CA1040188A - Phosphate salt of amine based polyol and low density polyurethane foams - Google Patents
Phosphate salt of amine based polyol and low density polyurethane foamsInfo
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- CA1040188A CA1040188A CA202,898A CA202898A CA1040188A CA 1040188 A CA1040188 A CA 1040188A CA 202898 A CA202898 A CA 202898A CA 1040188 A CA1040188 A CA 1040188A
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Abstract
ABSTRACT OF THE DISCLOSURE
Disclosed is the phosphate salt of amine based polyols which are useful in preparing low dinsity polyurethane foams. The phosphate salt of amine based polyols includes those compositions prepared by reacting alkoxylated mono-and/or polyamines with phosphoric acid. Rigid low density polyurethane foams are prepared from a polyol blend of a phos-phate salt of an amine based polyol and one or more other poly-hydroxy compounds.
Disclosed is the phosphate salt of amine based polyols which are useful in preparing low dinsity polyurethane foams. The phosphate salt of amine based polyols includes those compositions prepared by reacting alkoxylated mono-and/or polyamines with phosphoric acid. Rigid low density polyurethane foams are prepared from a polyol blend of a phos-phate salt of an amine based polyol and one or more other poly-hydroxy compounds.
Description
~ his inv~ntion rel2tes to the ~h~sph~te s~lt ~f arnine based polyols and to low density cellular polyurethanes n.ade therefrom ~ i.gid polyurethane foams have found extensive use in m~dern industrial applications with respect both to the struc-~ur~l and to th~ insulative capacities thereof Rigid low density polyurethane foams have in the past frequently exhibited disadvantageous characteristics of marked thermal instability, as evidenced by their tendency to shrink in volume at reduced teMperatures or even at ordinary temperatures. Such shrinkage is usually attributable to the collapse, upon condensation to a liquid of the gaseous foaming agent, of relatively attenuated, and consequently weak, cell wa ~s of the foam which result from the high ratio of such foaming agent to polyurethane mate.rials employed in the foam formulation in order to produce a foam oE low density.
It is an object of the present invention to provide novel phosphate salts of amine based polyols which can be used to ~r~pare rigid low density polyurethane foams which are stable at low temperatures.
It is the further object of the present invention to provide rigid low density, thermally stable cellular poly-urathanes.
It is another object of the present invention to pro-vide ri~id low density polyurethane compositions which exhibit excellen-t freezer stability while retaininy the insulation value, and other desirable physical property charac-teristics of riyid polyurethane foams.
`"~ .
It is an object of the present invention to provide novel phosphate salts of amine based polyols which can be used to ~r~pare rigid low density polyurethane foams which are stable at low temperatures.
It is the further object of the present invention to provide rigid low density, thermally stable cellular poly-urathanes.
It is another object of the present invention to pro-vide ri~id low density polyurethane compositions which exhibit excellen-t freezer stability while retaininy the insulation value, and other desirable physical property charac-teristics of riyid polyurethane foams.
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- 2 -These and other ~jects are ach-eved in accordance with the present invention through the u~e of a phosphate salt of an amine based polyol as a polyol component in the prepar-ation of polyurethane foams.
The phosphate salts of amine based polyols of the present invention are prepared by adding sufficient phosphoric acid to the amine based polyol so as to result in the form~tion o~ either a partially neutralized or completely neutralized amine based polyol.
The amine based polyols or polyoxyalkylene amines which are used as precursors in the preparation of the present phosphate salts of amine based polyols can be prepared from any of the well-known commercially available mono- and poly-amines. In general, such amines containing from about 1 to 10 carbon atoms can be used in accordance with the present inven- -tion; 7~owever, in a preferred er~bodiment of this invention, such amines containing 2 to 6 carbon atoms are utilized. ~mong the polyamines that can be used are any of the known diamines, triamines, and tetramines These amines, in turn, are reacted with an alkylene oxide to form polyoxyalkylene amines also known as polyethers.
The polyoxyalkylene amines which are used to make the amine based polyol phosphates of the present invention will generally have a hydroxyl number between about 350 and 800 and will contain from 3 to 30 mols of alkylene oxide per mol of amine. However, in a more preferred embodiment the polyol amines which are used to prepare the subject polyol amine phos-phates will contain from about 3 to 20 mols of alkylene oxide per mol of amine. The alkylene oxide used can contain from 2 to 6 carbon atoms but is preferably propylene oxide or mix-tures of ethylene oxide and propylene oxide.
_ 3 _ ~ ~ , In anoth ~ ~p~re~er~ed embodiment of the present in-vention the lower number of mols of alkylene oxide used to prepare the subject polyoxyalkylene amines should be that number which is sufficient to react with each amino hydrogen present in the amine and an upper limit of about 20 mols of alkylene o~ide per mol o~ amine.
In more preferred embodiments of the present invention, the polyol amine phosphates of the present invention based on a diamine will contain ~rom 4 to 8 mols of alkylene oxide per mol of diamine. Those amine polyol phosphates of the present in-vention based on monoamines will contain from 3 to 8 mols of alkylene oxide per mol of monoamine. Preferred amin~ polyol phosphates o~ the presen-t invention based on triamines will contain from 5 to 9 mols of alkylene oxide per mol of amine, whereas the polyol phosphate amines of the present invention based on tetramines will contain from 6 to 10 mols of alkylene oxide per mol of tetramine.
In the above discussion of polyoxyalkylene amines and their corresponding phosphates, it is understood that when it is stated that a polyol amine or polyol amine phosphate contains a "certain number" of mols of alkylene oxide per mol of amine, it is meant that the amine is suitably reacted with said "certain number" of mols of alkylene oxide and thus the resulting poly~
ether or polyoxyalkylene amine will actually contain groups or residues of the alkylene oxide used corresponding to the "ceXtain number" of mols of a lkylene oxide used to prepare the polyoxyalkylene amine.
In accordance with the present invention, the subject phosphate salts of aliphatic amine based polyols can be prepared by reacting polyoxyllkylene amines, as described above, with ` .
~L~P4~18~
from about 0 250/~ to ab~ut lOo~ by ~igh~ of ~c~ra~ed phoS
phoric acid (86%), based on the to~al weight of polyoxyalkylene amine-phosphoric acid reaction mixture, to form the phosphate salt thereof. In a more preferred embodiment from about 0.50%
to about 5.00% by weight of concentrated phosphoric acid (86%), based on the ~otal weight of polyoxyalkylene amine-phosphoric acid reaction mixture, is reacted with the above described polyoxyalkylene amines to prepare the subject phosphate salts of amine based polyols. It will be understood by those skilled in the present art ~hat the desired concentration of phosphoric acid as indicated above can be obtained through the use of a different strength acid (other than 860/o) The preparation of such phosphate salts is accomplished by mere mixing of the polyoxyalkylene amine and phosphoric acid so as to bring about a thorough and intimate contact between the two reactants ~or th~ purpose of reaction at temperatures from about room temper-ature (70F.) up to about 150F.for about 5 to 30 minutes.
Some o~ the preEerred novel phosphate salts of ali-phatic amine based polyols (polyethers) of the present inven-tion can be represented by the following general formulas:
(a) ~H(OR') ] NH3_z(H3PO4)n and Q Q
(b) Hl_m [H(OR~)y~m~N~R~I~N~ ~(OR )xH~pHl_p(H3PO4)t wherein R" is selected from the group consisting of alkylene ~`` Q
groups containing from 1 to 20 carbon atoms, -R-N-R- and Q Q
-R-N-R-N-R-, R is independently selected from the group con-sisting o~ alkylene groups containing from 1 to 6 carbon atoms, Q is independently selected from the group consisting of hydrogen ~d -(QR')y~ R' is i.ndependentl~ 5 e~ected ~rv~ the ~roup con-~i.sting of alkylene groups containing from 2 to 6 carbon atoms, y is a number of from l to 20, x is a number of from 1 to 20, z represents a number having an average v~lue of 3 and m and p .are independently selected values of 0 or l with the proviso that at least m or p is l, n has a value of from 0.03 to 0.5, t has a value of 0.03 to l.0 when the amine representea by formula (b) is a diamine, and a value of 0.05 to 1.5 and 0.05 to 2.0 when the amine represented by formula (b) is a triamine lG and tetramine, respectively. In a more preferred embodiment of the present invention, n has a value of about 0.05 to 0.5, t has a value of about 0.05 to l when the amine represented by formula ~b) is a diamine, and y and x independently represent numbers from 1 to 15. In the above formula n and t represent the number of mols of H3PO4 that are reacted with one mol of polyoxyalkylene amine.
Polyurethane foams of the present invention are made ., .
from polyol composition5 containing from about 5% to about 100%
more preferably 10% to 40% and most preferably 20% to 40% by weight, of the amine based polyol phosphates of the present invention as described above. The other portion of the polyol hlend that can be used in the preparation of the subject low density foams can be made up of any of the suitable commercially available hydroxyl-bearing compounds having terminal hydroxyl groups which are thoroughly described throughout the prior art : and hereinafter. In a preferred embodiment the polyol composi~
. tions of the present invention which can consist solely of the above-described amine based polyol phosphates or a blend of such phosphates with a second polyol or polyhydric alcohol, having a hydroxyl "functionality" of three or more, will have :i .
;'`
. .
gL88 a nydroxyL number wlthl-n the range o~ 350 ~o 65~, preferably 400 to 500.
The polyoxyalkylene amines (nitrogen-containing poly-~; ethers) which are used as precursors in the preparation of the novel phosphate salts of amine based polyols ~polyolamine phosphates) of the present invention are well known in the art, inasmuch as they have been extensively used as polyols in the preparation o~ polyure~hanes, and they can be prepared by known processes. For example, such nitrogen-comtaining polyethers can be prepared from any of the commercially available aliphatic amines containing from 1 to 10 carbon atoms, such as monoeth- -anolamine, triethanolamine, ethylenediamine, triethylenetetra-mine, diethylenetriamine, hexamethylenediamine, isopropylamine, 1,6-hexamethylenediamine, hexylamine, and butylamine, by reacting such amines with a 1:2-alkylene oxide. In most i~-stances, the alkylene oxide used is ethylene oxide or propylene oxide or a combination thereof; however, such alkylene oxides containing up to six carbon atoms can be used. The mothod of preparing such nitrogen-containing polyethers as stated above is well known in the art, ~or example, as disclosed in U.S.
The phosphate salts of amine based polyols of the present invention are prepared by adding sufficient phosphoric acid to the amine based polyol so as to result in the form~tion o~ either a partially neutralized or completely neutralized amine based polyol.
