GB1569319A

GB1569319A – Organosilicone polymers
– Google Patents

GB1569319A – Organosilicone polymers
– Google Patents
Organosilicone polymers

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Publication number
GB1569319A

GB1569319A
GB54166/76A
GB5416676A
GB1569319A
GB 1569319 A
GB1569319 A
GB 1569319A
GB 54166/76 A
GB54166/76 A
GB 54166/76A
GB 5416676 A
GB5416676 A
GB 5416676A
GB 1569319 A
GB1569319 A
GB 1569319A
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Prior art keywords
groups
average
copolymer
molecular weight
weight
Prior art date
1975-12-29
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GB54166/76A
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Union Carbide Corp

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Union Carbide Corp
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1975-12-29
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1976-12-24
Publication date
1980-06-11

1976-12-24
Application filed by Union Carbide Corp
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Union Carbide Corp

1980-06-11
Publication of GB1569319A
publication
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patent/GB1569319A/en

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Classifications

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H

C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof

C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule

C08G77/42—Block-or graft-polymers containing polysiloxane sequences

C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H

C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers

C08J2375/04—Polyurethanes

C08J2375/08—Polyurethanes from polyethers

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H

C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers

Description

PATENT SPECIFICATION ( 11) 15 (
M ( 21) Application No 54166 i 76 ( 22) Filed 24 Dec 1976 ó ( 31) Convention Application No644 838 ( 19) A ( 32) Filed 29 Dec 1975 in ( 33) United States of America (US) b C ( 44) Complete Specification published 11 June 1980
MI ( 51) INT CL 3 CO 8 G 77/46, 18/14 ( 52) Index at acceptance C 3 T 6 D 1 A 6 D 4 B 6 D 6 6 F 2 6 G 10 6 G 3 A 6 G 7 G 6 G 9 B C 3 R 32 B 1 A 32 BIB 32 B 1 X 32 B 2 A 2 32 B 3 B 32 D 6 J 32 D 6 K 32 D 6 L 32 E 1 32 E 2 A 32 E 2 Y 32 E 7 A 32 E 7 Y 32 G 1 Y 32 H 10 32 H 1 32 H 2 32 H 3 32 H 9 A 32 H 9 B 32 H 9 C 32 J 10 32 J 1 A 32 J 1 X 32 JIY 32 J 2 E 32 J 2 F 32 J 2 X 32 J 2 Y 32 J 3 A 32 J 3 B 32 J 3 Y 32 KG ( 54) ORGANOSILICONE POLYMERS ( 71) We, UNION CARBIDE CORPORATION, a Corporation organised and existing under the laws of the State of New York, United States of America, of 270 Park Avenue, New York, State of New York 10017, Uaited States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:-
The present invention relates to organosilicone polymers and their use in the manufacture of urethane cellular products, particularly flexible polyether polyolbased urethane foams.
It is well known that the urethane linkages of urethane foams are formed by the exothermic reaction of a polyfunctional isocyanate and a polyfunctional active hydrogen-containing compound in the presence of a catalyst, and that the cellular structure of the foam is provided by gas evolution and expansion during the urethane-forming reaction In accordance with the «one-shot process» which is the most widely used industrial technique, direct reaction is effected between all of the raw materials which include the polyisocyanate, the active hydrogencontaining compound, the catalyst system, blowing agent and surfactant A major function of the surfactant is to stabilize the urethane foam, that is, prevent collapse of the foam until the foamed product has developed sufficient gel strength to become selfsupporting.
Although certain techniques of urethane manufacture such as the «one-shot process» and certain components of the foam formulation such as the polyisocyanates, amine catalyst and blowing agent, are generally useful, a specific problem associated with the production of a particular type of urethane foam and the solution thereto are often peculiar to the chemical and physical structure of the desired foamed product In particular, the efficacy of the foam stabilizer is usually selective with respect to the formation of a particular type of foam One factor to be considered in the evaluation of stabilizing efficacy is surfactant potency which is reflected by two types of measurements One is the measured original height to which the foam rises as it is being formed From this standpoint, the greater the foam rise, the more potent is the surfactant The second potency measurement is concerned with the ability of the surfactant to maintain the original height of the foam once it has formed Foams produced with surfactants which have good potency in this second request undergo a minimum of settling or «top collapse» which may otherwise contribute to split formation and other foam defects.
It is also desirable that the foam stabilizer have good processing latitude, that is, ability to provide foams of satisfactory quality over a relatively wide range of operating variables such as, for example, concentration of surfactant and metal cocatalysts which are normally employed in the manufacture of flexible polyetherbased foams The more common co-catalysts are organic derivatives of tin and thus sensitivity to variation in co-catalyst concentration is more particularly referred to in the art as «tin operating latitude » Decreasing the concentration of these cocatalysts below normal levels is sometimes necessary to improve breathability of the foam but, if the effectiveness of the foam stabilizer is narrowly dependent on 9319 co-catalyst concentration (that is, its tin operating latitude is poor), the desired enhanced breathability may be offset by foam weakness due to split formation.
The search for improved surfactants for stabilization of polyurethane foams is further complicated by the tendency of these foams to ignite readily and burn and the need to reduce their flammability This characteristic is particularly 5 objectionable in the case of flexible polyurethane foams in view of the use of these foams in many applications where fire is especially hazardous such as their use in automotive seat cushions and household furniture cushioning One approach to reducing flammability of flexible foams is to include a flame-retarding agent such as various phosphorus and/or halogen-containing compounds as a component of 10 the foam-producing reaction mixture It is found, however, that surfactants which may otherwise be effective stabilizers of non-flame-retarded foams, may be deficient as stabilizers of foams containing a flame retardant It is also desirable that the siloxane surfactant possess a good combination of potency and processing latitude in the stabilization of flexible polyether urethane foams Thus, there is still 15 room in the art for improved organosilicone foam stabilizers.
In accordance with the present invention there is provided a polysiloxanepolyoxyalkylene block copolymer having the following empirical average formula:(R Si)t{(O Si R 2)wlO Si R(R’)l,lO(C H 2 n O)p R 2 lv(OR 4),_v} (I) 20 t+ 2 wherein:
R is a monovalent hydrocarbon radical having from I to 10 carbon atoms; R’ is a cyano-substituted radical of the formula-+O)a R 3 CN wherein R 3 is a bivalent alkylene radical containing from 2 to 6 carbon atoms or a bivalent alkyleneoxyalkylene radical containing from 4 to 12 carbon atoms, and a has a 25 value of 0 or 1; R 2 is a monovalent hydrocarbon radical containing from I to 12 carbon atoms; R 4 is an alkyl group containing from I to 10 carbon atoms; t for an individual molecule has an integral value of between 0 and 6, with an average non-integral value for the averaged co-polymer of from 0 8 to 4, preferably 30 from 0 8 to 2; w has an average value of from 3 to 100, preferably from 9 to 40; z has an average value of from 3 to 20, preferably from 3 to 15; n has a value of from 2 to 4 provided that from 20 to 65 weight percent of the oxyalkylene units of the polyoxyalkylene chain, (Cn H 2 n O)p, is composed of 35 oxyethylene units; p has an average value such that the average molecular weight of the polyoxyalkylene chain is from 800 to 6000, and is preferably no more than 4,000; and v has an average value of from U 8 to 1.
In addition to the aforesaid class of organo-silicone polymers, the present 40 invention also provides a process for producing a flexible polyether polyurethane foam which comprises reacting and foaming a reaction mixture of: (a) a polyether polyol reactant containing an average of at least two hydroxyl groups per molecule; (b) a polyisocyanate reactant containing at least two isocyanato groups per molecule; (c) a blowing agent; (d) a catalyst comprising an amine; (e) a co-catalyst 45 comprising an organic derivative of a polyvalent metal such as tin; and (f) a foam stabilizer comprising at least one polysiloxane-polyoxyalkylene block copolymer of this invention In addition to their efficacy as stabilizers of polyetherbased urethane foams, it has been found that the organosilicone polymers of this invention possess the further advantageous property of allowing for the formation 50 of flame-retarded foams containing a flame retardant of acceptable overall quality.
In accordance with this aspect of the present invention, flexible polyether-based urethane foams containing a flame retardant agent are provided by reacting and foaming reaction mixtures which also include a silicon-free, flameretardant agent.
In providing either the foams that are free of a flame retardant agent or the 55 foams containing a flame retardant agent, the organo-silicone polymers encompassed by Formula I above may be introduced to the foam-producing reaction mixtures either as such, in diluted form or preblended with one or more of the polyether polyol reactant, blowing agent, amine catalyst or flame retardant agent 60 The organosilicone polymer surfactants of this invention, as depicted by Formula I above, are polysiloxane-polyoxyalkylene block copolymers wherein the 1.569 319 olysiloxane and polyoxyalkylene blocks are linked through a silicon-tooxygen ond Thus from the standpoint of the nature of the linkage by which the blocks are joined, the copolymers of Formula I are hydrolyzable Although the monovalent hydrocarbon groups represented by R are bonded to silicon through Si-C linkages, the cyano-substituted groups, R’, may be bonded to silicon through either a silicon 5 to-carbon bond, -R 3 CN, or a silicon-to-oxygen bond -O-R 3-CN Thus, the organosilicone polymers of this invention may be ( 1) hydrolyzable with respect to both the polyoxyalkylene block and cyano-substituted groups, or as is more preferred ( 2) hydrolyzable with respect to the polyoxyalkylene block and nonhydrolyzable with respect to the cyano-substituted groups (i e, Si-R 3 CN) 10 The monovalent hydrocarbon groups (R of Formula I above) may contain from I to 10 carbon atoms and may each be for example an alkyl, aryl, e g phenyl, alkenyl or aralkyl radical Preferably R represents an alkyl radical, including linear and branched chain radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tbutyl, pentyl, hexyl, octyl, and decyl groups More preferred are the lower alkyl 15 radicals (that is, those having from one to four carbon atoms of which the methyl group is especially preferred) It is to be understood that the R groups may be the same throughout the polymer or they may differ as between or within units without departing from the scope of this invention.
