CA1064649A - Polyether based, high resilient polyurethane foam - Google Patents
Polyether based, high resilient polyurethane foamInfo
- Publication number
- CA1064649A CA1064649A CA205,851A CA205851A CA1064649A CA 1064649 A CA1064649 A CA 1064649A CA 205851 A CA205851 A CA 205851A CA 1064649 A CA1064649 A CA 1064649A
- Authority
- CA
- Canada
- Prior art keywords
- polyether polyol
- mixture
- foam
- weight
- polyether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Silicon Polymers (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A method is disclosed in which polyether based high resilient polyurethane foams are produced. The foams have low shrinkage and are free of voids. These two main physical properties are obtained without the sacrifice of other important physical properties. The results are achieved by utilizing novel siloxane-oxyalkylene copolymeric foam stabilizers of the general formula Me3Si(OSiMe2)h(OSiMeG)dOSiMe3 where h has an average value of about 0, 1 or 3, d has an average value of about 1 or 2, Me is the methyl radical and G is -(CH2)3(OCH2,CH)2OCH3 or -(CH2)3(OCH2,CH)2OCCH3 or -(CH2)3(OCH2,CH)2.5OCH3-.
A method is disclosed in which polyether based high resilient polyurethane foams are produced. The foams have low shrinkage and are free of voids. These two main physical properties are obtained without the sacrifice of other important physical properties. The results are achieved by utilizing novel siloxane-oxyalkylene copolymeric foam stabilizers of the general formula Me3Si(OSiMe2)h(OSiMeG)dOSiMe3 where h has an average value of about 0, 1 or 3, d has an average value of about 1 or 2, Me is the methyl radical and G is -(CH2)3(OCH2,CH)2OCH3 or -(CH2)3(OCH2,CH)2OCCH3 or -(CH2)3(OCH2,CH)2.5OCH3-.
Description
.; . ~.
The expansion of technology in the polyether based polyurethane foam system over the last 10-15 years ~- has been tremendous. It is natural, therefore, that the advent of a specialized area within that industry would materialize and take a significant portion of the commer-cial market. Such a specialized area is that of high ;~
resilience foams.
Resilience is defined as the work which a body can do in springing back after a deforming force has been removed. In defining resilience in polyurethane foams, the industry generally considers a sag factor --to differentiate conventional foams from high resilient ; foams. The sag factor is the ratio of indent load deflection at 65~ deflection to that of the indent load deflection at 25~ deflection. Indent load deflection :~ is measured in lbs./50 in2. Conventional foams have `~
a sag factor of 2.0 to 2.3 while high resilient foams ;~
have such a factor of 2.8 to 3.1.
Since its introduction several years ago, high resilience foams have~commanded a great amount of attention from the urethane foam industry. The material has foun~ widespread application, most sig-, .~ ` .
; nificantly in the automobile industry for molded parts, :- but also in the furniture and bedding industries. This ~I high acceptance has been due to the fact that most `~ techniques from the alrea~y established polyurethane foam industry can be utilized in high resilience foams l and, moreover, the properties of the foam itself differ i from ordinarily produced polyurethane foam to the extent 1 30 that for some applications, the high resilience foam is . ~ . . .
,:j :, .
.; -1- . ~ ~,:, .','' ' '~ ;
, .
. ,,~ ,. . .
: ,' ' ' : , , ~6~6~
preferred. The physical pr~perties most valuable are physical properties giving comfort~ fatigue resistance and flame resi.stance.
With some modifications, the high resilience - foam technology can be fitted into the already existing polyurethane f`oam technologyO
As the foregQing indicates, the technology of the ordinary polyurethane foam industry is applicable to high resilient foams, but one area of the technology is not readily transferred. The area is that portion of the foamable compositlon which stabilizes the composi-tion as it reacts, foams and finally solidifies. As a matter of fact, the foam stabilizers used in existing ~ -polyurethane foam systems cann.o.t be used.in the.new high resilient foams because they cause severe voids and splits in the foam and also cause severe shrinkage of the foam slab. ;-It has now been found that certain specially defined polymeric materials will stabilize high -~
resilience foams without causing voids, splits and : foam shrinkage while maintaining the other valuable physical properties. ;` ~:
It is theref~re an object of this invention to provide compositions and a process for producing high resilient polyurethane foam which ~ill consistently give foams which have a fine, uniform cell structure. ~ -.
It is a further object of this invention to provide compositions and a process for producing high ~. -resilient polyurethane foam which will consistently give foams which are free of voids and splits.
The expansion of technology in the polyether based polyurethane foam system over the last 10-15 years ~- has been tremendous. It is natural, therefore, that the advent of a specialized area within that industry would materialize and take a significant portion of the commer-cial market. Such a specialized area is that of high ;~
resilience foams.