The amine based polyols or polyoxyalkylene amines which are used as precursors in the preparation of the present phosphate salts of amine based polyols can be prepared from any of the well-known commercially available mono- and poly-amines. In general, such amines containing from about 1 to 10 carbon atoms can be used in accordance with the present inven- -tion; 7~owever, in a preferred er~bodiment of this invention, such amines containing 2 to 6 carbon atoms are utilized. ~mong the polyamines that can be used are any of the known diamines, triamines, and tetramines These amines, in turn, are reacted with an alkylene oxide to form polyoxyalkylene amines also known as polyethers.
The polyoxyalkylene amines which are used to make the amine based polyol phosphates of the present invention will generally have a hydroxyl number between about 350 and 800 and will contain from 3 to 30 mols of alkylene oxide per mol of amine. However, in a more preferred embodiment the polyol amines which are used to prepare the subject polyol amine phos-phates will contain from about 3 to 20 mols of alkylene oxide per mol of amine. The alkylene oxide used can contain from 2 to 6 carbon atoms but is preferably propylene oxide or mix-tures of ethylene oxide and propylene oxide.
_ 3 _ ~ ~ , In anoth ~ ~p~re~er~ed embodiment of the present in-vention the lower number of mols of alkylene oxide used to prepare the subject polyoxyalkylene amines should be that number which is sufficient to react with each amino hydrogen present in the amine and an upper limit of about 20 mols of alkylene o~ide per mol o~ amine.
In more preferred embodiments of the present invention, the polyol amine phosphates of the present invention based on a diamine will contain ~rom 4 to 8 mols of alkylene oxide per mol of diamine. Those amine polyol phosphates of the present in-vention based on monoamines will contain from 3 to 8 mols of alkylene oxide per mol of monoamine. Preferred amin~ polyol phosphates o~ the presen-t invention based on triamines will contain from 5 to 9 mols of alkylene oxide per mol of amine, whereas the polyol phosphate amines of the present invention based on tetramines will contain from 6 to 10 mols of alkylene oxide per mol of tetramine.
In the above discussion of polyoxyalkylene amines and their corresponding phosphates, it is understood that when it is stated that a polyol amine or polyol amine phosphate contains a "certain number" of mols of alkylene oxide per mol of amine, it is meant that the amine is suitably reacted with said "certain number" of mols of alkylene oxide and thus the resulting poly~
ether or polyoxyalkylene amine will actually contain groups or residues of the alkylene oxide used corresponding to the "ceXtain number" of mols of a lkylene oxide used to prepare the polyoxyalkylene amine.
In accordance with the present invention, the subject phosphate salts of aliphatic amine based polyols can be prepared by reacting polyoxyllkylene amines, as described above, with ` .
~L~P4~18~
from about 0 250/~ to ab~ut lOo~ by ~igh~ of ~c~ra~ed phoS
phoric acid (86%), based on the to~al weight of polyoxyalkylene amine-phosphoric acid reaction mixture, to form the phosphate salt thereof. In a more preferred embodiment from about 0.50%
to about 5.00% by weight of concentrated phosphoric acid (86%), based on the ~otal weight of polyoxyalkylene amine-phosphoric acid reaction mixture, is reacted with the above described polyoxyalkylene amines to prepare the subject phosphate salts of amine based polyols. It will be understood by those skilled in the present art ~hat the desired concentration of phosphoric acid as indicated above can be obtained through the use of a different strength acid (other than 860/o) The preparation of such phosphate salts is accomplished by mere mixing of the polyoxyalkylene amine and phosphoric acid so as to bring about a thorough and intimate contact between the two reactants ~or th~ purpose of reaction at temperatures from about room temper-ature (70F.) up to about 150F.for about 5 to 30 minutes.
Some o~ the preEerred novel phosphate salts of ali-phatic amine based polyols (polyethers) of the present inven-tion can be represented by the following general formulas:
(a) ~H(OR') ] NH3_z(H3PO4)n and Q Q
(b) Hl_m [H(OR~)y~m~N~R~I~N~ ~(OR )xH~pHl_p(H3PO4)t wherein R" is selected from the group consisting of alkylene ~`` Q
groups containing from 1 to 20 carbon atoms, -R-N-R- and Q Q
-R-N-R-N-R-, R is independently selected from the group con-sisting o~ alkylene groups containing from 1 to 6 carbon atoms, Q is independently selected from the group consisting of hydrogen ~d -(QR')y~ R' is i.ndependentl~ 5 e~ected ~rv~ the ~roup con-~i.sting of alkylene groups containing from 2 to 6 carbon atoms, y is a number of from l to 20, x is a number of from 1 to 20, z represents a number having an average v~lue of 3 and m and p .are independently selected values of 0 or l with the proviso that at least m or p is l, n has a value of from 0.03 to 0.5, t has a value of 0.03 to l.0 when the amine representea by formula (b) is a diamine, and a value of 0.05 to 1.5 and 0.05 to 2.0 when the amine represented by formula (b) is a triamine lG and tetramine, respectively. In a more preferred embodiment of the present invention, n has a value of about 0.05 to 0.5, t has a value of about 0.05 to l when the amine represented by formula ~b) is a diamine, and y and x independently represent numbers from 1 to 15. In the above formula n and t represent the number of mols of H3PO4 that are reacted with one mol of polyoxyalkylene amine.
Polyurethane foams of the present invention are made ., .
from polyol composition5 containing from about 5% to about 100%
more preferably 10% to 40% and most preferably 20% to 40% by weight, of the amine based polyol phosphates of the present invention as described above. The other portion of the polyol hlend that can be used in the preparation of the subject low density foams can be made up of any of the suitable commercially available hydroxyl-bearing compounds having terminal hydroxyl groups which are thoroughly described throughout the prior art : and hereinafter. In a preferred embodiment the polyol composi~
. tions of the present invention which can consist solely of the above-described amine based polyol phosphates or a blend of such phosphates with a second polyol or polyhydric alcohol, having a hydroxyl "functionality" of three or more, will have :i .
;'`
. .
gL88 a nydroxyL number wlthl-n the range o~ 350 ~o 65~, preferably 400 to 500.
The polyoxyalkylene amines (nitrogen-containing poly-~; ethers) which are used as precursors in the preparation of the novel phosphate salts of amine based polyols ~polyolamine phosphates) of the present invention are well known in the art, inasmuch as they have been extensively used as polyols in the preparation o~ polyure~hanes, and they can be prepared by known processes. For example, such nitrogen-comtaining polyethers can be prepared from any of the commercially available aliphatic amines containing from 1 to 10 carbon atoms, such as monoeth- -anolamine, triethanolamine, ethylenediamine, triethylenetetra-mine, diethylenetriamine, hexamethylenediamine, isopropylamine, 1,6-hexamethylenediamine, hexylamine, and butylamine, by reacting such amines with a 1:2-alkylene oxide. In most i~-stances, the alkylene oxide used is ethylene oxide or propylene oxide or a combination thereof; however, such alkylene oxides containing up to six carbon atoms can be used. The mothod of preparing such nitrogen-containing polyethers as stated above is well known in the art, ~or example, as disclosed in U.S.
3,094,434 and in standard texts such as Saunders et al., ~" "PolyurethaneS: Chemistry and Technology," Part I and Part II, Interscience Publishers, New York, 1962 and 1964, respectively.
~urther, polyoxyalkylene amine precursors used to prepare the novel phosphate salts of amine based polyols are commercially available.
Among the polyoxyalkylene amines which are suitable ~or use in the preparation o~ the phosphate salt amine based polyols o~ the present invention are: polyoxyethylene(8) ethylenediamine; polyoxypropylene(12)triethylenetetramine;
' ~4q~1B~3 Pol~oxypropylene(3)polyoxyethylene(1)ethylenediamine; poly-oxyethylene(3)polyoxypropylene(2)diethylenetriamlne; polyox~-propylene(2)ethanolamine; polyoxypropylene(3)diethanolamine;
polyoxypropylene(8)triethanolamlne; polyoxyethylene(6)-1,4-butanediamine, polyoxypropylene(5)-1,5-pentanediamine; poly-oxypropylene(5)ethylenediamine; polyoxypropylene(2)-polyoxyethyl-ene(2)ethylenediamine; and mixtures thereof The polyurethane compositions falling within the ambit of the present inven~ion are broadly~those cellular compositions comprising multiple urethane linkages formed by ~;
the reaction of an isocyanate and a compound containing a hydro-gen atom or atoms r~active therewith, as, ~or example, hydroxyl-bearing compounds having terminal hydroxyl groups such as poly-esters and polyethers~ Polyhydric compounds which are blended with the novel phosphate salt amine based polyols of the present invention to prepare polyurethane foam compositions of the p.resent invention comprise those having a hydroxyl "function-ality" of three or more. In general, polyhydric compounds, i.e., polyethers and polyesters, having from three to nine hydroxyl groups in the molecule thereo~ are used to prepare the poly-urethane foams of the present invention. These may be, for example, triols, tetrols, pentitols, hexitols, heptitols, octitols, nonitols, and mixtures therof in any proportion. In ~;accordance with this invention, however, such polyhydric com-:pounds will generally have a hydroxyl number between about 350 :.
and 650 inclusive.
The term "hydroxyl number" as used throughout this ~`specification denotes the number of milligrams of potassium hydroxyde equivalent to the acid required to esterify one gram ,~
,:
.
~4~ 8 o~ ~he ~,yero~ylic ~teriaJ- t~e equiva~ent ~ight ~ e hydroxylic material, therefore, is the weight in grams thereof which contains one gram mol of the hydroxyl radical, i.e., 56,100 divided by hydroxyl number.
Poly~ther hydroxyli~ compounds which may be used in combination with the subject phosphate salts of aliphatic amine based polyols to prepare polyurethane foam compositions in accordance with this invention comprise polyoxyalkylene ethers of polyhydric alcohols, such as polyoxyalkylene triols, tetrols, pentitols, hexitols, and polyethers of still higher function-ality. Such polyethers are exemplified by polyoxyalkylene tri-methylolethane, polyoxyalkylene trimethylolpropane, polyoxyal-kylene hexanetriol, polyoxyalkylene glycerol, polyoxyal~ylene butanetriol, polyoxyalkylene erythritol, polyoxyalkylene pen-taerythritol, polyoxyalkylene sorbitol, polyoxyalkylene methyl glucoside, polyoxyalkylene sucrose, polyoxyalkylene mannitol, polyoxyalkylene butanetetrol, polyoxyalkylene lactositol. and the like. The polyoxyalkylene ether of the polyhydric alcohol may be prepared, if desired, by reacting an al~ylene oxide co~pound With a selected polyhydric alcohol in the conventional manner.