In the silicon-bonded, cyano-substituted groups of Formula I above, when a is 20 0, R’ is -R 3 CN and when N is one, R’ is -O-R 3 CN where R 3 represents a bivalent alkylene radical including linear and branched radicals of the series Cc H 2 or bivalent alkyleneoxyalkylene radicals including linear and branched radicals of the series -Cc H 2 c-O Cc H 2 c where c has a value of from 2 to 6.
Examples of suitable groups represented by R 3 are ethylene, -CH 2 CH 2-; 25 propylene or trimethylene, (-CH 2 CH 2 CH 2-); isopropylene, l-CH 2 CH(CH 3)-l; tetramethylene and higher homologues to hexamethylene l (CH 2), l, as well as ethyleneoxyethylene (-CH 2 CH 2 OCH 2 CH 2-); propyleneoxyethylene l (CH 2)30 (CH 2)2-l; and higher alkyleneoxyalkylene homologues to l-(C Ha)e O(CH 2) -l Preferably a has a value of zero and the R 3 groups are usually 30 lower alkylene groups containing from two to four carbon atoms or lower alkyleneoxyalkylene groups containing from four to eight carbon atoms More preferably R 3 is a lower alkylene radical, especially a propylene, (-CH 2 CH 2 CH 2) group It is to be understood that the cyano-substituted R’ groups may be the same or different throughout the polymer and that the polymer may contain any 35 combination of cyanoalkyl (NC-R 3-) and cyanoalkyoxy (NC-R 3-O-) substituted siloxy units Likewise, it is understood that the polymers may contain any combination of cyano-substituted groups wherein R 3 of these groups are the same or different.
The average molecular weight of the polyoxyalkylene chain represented by 40 (C Hn O-)p in Formula I above, ranges from 800 to 6000 and from 20 to 65 weight percent thereof is composed of oxyethylene units The remainder of the polyoxyalkylene chain is usually formed of oxypropylene, oxybutylene or a combination of these units, although preferably the remainder is oxypropylene The preferred polyoxyalkylene blocks of the polymer of Formula I above have the formula, 45 R 2 O(C 3 He O)y(C H 4 O) wherein x and y have average values such that the average molecular weight of the polyoxyalkylene chain (C 3 H,,O)(C 2 H 40) is within the aforesaid range of 800 to 6000, and from 20 to 65 weight percent of the polyoxyalkylene chain is composed of oxyethylene units It is of course, understood that the oxyethylene and other oxyalkylene units may be randomly distributed 50 throughout the polyoxyalkylene chain such as when a mixture of alkylene oxides is polymerized or they can be arranged in respective sub-blocks such as when the respective alkylene oxides are polymerized sequentially, provided that the total average content of (C 2 H 40) in the chain is within the aforesaid range.
Accordingly the formulae employed herein to represent the polyoxyalkylene 55 chains and polyoxyalkylene blocks are intended to encompass both of these types of polyoxyalkylene chains and are not to be interpreted as merely being specifically directed to one of either of the two aforesaid types of oxyalkylene arrangements It is of course to be further understood that the organosilicone polymers of this invention may contain polyoxyalkylene chains of basically one type, e g a poly 60 oxyalkylene chain having essentially one average molecular weight or contain an admixture of two or more polyoxyalkylene chains, e g a polyoxyalkylene chain having a low average molecular weight and a polyoxyalkylene chain having a high average molecular weight.
Thus, a preferred embodiment of the polymers encompassed by Formula I are 65 1,569,319 those wherein the polyoxvalkylene block, -(OC H 2 n)p OR 2 is comprised of an admixture of Units X and Y of the formula, R 20 (C 3 H 80)Y(C 2 H 40)x wherein x and y’ are determined by the following conditions prevailing for Units X and Y:
Unit X represents from 50 to 95 weight percent, based on the total weight of Units X and Y in the admixture thereof, of low molecular weight poly(oxy 5 ethyleneoxypropylene) copolymers having an average molecular weight from 800 to 3000 and wherein from 20 to 65 weight percent of the oxyalkylene groups are oxyethylene groups, the remainder of the oxyalkylene groups being oxypropylene groups; Unit Y represents from 50 to 5 weight percent, based on the total weight of 10 Units X and Y in the admixture thereof, of a higher molecular weight poly(oxvethylene-oxypropylene) copolymer having an average molecular weight from 1600 to 6000 and wherein from 20 to 65 weight percent of the oxyalkylene groups are oxyethylene groups, the remainder of the oxyalkylene groups being oxypropylene groups: provided that the said admixture of Units X and Y has an average 15 molecular weight no higher than 6000.
In a further preferred embodiment of the admixture of Units X and Y, Unit X represents from 60 to 90 weight percent of low molecular weight poly(oxyethylene-oxypropylene) copolymer having an average molecular weight from 1400 to 2500, and Unit Y comprises from 40 to 10 weight percent of higher molecular 20 weight poly(oxyethylene-oxypropylene) copolymers having an average molecular weight from 2500 to 3500, and the average molecular weight of the admixture is no higher than 4000, the oxyethvlene c’ntent of respective Units X and Y being as aforesaid Most preferably, the average molecular weight of Unit X is no higher than 2200 The most preferred polyoxyalkylene block admixture consists 25 essentially of about 78 percent by weight of C 4 H 90 (C 2 H,40)8,4 (C 3 H 10)14 and about 22 percent by weight of C 4 H,(C 2 H 40)32,(C 3 H 80)243 As further indicated by the above Formula I, the polyoxyalkylene chain, (CH 2 n O), is terminated by R 2 which represents a monovalent hydrocarbon radical containing from I to 12 carbon atoms and is usually free of aliphatic 30 unsaturation Examples of these R 2 radicals are alkyl groups including linear and branched chain alkyl groups having the formula, Cf H 2 f,,-, whereinf is an integer from I to 12, such as, for example, methyl, ethyl, n-propyl, isopropyl, nbutyl, octyl and dodecyl groups; a cycloaliphatic radical including monocyclic and bicyclic groups such as, for example, cyclopentyl, cyclohexyl and bicyclol 2 2 1 lheptyl 35 groups; an aromatically unsaturated group including aryl, alkaryl and aralkyl radicals such as, for example, phenyl, naphthyl, xylyl, tolyl, cumenyl, mesityl, tbutylphenyl benzyl, beta-phenylethyl and 2-phenylpropyl groups: and alkyl and aryl substituted cycloaliphatic radicals such as, for example, methylcyclopentyl and phenylcyclohexyl radicals It is evident, therefore, that the polyoxyalkylene 40 chain is end-blocked with a terminal ( OR 2) group which may be an alkoxy, aryloxy, aralkoxy, alkaryloxy, or cycloalkoxy group It is to be understood that the terminal group of the respective polyoxyalkylene blocks of the polymers of this invention may be the same throughout the polymer or may differ.
The generally preferred R 2 groups are phenyl, lower alkyl radicals, the lower 45 alkyl-substituted aryl groups and the aryl-substituted lower alkyl groups, wherein the term «lower alkyl» denotes a C,-C 4 alkyl group Therefore, example of the preferred capping groups represented by R 2 of Formula I are: methyl, ethyl, propyl, butyl, phenyl, benzyl, and phenylethyl, (C 8 Hs-C 2 H 4-) Most preferably R 2 is a lower alkyl group, especially an n-butyl group 50 Examples of the most preferred organosilicone polymers of this invention are those encompassed by the following empirical average formula Me Me i lMe Si O 3/2 l(Si O)w(Si O)l(C 3 H 60)v(C 2 H 40)x R 213 (II) l l Me R 3 CN wherein Me is a methyl group: W has an average value of from 3 to 100, preferably from 9 to 40; z has an average value of from 3 to 20, preferably from 3 to 15; 55 wherein x and y have average values such that the average molecular weight of the polyoxyalkylene chain is within the range of from 800 to 6000, preferably from 1000 to 4000, and from 20 to 65 weight percent of the polyoxyalkylene chain is composed of oxyethylene; units; and R 2 and R 3 are as defined above, the preferred values of the polyoxyalkylene chain, R 2 and R 3 also being as defined above 60 1.569 319 It is, of course, to be understood that the class of polymers depicted by the above Formulae (I) and (II) also comprise polymers containing residual siliconbonded alkoxy group (Si-OR 4, where R 4 is an alkyl group containing from I to 10 carbon atoms, usually an ethyl group) derived from the monovalent hydrocarbontrialkoxysilanes (e g CH 3 Si(OC 2 Hs)3) employed in their preparation, and that R of 5 this residual alkoxy group may satisfy oxygen of the trifunctional and/or difunctional siloxy units Further while the polysiloxane-polyoxyalkylene block copolymers of this invention may be discrete chemical compounds, normally they are mixtures of various discrete block copolymeric species due at least in part to the manner in which they are made and the fact that the siloxane and polyoxy 10 alkylene reactants used to prepare the copolymers are themselves usually mixtures.
Thus consistent with convention in the art to which this invention relates, the formulae of the polymers indicate their overall average composition rather than any particular ordered arrangement of units or molecular weight of any particular polymer species 15 The organosilicone polymers of this invention may be easily prepared by a two-step process involving the preparation of cyano-modified, alkoxy endblocked siloxane intermediate fluid by base-catalyzed equilibration of trialkoxysiiane, e g.
R-Si(OR 4)3, or its partially hydrolyzed derivative, di-monovalent hydrocarbon depolymerizate, e g (R 2 Si O) cyclic compounds, and cyano-modified cyclic 20 compounds, e g lR(R 1)Si Ol cyclic compounds or cyano-modified mixed cyclic compounds e g l(R 2 Si O)3 (R(R 1)Si O)l, followed by transesterification of the cyanomodified alkoxy end-blocked siloxane intermediate fluids and various hydroxyl terminated polyethers, e g R 2 (O Cn H 2) OH, to produce the desired organosilicone polymers of this invention The transesterification reaction can be 25 illustrated by the following reaction scheme:Si-OR 4 + R 2 (OCH 2)p OH Si-O(CH 2 O)p R 2 + R 4 OH wherein R 2, R 4, and (O Cn H 2,), are as defined above The coefficient v in Formula I above describes the extent to which this reaction has occurred.
The polymerization catalyst employed in the conventional equilibration 30 process to produce the cyano-modified, alkoxy end-blocked siloxane intermediate fluids is preferably tetramethyl ammonium silanolate, although other basic catalysts such as potassium silanolate or cesium hydroxide or mixtures thereof will give siloxane intermediate fluids under suitable conditions The temperature at which the equilibrations are carried out depends on the catalyst employed With 35 tetramethyl ammonium silanolate a temperature of about 90 C is normally sufficient and the catalyst is usually employed in concentrations of from 80 to 150 parts per million as potassium equivalent (one drop of tetramethylammonium silanolate is equivalent to about 4 57 ppm as K) After the equilibration process is over as indicated by vapor phase chromatographic analysis the reaction mixture 40 product is heated to about 150 C, and held there for at least two hours to ensure deactivation of the catalyst The siloxane intermediate fluids are then generally filtered through a medium glass-fitted funnel to give clear straw colored fluids.
