat released during the combustion of the sample in the cone calorimeter, was measured. The value of the peak heat release rate is preferably less than 250. ASTM E-84 Combustion Pattern Calculated from Cone Calorimetry Results Expected Smoke Index Calculation and Expected Flame Spread Index Calculation. The cone calorimeter results were converted to the expected values in ASTM E-84 using mathematical equations previously derived from the cone calorimeter and ASTM E-84 correlation studies. The target value of the flame spread index is less than 25, preferably less than 20, and the target value of the smoke density index is less than 450, preferably less than 200. The term "smoke index" is short for "generated smoke density", which is also referred to as "generated smoke index" and "smoke density index".

For some samples, dimensional stability was determined; the preferred volume change in dimensional stability is ±15%. Some samples were tested for thermal conductivity and the R value was calculated from the thermal conductivity. The R-value (or R-value) is a measure of insulation efficiency or thermal resistance (the ability of a material to slow down heat transfer within it), and is often used in the construction and construction industries. The higher the R-value, the more material prevents heat transfer. The R-value of the polyurethane foam is preferably about 6.5 or greater.

Example 1-22

The results reported in Examples 1-16 are the average of three batches of 5 samples per batch (15 samples total for each test). Unless otherwise indicated, the volume ratio of Part A to Part B in each run was 1:1. The polyurethane foams of Examples 1-16 were prepared according to Procedure 1 below. The polyurethane foams of Examples 17-19 were prepared according to Procedure 2 below. The polyurethane foams of Examples 20-22 were prepared according to Procedure 1 below; Part A was ^Papi® 27 in all runs of Examples 1-22.

Procedure 1: To form Part B, weigh DBAA, polyol, surfactant, flame retardant, blowing agent, and catalyst into a 0.5 gallon (1.9 L) resealable container and use a butterfly agitator Blend at 2000 rpm for 60 seconds or until a homogeneous mixture is obtained with no visible phase separation. On a 450-g scale (sum of Parts A and B), the desired amount of the Part B mixture was weighed and added to a one-liter paper cup.

Wet tared polymeric MDI was determined as follows: Weigh approximately 10% of the required amount into a 250-mL paper cup, pour out polymeric MDI within 3 seconds, tare the wet 250-mL cup and add the entire amount of polymeric MDI MDI. The polymerized MDI was then poured into one liter cup containing the Part B mixture over a 3-second interval, and the contents of the one liter paper cup were immediately mixed for 5 seconds at 2000 rpm. By this method, the amount of MDI used is within ±1% of the desired amount.

Invert and hold the paper cup on the cardboard while the foam rises, but before the foam reaches the top of the one liter paper cup. As the foam continues to rise, guide the paper cup upwards without hindering the rise of the foam. Stop guiding the cup when the foam has enough strength to support itself and the cup. After the foam was allowed to sit for at least 24 hours, it was cut to produce specimens for cone calorimeter testing. Each sample was weighed to determine foam density.

Procedure 2: To prepare each polyurethane foam, a blend of the Part B components (DBAA, polyol, surfactant, flame retardant, and blowing agent) excluding the catalyst was prepared. The polyisocyanate and Part B formulation were weighed into a 16 oz. (473 mL) paper cup and then mixed with a butterfly stirrer at 2000 rpm for 15 seconds, at which point the catalyst was injected into the mixture while stirring continued. At the 20-second mark, stirring was stopped, and the reaction mixture was immediately poured into a 10-in x 10-in x 10-in (25.4cm x 25.4cm x 25.4cm) wooden box mold that had been prelined with polyethylene bags , and the box is closed. After 15 minutes, the square-shaped foam wrapped in a polyethylene bag was removed from the mold. After the foam was allowed to sit for at least 24 hours, it was cut to produce specimens for cone calorimeter testing. Each sample was weighed to determine foam density. The catalyst is added after contacting Part A with Part B, which is related to laboratory scale handling and timing; on larger scales, the catalyst is included in the Part B formulation.

In Examples 1-4, open cell spray polyurethane foams were prepared. Examples 2 and 3 are comparative examples. The amounts of components and method information are listed in Table 1; the test results are summarized in Table 2. In Examples 1-4, water was the only blowing agent.

In Examples 5-10, closed cell spray polyurethane foams were prepared. Examples 5, 6, 8 and 9 are comparative examples. In Example 9, ^Saytex® RB-79 flame retardant was added as a solution in 2-butoxy alcohol. The amounts of the components and method information are listed in Table 3; the test results are summarized in Table 4.

In Examples 11-16, closed cell spray polyurethane foams were prepared. Examples 12-16 are comparative examples. The amounts of components and method information are listed in Table 5; the test results are summarized in Table 6.

In Examples 17-19, panel polyurethane foams were prepared. Examples 17 and 18 are comparative examples. The amounts of components and method information are listed in Table 7; the test results are summarized in Table 8.

In Examples 20-22, closed cell spray polyurethane foams were prepared. Operation 1 of Example 21 and Operations 1 and 2 of Example 22 are comparison operations. Component amounts and method information for Examples 20-22 are listed in Tables 9A-B, 11A-B, and 13A-C; test results for Examples 20-22 are summarized in Tables 10A-B, 12A-B, and 14A-C.

Tables 1 and 2 show that much lower amounts of DBAA relative to TCPP and RB-79 can be used in open cell foams to achieve a Class 1 flame retardancy rating for the foam. Polyurethane foams containing DBAA have much better dimensional stability than foams containing TCPP or Saytex ^® RB-79 flame retardant.