More specifically, among the hydroxyl-~earing com-pounds which may suitably be used in combination with the novel phosphate salts of aliphatic amine based polyols to prepare polyurethane foams in accordance witn this inven-t}~n are:
polyoxypropylene(lO)sorbitol, polyoxypropylene(4)hexanetriol, polyoxybutylene(8)glycerol, polyoxypropylene(5)mannitol, poly-oxypropylene(3~trimethylolethane, polyoxypropylene(8)trimethyl-olpropane, polyoxypropylene(4)sorbitol, polyoxybutylene(20) lactositol, polyoxyethylene(6)methyl glucoside, polyoxypropyl-_ g e~e (.l~)sorbitan, polyox~Tp~o~ylene ~8)er~rthri~ , p~ly~xy-butylene(4)penta~rythritol, polyoxyethylene(3~polyoxypropyl-ene(7)mannitan, polyoxyethylene(~)polyoxypropylene(lO)sucrose and mixtures thereof and many others. Generally, such poly-ethers will contain from 3 to 20 mols (residues) of alkylene oxide per mol of polyhydric alcohol~
Since the hydroxyl number of the polyol is a func~ion of the number of hydroxyl groups per molecule thereof and the molecular weight of the compounds, it will be evident that the overall range of oxyalkylation in the polyol used in accordance with this invention is limited by the previously defined per-missible range in hydroxyl number thereof.
Polyesters suitable for use in the preparation of po~:yurethane foams of this invention may be obtained by ester-i*ication condensation reaction oE an aliphatic dibasic car-bo~ylic acid with a triol or an alcohol of higher hydroxylic functionality, or mixtures thereof, in such proportion that the resultant polyesters possess predo~inately -terminal hydroxyl groups.
Polyhydroxylic compounds suitable to the prepara-tion of such polyesters are exempliEied by glycerol, 1,2-hexanetritol, trimethylolethane, trimethylolpropane, sorbitol, methyl glucoside, lactositol, mannitol, and, in general, any similar polyhydric compound which when reacted in suitable proportion with a dibasic acid will provide a polyest~r with ;~ a hydroxylic functionality within the range of three to nine.
Aliphatic dicarboxylic acids which may be used to prepare such polyesters comprise adipic acid, fumaric acid, sebacic acid, phthalic acid, maleic acid, and many other acids of the kind.
-- 10. --, L8~3 ~ .etl~ ds of preE~raticsn c3f polyest~rs sui~a~lP f~r use in the preparation of polyurethane foams are abundantly described in U.S. Patent Numbers 2,543,644; 2,593,787;
2,409,633; 2,443,735; 2,443,741; 2,450,552; 2,255,313;
2,512,410; 2,634,251; 2,662,069; and 2,662,070.~ ~
A wide variety of organic isocyanate compounds may be used to prepare the novel polyurethane foam compositions of the present invention among which are included toluene di-isocyanate (both the 2,4- and 2,6-isomers and any mixture 10 thereoE), biphenyl diisocyanatè, terphenyl diisocyanate, chloro -phenylene-1,4-diisocyanate, 1,4-tetramethylene diisocyanate, p-phenylene diisocyanate, polyrnethylene polyphenyl isocyanate (PAPI), 3,3'-dimethoxy~,4'-biphenylene diisocyanate, diphenyl-methane, 4,4'-diisocyanate, and others.
Catalysts which may be used in the preparation of polyurethane foams of the present invention may include well-known amine catalysts which have been used to catalyze such reactions in the prior art. Among the suitable amine catalysts are dimethylethanolamine, N-me-thyldicyclohexylamine, and N,N-20 dimethylcyclohexylamine. These amine catalysts are generally -` used in amounts ~rom about 0.05% to about 2% by weight o~
the hydroxyl-bearing compounds reacted with the isocyanate compound. In instances where the amine based polyol phosphate compounds of the present invention contain excess or unreacted phosphoric acid (not reacted with the amine based polyol re-actant), additional quantities of amine catalyst may be used so as to neutralize the excess phosphoric acid and provide a catalytic concentration of the amine catalyst to catalyze the isocyanate-polyol reaction.
~ am~les ~f useful surface active a~ents whieh can be present in amounts of from about 0.05% to about 2% by weight of the hydroxyl-bearing components used to prepare the polyurethane foams are water-soluble siloxane-oxyalkylene blo~k copolymers as described in U.S. Patent Number 2,834,748 to Bailey et al., issued May 13, 1958. Other surfactants which may be used are condensates of ethylene oxide with a hydrophobic case formed by condensing propylene oxide with a propylene glycol. These surfactants have a molecular weight 10 within the range of about 2000 to about 8000 and are generally ascribed the formula:
HO(CzH~O)a(C~H6O)b(CzH~O)cH
Illustrative examples of foaming agents which may be used in the preparation of polyurethane foams of the present invention include water, a halogenated saturated aliphatic hydrocarbon or a mixture of such halogenated saturated alipha-tic hydrocarbons, for example, trichlorofluoromethane (Freon 11); monochloroethane; monochloromonofluoroethane; 1,2-dibromo-1,1,2,2-tetrafluoroethane; 1,1,2-tri~luoroethane;
20 1,1,2,2-tetrafluoro-1,2-dichloroethane; 1,2-difluoro-1,1,2,2-tetrachloroethane; dichloromethane; dibromomethane, and their .
mixtures. A mixture of a halogenated saturated aliphatic hydrocarbon and water is a preferred foaming agent. In ac-cordance with the method of this invention, not less than about 10% by weight nor more than about 25% by weight based on the total foam formulatlon of a suitable foaming agent, such as any of those set forth above or other similar foam-ing agents, is used to prepare the low density foam compo--sitions included within ~he purview of this invention~
Within the context of this specification, the ; term "low density", when used with reference to the cellular polyurethane compositions of this invention, denotes foams having a density within the range of about 0.75 pound per cubic foot to about 1.7 pounds per cubic foot. Prefera~bly, the foams of the present invention have a density lying within a range of about 1.2 pounds per cubic foot to about 1.5 pounds per cubic foot. Polyurethane foams having a den-sity greater than 1.7 pounds per cubic foot are not deemed to be foams of low density within the meaning of that term as used herein.
The polyurethane foams provided in accordance with this invention are rigid foams as distinguished from flexible or semi-rigid foams. Throughout this specification the term ` "rigi~", when used with references to the polyurethane foams of this invention, denotes foams ~aving less than about 20%
volume recovery when compressed by about 10% of the volume thereof. Rigid foams of this invention, moreover, comprise foams having not less than about 75% of the cells thereof in the form of closed cells. If more than about 25% of the cells oE the said foams were open cells, the insulation values of the foams would be unsatis~actory.
The cellular polyurethane compositions of this invention may be prepared in the conventional manner thoroughly ; described in the prior art by mixing a polyhydroxylic blend, as hereinbefore described, with a polyisocyanate compound, as hereinbe~ore specified', in approximately stoichiometric propor-tion, based upon the ny~roxyl num~er or ~ne polyhyaric component. In general, polyurethane foams of the present invention are prepared by reacting a hydroxyl-bearing com~
ponent with an organic isocyanate in suitable proportion to provide a ratio of isocyanate groups to hydroxyl groups with a range of about 0.9 to about 1.25 with a preferred range for said ratio from about 1.0 to about 1.1. The polyol component and the ~socyanate component are mixed vigorously to promote reaction and thereafter the reaction mixture is poured and allowed to foam to completion.
The following examples are illustrative of composi-tions which are useful as the polyol component for preparing the polyurethane compositions of th~s invention. These examples are set forth solely for the purpose of illustration and any specific enumeration of details contained therein should not be interpreted as expressing limitations of this invention.
It will be readily apparent to those skilled in the art that other compositions may be prepared by substituting other polyols, polyisocyanates, catalysts, sur~ac-kants, and blowing agents for those recited in the following examples. All per-centages are by weight.
172.4 pounds of molten sorbitol containing less ;~ than 0.2% water were mixed with 480 grams of powdered sodium hydroxide and placed in an autoclave. The autoclave was ` sealed, flushed three times at 10 psig with nitrogen gas, heated to 165~C, and then a vacuum was drawn on the autoclave down to about 50 millimeters of mercury pressure. Propylene oxide (477.6 pounds) was added at 165C/85 psig to the auto-clave and the contents of the autoclave pumped through a heat exchanger to maintain the temperature and cause mixing of the mixture until the pressure was substantially zero~
The mixture was then deodorized by vacuum stripping 15 minutes at 1~0c. The resul-ting polyol was then diluted with an equal amount of distilled water and the diluted mixture was passed through a cation and anion exchange column and then vacuum strlpped at 120C for one hour to yield the desired polyol containing less than 0.1% water. The resulting poly-oxypropylene sorbitol product had a hydroxyl number of 420, 10 viscosity of 18,600 centipoises at 25C, and a water content of 0.09%.
Ethylenediamine (40 pounds) containing 0.25% water was placed in an autoclave and flushed three times with nitrogen gas and then heated to 120C by circulation through a heat exchanger. Then 60 pounds of propylene oxide were added at a rate to keep the temperature and pressure within the autoclave at about 135C/25 psig. The mix-ture in the auto-clave was agitated and 96.6 pounds more propylene oxide were 20 added at a rate to keep temperature and pressure at about 135C/25 psig. The reaction mixture in the autoclave was heated for about three hours at about 135C, initially at a pressure of about 25 psig, until the pressure dropped to sub-stantially zero. The reaction mi~xture was then cooled to 100C.
74 grams of powdered sodium hydroxide were added to the re-action mixture in the autoclave under a nitrogen gas flow, and then the autoclave was heatad to 155C/55 psig, while the reaction mixture was circulated through a heat exchanger until a substantially zero pressure was obtained. The resulting 30 polyoxypropylene ethylenediamine polyol was then deodorized by vacuum of about 50 millimeters of mercury pressu~e. Then, to dea~sh the polyol product, 1.6% sodium acid p~rophosphate and 5% distilled water were added to the resultlng polyol.
This blend was then agitated for two hours and then stripped at 110C at a final vacuum of about 50 millimeters of mercury pressure to a water content o~ less than 0.08%. Then 0.2%
magnesium silicate and 0.4% "Supercel"* were added to the polyol. The resulting mixture was then filtered and the re-sulting polyoxypropylene ethylenediamine polyol product had a hydroxyl number of 464 and a water content of 0.06%.
36.9 pounds of polyoxyethylene(4)-ethylenediaMine were treated wi-th 14 grams of powdered sodium hydroxide cata-lyst and 27.7 pounds of propylene oxide by the process of Example 1 to yield a polyoxyethylene(4)polyoxypropylene-ethylenediamine polyol. This product was deashed by the following procedure. 39.2 ~rams of 85% phosphoric acid and 5~.5 grams of water were added to the above polyol product and heated at a temperature of 100C for two hours with agi-tation. ~he produc-t was then vacuum stripped a-t 110C to ~; yield a polyol containing 0.08% water. 54.5 grams of mag-nesium silicate were then added to the polyol and the mix-ture was filtered to yield a polyoxyethylene polyoxypropylene ethylenediamine polyol having an acid number of 0.50, and a hydroxyl number of 443. The polyol product had a viscosity of 4,520 centipoises at 25C.