The desired organosilicone polymers of this invention are then readily prepared from the corresponding siloxane intermediate fluids and hydroxyl 45 terminated polyethers, using conventional transesterification procedures The transesterification process is preferably carried out in the presence of trifluoro acetic acid/potassium acetate catalyst and toluene as the solvent although other catalysts and solvents may be used if desired The temperature of the reaction process is preferably in the range of from 60 C to 150 C At temperatures below 50 this range the condensation reaction proceeds at a slow rate or not at all.
The transesterification reaction shown in Equation ( 2) above requires the removal of the alcoholic by-product, R 40 H The ultimate quantity of this alcoholic by-product removed from each reaction mixture provides an indication of the extent to which that particular condensation reaction between the siloxane and the 55 polyether-ol reactants has reached completion Additionally, the rate at which the alcoholic by-product is removed serves to indicate the rate at which the reaction is progressing.
The removal or neutralization of the acid catalyst employed in the transesterification reaction is also desirable to provide a stable block copolymer 60 product The degradation of siloxane-oxyalkylene block copolymers in the presence of strong acids and bases are well known Neutralization of the acid catalyst can be easily accomplished by conventional methods such as by the 1,569,319 R addition of sodium bicarbonate followed by filtration to recover the desired organosilicone polymers of this invention.
Catalysts that may be employed in the transesterification process are, in general, the carboxylic acids, including trifluoroacetic acid, perfluorobutyric acid, monochloroacetic acid, acetic acid, Group IA metal carboxylates of the same 5 acids, and mixtures thereof The catalysts are active with most starting materials and may be effective in low concentrations, e g as low as 0 1 percent based on the weight of the starting materials, although the catalyst is usually employed in a concentration of from 0 1 to one weight percent based on the weight of the starting materials 10 The starting materials and/or methods for their preparation used in the above equilibration and transesterification processes to produce the desired organosilicone polymers of this invention are well known in the art and need not be further detailed since the particular starting materials involved, as well as the mole ratios of the starting materials used, in a given process will merely depend upon the 15 polysiloxanepolyoxyalkylene block copolymer product of this invention that is desired to be produced Moreover, optimization of the reaction conditions of these processes as further taught herein is well within the capabilities of even one of average skill in the art.
Another aspect of this invention relates to the use of the organosilicone 20 polymers of this invention as surfactant foam stabilizers in the process for producing flexible polyether polyurethane foam The above-described polysiloxane-polyoxyalkylene block copolymers of this invention may be so employed as a 100 percent active stream or in dilute form as a solution in various types or organic liquids including polar and non-polar solvents For example, the 25 copolymers may be diluted with non-polar solvents such as the normally liquid aliphatic and aromatic unsubstituted and halogen-substituted hydrocarbons such as e.g heptane, xylene, toluene, and chlorobenzene When used, the preferred diluents are polyoxyalkylene compounds encompassed by the formula:
wherein: ZO(Z’O)t Z» 30 Z is a hydrogen atom or a monovalent hydrocarbon group such as an alkyl (e g.
methyl, ethyl, propyl or butyl), aryl (e g, phenyl or tolyl) or aralkyl (e g, benzyl) group; Z’ is a bivalent alkylene group (e g, ethylene, propylene, trimethylene or 35 butylene group):
Z» is a monovalent hydrocarbon group defined for Z; and t has an average value of at least two.
When Z is a hydrogen atom, it is preferred that the ZO groups (that is, OH) represent no more than about 5 weight percent of the solvent Suitable solvents are 40 alkylene oxide adducts of starters such as water, rrono-ols, diols and other polyols.
These organic starters are typically illustrated by butanol, propylene glycol, glycerol and 1,2,6-hexantriol Preferred adducts of the organic starters are the mixed alkylene oxide adducts, particularly those containing a combination of oxyethylene and oxypropylene units For example, one class of these organic 45 solvents which may be present in combination with polysiloxanepolyoxyalkylene copolymers of the present invention are mixed ethylene oxide-propylene oxide adducts of butanol which are represented by the general formula, HO(C 2 H 40),(C 3 H O)UC 4 H,, wherein S has an average value from 8 to 50, and u has an average value from 6 to 40 Preferably, the values of S and u are such that the 50 weight percent of oxyethylene units is about equal to the weight percent of the oxypropylene units.
When used, the aforesaid diluents are usually present in an amount from I to weight percent based on the weight of the polysiloxane-polyoxyalkvlene copolymer in the resulting solution More usually, when these diluents are present, 55 they are contained in the solution in an amount from 5 to 45 weight percent, again based on the weight of the organosilicone polymer contained therein It is to be understood, however, that these solutions may have higher contents of diluent and that the extent of dilution, if any, depends largely on the activity specifications of any given foam formulation 60 -The organosilicone polymers of the present invention may also be used in combination with non-ionic organic surfactants such as adducts produced by reacting k moles of ethylene oxide (wherein k has an average value from 4 to 40, I 1,569,319 inclusive of whole and fractional numbers) per mole of any of the following hydrophobes: n-undecyl alcohol, myristyl alcohol, lauryl alcohol, trimethyl nonanol, tridecyl alcohol, pentadecyl alcohol, cetyl alcohol, nonylphenol, dodecylphenol, or tetradecylphenol Especially useful are ethylene oxide adducts of nonylphenol having the average composition, Cg H 9-CH 4 (OC 2 H 4)h OH, 5 wherein h has an average value from 9 up to 20 or more, including whole and fractional numbers such as 9, 10 5, 13, 14 5 and 15 When used, these nonionic organic surfactants are used in amounts from 2 to 20 weight percent, based on the weight of the organosilicone polymer in any given solution.
In addition to the organosilicone polymer surfactant foam stabilizers of this 10 invention, the other essential types of components and reactants employed in providing flexible polyether polyurethane foams as described herein are polyether polyols, organic polyisocyanates, the catalyst system and blowing agent The foamproducing reaction mixture may also contain a flame-retardant The organo-silicone polymers of the present invention are usually present in the final foam 15 producing reaction mixtures in amounts of from 0 1 to 5 parts by weight and preferably from 0 2 to 2 parts by weight per 100 parts by weight of the polyether polyol reactant.
In producing the flexible polyurethane polymers of the present invention, one or more polyether polyols is employed for reaction with the polyisocyanate 20 reactant to provide the urethane linkage These polyols have an average of at least two, and usually not more than six, hydroxyl groups per molecule and include compounds which consist of carbon, hydrogen and oxygen and compounds which also contain phosphorus, a halogen and/or nitrogen.
Among suitable polyether polyols that may be employed are the poly(oxy 25 alkylene) polyols, that is, alkylene oxide adducts of water or a polyhydric organic compound as the initiator or starter For convenience, this class of polyether polyols is referred to herein as Polyol I Examples of suitable polyhydric organic initiators are any one of the following which may be employed individually or in combination: ethylene glycol; diethylene glycol; propylene glycol; 1,5pentanediol; 30 hexylene glycol; dipropylene glycol; trimethylene glycol; 1,2cyclohexanediol; 3cyclohexane-l, 1-dimethanol and dibromo-derivative thereof; glycerol; 1,2, 6hexanetriol 1, l,1 -trimethylolethane; 1, 1, 1 -trimethyolpropane; 3-( 2hydroxyethoxy) and 3-( 2-hydroxyl propoxy)-I 2-propanediols; 2,4-dimethyl-2-( 2hydroxyethoxy)methylpentanediol-1,5; 1,1,1-trisl( 2-hydroxyethoxy)methyllethane; 1,1,1 35 trisl( 2-hydroxyethoxy)methyllpropane; pentaerythritol; sorbitol; sucrose; alphamethyl glucoside; other such polyhydric compounds consisting of carbon, hydrogen and oxygen and having usually not more than about 15 carbon atoms per molecule; and lower alkylene oxide adducts of any of the aforesaid initiators such as propylene oxide or ethylene oxide adducts having a relatively low average mole 40 cular weight up to about 800.
The above-described polyether polyols are normally liquid materials and, in general, are prepared in accordance with well known techniques comprising the reaction of the polyhydric starter and an alkylene oxide in the presence of an oxyalkylation catalyst which is usually an alkali metal hydroxide such as, in particular, 45 potassium hydroxide The oxyalkylation of the polyhydric initiator is carried out at temperatures ranging from 90 to 150 C and usually at an elevated pressure up to about 200 p s i g, employing a sufficient amount of alkylene oxide and adequate reaction time to obtain a polyol of desired molecular weight which is conveniently followed during the course of the reaction by standard hydroxyl number 50 determinations As is well known to this art, the hydroxyl numbers are determined by, and are defined as, the number of milligrams of potassium hydroxide required for the complete neutralization of the hydrolysis product of the fully acetylated derivative prepared from I gram of polyol or mixture of polyols The hydroxyl number is also defined by the following equation which indicates its relationship 55 with the molecular weight and functionality of the polyol:
OH = 56 1 x 1000 xf M.W.
wherein OH = hydroxyl number of the polyol, f = average functionality, that is, the average number of hydroxyl groups per 60 molecule of polyol, and M.W = average molecular weight of the polyol.