Tables 3 and 4 show that much lower amounts of DBAA can be used in closed cell foams relative to RB-79 alone or the combination of TCPP and RB-79 to achieve a Class 1 flame retardancy rating for the foam. Polyurethane foams containing DBAA have improved R-values compared to foams containing TCPP and/or Saytex ^® RB-79 flame retardants.

Tables 7 and 8 show the use of DBAA in panel foam to achieve a Class 1 flame retardancy rating for the foam.

Anywhere in this specification or the scope of its claims, a component referred to by chemical name or formula, whether in the singular or in the plural, shall be deemed to be Another substance (eg, another component, solvent, or the like) is present prior to contacting. It does not matter what chemical changes, transformations and/or reactions, if any, take place in the resulting mixture or solution, as such changes, transformations and/or reactions bring together the specified components under the conditions required in accordance with the present invention A natural consequence of being together. Accordingly, the components are identified as components that are combined to perform the desired operation or to be brought together in forming the desired composition. In addition, although the claims below may refer to substances, components and/or ingredients in the present tense ("comprises", "is", etc.), reference is made to one or more of the Other substances, components and/or ingredients that are present before contacting, admixing or mixing. Therefore, the fact that a substance, component or ingredient may have lost its original identity through chemical reaction or transformation during the contacting, blending or mixing operation is not practical if carried out in accordance with the present invention and in the ordinary skill of a chemist significance.

The scope of the invention described and claimed herein is not to be limited by the specific examples and embodiments disclosed herein, which are intended to be illustrative of several aspects of the invention. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.

Claims (20)

A polyurethane foam formed from components comprising 2,3-dibromoallyl alcohol and a blowing agent. The polyurethane foam of claim 1, which is a flexible polyurethane foam. The polyurethane foam of claim 1, which is a rigid polyurethane foam. The polyurethane foam of any one of claims 1 to 3, which also comprises tetrabromophthalic anhydride with diethylene glycol and propylene glycol and/or ginseng (1-chloro-2-propyl) Mixed esters of phosphoric acid esters. A polyurethane foam formed from components comprising: 2,3-dibromoallyl alcohol, at least one polyol, at least one blowing agent, at least one catalyst, and at least one surfactant. The polyurethane foam of claim 5, wherein the polyol is a polyether polyol and/or a polyester polyol. The polyurethane foam of claim 5 or 6, wherein the blowing agent comprises water. The polyurethane foam of claim 5 or 6, wherein the 2,3-dibromoallyl alcohol is present in an amount of about 1 wt % to about 25 wt % based on the total weight of the polyurethane foam , the amount of the polyol is from about 40 wt % to about 80 wt %, the amount of the surfactant is from about 0.1 wt % to about 5 wt %, the amount of the blowing agent is from 0.5 wt % to about 20 wt %, and/or the The amount of catalyst is from about 0.25 wt% to about 10 wt%. The polyurethane foam of claim 5 or 6, wherein the functionality of the polyol is from about 3 to about 7. The polyurethane foam of claim 7 wherein water is the only blowing agent. The polyurethane foam of claim 7, wherein the 2,3-dibromoallyl alcohol is present in an amount of about 1 wt % to about 25 wt % based on the total weight of the polyurethane foam, the The amount of polyol is from about 40 wt % to about 80 wt %, the amount of the surfactant is from about 0.1 wt % to about 5 wt %, the amount of the blowing agent is from 0.5 wt % to about 20 wt %, and/or the amount of the catalyst is and/or wherein the functionality of the polyol is from about 3 to about 7. A polyurethane foam formed from components comprising at least one polyisocyanate and the polyurethane foam of any one of claims 5 to 11. A method of forming a polyurethane foam, the method comprising: (i) combining A) at least one isocyanate and/or polyisocyanate with B) 2,3-dibromoallyl alcohol, at least one polyol, at least one A blowing agent, at least one catalyst, and at least one surfactant form a formulation in contact to form a mixture; and (ii) allowing the mixture to cure to form a polyurethane foam. The method of claim 13, wherein A) and B) are in amounts such that the isocyanate index is from about 80 to about 200, and wherein a flexible polyurethane foam is formed. The method of claim 13, wherein A) and B) are in amounts such that the isocyanate index is from about 85 to about 1000, and wherein a rigid polyurethane foam is formed. A polyurethane foam formed as in any one of claims 13 to 15. A polyurethane foam formed from components comprising: 2,3-dibromoallyl alcohol, at least one polyol, at least one blowing agent, at least one catalyst, at least one surfactant, and at least one A polyisocyanate. The polyurethane foam of claim 17, wherein the polyol is an aromatic polyester polyol and a polyether polyol or at least one sucrose/glycerol polyol; the foaming agent is water, trans-1-chloro -3,3,3-trifluoropropene, 1,2-bis(trifluoromethyl)ethylene or a mixture of any two or more of these; the catalyst is potassium octoate and/or dibutyl Bis(dodecylsulfide)stannane; the surfactant is polysiloxane; and/or the polyisocyanate is diphenylmethane diisocyanate. The polyurethane foam of claim 17 or 18, wherein the 2,3-dibromoallyl alcohol is present in an amount of about 1.5 wt % to about 10 wt % based on the total weight of the polyurethane foam %, the amount of the polyol is from about 25 wt % to about 35 wt %, the amount of the catalyst is from about 0.5 wt % to about 4 wt %, and/or the amount of the surfactant is from about 0.25 wt % to about 2.5 wt %. The polyurethane foam of claim 18, wherein the aromatic polyester polyol has a functionality of about 1.75 to about 2.75 and a hydroxyl number in the range of about 200 to about 350.