80.8 pounds of molten sorbitol and 240 grams of powdered sodium hydroxide were charged into an autoclave by the method of Example 2, and the mixture was treated with *Reg. Trade Mark 185.6 pounds oE propylene oxide initially followed by the addition o~ 58.6 pounds more of ethylene oxide. The polyol product obtained was also deashed by the method of Example 2.
The resulting polyoxypropylene polyoxyethylene sorbitol polyol product had a hydroxyl number of 447, an acid number of 0.16 and a water content of 0.055% The polyol product had a viscosity of 13,100 centipoises at 25C.
:
By the method of Example 1, 80 pounds of molten sorbitol, 240 grams of powdered sodium hydroxide, and 245 pounds of propylene oxide were charged to an autoclave and reacted to form a polyoxypropylene sorbitol polyol. The po~yol obtained was then deashed hy the method of Example 2.
The resulting product had a hydroxyl number of 440, water content of 0.07%, and an acid num~er of 0.15. The polyol product had a viscosity of 22,300 centipoises a-t 25C.
~urther, polyoxyalkylene amine precursors used to prepare the novel phosphate salts of amine based polyols are commercially available.
Among the polyoxyalkylene amines which are suitable ~or use in the preparation o~ the phosphate salt amine based polyols o~ the present invention are: polyoxyethylene(8) ethylenediamine; polyoxypropylene(12)triethylenetetramine;
' ~4q~1B~3 Pol~oxypropylene(3)polyoxyethylene(1)ethylenediamine; poly-oxyethylene(3)polyoxypropylene(2)diethylenetriamlne; polyox~-propylene(2)ethanolamine; polyoxypropylene(3)diethanolamine;
polyoxypropylene(8)triethanolamlne; polyoxyethylene(6)-1,4-butanediamine, polyoxypropylene(5)-1,5-pentanediamine; poly-oxypropylene(5)ethylenediamine; polyoxypropylene(2)-polyoxyethyl-ene(2)ethylenediamine; and mixtures thereof The polyurethane compositions falling within the ambit of the present inven~ion are broadly~those cellular compositions comprising multiple urethane linkages formed by ~;
the reaction of an isocyanate and a compound containing a hydro-gen atom or atoms r~active therewith, as, ~or example, hydroxyl-bearing compounds having terminal hydroxyl groups such as poly-esters and polyethers~ Polyhydric compounds which are blended with the novel phosphate salt amine based polyols of the present invention to prepare polyurethane foam compositions of the p.resent invention comprise those having a hydroxyl "function-ality" of three or more. In general, polyhydric compounds, i.e., polyethers and polyesters, having from three to nine hydroxyl groups in the molecule thereo~ are used to prepare the poly-urethane foams of the present invention. These may be, for example, triols, tetrols, pentitols, hexitols, heptitols, octitols, nonitols, and mixtures therof in any proportion. In ~;accordance with this invention, however, such polyhydric com-:pounds will generally have a hydroxyl number between about 350 :.
and 650 inclusive.
The term "hydroxyl number" as used throughout this ~`specification denotes the number of milligrams of potassium hydroxyde equivalent to the acid required to esterify one gram ,~
,:
.
~4~ 8 o~ ~he ~,yero~ylic ~teriaJ- t~e equiva~ent ~ight ~ e hydroxylic material, therefore, is the weight in grams thereof which contains one gram mol of the hydroxyl radical, i.e., 56,100 divided by hydroxyl number.
Poly~ther hydroxyli~ compounds which may be used in combination with the subject phosphate salts of aliphatic amine based polyols to prepare polyurethane foam compositions in accordance with this invention comprise polyoxyalkylene ethers of polyhydric alcohols, such as polyoxyalkylene triols, tetrols, pentitols, hexitols, and polyethers of still higher function-ality. Such polyethers are exemplified by polyoxyalkylene tri-methylolethane, polyoxyalkylene trimethylolpropane, polyoxyal-kylene hexanetriol, polyoxyalkylene glycerol, polyoxyal~ylene butanetriol, polyoxyalkylene erythritol, polyoxyalkylene pen-taerythritol, polyoxyalkylene sorbitol, polyoxyalkylene methyl glucoside, polyoxyalkylene sucrose, polyoxyalkylene mannitol, polyoxyalkylene butanetetrol, polyoxyalkylene lactositol. and the like. The polyoxyalkylene ether of the polyhydric alcohol may be prepared, if desired, by reacting an al~ylene oxide co~pound With a selected polyhydric alcohol in the conventional manner.
More specifically, among the hydroxyl-~earing com-pounds which may suitably be used in combination with the novel phosphate salts of aliphatic amine based polyols to prepare polyurethane foams in accordance witn this inven-t}~n are:
polyoxypropylene(lO)sorbitol, polyoxypropylene(4)hexanetriol, polyoxybutylene(8)glycerol, polyoxypropylene(5)mannitol, poly-oxypropylene(3~trimethylolethane, polyoxypropylene(8)trimethyl-olpropane, polyoxypropylene(4)sorbitol, polyoxybutylene(20) lactositol, polyoxyethylene(6)methyl glucoside, polyoxypropyl-_ g e~e (.l~)sorbitan, polyox~Tp~o~ylene ~8)er~rthri~ , p~ly~xy-butylene(4)penta~rythritol, polyoxyethylene(3~polyoxypropyl-ene(7)mannitan, polyoxyethylene(~)polyoxypropylene(lO)sucrose and mixtures thereof and many others. Generally, such poly-ethers will contain from 3 to 20 mols (residues) of alkylene oxide per mol of polyhydric alcohol~
Since the hydroxyl number of the polyol is a func~ion of the number of hydroxyl groups per molecule thereof and the molecular weight of the compounds, it will be evident that the overall range of oxyalkylation in the polyol used in accordance with this invention is limited by the previously defined per-missible range in hydroxyl number thereof.
Polyesters suitable for use in the preparation of po~:yurethane foams of this invention may be obtained by ester-i*ication condensation reaction oE an aliphatic dibasic car-bo~ylic acid with a triol or an alcohol of higher hydroxylic functionality, or mixtures thereof, in such proportion that the resultant polyesters possess predo~inately -terminal hydroxyl groups.
Polyhydroxylic compounds suitable to the prepara-tion of such polyesters are exempliEied by glycerol, 1,2-hexanetritol, trimethylolethane, trimethylolpropane, sorbitol, methyl glucoside, lactositol, mannitol, and, in general, any similar polyhydric compound which when reacted in suitable proportion with a dibasic acid will provide a polyest~r with ;~ a hydroxylic functionality within the range of three to nine.
Aliphatic dicarboxylic acids which may be used to prepare such polyesters comprise adipic acid, fumaric acid, sebacic acid, phthalic acid, maleic acid, and many other acids of the kind.
-- 10. --, L8~3 ~ .etl~ ds of preE~raticsn c3f polyest~rs sui~a~lP f~r use in the preparation of polyurethane foams are abundantly described in U.S. Patent Numbers 2,543,644; 2,593,787;
2,409,633; 2,443,735; 2,443,741; 2,450,552; 2,255,313;
2,512,410; 2,634,251; 2,662,069; and 2,662,070.~ ~
A wide variety of organic isocyanate compounds may be used to prepare the novel polyurethane foam compositions of the present invention among which are included toluene di-isocyanate (both the 2,4- and 2,6-isomers and any mixture 10 thereoE), biphenyl diisocyanatè, terphenyl diisocyanate, chloro -phenylene-1,4-diisocyanate, 1,4-tetramethylene diisocyanate, p-phenylene diisocyanate, polyrnethylene polyphenyl isocyanate (PAPI), 3,3'-dimethoxy~,4'-biphenylene diisocyanate, diphenyl-methane, 4,4'-diisocyanate, and others.
Catalysts which may be used in the preparation of polyurethane foams of the present invention may include well-known amine catalysts which have been used to catalyze such reactions in the prior art. Among the suitable amine catalysts are dimethylethanolamine, N-me-thyldicyclohexylamine, and N,N-20 dimethylcyclohexylamine. These amine catalysts are generally -` used in amounts ~rom about 0.05% to about 2% by weight o~
the hydroxyl-bearing compounds reacted with the isocyanate compound. In instances where the amine based polyol phosphate compounds of the present invention contain excess or unreacted phosphoric acid (not reacted with the amine based polyol re-actant), additional quantities of amine catalyst may be used so as to neutralize the excess phosphoric acid and provide a catalytic concentration of the amine catalyst to catalyze the isocyanate-polyol reaction.
~ am~les ~f useful surface active a~ents whieh can be present in amounts of from about 0.05% to about 2% by weight of the hydroxyl-bearing components used to prepare the polyurethane foams are water-soluble siloxane-oxyalkylene blo~k copolymers as described in U.S. Patent Number 2,834,748 to Bailey et al., issued May 13, 1958. Other surfactants which may be used are condensates of ethylene oxide with a hydrophobic case formed by condensing propylene oxide with a propylene glycol. These surfactants have a molecular weight 10 within the range of about 2000 to about 8000 and are generally ascribed the formula:
HO(CzH~O)a(C~H6O)b(CzH~O)cH
Illustrative examples of foaming agents which may be used in the preparation of polyurethane foams of the present invention include water, a halogenated saturated aliphatic hydrocarbon or a mixture of such halogenated saturated alipha-tic hydrocarbons, for example, trichlorofluoromethane (Freon 11); monochloroethane; monochloromonofluoroethane; 1,2-dibromo-1,1,2,2-tetrafluoroethane; 1,1,2-tri~luoroethane;
20 1,1,2,2-tetrafluoro-1,2-dichloroethane; 1,2-difluoro-1,1,2,2-tetrachloroethane; dichloromethane; dibromomethane, and their .
mixtures. A mixture of a halogenated saturated aliphatic hydrocarbon and water is a preferred foaming agent. In ac-cordance with the method of this invention, not less than about 10% by weight nor more than about 25% by weight based on the total foam formulatlon of a suitable foaming agent, such as any of those set forth above or other similar foam-ing agents, is used to prepare the low density foam compo--sitions included within ~he purview of this invention~
Within the context of this specification, the ; term "low density", when used with reference to the cellular polyurethane compositions of this invention, denotes foams having a density within the range of about 0.75 pound per cubic foot to about 1.7 pounds per cubic foot. Prefera~bly, the foams of the present invention have a density lying within a range of about 1.2 pounds per cubic foot to about 1.5 pounds per cubic foot. Polyurethane foams having a den-sity greater than 1.7 pounds per cubic foot are not deemed to be foams of low density within the meaning of that term as used herein.