1,569,319 The alkylene oxides usually employed in providing the polyether polyol reactants are the lower alkylene oxides, that is, compounds containing from 2 to 4 carbon atoms including ethylene oxide, propylene oxide, butylene oxides ( 1,2 or 2,3-) and combinations thereof When more than one type of oxyalkylene unit is desired in the polyol product, the alkylene oxide reactants may be fed to the reaction system 5 sequentially to provide polyoxyalkylene chains containing respective blocks of different oxyalkylene units or they may be fed simultaneously to provide substantially random distribution of units Alternatively, the polyoxyalkylene chains may consist essentially of one type of oxyalkylene unit such as oxypropylene capped with oxyethylene units 10 A second class of polyether polyols that are suitable for use in preparing the flexible polyurethane foams of the present invention are polymer/polyether polyols which, for convenience, are referred to herein as Polyol II These reactants are produced by polymerizing one or more ethylenically unsaturated monomers dissolved or dispersed in a polyether polyol in the presence of a free radical 15 catalyst Suitable polyether polyols for producing these compositions include, for example, any of the above-described polyols encompassed by the definition of Polyol I Examples of suitable ethylenically unsaturated monomers are those encompassed by the general formula, R 0000 Ro o -C=CH 2 where: RO is a hydrogen atom or a methyl group or any of the halogens (i e a fluorine, chlorine, bromine or iodine atom); and R O is R or a cyano, phenyl, methyl-substituted phenyl, or alkenyl group containing from 2 to 6 carbon atoms such as vinyl, allyl or isopropenyl group Typical examples of these polymerizable monomers are the following which may be employed individually or in 25 combination: ethylene, propylene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, styrene, alpha-methylstyrene, and butadiene These and other polymer/polyol compositions which are suitably employed either individually or in combination with Polyol I are those described in British Patent Specification No.
1,063,222 and United States Patent Specification No 3,383,351 30
These compositions are prepared by polymerizing the monomers in the polyol at a temperature between 40 C and 150 C employing any free radical generating initiator including peroxides, persulfates, percarbonates, perborates, azo compounds such as, for example, hydrogen peroxide, dibenzoyl peroxide, benzoyl hydroperoxide, lauroyl peroxide, and azobis(isobutyronitrile) The 35 polymer/polyether polyol product may also contain a small amount of unreacted polyether, monomer and free polymer.
When used in the practice of this invention, the polymer/polyol compositions usually contain from 5 to 50, and more usually from 10 to 40 weight percent of the ethylenically unsaturated monomer polymerized in the polyether polyol Especially 40 suitable polymer/polyols are those containing:
(A) from 10 to 30 weight percent of a copolymer of ( 1) acrylonitrile or methacrylonitrile, and ( 2) styrene or alpha-methylstyrene, the said copolymer containing from 50 to 75 and from 50 to 25 weight percent of ( 1) and ( 2) , respectively; and 45 (B) from 90 to 70 weight percent of the polyether polyol, and particularly trifunctional polyols such as alkylene oxide adducts of glycerol.
In preparing polyurethane foams in accordance with the present invention, it is to be understood that mixtures of any of the aforesaid polyether polyols encompassed by Polyol I and Polyol II can be employed as reactants with the 50 organic polyisocyanate The particular polyether polyol or polyols employed depends upon the end-use of the polyurethane foam Usually diols provide soft foams; firmer foams are obtained by the incorporation of polyether polyols having more than two hydroxyl groups, including triols, tetraols, pentols and hexols When it is desired to produce polyurethanes having comparatively high loadbearing 55 properties and/or diecutability, polymer/polyether polyols of the aforesaid type are used.
The hydroxyl number of the polyether polyol reactant including mixtures of polyols employed in the production of the flexible polyurethane foams of this invention may vary over a relatively wide range such as from 28 to 150, and is 60 usually no higher than 80.
1,569,319 9 1,569,319 9 The polyisocyanates used in the manufacture of polyurethanes are known to the art and any such reactants are suitably employed in producing the flexible polyether-based polyurethane foams of the present invention Among suitable polyisocyanates are those represented by the general formula:
Q'(NCO), wherein: i has an average value of at least two and is usually no more than six, and Q’ represents an aliphatic, cycloaliphatic or aromatic radical which may be an unsubstituted hydrocarbyl group or a hydrocarbyl group substituted, for example, with a halogen atom or an alkoxy group For example, Q’ may be an alkylene, cycloalkylene, arylene, alkyl-substituted cycloalkylene, alkarylene or aralkylene 10 radical including corresponding halogen and alkoxy-substituted radicals Typical examples of polyisocyanates for use in preparing the polyurethanes of this invention are any of the following including mixtures thereof: 1,6hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1-methyl-2,4diisocyanatocvclot S hexane, bis( 4-isocyanatophenyl)methane, phenylene diisocyanates such as 4 15 methoxy 1,4-phenylenediisocyanate, 4-chloro-1,3-phenylenediisocyanate, 4bromo-1,3-phenylenediisocyanate, 5,6-dimethyl-1,3-phenylenediisocyanate, 2,4tolylene diisocyanate, 2,6-tolylene diisocyanate, crude tolylene diisocyanates, 6isopropyl-1,3-phenylenediisocyanate, durylene diisocyanate, triphenylmethane4,4 ‘,4 «-triisocyanate, and other organic polyisocyanates known to the poly 20 urethane art Other suitable polyisocyanate reactants are ethylphosphonic diisocyanate and phenylphosphonic diisocyanate Of the aforesaid types of polyisocyanates, those containing aromatic nuclei are generally preferred.
Also useful as the polyisocyanate reactant are polymeric isocyanates having units of the formula: 25 NCO CH 2 -j wherein R»‘ is a hydrogen atom and/or a lower alkyl group and j has an average value of at least 2 1 Preferably the lower alkyl radical is a methyl radical and j has an average value of from 2 1 to 30 Particularly useful polyisocyanates of this type are the polyphenylmethylene polyisocyanates produced by phosgenation of the 30 polyamine obtained by acid-catalyzed condensation of aniline with formaldehyde.
Polyphenylmethylene polyisocyanates of this type are available commercially under such trade marks as PA Pl (Registered Trade Mark), NIAX (Registered Trade Mark) Isocyanate AFPI, Mondur (Registered Trade Mark) MR, Isonate (Registered Trade Mark) 390 P, NCO-120, Thanate P-220 (THANOL is a 35 Registered Trade Mark), NCO-10 and NCO-20 These products are low viscosity ( 50-500 centipoises at 25 C) liquids having average isocyanato functionalities in the range of 2 25 to 3 2 or higher, depending upon the specific anilinetoformaldehyde molar ratio used in the polyamine preparation.
Other useful polyisocyanates are combinations of diisocyanates with 40 polymeric isocyanates containing more than two isocyanate groups per molecule.
Examples of these combinations are: a mixture of 2,4-tolylene diisocyanate, 2,6tolylene diisocyanate and the aforesaid polyphenylmethylene polyisocyanates and/or polymeric tolylene diisocyanates obtained as residues from the manufacture of the diisocyanates 45 On a combined basis, the polyether polyol and organic polyisocyanate usually comprise the major proportion by weight of the polyurethane-forming reaction mixture In general, the polyisocyanate and polyether polyol reactants are employed in relative amounts such that the ratio of total -NCO equivalents to total active hydrogen equivalent (of the polyether polyol and any water, when used) 50 is from 0 8 to 1 5, preferably from 0 9 to 1 1, equivalents of-NCO per equivalent of active hydrogen This ratio is known as the Isocyanate Index and is often also 1,569,319 expressed as a percent of the stoichiometric amount of polyisocyanate required to react with total active hydrogen When expressed as a percent, the Isocyanate Index may be from 80 to 150, and is preferably within the range from 90 to 110.
The urethane-forming reaction is effected in the presence of a minor amount of a catalyst comprising an amine This component of the polyurethaneforming 5 reaction mixture is usually a tertiary amine Suitable amine catalysts include one or more of the following: N-methylmorpholine; N-ethylmorpholine; N-octadecylmorpholine; triethylamine; tributylamine, trioctylamine; N,N,N’,N’tetramethylethylenediamine; N,N,N’,N’-tetramethyl 1,3-butanediamine; triethanolamine; N,N-dime»-vlethanolamine; triisopropanolamine; N-methyldiethanolamine; hexa 10 decyldimethylamine; N,N-dimethylbenzylamine; trimethylamine; N,N-dimethyl2( 2-dimethylaminoethoxy)ethylamine, also known as bis( 2dimethylaminoethyl)ether; triethylenediamine (i e, diazabicyclol 2 2 21 octane); the formate and other salts of triethylenediamine, oxyalkylene adducts of the amino groups of primary and secondary amines and other such amine catalysts which are well known in the 15 art of polyurethane manufacture Also useful are the beta-tertiary amino amides and esters described in United States Patent Specification No 3,821,131, as exemplified by 3-dimethylamino-N,N-dimethylpropionamide Also useful as the amine catalyst are the beta-tertiary-amino nitriles described in United States Patent No 3,925,268 of W R Rosemund, M R Sandner and D J Trecker, as, 20 exemplified by 3-dimethylaminopropionitrile as such or in combination with other tertiary amines such as bisl 2-(N,N-dimethylamino)ethyllether The amine catalyst may be introduced to the polyurethane-producing reaction mixture as such or as a solution in suitable carrier solvents such as diethylene glycol, dipropylene glycol, and 2-methyl-2,4-pentanediol («hexylene glycol») 25 The amine catalyst is usually present in the final urethane-producing reaction mixture in an amount of from 0 05 to 3 parts by weight of active catalyst (that is, the amine exclusive of other components present in solutions thereof) per 100 parts by weight of the polyether polyol reactant.
In producing polyurethanes from polyether polyols usual practice is to include 30 as a further component of the reaction mixture a minor amount of certain metal catalysts which are useful in promoting gellation of the foaming mixture These supplementary catalysts are well known to the art of flexible polyetherbased polyurethane foam manufacture For example, useful metal catalysts include organic derivatives of tin, particularly tin compounds of carboxylic acids such as stannous 35 octoate, stannous oleate, stannous acetate, stannous laurate, dibutyl tin dilaurate, and other such tin salts Additional metal catalysts are organic derivatives of other polyvalent metals such as zinc and nickel (e g, nickel acetylacetonate) In general, the amount of these metal co-catalysts which may be present in the polyurethaneproducing reaction mixture is within the range of from 0 05 to 2 parts by weight per 40 parts by weight of the polyether polyol reactant.
Foaming is accomplished by the presence in the reaction mixture of varying amounts of a polyurethane blowing agent such as water which, upon reaction with isocyanate generates carbon dioxide in situ, or through the use of blowing agents which are vaporized by the exotherm of the reaction, or by a combination of the 45 two methods These various methods are known in the art Thus, in addition to or in place of water, other blowing agents which may be employed include methylene chloride, liquefied gases which have boiling points below 80 F and above -60 F, or other inert gases such as nitrogen, carbon dioxide added as such, methane, helium and argon Suitable liquefied gases include aliphatic and cycloaliphatic 50 fluorocarbons which vaporize at or below the temperature of the foaming mass.
These gases are at least partially fluorinated and may also be otherwise halogenated Fluorocarbon blowing agents suitable for use in foaming the formulations of this invention include trichlorofluoromethane, dichlorodifluoromethane, 1,1-dichloro I -fluoroethane, 1,1,1-trifluoro-2-fluoro-3,3difluoro-4,4,4 55 trifluorobutane, hexafluorocyclobutene and octafluorocyclobutane The generally preferred method of foaming for producing flexible foams is the use of water or a combination of water plus a fluorocarbon blowing agent such as trichlorofluoromethane.
The amount of blowing agent employed will vary with factors such as the 60 desired density of the foamed product Usually, however, from I to 30 parts by weight of the blowing agent per 100 parts by weight of the polyether polyol reactant is preferred Foam densities may be within the range of from 0 8 to 5 pounds per cubic foot (pcf) Polyurethane foam of relatively low density such as 2 pcf and less is usually prepared employing blowing agent comprising water in an amount of at 65 1,569,319 least about 3 parts by weight per 100 parts by weight of polyether polyol reactant, whereas higher density foam is provided at lower levels of water with and without the use of an auxiliary fluorocarbon blowing agent It is to be understood, however, that these are general guidelines and that the choice of the particular amount of blowing agent employed to obtain a desired foam density specification varies from 5 formulation to formulation and is well within the skill of the art to which the present invention relates.
The organic flame-retardants that may be employed in producing flexible polyether foams in accordance with the teaching of this invention may be chemically combined in one or more of the other materials used (e g, in the 10 polyether polyol or polyisocyanate), or they may be used as discrete chemical compounds added as such to the foam formulation The organic flameretardants preferably contain phosphorus or halogen, or both phosphorus and halogen.
Usually, the halogen, when present, is chlorine and/or bromine Flameretardants of the discrete chemical variety include: 2,2-bis(bromomethyl)-1,3propanediol 15 (also known as dibromoneopentyl glycol); 2,3-dibromopropanol, tetrabromophthalic anhydride; brominated phthalate ester diols such as those produced from tetrabromophthalic anhydride, propylene oxide and propylene glycol; tetrabromo-bisphenol-A; 2,4,6-tribromophenol; pentabromophenol; brominated » 120 anilines and dianilines; bis( 2,3-dibromopropyl)ether of sorbitol; tetrachloro 20 phthalic anhydride; chlorendic acid; chlorendic anhydride; diallyl chlorendate; chlorinated maleic anhydride; tris( 2-chloroethyl)phosphate l(C 1 CH 2 CH 2 O)3 P(O)l; tris( 2,3-dibromopropyl)phosphate; tris( 1 I,3-dichloropropyl)phosphate; tris( 1bromo-3-chloroisopropyl)phosphate; bis( 2,3-dibromopropyl) phosphoric acid or :’:25 salts thereof; oxypropylated phosphoric and polyphosphoric acids; polyol 25 phosphites such as tris(dipropylene glycol)phosphite; polyol phosphonates such as bis(dipropylene glycol)hydroxymethyl phosphonate; di-poly(oxyethylene)hydroxymethyl phosphonate; di-poly(oxypropylene)phenyl phosphonate; dipoly(oxypropylene)chloromethyl phosphonate; di-poly(oxypropylene)butyl phosphonate; and O,O-diethyl-N,N-bis( 2-hydroxyethyl)aminomethyl phos 30 phonate Also suitable are compounds having the formulae:
0 II (C 1 CH 2) 2 ClCH 2 o( O p (o C 2 CH 2 C’L) 22 l and 0 O CH 3 O 11 11 1, If II I 3 C 1 CH 2 CH 20-P-O H 1 P O-CH-P ( O C’I 2 C 2 C 1)2 C 1 CH 2 C% CH c 3 OCCH’2 C 1 n which are available from Monsanto Chemical Company under the names Phosgard 35 2 XC-20 and Phosgard C-22-R, respectively PHOSGARD is a Registered Trade Mark Other suitable flame-retardants comprise halogen-containing polymeric resins such as polyvinylchloride resins in combination with antimony trioxide and/or other inorganic metal oxides such as zinc oxide, as described in United States Patent Specifications Nos 3,075,927; 3,075,928; 3,222,305; and 3, 574,149 It 40 is to be understood that other flame-retardants known to the art may be used and that the aforesaid compounds may be employed individually or in combination with one another.
Those of the above flame-retardants of the discrete chemical compound variety which contain groups reactive with hydroxyl or isocyanato groups may be 45 used as reactants in producing the polyether polyol reactant or they may be reacted with organic polyisocyanates, to produce modified polyols or polyisocyanates having chemically combined flame-retarding groups These modified polyether polyols and polyisocyanates are also useful as reactants in the process of this invention In these cases, due regard must be given to the possible effect of the 50 functionality of the compound on the other properties (e g, degree of flexibility) of the resulting foam.
1,569,319 II The flame-retarding agent may be used in an amount from I to 30 parts by weight per 100 parts by weight of the polyether polyol reactant, and is usually employed in an amount of at least 5 parts by weight It is evident that the particular amount of flame-retardant employed depends largely on the efficiency of any given agent in reducing flammability 5 The polyether-based polyurethane foams of this invention may be formed in accordance with any of the processing techniques known to the art such as, in particular, the «one-shot» technique In accordance with this method, foamed products are provided by carrying out the reaction of the polyisocyanate and polyether polyol simultaneously with the foaming operation It is sometimes 10 convenient to add the foam stabilizing component comprising the organosilicone polymer of the present invention, to the reaction mixture as a premixture with one or more of the blowing agent, polyether polyol, amine catalyst and, when used, the flame-retardant It is to be understood that the relative amounts of the various components of the foam formulations are not narrowly critical The polyether 15 polyol and polvisocyanate are present in the foam-producing formulation in a major amount The relative amounts of these two components is the amount required to produce the urethane structure of the foam and these relative amounts are well known in the art The source of the blowing action such as water, auxiliary blowing agents, amine catalyst, metal co-catalyst and the foam stabilizing organo 20 silicone polymers of the present invention are each present in a minor amount necessary to achieve the function of the component Thus, the blowing agent is present in an amount sufficient to foam the reaction mixture, the amine catalyst is present in a catalytic amount (i e, an amount sufficient to catalyze the reaction to produce the urethane at a reasonable rate), and the organosilicone polymer of this 25 invention is present in a foam-stabilizing amount, that is, in an amount sufficient to stabilize the foam The preferred amounts of these various components are as given hereinabove.
If desired, other additional ingredients may be employed in minor amounts in producing the polyurethane foams in accordance with the process of this invention 30 Examples of these additives that may be employed are: e g cross-linking agents such as glycerol, triethanolamine and their oxyalkylene adducts, as well as fillers, dyes, pigments, and anti-yellowing agents The polyurethanes produced in accordance with the present invention are used in the same areas as conventional flexible polyether polyurethanes and are especially useful where improved fire 35 resistance properties are beneficial Thus, the foams of the present invention are used with advantage in the manufacture of textile interliners, cushions, mattresses, paddings, carpet underlay, packaging, gaskets, sealers, and thermal insulators.
The organosilicone polymers of this invention as seen by the following Examples, have been found to be effective foam stabilizers for flexible polyether 40 urethane foam, even when a flame retardant is employed in the foam formulation.
These polymers have also been found to help provide good breathability and have a wide operating range.
The following Examples illustrate the present invention and are not to be regarded as limitative It is to be understood that all parts, percentages and 45 proportions referred to herein and in the claims are by weight unless otherwise indicated Moreover, as used herein, the following terms and symbols have the indicated significance:
In the formulae «Me» designates a methyl group, -CH 3; «Et» designates an ethyl group, -C 2 H,; the bridging group, -C 3 H 6 represents -CH 2 CH 2 CH 2-; 50 «Bu» designates a n-butyl group, C 4 H 9-; the symbol T represents a siloxy unit of the formula (Me Si O,), the symbol D represents siloxy unit of the formula (Me 2 Si O); the symbol D» represents a siloxy unit of the formula (Me Si O) C 3 H,l CN and the symbol (PE) represents a mixture of randomly distributed oxyalkylene 55 radicals consisting of 78 wt %, (C 3 H 80),4 (C 2 H 40),84 C 4 H, and 22 wt %(C 3 H 0)243 (C 2 H 40)321 C 4 H, If desired the mixture represented by (PE) can also be written as a polyether radical having the average composition -(C 3 H 0)176 (C 2 H 40)233 Bu.
1,569,319 Moreover, in the Examples and comparative runs which follow various organosilicone polymers within and without the scope of the present invention were evaluated as the foam stabilizing component of a variety of foamproducing reaction mixtures to provide flexible polyether polyurethane foam with and without a flame-retardant These various reaction mixtures are referred to herein 5 as Foam Formulations A to D The components and relative proportions of components in the reaction mixtures are as indicated in the following Tables I to IV, respectively.
TABLE I FOAM FORMULATION A Component Parts by Weight Polyether polyol having a hydroxyl number 100 0 of 56 produced by reacting mixture of glycerol and dipropylene glycol and propylene oxide to a hydroxyl number of 59, and capping this product with ethylene oxide to the final hydroxyl number /1/ Tolylene Diisocyanate (Index 105) 34 4 Water 2 5 A mixture of 70 % Bis l 2-(N,N-dimethyl 0 1 amino)ethylllether and 30 % dipropylene glycol (amine catalyst) A mixture of 33 % triethylenediamine 0 225 and 67 % dipropylene glycol (amine catalyst) Stannous Octoate (tin catalyst) Varied, see Table VII
Monsanto PHOSGARD Varied, see 2 XC-20 Flame Retardant Table VII (CICH 2)2 ClCH 2 OP(O)(OCH 2 CH 2 CI)2 l 2 Surfactant Foam Stabilizer Varied, see Table VII /1/ This component was a mixture of the 2,4 and 2,6-isomers of tolylene diisocyanate present in a weight ratio of 80:20.
respectively Index 105 designates that the amount of mixture employed was 105 weight percent of the stoichiometric amount required to react with total reactive hydrogens from the polyether polyol and water present in the foam formulation.