The polyurethane foams provided in accordance with this invention are rigid foams as distinguished from flexible or semi-rigid foams. Throughout this specification the term ` "rigi~", when used with references to the polyurethane foams of this invention, denotes foams ~aving less than about 20%
volume recovery when compressed by about 10% of the volume thereof. Rigid foams of this invention, moreover, comprise foams having not less than about 75% of the cells thereof in the form of closed cells. If more than about 25% of the cells oE the said foams were open cells, the insulation values of the foams would be unsatis~actory.
The cellular polyurethane compositions of this invention may be prepared in the conventional manner thoroughly ; described in the prior art by mixing a polyhydroxylic blend, as hereinbefore described, with a polyisocyanate compound, as hereinbe~ore specified', in approximately stoichiometric propor-tion, based upon the ny~roxyl num~er or ~ne polyhyaric component. In general, polyurethane foams of the present invention are prepared by reacting a hydroxyl-bearing com~
ponent with an organic isocyanate in suitable proportion to provide a ratio of isocyanate groups to hydroxyl groups with a range of about 0.9 to about 1.25 with a preferred range for said ratio from about 1.0 to about 1.1. The polyol component and the ~socyanate component are mixed vigorously to promote reaction and thereafter the reaction mixture is poured and allowed to foam to completion.
The following examples are illustrative of composi-tions which are useful as the polyol component for preparing the polyurethane compositions of th~s invention. These examples are set forth solely for the purpose of illustration and any specific enumeration of details contained therein should not be interpreted as expressing limitations of this invention.
It will be readily apparent to those skilled in the art that other compositions may be prepared by substituting other polyols, polyisocyanates, catalysts, sur~ac-kants, and blowing agents for those recited in the following examples. All per-centages are by weight.
172.4 pounds of molten sorbitol containing less ;~ than 0.2% water were mixed with 480 grams of powdered sodium hydroxide and placed in an autoclave. The autoclave was ` sealed, flushed three times at 10 psig with nitrogen gas, heated to 165~C, and then a vacuum was drawn on the autoclave down to about 50 millimeters of mercury pressure. Propylene oxide (477.6 pounds) was added at 165C/85 psig to the auto-clave and the contents of the autoclave pumped through a heat exchanger to maintain the temperature and cause mixing of the mixture until the pressure was substantially zero~
The mixture was then deodorized by vacuum stripping 15 minutes at 1~0c. The resul-ting polyol was then diluted with an equal amount of distilled water and the diluted mixture was passed through a cation and anion exchange column and then vacuum strlpped at 120C for one hour to yield the desired polyol containing less than 0.1% water. The resulting poly-oxypropylene sorbitol product had a hydroxyl number of 420, 10 viscosity of 18,600 centipoises at 25C, and a water content of 0.09%.
Ethylenediamine (40 pounds) containing 0.25% water was placed in an autoclave and flushed three times with nitrogen gas and then heated to 120C by circulation through a heat exchanger. Then 60 pounds of propylene oxide were added at a rate to keep the temperature and pressure within the autoclave at about 135C/25 psig. The mix-ture in the auto-clave was agitated and 96.6 pounds more propylene oxide were 20 added at a rate to keep temperature and pressure at about 135C/25 psig. The reaction mixture in the autoclave was heated for about three hours at about 135C, initially at a pressure of about 25 psig, until the pressure dropped to sub-stantially zero. The reaction mi~xture was then cooled to 100C.
74 grams of powdered sodium hydroxide were added to the re-action mixture in the autoclave under a nitrogen gas flow, and then the autoclave was heatad to 155C/55 psig, while the reaction mixture was circulated through a heat exchanger until a substantially zero pressure was obtained. The resulting 30 polyoxypropylene ethylenediamine polyol was then deodorized by vacuum of about 50 millimeters of mercury pressu~e. Then, to dea~sh the polyol product, 1.6% sodium acid p~rophosphate and 5% distilled water were added to the resultlng polyol.
This blend was then agitated for two hours and then stripped at 110C at a final vacuum of about 50 millimeters of mercury pressure to a water content o~ less than 0.08%. Then 0.2%
magnesium silicate and 0.4% "Supercel"* were added to the polyol. The resulting mixture was then filtered and the re-sulting polyoxypropylene ethylenediamine polyol product had a hydroxyl number of 464 and a water content of 0.06%.
36.9 pounds of polyoxyethylene(4)-ethylenediaMine were treated wi-th 14 grams of powdered sodium hydroxide cata-lyst and 27.7 pounds of propylene oxide by the process of Example 1 to yield a polyoxyethylene(4)polyoxypropylene-ethylenediamine polyol. This product was deashed by the following procedure. 39.2 ~rams of 85% phosphoric acid and 5~.5 grams of water were added to the above polyol product and heated at a temperature of 100C for two hours with agi-tation. ~he produc-t was then vacuum stripped a-t 110C to ~; yield a polyol containing 0.08% water. 54.5 grams of mag-nesium silicate were then added to the polyol and the mix-ture was filtered to yield a polyoxyethylene polyoxypropylene ethylenediamine polyol having an acid number of 0.50, and a hydroxyl number of 443. The polyol product had a viscosity of 4,520 centipoises at 25C.
80.8 pounds of molten sorbitol and 240 grams of powdered sodium hydroxide were charged into an autoclave by the method of Example 2, and the mixture was treated with *Reg. Trade Mark 185.6 pounds oE propylene oxide initially followed by the addition o~ 58.6 pounds more of ethylene oxide. The polyol product obtained was also deashed by the method of Example 2.
The resulting polyoxypropylene polyoxyethylene sorbitol polyol product had a hydroxyl number of 447, an acid number of 0.16 and a water content of 0.055% The polyol product had a viscosity of 13,100 centipoises at 25C.
:
By the method of Example 1, 80 pounds of molten sorbitol, 240 grams of powdered sodium hydroxide, and 245 pounds of propylene oxide were charged to an autoclave and reacted to form a polyoxypropylene sorbitol polyol. The po~yol obtained was then deashed hy the method of Example 2.
The resulting product had a hydroxyl number of 440, water content of 0.07%, and an acid num~er of 0.15. The polyol product had a viscosity of 22,300 centipoises a-t 25C.
4.8 Pounds monoethanolamine were charged into an autoclave and 11.2 pounds of sucrose were slowly added and mixed into the monoethanolamine. Then 109 grams of powdered sodium hydroxide were stirred into the above mixture and the autoclave was sealed and flushed three times at 10 psig with nitrogen. A nitrogen blanket was then applied at atmospheric pressure and the reaction was heated to 110C. Then 54 pounds of propylene oxide were slowly added to the autoclave at a rate so as to maintain the temperature at about 110C
to 115C/40 to 50 psig. The reaction mixture was maintained at this temperature and stirred until the pressure was sub-stantially zero for 30 minutes. The resulting produc-t was then deodorized by vacuum stripping for 15 minutes at about C. When the tempera-ture of the product was about 105C, 0.988% by weight of phosphoric acid (85%) was added to the reaction mixture which was then stirred for about 30 minutes.
The resulting mixture was then vacuum stripped at about 100C
under vacuum of about 50 millimeters of mercury until the water content was less than 0.05%. 0.1% of a hindered phenol anti-oxidant was then added to the resulting polyol product and thoroughly agitated therein and then the result-ing product was filtered through paper to yield a polyol blend consisting of polyoxypropylene monoethanolamine and polyoxypropylene sucrose having a hydroxyl number of 408, water content of 0.18%, and acid number of 2.00. The polyol product had a viscosity of 4,030 centipoises at 25C.
In the following Examples 8, 9, 11, 12, 14, and 15, polyurethane foams were prepared usin~ novel phosphate salt amine based polyols of the present invention. Examples :
7 and 10 are controls for Examples 8, 9, 11, and 12, and Example 13 is the control for Examples 14 and 15. The foams ;` of Examples 7 to 15 were prepared using the following hand-. 20 mixing procedure.
Hand-Mixing Procedure The polyols were weighed into a 12-ounce uncoated paper cup. Those polyols having phosphoric acid added thereto to prepare the novel phosphate salts of the amine based polyols were first heated to about 120F along with the added phospho-ric acid under mechanical agitation for about 20 minutes in order to eEfect the preparation of the desired phosphate salts of -the amine based polyols. Chemical analysis confirmed the ~ormation of the said phosphate salts of the amine based polyols.
~:~4~8~
The other B component ingredients were then added ln the order listed from top to bottom, each being weighed into the cup until all the ingredients were added except the isocyanate. These were then mixed with a conventional laboratory electric stirrer at approximately 1,500 rpm until homogenous. The weight was then rechecked and any halo-genated hydrocarbon blowing agent loss was made up by adding back the weight lost. This mixture constitutes what is referred to as B component in the listing of ingredients under each example. The isocyanate (referred to as the A com-ponent) is then added rapidly to the cup (s compenent) and the total foam ingredients were mixed for ten seconds with the previousl~ mentioned mixer. The resulting mixture is then poured rapidly into a mould. The mould utilized was a metal mould, two inches by seven inches b~ twelve inches, inside dimensions. The foam was allowed to rise in the twelve-inch direction. The "free blown foam panels" were made with the top of the mould open, and the "packed foam panels" were made with the top closed. The percent packing was calculated by using the formula:
Weight Packed Foam Panel Minus Weight Free Blown Foam Panel X 100 = Percent Weight Free Blown Foam Panel Packing The percent freezer shrinkage of the products of the following Examples 7 to 15 were determined by measuring the shrinkage of the moulded polyurethane foam in the seven-inch direction af-ter exposure of the foam to -20F tempera-ture for 16 hours. For most commercial uses it is preferred that "free blown foam panels" should have a shrinkage less than 10% under the above-stated testing procedure; whereas ~46~8 ~ c~d ~o~m panels 3~0uld hava a shrin~a~e ~elow 3,' un~e~
the same ~est conditions. However, "free blown foam panels"
which exhibit a shrinkage less than 20% and "packed foam panels"
~:xhibiting a shrinkage less than 15% under the above-stated testing procedure are also within the bounds of the present invention inasmuch as such products can be utilized in areas and uses when the thermal conditions are not quite so severe.
Component APercent by Weight Nacconate* 5050 (commercial ~olylene ~ diisocyanate containing a mixture of 80% ~,4- and 20% 2-,-6- isomers). 44.26 Component BPercent ~y Weight Polyol of Example 1 25,00 Polyol of Example 3 6.74 ~l)~ethylene oxide-(3)-propylene oxide ethylene diamine 3.95 : Oxgano-silicone sur~actant L-5340 ~Unlon Carbide Co.). 0.60 M,N-dimethylcyclohexylamine0.70 : Water 0.75 Trichlorofluoromethane (Freon llB) 18.00 Free Blown Panel Density - 1.23 pounds/cubic foot Freezer Shrinkage - 27.0%
Packed Panel Density - 1.38 pounds/cubic foot Packing - 12%
~ree~er ShrinXage - 22.9 %
*Reg. Trade Mark ~p~
~XA~PLE ~
Component APercent by Weight Nacconate* 5050 (commerclal tolylene diisocyanate containing a mix~ure of 2,4- and 2,6- isomers). 44.26 Component BPercent by Weight : Polyol of Example 1 25.00 Polyol of Example 3 1.74 Polyol of Example 3 containing the addition of 1% phosphoric acid (86%) by weight, based on the total weight of acid and polyol. 5.00 (l)~ethylene oxide-(3)-propylene oxide ethylenediamine 3.95 Organo-silicone surfactant L-5340 0.60 N,N-dimethylcyclohexylamine0,70 Water 0.75 Trichlorofluoromethane (Freon llB) 18.00 Eree Blown Panel Density - 1.27 pounds/cubic foot Freezer Shrinkage - 17.4%
Packed Panel Density - 1.41 pounds/cubic foot packing - 10%
Freezer Shrinkage - 11.7%
Component A Percent by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers). 44.26 Component B Percent by Weight Polyol of Example 1 25.00 Polyol of Example 3 1.74 *Reg. Trade Mark _ 21 -Component B (con~.\p~rcent by W2ight (~o~`
Polyol of Example 3 containing the addition of 2% phosphoric acid (86%) by weight, based on the total weight of acid and polyol. 5.00 (l)-ethylene oxide-(3)-propylene : oxide ethylenediamine 3.95 Organo-silicone surfactant L-5340 0.60 ~,N-dimethylcyclohexylamine 0.70 Water 0 75 Trichlorofluoromethane (Freon llB) 18.00 Eree slown Panel Density - 1.30 pounds/cubic foot Freezer Shrinkage - 10.1%
packed Pane DenRity - 1.41 pounds/cubic foot :; Packing - 8%
Freeæer Shrinkage - 2.15%
EX~MPLE 10 Component A Percent by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers). 44.26 Component B Percent by Weight Polyol o~ Example 1 18.40 Polyol of Example 3 10.70 Polyoxypxopylene(8)sorbitol 6.59 Organo-silicone surfactant L-5340 (Union Carbide Co.) 0.60 N,N-dimethylcyclohexylamine 0.70 Water 0 75 Trichlorofluoromethane (Freon llB) 8.00 *Reg. Trade Mark ~6~4~ 8 Free Blown Panel Density - 1.23 pounds/eubic foot Freezer Shrinkage - 38.2%
P~cked Panel Density - 1.38 pounds/cubie ~oot Packing - 12%
Freezing Shrinkage - 24.3%
Component A Percent by Weight Naeeonate* 5050 (commercial tolylene , diisocyanate containing a mixture of 2,4- and 2,6~ isomers). 44~26 Component B Pereent by Weight Polyol of Example 1 18.4 Polyol of Example 3 5,70 Polyol of Example 3 eontaining the addition o~ 1% phosphorie aeid (86%) by weight, based on the total weight o~ aeid and polyol . 5 ~ 00 Polyoxypropylene~8)sorbitol 6.59 Organo-silieone surfactant L-5340 (Union Carbide Co.) 0.60 N,N-dimethyleyelohexylamine 0.70 Water 0- 75 Triehlorofluoromethane (Freon 11B) 18.00 Free Blown Panel Density - 1.28 pounds/cubic foot Freezer Shrinkage - 11.6%
Packed Panel Density - 1.34 pounds/eubie foot Packing - 5%
Freezer Shrinkage -5.8%
*Reg. Trade Mark : - 23 _ .. ..
~XAMPL~ 12 .
Component APercent by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers). 44.26 : Component BPercent by Wei~ht Polyol of Example 1 18 .4 0 Polyol of Example 3 5,70 Polyol of Example 3 containing the addition of 2% phosphoric acid (86%) by weight, based on the total weight : 10 of acid and polyol. 5.00 Polyoxypropylene(8) sorbitol6.54 Organo-silicone surfactant L-5340 0.60 N,N-dimethylcyclohexylamine0.70 Water 0.75 Trichlorofluoromethane (Freon llB) 18.00 Free Blown Panel Density - 1.31 pounds/cubic foot : Freezer Shrinkage - 1.45%
Packed Panel Density - 1.38 pounds/cubic foot Packing - 6%
Freezer Shrinkage - 1.43%
Component A Percent by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers). 42.61 *Reg. Trade Mark - 24 _ ~, .~
~34¢~
. ~omFon~nt ~Percent ~y ~eigh~
Polyol of Example 6 38.14 Organo-silicone surfactant L-5420 0~60 N,N-dimethylcyclohexylamine1.00 Water 0~75 Trichlorofluoromethane (Freon llB) 17.00 Free Blown Panel Density - 1.35 pounds/cubic foot ~reezer Shrinkage - 19%
acked Panel - Density - 1.46 pounds/cubic foot Packing - 8.5%
Freezer Shrinkage - 6.5%
EX~MPLE 14 Component A Percent by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4~ and 2,6- isomers). 42.52 Component B Percent by Weight Polyol of Example 6 38.03 Phosphoric Acid (86%) 0.20 : Organo-silicone surfactant L-5420 0.60 N,N-dimethylcyclohexylamine1.00 Water 0.75 Trichlorofluoromethane (Freon llB) 17.00 Free Blown Panel Density - 1.37 pounds/cubic foot Freezer Shrinkage - 10.1%
packed Panel Density - 1.51 pounds/cubic ~oot Packing - 10%
Freezer Shrinkage - 0%
*Reg. Trade Mark Component A Percent by Weight acconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6 isomers). 42.475 Component B Percent by Weight Polyol of Example 6 37.975 Phosphoric Acid (86%) 0.30 Organo-silicone surfactant L~5420 0.60 N,N-dimethylcyclohexylamine 1.00 Water 0-75 Trichlorofluoromethane (Freon lls) 17.00 Free Blown Panel Density - 1.36 pounds/cubic foot Freezer Shrinkage - 1.45%
Packed Panel Density - 1.485 pounds/cubic foot Packing _ 9%
Freezer Shrinkage - 0%
The following Examples 16 to 21jrepresent foams which were made by machine runs by the following process. The poly-ols were blended in a five-gallon container and the phosphoric acid, silicone surfactant, catalyst, and water were added to the polyol blend with stirring. The resulting blend was thoroughly mixed for about ten minutes at a temperature of about 72F. Chemical analysis of the resulting blend of poly-ols, phosphoric acid, surfactant, catalyst, and water confirm the formation of the desired phosphate salts of the polyoxy-alkylene amine based polyols utilized. Then the halogenated hydrocarbon blowing agent was incorporated in the polyol blend.
.~
*~eg. Trade Mark ~ 26 -. .
~L~ 4~
The above polyol blend ;5 descr~be~ here;na~ter as ~he ~
component. Then the B component and A component (which is the polyisocyanate) were loaded into two tanks on an Admiral Urethane Foam Machine (manufactured by Admiral Equipment Corporation, Akron, Ohio). The temperature of each component was adjusted to 70F and the correct ratio of A and s components was obtained by weighing a sample shot of material from the head or discharge opening in the foam machine without the mixer in place, Then the mixer was placed on the machine and ~oam was made at 26,8 pounds per minute at mixer speed of 6,000 rpm, The foam was poured into a 2 x 18 x 24 inch mould to free rise density, The top of the foam was then cut off level with the mould and the foam content of the mould weighed to determine the free rise density. For packed foams, approxi-mately 10% more of the mixture of the A and B components were added to the mould than normally used; and a tight cover was , placed over the mould. Then the foam was allowed to rise to fill the confined volume o~ the mould to give a 10%-packed foam.
The percent freezer shrinkage of the products of the following Examples 16 to 21 were determined by measuring the shrinkage of the moulded polyurethane foam in the 18-inch di-rection after exposure of the foam to -20F temperatures for 16 hours. In Examples 16 to 21 the percent of shrinkage con-sidered acceptable within the bounds of the present invention for "free blown foam panels" and "packed foam panels" under the immediately above-described testing procedure is the same as that stated above in relation to the "free blown foam panels"
and "packed panels" of Examples 7 to 15.
In the following Examples 16 to 21, all parts are by weight.
: EXAMPI~ 16 . . .
Component AParts by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers) 44.26 Component BParts by Weight Polyol of Example 1 18.40 Polyol of Example 3 10.60 Phosphoric Acid (86%) 0.10 Polyoxypropylene(8)-sorbitol6.59 Organo~silicone surfactant L-5340 (Union Carbide Co,) 0.60 N,N-dimethylcyclohexylamine0.70 : Water 0 75 Trichlorofluoromethane (Freon llB) 17.00 Free Blown Panel Density - 1.22 pounds/cubic foot Freeæer Shrinkage - 12.5%
Packed Panel Density - 1.33 pounds/cubic foot Freezer Shrinkage - 5.4%
Com~onent A Parts bv Weiqht : Nacconate* 5050 (commercial tolylene :: diisocyanate containing a mixture of 2,4- and 2,6- isomers). 45.73 Component BParts by Weight Polyol of Example 1 19.20 :~ Polyol of Example 3 11.02 Polyol of Example 6 6.85 :`
*Reg. Trade Mark Phosphoric Acid (86%) 0.15 Organo-silicone surfactan-t L-5340 0.60 N,N-dime-thylcyclohexylamine 0~70 Water 0075 Trichlorofluoromethane (Freon llB) 15.00 Free Blown Panel Density - 1.35 pounds/cubic foot Freezer Shrinkage - 10.1%
packe~ Panel Density - 1.5 pounds/cubic foot Freezer Shrinkage - 4.8%
Component A Parts by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers) 45.24 Component B Parts by Weight Polyol o~ Example l 18.94 Polyol of Example 3 10.75 Polyol of Example 6 6.77 Phosphoric Acid (86%) 0.25 organ!o~silicone surfactant L-5340 0.60 N,N-dimethylcyclohexylamine 0.70 Water 0.75 Trichlorofluoromethane (Freon llB)16.00 : Free Blown Panel Density - 1.3 pounds/cubic foot Freezer Shrinkage - 15.5%
Packed Panel Density - 1.45 pounds/cubic foot Freezer Shrinkage - 4.75%
*Reg. Trade Mark EXAlMPL~ ;~
Com~onent AParts by Wei~ht Hylene TIC (commercial tolylene diisocyanate containing a mixture ~: of 2,4- and 2,6- isomers) 45.24 Component BParts by Weight Polyol of Example 1 18.95 Polyol of Example 3 10.75 Polyol of Example 6 6.77 Phosphoric Acid (86%) Q.25 Organo-silicone surfactant L-5340 0.60 N,N-dimethylcyclohexylamine0.70 Water 0~75 Trichlorofluoromethane (Freon 11B1 16.00 Free Blown Panel Density - 1.36 pounds/cubic foot Freezer Shrinkage - 9.0%
Packed Panel_ Density - 1.45 pounds/cubic ~oot Freezer Shrinkage - 5.6%
Component A Parts by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers) 44.82 Component B Parts b~ Weight . , : Polyol of Example 5 26.31 ~ Polyol of Example 2 11.27 ,:
: Phosphoric Ac.id (86%) 0.25 Organo-silicone surfactant L-5340 0.60 N,N-dimethylcyclohexylamine1.00 Water 0.75 Trichlorofluoromethane (Freon llB) 15.00 ` *Reg. ~rade Mark ~f~
Free Blown Panel Density - 1.32 pounds/cubic foot Freezer Shrinka ge - 14 .1%
; Packed Panel Density - 1.45 pounds/cubic foot ~reezer Shrinkage - 4.5%
EXAMPLE ~1 Component A Parts b~ Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers) 45.01 Component B Parts by Weight Polyol of Example 4 26 45 Polyol oE Example 2 11.34 Phosphoric Acid (86%) 0.25 Organo-silicone surfactant L-5340 0.60 ; N,N-dimethylcyclohexylamine 0.60 Water 0.75 Txichloro~luoromethane (Freo~ llB) 15.00 Free Blown Panel Density - 1.48 pounds/cubic foot ~reezer Shrinkage -9.6%
Packed Panel ; Density - 1.59 pounds/cubic foot . Freezer Shrinkage -3,9%
Having descrihed the invention, what is desired to be secured by Letters Patent is:
*R~g. Trade Mark - 31 -
to 115C/40 to 50 psig. The reaction mixture was maintained at this temperature and stirred until the pressure was sub-stantially zero for 30 minutes. The resulting produc-t was then deodorized by vacuum stripping for 15 minutes at about C. When the tempera-ture of the product was about 105C, 0.988% by weight of phosphoric acid (85%) was added to the reaction mixture which was then stirred for about 30 minutes.