1,569,319 1,569,319 TABLE II FOAM FORMULATION B Components Polyether Polyol having a Hydroxyl Number of about 46 produced by reacting glycerol, propylene oxide and ethylene oxide.
Toly’ ‘re Diisocyanate (Index 105) /1/ Water Trichlorofluoromethane Dimethyl ethanol amine Stannous octoate Surfactant Foam Stabilizer Parts by Weight 57.0 4.85 15.0 0.35 0.3 Varied, see Table VIII
1/ Same as defin-d in Foam Formulation A.
TABLE III FOAM FORMULATION C Components Polyether Polyol having a hydroxyl Number of 56 produced by reacting glycerol and propylene oxide Tolylene Diisocyanate (Index 105) /1/ Tri s( 2-chloroethyl)phosphate Water A mixture of 70 % Bisl 2-(N,N-dimethylamino)ethyllether and 30 % dipropylene glycol Stannous octoate Surfactant Foam Stabilizer Parts by Weight 0 49.73 4.0 0.1 0.35 Varied, see Table IX /1/ Same as defined in Foam Formulation A.
14.
TABLE IV FOAM FORMULATION D Components Parts by Weight Polyether Polyol,’1/ 100 Tolylene Diisocyanate (Index 105) I 2,’ 49 9 Water 4 0 A mixture of 70 % Bi sl 2-(N,N-dimethyl 0 075 amino/ethyll ether and 30 % dipropylene glycol A mixture of 33 % triethylene 0 225 diamine and 67 % dipropylene glycol Stannous octoate (tin catalyst) Varied, see Table X
Monsanto PHOSGARD Varied, see 2 XC-20 Flame Retardant Table X (CICH 2)2 ClCH 2 OP(O)(OCH 2 CH 2 CI)2 l 2 Surfactant, Foam Stabilizer Varied, see Table X /1/ Same as defined in Foam Formulation A.
/2/ Same as defined in Fnam Formulation A.
Except as noted, the foams of the following examples and comparative runs were prepared employing substantially the same procedure which entails the following manipulative steps: After dispensing the polyether polyol reactant in a container, the flame-retardant (when used) is added thereto and dispersed therein 5with a spatula The surfactant foam stabilizer is then added from a syringe and is also dispersed with a spatula After inserting a baffle, a premixture of the amine catalyst and blowing agent is added but not dispersed The resulting blend is then placed in a drill press and the mixture agitated 15 seconds at 2000 revolutions per minute Agitation is then stopped and the stannous octoate co-catalyst is added 10 from a syringe Agitation is continued for an additional 8 seconds, after which the diisocyanate reactant is added rapidly and the agitation is continued for another 7 seconds After the mixing cycle, the mixture is poured into a parchmentlined container supported by a wooden mold The foam is allowed to rest in the container for at least 3 minutes and is then cured in an oven for 10-15 minutes at 15 1301 C After cutting, the height of the foam rise is measured, and foam samples are prepared for breathability and burning extent determinations.
«Breathability» denotes the porosity of a foam and is roughly proportional to the number of open cells in a foam As reported herein, breathability was determined in accordance with the NOPCO (Registered Trade Mark) test 20 procedure described by R E Jones and G Fesman, «Journal of Cellular Plastics» (January, 1965), as follows: A 2 inch x 2 inch x 1 inch piece of foam is cut from near the center of the bun Using a Nopco Foam Breathability Tester, Type GP-2 Model DG 10, air is drawn through the foam sample at a pressure differential of 0 5 inches of water less than atmospheric pressure The air flow is parallel to the 25 direction of original foam rise The degree of openness of the foam (or foam breathability) is measured by the rate of air flow through the foam and is reported in standard cubic feet per minute (SCFM).
«Burning Extent» was determined in accordance with standard flammability test procedure ASTM D 1692-68, except that five test specimens of foam were used 30 instead of ten Burning extent denotes the burned length (in inches) of the foam and is reported as the average of the results obtained with the various test specimens of a given foam On the basis of this test, an average burning extent of less than 5 0 inches qualifies the foam for a self-extinguishing («SE») rating When the burning extent of at least one test specimen of 5 0 inches or greater, the foam is 35 assigned a burning (Burns) rating and usually no further specimens of that foam are tested.
I 1,569,319 «Burning Time» denotes the average time (in seconds) taken to give the specified burning extent.
As used herein, the abbreviation «p h p » means that the concentration of a particular component of the foam formulation is expressed in parts by weight per 100 parts by weight of the polyether polyol reactant contained in the formulation 5 Example 1.
A cyano-modified siloxane intermediate fluid (Fluid No 11 in Table V) was prepared by the following method:
Into a 1000 ml, three-necked flask, equipped with thermometer, heating mantle, mechanical stirrer, condenser, and positive nitrogen atmosphere were 10 charged 42 7 grams ( 0 24 mole) Me Si(O Et) (distilled), 391 2 grams ( 5 28 mole) distilled (Me 2 Si O)4 cyclic tetramer, and 183 0 grams ( 1 44 mole) cyclic gammacyanopropylmethylsiloxane This heterogeneous mixture was stirred and heated to C At 90 C, tetramethyl ammonium silanolate catalyst ( 100 ppm as K) was added, and the mixture became colored and homogeneous almost immediately 15 The mixture was held at 90 C with stirring for three hours It was then heated to C and held for two hours at this temperature to insure deactivation of the catalyst After cooling to room temperature, the product was filtered through a medium glass-fitted funnel to give a clear, orange-yellow colored fluid Ethoxy content: theoretical: 5 25 percent, found: 5 31 percent The cyanomodified alkoxy 20 end-blocked siloxane intermediate fluid product has the average formula:
(Me Si O 3,)(Me 2 Si O)22 lMe(NCC 3 H 8)Si Oll(Et)3 and is hereinafter designated as Intermediate Fluid No 11, as shown in Table V below.
Except as noted, a series of other cyano-modified, alkoxy end-blocked 25 siloxane intermediate fluids were prepared employing substantially the same procedure as Example 1, as shown in the following Table V.
1,569,319 -4 TABLE V
PREPARATION OF CYANO-MODIFIED, ALKOXY ENDBLOCKED SILOXANE INTERMEDIATE FLUIDS Me Si(O Et)3 Used Cyclic (Me 25 i O) Used Cyclic l(Me)(NCC 3 H 6)Si Ol Used Moles Grams Moles Grams Moles Grams %, O Et in Product Cal’d Found Used in Surfactant Prep 1,’ Remark s TD 2 D 14 «(Et)3 TD 4 D 4 ‘(Et)3 TD Is D 4 «(Et)3 TD, D,'(Et)3 TD 9 D'(Et), TD, Dg(Et), TD 22 D, (Et)3 TD 20 D 3 «(Et)3 TD 18 s S Dl»(Et)3 TD 22 D 6 «(Et)3 TD 22 D 6 ‘(Et)03 TD 22 D 6 ‘-(Et)3 TD 22 D 6 ‘-(Et) x TD 16,2 (Et),3 T Ds fi E 03 TD 182 (Et)3 TD,8 2 (Et) x 0.05 0.05 0.05 0.05 0.08 0.05 0.039 0.049 0.06 0.24 0.24 0.24 0.04 0.130 0.07 0.07 8.9 8.9 8.9 8.9 14.2 8.9 6.9 8.7 10.7 42.7 42.7 47.7 7.1 23.2 12.5 12.5 0.60 0.70 0.90 0.45 0.72 0.45 0.86 0.98 1.11 5.28 5.28 5.28 0.88 2.37 1.27 1.27 44.5 51.9 66.7 33.3 53.4 33.3 63.6 72.6 82.3 391 2 391 2 391 2 65.2 3 94.4 94.4 0.20 0.20 0.20 0.30 0.24 0.45 0.23 0.15 0.06 1.44 1.44 1.44 0.24 None None None None 25.4 25.4 25.4 38.1 30.5 57.2 29.7 18.7 7.6 183 0 183 0 183 0 30.5 None None None None 8.6 % 7.8 % 6.7 % 8.4 % 11.0 ‘% 6.8 % 5.25 ‘; 6.6 % 7.6,’ 5.25 % 5.25 % 5.25 % 5.1 % 8.8 % 8.8 % 8.8 % 8.6 %i 7.4 %c 7.7 % 6.8 % 8.4 % 11.1 % 6.7 T 7 5.5 % 6.5 % 7.8 % 5.0 % 5.3 % 5.25 % 4.6 %’ 8.8 %’ 8.9 % 9.3 % 8.2 % II III IV V VI VII I VIII IX X, XI Ia, XII, XIII XIV to XVIII XIX to XXI B Ba,Bh Bec Bd, Be Bf, Bg Intermediate Fluid No.
Average Formula 1 2 3 4 6 7 8 9 11 12 13 14 16 11 ^ 0 ‘ o L.»
\.
2 ‘ 4.’ /3 ‘ /4, / /6 ‘ /’5 -4 Footnotes for Table V TD 12 D 4 » (Et)3 represents the average formula:
(Me Si O 3,2)(Me 2 Si O),2 (Me Si O)4 (Et)3.
C 3 H 6 CN TD, 2 (Et)3 represents the average formula:
(Me Si O 3,2)(Me 2 Si O),82 (Et)3 5 The other intermediate fluids have the corresponding meanings shown in their average formulas.
( 1) Indicates which Surfactant Foam Stabilizer in Table VI below was produced with the corresponding Intermediate Fluid of Table V.
( 2) Stripped 10 ( 3) Equilibrated twice.
( 4) Fresh tetramethyl ammonium silanolate catalyst was used.
( 5) Plant grade Me Si(O Et)3 used; ethoxy content 73 5 % rather than 77 % for pure Me Si(O Et)3.
( 6) Plant produced using Me Si(O Et)3; ethoxy content ’73 5 %:ather than 77 % 15 for pure Me Si(O Et)3.
Example 2.
A siloxane surfactant (Surfactant Ia in Table VI) was prepared by the following method:
Into a 1000 ml, three-necked flask, equipped with thermometer, heating 20 mantle, mechanical stirrer, two-foot long packed column, distillation head, and receiver, and positive nitrogen atmosphere were charged 70 1 grams ( 6 8 percent molar deficiency) of a polyether blend of 78 weight percent Bu O(C 2 H 40)184 (C 3 H 60)14 H and 22 weight percent of Bu O(C 2 H 40) 321 (C 3 H,0)243 H; percent of total OH= 0 8 and the oxyalkylene groups of the two polyethers are 25 randomly distributed This represents a polyether of 2125 molecular weight with the following average structure Bu O(C 2 H 40)233 (C 3 HO)176 H, and 50 m l of toluene ( 30 weight percent of final pot) This mixture was heated to reflux and the moisture was removed as the toluene-water azeotrope at the hood Heating was then stopped and the mixture was allowed to cool below 70 C 30 At this time, 30 grams ( 0 0354 mole Et O) of the cyano-modified Intermediate Fluid No 11 in Table V ( 5 31 percent ethoxyl content) prepared as in Example 1, was added to the mixture along with 10 ml of toluene, giving a heterogeneous mixture The reaction mixture was then catalyzed at < 50 C with 0 05-0 07 grams KOOCCH 3 and 0 25 grams trifluoroacetic acid Heating was applied and reflux 35 temperature was reached within ten minutes After five more minutes, the mixture cleared, exhibiting a slight yellowish color and substantial foaming The Et OHtoluene azeotrope at the head was removed slowly, dropwise, over a onehour period, with the head temperature rising through the range 76-1100 C and the pot temperature rising through the range 129-139 C After approximately 1 3 hours 40 from time of catalysis heating was topped and the product solution was allowed to cool to about 50 C Five grams of Na HCO 3 was then added to the pot and vigorous stirring followed for over 30 minutes. The product solution was then filtered through a 5 microns pad in a pressure filter and the clear filtrate was desolvated by rotary evaporation at 55 C /1 mm 45 About 96 grams of desired polysiloxane-polyoxyalkylene block copolymer product, which was a light yellow fluid of 960 cps viscosity, was obtained The copolymer product hereinafter designated as Surfactant Ia, as shown in Table VI below had the average formula: (Me 3 Si O 3/2)(Me 2 Si O)22 (Me Si O)6 l(CH 60),70 (C 2 H 40)23 Bul 3 s C 3 H 6 CN Ethoxy content, found: 0 027 percent. 