The resulting mixture was then vacuum stripped at about 100C
under vacuum of about 50 millimeters of mercury until the water content was less than 0.05%. 0.1% of a hindered phenol anti-oxidant was then added to the resulting polyol product and thoroughly agitated therein and then the result-ing product was filtered through paper to yield a polyol blend consisting of polyoxypropylene monoethanolamine and polyoxypropylene sucrose having a hydroxyl number of 408, water content of 0.18%, and acid number of 2.00. The polyol product had a viscosity of 4,030 centipoises at 25C.
In the following Examples 8, 9, 11, 12, 14, and 15, polyurethane foams were prepared usin~ novel phosphate salt amine based polyols of the present invention. Examples :
7 and 10 are controls for Examples 8, 9, 11, and 12, and Example 13 is the control for Examples 14 and 15. The foams ;` of Examples 7 to 15 were prepared using the following hand-. 20 mixing procedure.
Hand-Mixing Procedure The polyols were weighed into a 12-ounce uncoated paper cup. Those polyols having phosphoric acid added thereto to prepare the novel phosphate salts of the amine based polyols were first heated to about 120F along with the added phospho-ric acid under mechanical agitation for about 20 minutes in order to eEfect the preparation of the desired phosphate salts of -the amine based polyols. Chemical analysis confirmed the ~ormation of the said phosphate salts of the amine based polyols.
~:~4~8~
The other B component ingredients were then added ln the order listed from top to bottom, each being weighed into the cup until all the ingredients were added except the isocyanate. These were then mixed with a conventional laboratory electric stirrer at approximately 1,500 rpm until homogenous. The weight was then rechecked and any halo-genated hydrocarbon blowing agent loss was made up by adding back the weight lost. This mixture constitutes what is referred to as B component in the listing of ingredients under each example. The isocyanate (referred to as the A com-ponent) is then added rapidly to the cup (s compenent) and the total foam ingredients were mixed for ten seconds with the previousl~ mentioned mixer. The resulting mixture is then poured rapidly into a mould. The mould utilized was a metal mould, two inches by seven inches b~ twelve inches, inside dimensions. The foam was allowed to rise in the twelve-inch direction. The "free blown foam panels" were made with the top of the mould open, and the "packed foam panels" were made with the top closed. The percent packing was calculated by using the formula:
Weight Packed Foam Panel Minus Weight Free Blown Foam Panel X 100 = Percent Weight Free Blown Foam Panel Packing The percent freezer shrinkage of the products of the following Examples 7 to 15 were determined by measuring the shrinkage of the moulded polyurethane foam in the seven-inch direction af-ter exposure of the foam to -20F tempera-ture for 16 hours. For most commercial uses it is preferred that "free blown foam panels" should have a shrinkage less than 10% under the above-stated testing procedure; whereas ~46~8 ~ c~d ~o~m panels 3~0uld hava a shrin~a~e ~elow 3,' un~e~
the same ~est conditions. However, "free blown foam panels"
which exhibit a shrinkage less than 20% and "packed foam panels"
~:xhibiting a shrinkage less than 15% under the above-stated testing procedure are also within the bounds of the present invention inasmuch as such products can be utilized in areas and uses when the thermal conditions are not quite so severe.
Component APercent by Weight Nacconate* 5050 (commercial ~olylene ~ diisocyanate containing a mixture of 80% ~,4- and 20% 2-,-6- isomers). 44.26 Component BPercent ~y Weight Polyol of Example 1 25,00 Polyol of Example 3 6.74 ~l)~ethylene oxide-(3)-propylene oxide ethylene diamine 3.95 : Oxgano-silicone sur~actant L-5340 ~Unlon Carbide Co.). 0.60 M,N-dimethylcyclohexylamine0.70 : Water 0.75 Trichlorofluoromethane (Freon llB) 18.00 Free Blown Panel Density - 1.23 pounds/cubic foot Freezer Shrinkage - 27.0%
Packed Panel Density - 1.38 pounds/cubic foot Packing - 12%
~ree~er ShrinXage - 22.9 %
*Reg. Trade Mark ~p~
~XA~PLE ~
Component APercent by Weight Nacconate* 5050 (commerclal tolylene diisocyanate containing a mix~ure of 2,4- and 2,6- isomers). 44.26 Component BPercent by Weight : Polyol of Example 1 25.00 Polyol of Example 3 1.74 Polyol of Example 3 containing the addition of 1% phosphoric acid (86%) by weight, based on the total weight of acid and polyol. 5.00 (l)~ethylene oxide-(3)-propylene oxide ethylenediamine 3.95 Organo-silicone surfactant L-5340 0.60 N,N-dimethylcyclohexylamine0,70 Water 0.75 Trichlorofluoromethane (Freon llB) 18.00 Eree Blown Panel Density - 1.27 pounds/cubic foot Freezer Shrinkage - 17.4%
Packed Panel Density - 1.41 pounds/cubic foot packing - 10%
Freezer Shrinkage - 11.7%
Component A Percent by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers). 44.26 Component B Percent by Weight Polyol of Example 1 25.00 Polyol of Example 3 1.74 *Reg. Trade Mark _ 21 -Component B (con~.\p~rcent by W2ight (~o~`
Polyol of Example 3 containing the addition of 2% phosphoric acid (86%) by weight, based on the total weight of acid and polyol. 5.00 (l)-ethylene oxide-(3)-propylene : oxide ethylenediamine 3.95 Organo-silicone surfactant L-5340 0.60 ~,N-dimethylcyclohexylamine 0.70 Water 0 75 Trichlorofluoromethane (Freon llB) 18.00 Eree slown Panel Density - 1.30 pounds/cubic foot Freezer Shrinkage - 10.1%
packed Pane DenRity - 1.41 pounds/cubic foot :; Packing - 8%
Freeæer Shrinkage - 2.15%
EX~MPLE 10 Component A Percent by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers). 44.26 Component B Percent by Weight Polyol o~ Example 1 18.40 Polyol of Example 3 10.70 Polyoxypxopylene(8)sorbitol 6.59 Organo-silicone surfactant L-5340 (Union Carbide Co.) 0.60 N,N-dimethylcyclohexylamine 0.70 Water 0 75 Trichlorofluoromethane (Freon llB) 8.00 *Reg. Trade Mark ~6~4~ 8 Free Blown Panel Density - 1.23 pounds/eubic foot Freezer Shrinkage - 38.2%
P~cked Panel Density - 1.38 pounds/cubie ~oot Packing - 12%
Freezing Shrinkage - 24.3%
Component A Percent by Weight Naeeonate* 5050 (commercial tolylene , diisocyanate containing a mixture of 2,4- and 2,6~ isomers). 44~26 Component B Pereent by Weight Polyol of Example 1 18.4 Polyol of Example 3 5,70 Polyol of Example 3 eontaining the addition o~ 1% phosphorie aeid (86%) by weight, based on the total weight o~ aeid and polyol . 5 ~ 00 Polyoxypropylene~8)sorbitol 6.59 Organo-silieone surfactant L-5340 (Union Carbide Co.) 0.60 N,N-dimethyleyelohexylamine 0.70 Water 0- 75 Triehlorofluoromethane (Freon 11B) 18.00 Free Blown Panel Density - 1.28 pounds/cubic foot Freezer Shrinkage - 11.6%
Packed Panel Density - 1.34 pounds/eubie foot Packing - 5%
Freezer Shrinkage -5.8%
*Reg. Trade Mark : - 23 _ .. ..
~XAMPL~ 12 .