1,569,319 Except as noted, a series of other poly/oxanpolyoxyalkyene block copolymer surfactants were prepared employingsubsantiallythe procedure. as Example 2 as shown in the following Table VI. TABLE VI PREPARATION OF POLYSILOXANE-POLYOXYALKYLENE BLOCK COPOLYMER SURFACTANTS Surfactant Average No Formula B TD 16 2 (PE)3 TD 22 D 6 (PE)3 TD,12 D 6-(PE)3 TD:2 D 4,'(PE), TD,4 D 4 '(PE). TD,1 D 4 '(PE)3 TD 9 D 6 "(PE)3 TD, D-(PE)3 TD 9 D Qg(PE)3 TD 2 o D 3 "(PE)3 TD 1 5 s D,'"(PE)3 TD 22 D 6 (PE)3 TD 22 D 6 "(PE)3 TD 22 D 6 -(PE)3 TD 22 D 6 (PE)3 TD 22 D 6 (PE)3 TD 22 D 6 '-(PE)x TD 22 D 6-(PE) x TDD 6 (PE)X TD, 2 (PE), TD,8,2 (PE)3 TD 18,2 (PE)3 TD 1, 2 (PE)3 TD 1 82 (PE), T Dt 8 a 2 'PE) x T Dsj(PE) x Intermediate Fluid Used++ Nominal OH/Et Ratio 14 2 % Deficiency 7 6 8 %, 11 7 % 1 13 % Rxcess 2 1 % Def. 3 4 %,, 4 2 %,, 3 %,, 6 1 % Excess 8 7 % Def. 9 7 %,, 8 % Excess 7 % Def. 11 1:1 11 15 % Def. 12 6 %, 13 1:1 13 1:1 13 1:1 8 % Def. 8 %,, 16 1:1 16 1:1 16 1:1 17 4 % Excess 17 4 %, Amt of Amt of Intermediate roiyether Amt of Fluid Used++ Used +++ Toluene Used Grams Moles Et O Grams Moles OH Wt % 43 0 0841 59 540 61.5 232 0.0721 0.0354 0.0658 0.0684 0.0604 0.0693 0.0863 0.0670 0.0436 0.0861 0.605 0.0689 0.0354 0.0354 0.271 34 0 0348 34 0 0348 34 0 0348 22 0 0435 44 0 0870 0 0413 0 0413 0 0413 0 0364 0 0364 0 0824 143 6 70.1 158 6 144 3 123 8 143 9 178 5 143 6 86.3 5 138 6 136 8 74.2 63.1 537 0.0676 0.0330 0.0746 0.0679 0.0583 0.0677 0.0840 0.0676 0.0406 0.0802 0.652 0.0644 0.0354 0.0301 0.256 73.2 0 0348 73.2 0 0348 73.2 0 0348 85.4 0 0402 8 0 0804 86.7 0 0413 86.7 0 0413 86.7 0 0413 79.4 O 0378 79.4 0 0378 Reaction time (Hours) Viscosity of Product (Cps) 3 0 1100 1 5 900 1 3 960 1 5 500 3 0 870 3 0 820 3 5 750 3 O 850 2 5 920 1 3 1000 1 6 1000 1 5 780 1 5 940 1 3 1000 1 3 1000 1 3 800 0 5 880 1 0 750 1 8 Q 20 3 0 1020 2 0 1250 1 5 970 3 0 1320 2 0 1050 2 0 920 3 0 920 Residual O Et % I la 11 III IV V VI VII VIII IX X XI Xl I XIII XIV to XVIII XIX XX XXI Ba Bb Bc Bd Be Bf Bg 0 o N O 0.2 0.08 0.03 0.2 0.06 0.03 0.04 0.05 0.04 0.09 0.06 0.33 0.24 0.03 0.05 0.15 0.39 0.67 0.07 0.05 0.04 016 0.09 0.11 0.15 0.26 ootnotes for TABLE VI: '1)221)6 " (PE)3 represents the awerage formula (Me Si O 3 W 2)(M e 2 Si O)22 (Me Si O)81 (C 311 e 0) 11,(C 2 H 40)23 3 B u 13 C 3 He CN The other siloxane surfactants have the corresponding meanings shown in their average formulas. These surfactants were made from production using Me Si(O Et)3 having an ethoxy content of 73 5 ", rather than 77 for pure Me Si(O Et)3. Optimized Blend of five surfactants from five identical preparations. ++ Avg formula as shown in T'FABLE V 10 + -t The hydroxy end-blocked polyether reactant in each instance was a mixture of 78 Wt " Bu O(C 2 H 40)184 (C 3 H 0),4 Hand 22 wt % Bu O(C 2 H 40)32 1 (C Hs O)243 H polyethers, the oxyalkylene groups of both polyethers being randomly distributed Said mixture may also be written as an average composition of Bu O(C 2 H 40)233 (C 3 HO)17 e H 51. Example 3. In accordance with this example a series of flexible polyether urethane foams vere produced using various surfactant foam stabilizers, FOAM FORMULATION A, and the foaming process detailed above The results of these various flexible polyether foam preparations, which contain a flame retardant, are 20 given in TABLE VII below. J 1,569,319 TABLE VII Flamne Tin Foam Breath Cells Burning Burning Surfactant Surfactant Retardant Conc Rise ability Density Per Extent Time Number Conc (php) Conc (php) (php) Inches (SCFM) (pcf) Inch (Inches) Rating (Seconds) A 1 3 6 0 07 -4 1 1 6 2 53 30/35 Full Burns t A 1 3 3 0 07 4 1 1 7 2 54 30/35 Full Burns A 1 3 1 0 1 4 1 1 5 2 44 30/35 Full Bums Ba 1 3 3 0 09 4 1 2 5 -2 50 30/35 Full Burns C 0 35 6 0 09 4 1 1 2 2 66 30/35 0 9 SE 20 C 0 35 3 0 09 4 2 1 5 2 50 30/35 1 3 SE 23 C 0 35 1 0 09 4 1 1 5 2 47 30/35 1 7 SE 28 I 1 3 6 0 09 4 1 1 7 2 56 30/35 0 9 SE 17 I -1 3 3 O 09 4 2 2 3 2 50 25/30 1 4 SE 27 I 1 3 2 6 1 4 2 1 g 2 49 25/30 1 6 SE 26 -I 1 3 1 O 1 4 1 2 1 2 47 25/30 Full Burns Ia 1 3 3 0 09 4 2 1 85 2 60 30,35 1 5 SE 32 XII 1 3 3 0 09 4 1 2 1 2 57 30//35 1 5 SE 31 XII 1 3 3 0 09 4 1 3 2 2 54 30/35 1 7 SE 35 XIII 1 3 3 O 09 4 2 3 2 2 50 30 '35 1 6 SE 31 XXI 1 3 3 0 09 4 1 3 0 2 65 30,/35 18 SE 36 XIV-XVIII# 1 3 3 O 09 4 1 2 6 2 60 30/35 2 O SE 40 VIII 1 3 3 0 09 4 2 2 7 2 50 30/35 2 8 SE 63 IX 1 3 3 0 09 4 2 3 1 2 48 ' 30/35 Full Burns Footnotes for TABLE VII: # Blend Unless otherwise indicated the structure of the surfactant used as the foam stabilizer can be found in TABLE VI, 5 A This Surfactant has the average formula (Me 3 Si O 3,2)(Me 2 Si O)162 l(C 3 Ho 0)e 3 (C 2 H 40)21 6 Bul 3 C This Surfactant has the average formula: Me 3 Si O(Me 2 Si O),o(Me Si O),o(Me Si O)e Si Me 3 C 3 Hs CN C 3 Hs O(C 3 H 8 O)2 s (C 2 H 40)249 Me 22 1,569,319 22 The data in TABLE VII clearly shows that the use of Surfactants I, Ia, VIII, XII, XIII, the blend of XIV to XVIII, and XXI which are representative of the present invention gave better foam breathability results than comparative Surfactants A and C which are outside of the scope of the present invention, while also provided a better foam burning rating than Surfactant A, as well as Surfactants Ba and IX which are also outside of the scope of the present invention. Example 4. In accordance with this example, a series of flexible polyether urethane foams were prepared using various "urfactant foam stabilizers, FOAM FORMULATION B, and the foaming process detailed above The results of these various flexible polyether foam preparations, which are free of a flame retardant, are given in TABLE VIII below. TABLE VIII Surfactant Surfactant Number Concentration (php) A B B B C I I I Ia Ia III IV IV IV V VI VII VIII VIII 111 VIII IX IX 1.0 0.8 1.0 1.2 0.6 0.6 0.8 1.0 1.2 0.6 1.2 2.0 1.0 0.8 1.0 1.2 3.0 3.0 3.0 0.6 1.2 0.6 1.2 Foam Rise Inches 10.7 11.0 11.5 11.9 11.7 10.7 11.2 11.3 11.4 11.1 11.6 Collapsed 10.2 11.1 11.1 11.6 10.3 Collapsed Collpased 11.7 12.2 11.1 11.9 Breathability (SCFM) 3.5 4.9 4.9 4.8 4.6 4.9 4.2 5.3 4.8 4.9 3.3 5.6 4.4 6.1 5.5 Top Collapse (Inches) 0.3 1.0 0.8 0.6 0.4 0.9 0.4 0.9 0.5 0.4 1.8 0.7 0.3 0.9 0.3 Footnote for TABLE VIII: Unless otherwise indicated the average formula of the Surfactant used as the foam stabilizer can be found in TABLE VI. The average formulas of Surfactants A and C are found in the footnotes of TABLE VII. The data in TABLE VIII above indicates that the Surfactants have the following potency ratings: 1,569,319 22, 1,569,319 Surfactant B I Ia II III IV V VI VII VIII IX Rating Good Good Excellent Failed Poor Fair Failed Failed Failed Excellent Excellent Additional potency determinations with FOAM FORMULATION B were made on the remainder of the surfactants of TABLE VI The results were as follows. Surfactant Potency X Poor XI Good XII Fair XIII Good XIV-XVII (Blend) XIX XX XXI Ba Bb to Bf B 9 Good Very poor Failed Fair Good All Excellent Very Good Example 5. In accordance with this example, a series of flexible polyether urethane foams were prepared using various surfactant foam stabilizers, FOAM FORMULATION C, and the foaming process detailed above The results of these various flexible polyether foam preparations, which contain a flame retardant are given in TABLE IX below. t O 4. TABLE IX Foam Rise (Inches) Breathability (SCFM) Burning Density Extent (pcf) (inches) Burning Time (sec) Cells per Inch 3.5 1 64 Ful 3.5 1 64 Ful 3.5 1 7 2 2 4.3 1 69 3.9 1 69 2.6 2 05 4.0 1 71 4.3 4.2 3.6 1.64 1.65 2.2 2.2 1.8 2.6 2.5 2.6 1.9 22 44 Coarse Footnotes for TABLE IX: Unless otherwise indicated the avg formula of the foam stabilizer can be found in,TABLE VI. Surfactant used as the The avg formulas of Surfactants A and C are found in the footnotes of TABLE VII. The data in TABLE IX clearly shows that the use of Surfactants I, II, III, IV and V which represent the present invention are effective stabilizers of flexible polyether foam and offer the further advantage of allowing for the formation of foams containing a flame retardant of a significantly lower flammability rating than foams stabilized by comparative Surfactants A and B. Surfactant No Surfactant Conc (php) B 1.0 1.0 I 0.5 I 1.0 II 1.4 III 30/35 30/,35 2.0 7.8 7.6 7.7 7.4 7.2 6.2 7.3 7.6 7.8 6.3 IV 1.0 IV V 1.0 1.4 2.0 30/,'335 30/35 30/35 Voids 30/35 30/35 30/35 Coarse Lo t, j 1.9 2 2 Example 6. In accordance with this example a series of flexible polyether urethane foams were prepared whereby Surfactant I (TABLE VI above) representing the present invention was compared with Surfactant A (TABLE VII above) which is outside the scope of the present invention The foams were prepared using FOAM FORMULATION D and the foaming process detailed above The tin catalyst and flame retardant concentrations were also varied The results of these flexible polyether foam preparations, which also contain a flame retardant, are given in TABLE X below. TABLE X Surfactant I 1 2 3 4 55 l 6 Run Number Surfactant A 7 8 9 10 11 12 13 14 15 Stannous Octoate, (php) Surfactant, (php) Flame Retardant (php) 0.20 1.50 10.0 0.20 O 20 0 15 0.70 0 70 1 50 7.5 5 0 10 0 0.25 1.50 10.0 0.15 0 15 0 15 0.70 1 5 1 5 0 Cream Time, sec. Rise Time, sec. Top Collapse, in. Splits Density, lb/ft 3 Cells/Inch Nopco Breathability, (scfm) Burn Extent, in. Burn Time, sec. 10.0 95.0 0.0 1.61 4050.0 4.20 10.0 10 0 11 0 87.0 83 0 105 0 0.0 0 0 4 0 Split 1.58 4050.0 4.20 1.57 4050.0 3.90 3.00 3 23 5 O 41.0 42 67 63 67 1.61 4050.0 4.7 () 9.0 86.0 0.0 1.58 4050.0 2.65 2.63 2 4 39.67 32 67 10.0 82.0 0.4 Split 1.53 4550.0 5.5 10.0 86.0 0.05 1.50 4550.0 5.25 9.0 92.0 0.10 Split 1.71 4550.0 4.3 9.0 97.0 0.02 1.59 4550.0 4.0 9.0 94.0 0.02 1.61 4550.0 2.65 9.0 87.0 0.0 10.0 93.0 0.15 Split 10.0 112 0 0.10 Split 1.54 4550.0 1.90 4 3 5 0 4 9 2 85 3 9 2 3 61 3 64 0 62 3 40 75 51 7 41 0 0.175 1.5 10.0 0.20 1.5 10.0 0.25 1.5 10.0 0.20 0.70 10.0 -7 0 " O O 0.175 1.5 15.0 0.15 0 15 0.70 1 5 3.0 3 0 10.0 84.0 0.5 Split 10.0 88.0 0.1 4 " Split I I t O 26 1,569,319 26 2 The data in TABLE X above, clearly shows that Surfactant I of the present invention was superior to control Surfactant A in limiting burning of the foams produced. Claims (1) WHAT WE CLAIM IS:- 5 1 A polysiloxane-polyoxyalkylene block copolymer having the average 5 formula: (R Si) t{(O Si R,)wlO Si R(Rl)lzlO(CHH 2 O),R 2 lv 1 (OR 4)_} t+ 2 wherein: R is a monovalent hydrocarbon radical containing from 1 to 10 carbon atoms; R' is a cyano-substituted radical of the formula-(-O)0 R 3 CN wherein R 3 is a 10 bivalent alkylene radical containing from 2 to 6 carbon atoms or a bivalent alkyleneoxyalkylene radical containing from 4 to 12 carbon atoms, and a has a value of 0 or 1; R 2 is a monovalent hydrocarbon radical containing from 1 to 12 carbon atoms; R 4 is an alkyl group containing from 1 to 10 carbon atoms; 15 t for an individual molecule has an integral value of between 0 and 6, with an average non-integral value for the averaged copolymer of from 0 8 to 4; w has an average value cf from 3 to 100, z has an average value of from 3 to 20; N has a value of from 2 to 4 provided that from 20 to 65 weight percent of the 20 oxyalkylene units of the polyoxyalkylene chain, (CH 2,O)p, is composed of oxyethylene units; p has an average value such that the average molecular weight of the polyoxyalkylene chain is from 800 to 6000, and v has an average value of from 0 8 to 1 25 2 A copolymer as claimed in claim 1, wherein R is a C, to C 4 alkyl radical, a has a value of 0; t has a value of from 0 8 to 2; W has a value of from 9 to 40; z has a value of from 3 to 15 and the average molecular weight of the polyoxyalkylene chain is from 800 to 4000. 3 A copolymer as claimed in claim I or claim 2, wherein the polyoxyalkylene 30 chain is a poly(oxyethyleneoxypropylene) radical. 4 A copolymer as claimed in claim 3 wherein the polyoxyalkylene chain comprises a mixture consisting essentially of (a) from 50 to 95 percent by weight of low molecular weight poly(oxyethylene-oxypropylene) groups having an average molecular weight of from 800 to 3000 and wherein frohl 20 to 65 weight percent of 35 the oxyalkylene groups are oxyethylene groups, the remainder of the oxyalkylene groups being oxypropylene groups, and (b) from 50 to 5 percent by weight of high molecular weight poly(oxyethylene-oxypropylene) groups having an average molecular weight of from 1600 to 6000 and wherein from 20 to 65 weight percent of the oxyalkylene groups are oxyethylene groups, the remainder of the oxyalkylene 40 groups being oxypropylene groups; provided that the said mixture has an average molecular weight no higher than 4000. A copolymer as claimed in any one of claims 1 to 4 wherein R is a methyl radical, R 2 is a n-butyl radical, R 3 is a-CH 2 CH 2 CH 2 group, and the oxyalkylene units of the polyoxyalkylene chain are randomly distributed 45 6 A copolymer as claimed in claim 1 having the average tormula: Me Me l l lMe Si O 3,2 l(Si O)w(Si O)zl(C 3 H 8 O)v(C 2 H 40)x R 2 l 3 Me R 3 CN wherein Me is a methyl group, and x and y have average values such that the average molecular weight of the polyoxyalkylene chain is within the range of from 800 to 6000 and from 20 to 65 weight percent of the polyoxyalkylene chain is 50 composed of oxyethylene groups. 7 A copolymer as claimed in claim 6, wherein W has an average value of from 9 to 40, z has an average value of from 3 to 15; wherein the average molecular weight of the polyoxyalkylene chain is within the range of from 1000 to 4000, R 3 is an alkylene radical containing from 2 to 4 carbon atoms and R 2 is an alkyl radical 55 containing from I to 4 carbon atoms. 1,569,319 8 A copolymer as claimed in claim 7, wherein the polyoxyalkylene chain comprises a mixture consisting essentially of (a) from 60 to 90 percent by weight of low molecular weight poly(oxyethylene-oxypropylene) groups; having an average molecular weight of from 1400 to 2500 and wherein from 20 to 65 weight percent of the oxyalkylene groups are oxyethylene groups, the remainder of the oxyalkylene 5 groups being oxypropylene groups, and (b) from 40 to 10 percent by weight of high molecular weight poly(oxyethylene-oxypropylene) groups having an average molecular weight from 2500 to 3500 and wherein from 20 to 65 weight percent of the oxyalkylene groups are oxyethylene groups, the remainder of the oxyalkylene groups being oxypropylene groups; provided that the said mixture has an average 10 molecular weight no higher than 4000. 9 A copolymer as claimed in claim 8, wherein R 2 is a n-butyl radical and R 3 is a -CH 2 CH 2 CH 2 group and the oxyalkylene units of the polyoxyalkylene chain are randomly distributed. 10 A copolymer as claimed in claim 9, wherein the polyoxyalkylene chain 15 comprises a mixture consisting essentially of about 78 percent by weight of (C 3 H,0),4 (C 2 H 40)1, 4 C 4 H 9 and about 22 percent 'by weight of (C 3 H 60)24 3 (C 2 H 40)32 1 C 4 H 9. 11 A copolymer as claimed in claim 10 having the average formula:lMe Si O 3/2 l(Me 2 Si O)22 (Me Si O)6 l(C 3 H 60) 17 6 (C 2 H 40)233 C 4 Hl 320 (CH 2)3 CN 12 A copolymer as claimed in claim 1 substantially as hereinbefore described. 13 A copolymer as claimed in claim I substantially as hereinbefore described in any one of Examples 2 to 6. 14 A method of preparing a copolymer as claimed in claim I substantially as hereinbefore described 25 A method of preparing a copolymer as claimed in claim I substantially as hereinbefore described in Example 2. 16 A process for producing flexible polyurethane foam, which comprises reacting and foaming a reaction mixture comprising: (a) a polyether polyol reactant containing an average of at least two hydroxyl groups per molecule; (b) a poly 30 isocyanate reactant containing at least two isocyanato groups per molecule; (c) a blowing agent; (d) a catalyst comprising an amine; and (e) as the foam stabilizer, a polysiloxane-polyoxyalkylene block copolymer as claimed in any one of claims I to 13. 17 A process as claimed in claim 16 wherein a flame-retardant is present as an 35 additional component of the reaction mixture. 18 A process as claimed in claim 16 or claim 17 wherein water is a source of the blowing action, wherein the catalyst is a tertiary amine and wherein a cocatalyst comprising an organic derivative of tin is present as an additional component of the reaction mixture 40 19 A process as claimed in any one of claims 16 to 18 wherein a crosslinking agent, a filler, a dye, a pigment, or an anti-yellowing agent is present as an additional component of the reaction mixture. A process as claimed in claim 16 substantially as hereinbefore described. 21 A process as claimed in claim 16 substantially as hereinbefore described in 45 any one of Examples 3 to 6. 22 A flexible polyurethane foam when produced by a process as claimed in any one of claims 16 to 21. 23 A textile interliner, cushion, mattress, carpet underlay, gasket, or sealer, or padding, packaging or thermal insulation material when made from or comprising a 50 flexible polyurethane foam as claimed in claim 22. BOULT, WADE & TENNANT, Chartered Patent Agents, 34 Cursitor Street, London, EC 4 A 1 PQ. Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1980. Published by the Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained. 1,569,319 GB54166/76A 1975-12-29 1976-12-24 Organosilicone polymers Expired GB1569319A (en) Applications Claiming Priority (1) Application Number Priority Date Filing Date Title US05/644,838 US4045381A (en) 1975-12-29 1975-12-29 Organosilicone polymers Publications (1) Publication Number Publication Date GB1569319A true GB1569319A (en) 1980-06-11 Family ID=24586547 Family Applications (1) Application Number Title Priority Date Filing Date GB54166/76A Expired GB1569319A (en) 1975-12-29 1976-12-24 Organosilicone polymers Country Status (7) Country Link US (1) US4045381A (en) JP (2) JPS5283000A (en) BE (1) BE849916A (en) CA (1) CA1092607A (en) DE (1) DE2659252C2 (en) FR (1) FR2337160A1 (en) GB (1) GB1569319A (en) Families Citing this family (6) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title JPS56175661U (en) * 1980-05-29 1981-12-25 JPS5883155A (en) * 1981-11-11 1983-05-18 Toyo Soda Mfg Co Ltd Heat-receiving body DE3807247C1 (en) * 1988-03-05 1989-05-24 Th. Goldschmidt Ag, 4300 Essen, De US5057361A (en) * 1989-11-17 1991-10-15 Kimberly-Clark Corporation Wettable polymeric fabrics US5432206A (en) 1994-07-29 1995-07-11 Dow Corning Corporation Polyether silicone surfactants for the manufacture of urethane foams KR20090015591A (en) * 2007-08-09 2009-02-12 삼성전자주식회사 Composition for preparing polyurethane foam, polyurethane foam made therefrom, and preparation method thereof Family Cites Families (11) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title GB1114428A (en) * 1964-09-14 1968-05-22 Union Carbide Corp Improvements in the production of flexible polyurethane foams GB1058159A (en) * 1964-09-14 1967-02-08 Ici Ltd Organosilicon polymers FR1511661A (en) * 1966-12-23 1968-02-02 Rhone Poulenc Sa New siloxane-polyoxyalkylene copolymers US3564037A (en) * 1966-12-29 1971-02-16 Rhone Poulenc Sa Novel polysiloxane-polyalkylene copolymers US3741917A (en) * 1970-10-26 1973-06-26 Union Carbide Corp Cold cure high resilience foam US3793300A (en) * 1972-06-26 1974-02-19 Union Carbide Corp Flexible polyester urethane foams using liquid siloxane-oxyalkylene polymeric foam stabilizers US3887500A (en) * 1972-08-11 1975-06-03 Union Carbide Corp Organosilicone polymers US3846462A (en) * 1972-08-11 1974-11-05 Union Carbide Corp Organosilicone polymers US3905924A (en) * 1973-01-22 1975-09-16 Union Carbide Corp Process for preparation of high resilience polyether urethane foam US3966784A (en) * 1973-02-22 1976-06-29 Union Carbide Corporation Polyether urethane foam US3954824A (en) * 1974-04-03 1976-05-04 Union Carbide Corporation Organosilicone polymers and polyester urethane foam produced therewith 1975 1975-12-29 US US05/644,838 patent/US4045381A/en not_active Expired - Lifetime 1976 1976-12-10 CA CA267,680A patent/CA1092607A/en not_active Expired 1976-12-24 GB GB54166/76A patent/GB1569319A/en not_active Expired 1976-12-28 BE BE173688A patent/BE849916A/en not_active IP Right Cessation 1976-12-28 FR FR7639317A patent/FR2337160A1/en active Granted 1976-12-28 DE DE2659252A patent/DE2659252C2/en not_active Expired 1976-12-28 JP JP15770176A patent/JPS5283000A/en active Granted 1980 1980-03-17 JP JP55032810A patent/JPS5820966B2/en not_active Expired Also Published As Publication number Publication date JPS5535410B2 (en) 1980-09-13 JPS5283000A (en) 1977-07-11 JPS5820966B2 (en) 1983-04-26 CA1092607A (en) 1980-12-30 DE2659252A1 (en) 1977-07-07 BE849916A (en) 1977-06-28 FR2337160A1 (en) 1977-07-29 US4045381A (en) 1977-08-30 DE2659252C2 (en) 1983-06-01 FR2337160B1 (en) 1981-07-10 JPS55133418A (en) 1980-10-17 Similar Documents Publication Publication Date Title US4025456A (en) 1977-05-24 Polysiloxane-polyoxyalkylene block copolymers US3980688A (en) 1976-09-14 Polysiloxane-polyoxyalkylene block copolymers US3686254A (en) 1972-08-22 Siloxane-polyoxyalkylene block copolymers US4814409A (en) 1989-03-21 Polysiloxane-polyoxyalkylene terpolymers for polyurethane foam manufacture US4147847A (en) 1979-04-03 Method of preparing flexible flame retardant polyether based one-shot polyurethane foams and compositions therefore US3846462A (en) 1974-11-05 Organosilicone polymers EP0275563B1 (en) 1993-11-03 Polysiloxane-polyoxyalkylene compositions for polyurethane foam manufacture CA1040788A (en) 1978-10-17 Beta-amino nitrile catalysts for polyurethane preparation US4018723A (en) 1977-04-19 Morpholino-modified polysiloxane-polyoxyalkylene copolymers and their use as foam stabilizers in polyurethanes US3384599A (en) 1968-05-21 Siloxane-polyol compositions and process therefor US3796676A (en) 1974-03-12 Organosilicone polymeric foam stabilizer composition and polyester urethane foam produced therewith US4855329A (en) 1989-08-08 Polysiloxane-polyoxyalkylene terpolymers for polyurethane foam manufacture CA1203350A (en) 1986-04-15 Amino catalyst mixture for stabilization of polyurethane foam US3887500A (en) 1975-06-03 Organosilicone polymers US3703489A (en) 1972-11-21 Process for producing polyurethane foams US4110271A (en) 1978-08-29 Formation of polyurethane foam in the presence of sulfolanyl-bearing polysiloxane-polyoxyalkylene polymers US3887601A (en) 1975-06-03 Organosilicone polymers US3793300A (en) 1974-02-19 Flexible polyester urethane foams using liquid siloxane-oxyalkylene polymeric foam stabilizers US3793360A (en) 1974-02-19 Organosilicone polymers US3779956A (en) 1973-12-18 Process for reducing flammability of polyurethane foams US4045381A (en) 1977-08-30 Organosilicone polymers US3935123A (en) 1976-01-27 Polysiloxane-polyoxyalkylene compositions used in polyurethane foam US4138391A (en) 1979-02-06 Acrylonitrile-capped polyether-siloxanes US3833512A (en) 1974-09-03 Solution compositions of organo-silicone polymers US4014825A (en) 1977-03-29 Tertiary alcohol-bearing organosilicone polymers Legal Events Date Code Title Description 1980-08-28 PS Patent sealed [section 19, patents act 1949] 1986-08-06 PCNP Patent ceased through non-payment of renewal fee
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