Component APercent by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers). 44.26 : Component BPercent by Wei~ht Polyol of Example 1 18 .4 0 Polyol of Example 3 5,70 Polyol of Example 3 containing the addition of 2% phosphoric acid (86%) by weight, based on the total weight : 10 of acid and polyol. 5.00 Polyoxypropylene(8) sorbitol6.54 Organo-silicone surfactant L-5340 0.60 N,N-dimethylcyclohexylamine0.70 Water 0.75 Trichlorofluoromethane (Freon llB) 18.00 Free Blown Panel Density - 1.31 pounds/cubic foot : Freezer Shrinkage - 1.45%
Packed Panel Density - 1.38 pounds/cubic foot Packing - 6%
Freezer Shrinkage - 1.43%
Component A Percent by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers). 42.61 *Reg. Trade Mark - 24 _ ~, .~
~34¢~
. ~omFon~nt ~Percent ~y ~eigh~
Polyol of Example 6 38.14 Organo-silicone surfactant L-5420 0~60 N,N-dimethylcyclohexylamine1.00 Water 0~75 Trichlorofluoromethane (Freon llB) 17.00 Free Blown Panel Density - 1.35 pounds/cubic foot ~reezer Shrinkage - 19%
acked Panel - Density - 1.46 pounds/cubic foot Packing - 8.5%
Freezer Shrinkage - 6.5%
EX~MPLE 14 Component A Percent by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4~ and 2,6- isomers). 42.52 Component B Percent by Weight Polyol of Example 6 38.03 Phosphoric Acid (86%) 0.20 : Organo-silicone surfactant L-5420 0.60 N,N-dimethylcyclohexylamine1.00 Water 0.75 Trichlorofluoromethane (Freon llB) 17.00 Free Blown Panel Density - 1.37 pounds/cubic foot Freezer Shrinkage - 10.1%
packed Panel Density - 1.51 pounds/cubic ~oot Packing - 10%
Freezer Shrinkage - 0%
*Reg. Trade Mark Component A Percent by Weight acconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6 isomers). 42.475 Component B Percent by Weight Polyol of Example 6 37.975 Phosphoric Acid (86%) 0.30 Organo-silicone surfactant L~5420 0.60 N,N-dimethylcyclohexylamine 1.00 Water 0-75 Trichlorofluoromethane (Freon lls) 17.00 Free Blown Panel Density - 1.36 pounds/cubic foot Freezer Shrinkage - 1.45%
Packed Panel Density - 1.485 pounds/cubic foot Packing _ 9%
Freezer Shrinkage - 0%
The following Examples 16 to 21jrepresent foams which were made by machine runs by the following process. The poly-ols were blended in a five-gallon container and the phosphoric acid, silicone surfactant, catalyst, and water were added to the polyol blend with stirring. The resulting blend was thoroughly mixed for about ten minutes at a temperature of about 72F. Chemical analysis of the resulting blend of poly-ols, phosphoric acid, surfactant, catalyst, and water confirm the formation of the desired phosphate salts of the polyoxy-alkylene amine based polyols utilized. Then the halogenated hydrocarbon blowing agent was incorporated in the polyol blend.
.~
*~eg. Trade Mark ~ 26 -. .
~L~ 4~
The above polyol blend ;5 descr~be~ here;na~ter as ~he ~
component. Then the B component and A component (which is the polyisocyanate) were loaded into two tanks on an Admiral Urethane Foam Machine (manufactured by Admiral Equipment Corporation, Akron, Ohio). The temperature of each component was adjusted to 70F and the correct ratio of A and s components was obtained by weighing a sample shot of material from the head or discharge opening in the foam machine without the mixer in place, Then the mixer was placed on the machine and ~oam was made at 26,8 pounds per minute at mixer speed of 6,000 rpm, The foam was poured into a 2 x 18 x 24 inch mould to free rise density, The top of the foam was then cut off level with the mould and the foam content of the mould weighed to determine the free rise density. For packed foams, approxi-mately 10% more of the mixture of the A and B components were added to the mould than normally used; and a tight cover was , placed over the mould. Then the foam was allowed to rise to fill the confined volume o~ the mould to give a 10%-packed foam.
The percent freezer shrinkage of the products of the following Examples 16 to 21 were determined by measuring the shrinkage of the moulded polyurethane foam in the 18-inch di-rection after exposure of the foam to -20F temperatures for 16 hours. In Examples 16 to 21 the percent of shrinkage con-sidered acceptable within the bounds of the present invention for "free blown foam panels" and "packed foam panels" under the immediately above-described testing procedure is the same as that stated above in relation to the "free blown foam panels"
and "packed panels" of Examples 7 to 15.
In the following Examples 16 to 21, all parts are by weight.
: EXAMPI~ 16 . . .
Component AParts by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers) 44.26 Component BParts by Weight Polyol of Example 1 18.40 Polyol of Example 3 10.60 Phosphoric Acid (86%) 0.10 Polyoxypropylene(8)-sorbitol6.59 Organo~silicone surfactant L-5340 (Union Carbide Co,) 0.60 N,N-dimethylcyclohexylamine0.70 : Water 0 75 Trichlorofluoromethane (Freon llB) 17.00 Free Blown Panel Density - 1.22 pounds/cubic foot Freeæer Shrinkage - 12.5%
Packed Panel Density - 1.33 pounds/cubic foot Freezer Shrinkage - 5.4%
Com~onent A Parts bv Weiqht : Nacconate* 5050 (commercial tolylene :: diisocyanate containing a mixture of 2,4- and 2,6- isomers). 45.73 Component BParts by Weight Polyol of Example 1 19.20 :~ Polyol of Example 3 11.02 Polyol of Example 6 6.85 :`
*Reg. Trade Mark Phosphoric Acid (86%) 0.15 Organo-silicone surfactan-t L-5340 0.60 N,N-dime-thylcyclohexylamine 0~70 Water 0075 Trichlorofluoromethane (Freon llB) 15.00 Free Blown Panel Density - 1.35 pounds/cubic foot Freezer Shrinkage - 10.1%
packe~ Panel Density - 1.5 pounds/cubic foot Freezer Shrinkage - 4.8%
Component A Parts by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers) 45.24 Component B Parts by Weight Polyol o~ Example l 18.94 Polyol of Example 3 10.75 Polyol of Example 6 6.77 Phosphoric Acid (86%) 0.25 organ!o~silicone surfactant L-5340 0.60 N,N-dimethylcyclohexylamine 0.70 Water 0.75 Trichlorofluoromethane (Freon llB)16.00 : Free Blown Panel Density - 1.3 pounds/cubic foot Freezer Shrinkage - 15.5%
Packed Panel Density - 1.45 pounds/cubic foot Freezer Shrinkage - 4.75%
*Reg. Trade Mark EXAlMPL~ ;~
Com~onent AParts by Wei~ht Hylene TIC (commercial tolylene diisocyanate containing a mixture ~: of 2,4- and 2,6- isomers) 45.24 Component BParts by Weight Polyol of Example 1 18.95 Polyol of Example 3 10.75 Polyol of Example 6 6.77 Phosphoric Acid (86%) Q.25 Organo-silicone surfactant L-5340 0.60 N,N-dimethylcyclohexylamine0.70 Water 0~75 Trichlorofluoromethane (Freon 11B1 16.00 Free Blown Panel Density - 1.36 pounds/cubic foot Freezer Shrinkage - 9.0%
Packed Panel_ Density - 1.45 pounds/cubic ~oot Freezer Shrinkage - 5.6%
Component A Parts by Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers) 44.82 Component B Parts b~ Weight . , : Polyol of Example 5 26.31 ~ Polyol of Example 2 11.27 ,:
: Phosphoric Ac.id (86%) 0.25 Organo-silicone surfactant L-5340 0.60 N,N-dimethylcyclohexylamine1.00 Water 0.75 Trichlorofluoromethane (Freon llB) 15.00 ` *Reg. ~rade Mark ~f~
Free Blown Panel Density - 1.32 pounds/cubic foot Freezer Shrinka ge - 14 .1%
; Packed Panel Density - 1.45 pounds/cubic foot ~reezer Shrinkage - 4.5%
EXAMPLE ~1 Component A Parts b~ Weight Nacconate* 5050 (commercial tolylene diisocyanate containing a mixture of 2,4- and 2,6- isomers) 45.01 Component B Parts by Weight Polyol of Example 4 26 45 Polyol oE Example 2 11.34 Phosphoric Acid (86%) 0.25 Organo-silicone surfactant L-5340 0.60 ; N,N-dimethylcyclohexylamine 0.60 Water 0.75 Txichloro~luoromethane (Freo~ llB) 15.00 Free Blown Panel Density - 1.48 pounds/cubic foot ~reezer Shrinkage -9.6%
Packed Panel ; Density - 1.59 pounds/cubic foot . Freezer Shrinkage -3,9%
Having descrihed the invention, what is desired to be secured by Letters Patent is:
*R~g. Trade Mark - 31 -
Claims (7)
1 A polyol composition represented by the formulas:
(a) and (b) wherein R" is selected from the group consisting of alkylene groups containing from 1 to 20 carbon atoms, and R is independently selected from the group consisting of alkylene groups containing from 1 to 6 carbon atoms, Q is independently selected from the group consisting of hydrogen and -(OR')yH, R' is independently selected from the group consisting of alkylene groups containing from 2 to 5 carbon atoms, y is a number of from 1 to 20, x is a number of from
1 to 20, z represents a number having an average value of 3 and m and p are independently selected values of 0 or 1 with the proviso that at least m or p is 1, n has a value of from 0.03 to 0.5, t has a value of 0.03 to 1.0 when the amine represented by formula (b) is a diamine and a value of 0.05 to 1.5 and 0.05 to 2.0 when the amine represented by formula (b) is a triamine and tetramine, respectively.
2. A polyol composition of Claim 1 comprised of a phosphate salt of polyoxyalkylene ethylenediamine containing an average of 4 to 20 oxyalkylene groups per mol of ethylene-diamine
3. A polyol composition of Claim 1 comprised of a phosphate salt of polyoxyethylene ethylenediamine containing an average of 4 to 8 ethylene oxide groups per mol of ethylene-diamine.
4. A polyol composition of Claim 1 comprised of a phosphate salt of polyoxypropylene ethylenediamine containing an average of from 4 to 8 propylene oxide groups per mol of ethylenediamine.
5. A polyol composition of Claim 1 comprised of a phosphate salt of polyoxypropylene monoethanolamine containing an average of 3 to 8 propylene oxide groups per mol of mono-ethanolamine.
6. A polyol composition of Claim 1 comprised of a phosphate salt of polyoxypropylene diethylenetriamine containing an average of from 5 to 9 propylene oxide groups per mol of diethylenetriamine.
7, A polyol composition of Claim 1 comprised of a phosphate salt of polyoxypropylene triethanolamine containing an average of 3 to 8 propylene oxide groups per mol of tri-ethanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA202,898A CA1040188A (en) | 1974-06-18 | 1974-06-18 | Phosphate salt of amine based polyol and low density polyurethane foams |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA202,898A CA1040188A (en) | 1974-06-18 | 1974-06-18 | Phosphate salt of amine based polyol and low density polyurethane foams |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1040188A true CA1040188A (en) | 1978-10-10 |
Family
ID=4100435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA202,898A Expired CA1040188A (en) | 1974-06-18 | 1974-06-18 | Phosphate salt of amine based polyol and low density polyurethane foams |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1040188A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117327251A (en) * | 2023-12-01 | 2024-01-02 | 山东一诺威聚氨酯股份有限公司 | High-strength flame-retardant polyurethane rigid foam and preparation method thereof |
-
1974
- 1974-06-18 CA CA202,898A patent/CA1040188A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117327251A (en) * | 2023-12-01 | 2024-01-02 | 山东一诺威聚氨酯股份有限公司 | High-strength flame-retardant polyurethane rigid foam and preparation method thereof |
| CN117327251B (en) * | 2023-12-01 | 2024-04-12 | 山东一诺威聚氨酯股份有限公司 | High-strength flame-retardant polyurethane rigid foam and preparation method thereof |
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