Resilience is defined as the work which a body can do in springing back after a deforming force has been removed. In defining resilience in polyurethane foams, the industry generally considers a sag factor --to differentiate conventional foams from high resilient ; foams. The sag factor is the ratio of indent load deflection at 65~ deflection to that of the indent load deflection at 25~ deflection. Indent load deflection :~ is measured in lbs./50 in2. Conventional foams have `~
a sag factor of 2.0 to 2.3 while high resilient foams ;~
have such a factor of 2.8 to 3.1.
Since its introduction several years ago, high resilience foams have~commanded a great amount of attention from the urethane foam industry. The material has foun~ widespread application, most sig-, .~ ` .
; nificantly in the automobile industry for molded parts, :- but also in the furniture and bedding industries. This ~I high acceptance has been due to the fact that most `~ techniques from the alrea~y established polyurethane foam industry can be utilized in high resilience foams l and, moreover, the properties of the foam itself differ i from ordinarily produced polyurethane foam to the extent 1 30 that for some applications, the high resilience foam is . ~ . . .
,:j :, .
.; -1- . ~ ~,:, .','' ' '~ ;
, .
. ,,~ ,. . .
: ,' ' ' : , , ~6~6~
preferred. The physical pr~perties most valuable are physical properties giving comfort~ fatigue resistance and flame resi.stance.
With some modifications, the high resilience - foam technology can be fitted into the already existing polyurethane f`oam technologyO
As the foregQing indicates, the technology of the ordinary polyurethane foam industry is applicable to high resilient foams, but one area of the technology is not readily transferred. The area is that portion of the foamable compositlon which stabilizes the composi-tion as it reacts, foams and finally solidifies. As a matter of fact, the foam stabilizers used in existing ~ -polyurethane foam systems cann.o.t be used.in the.new high resilient foams because they cause severe voids and splits in the foam and also cause severe shrinkage of the foam slab. ;-It has now been found that certain specially defined polymeric materials will stabilize high -~
resilience foams without causing voids, splits and : foam shrinkage while maintaining the other valuable physical properties. ;` ~:
It is theref~re an object of this invention to provide compositions and a process for producing high resilient polyurethane foam which ~ill consistently give foams which have a fine, uniform cell structure. ~ -.
It is a further object of this invention to provide compositions and a process for producing high ~. -resilient polyurethane foam which will consistently give foams which are free of voids and splits.
-2-Still another ob,ject of this invention is to provide compositions and a process for producing foam which will consistently maintain the foamed~ cured heighth without shrinking upon cure. Yet another object of this invention is to provide the industry with more processing latitude than has been possible heretofore.
It has now been found that the use of certain ~-; siloxane-oxyalkylene copolymers as foam stabilizers in polyether based high resilient polyurethane fQams will allow the production of foams which will have no voi~s or splits, no slab shrinkage and useful physical `~
properties. In addition, the foam stabilizers of this invention give the pro~ucer more process latitude in ~
-~ that he can not only utilize the foam stabilizer in ~ -various quantities to fit his own peculiar polyurethane ;~
foam need~, but he can utilize the foam stabilizers in both of the current, popular polyurethane foam processing systems i.e. the polymer in p~ly~l and the cr~ss-linked systems. ~ ~`
More speci~ically, the invention deals with ; a ~rocess for pre~aring high res1lient polyurethane foam, which process includes the steps:
[I] Preparing a homogeneous mixture consisting , i ~
~- essentially of (A) 100 parts by weight of a base polyether ~ polyol selecte~ from a group consisting of ~`~
`~ (i) a polyether triol containing at least 40 m~le ~ercent primary hydroxyl groups and `~
having a molecular weight in the range of 2,000 to 8,ooo grams per mole and (ii) a mixture of (i) and an additional ., ,,, . .
It has now been found that the use of certain ~-; siloxane-oxyalkylene copolymers as foam stabilizers in polyether based high resilient polyurethane fQams will allow the production of foams which will have no voi~s or splits, no slab shrinkage and useful physical `~
properties. In addition, the foam stabilizers of this invention give the pro~ucer more process latitude in ~
-~ that he can not only utilize the foam stabilizer in ~ -various quantities to fit his own peculiar polyurethane ;~
foam need~, but he can utilize the foam stabilizers in both of the current, popular polyurethane foam processing systems i.e. the polymer in p~ly~l and the cr~ss-linked systems. ~ ~`
More speci~ically, the invention deals with ; a ~rocess for pre~aring high res1lient polyurethane foam, which process includes the steps:
[I] Preparing a homogeneous mixture consisting , i ~
~- essentially of (A) 100 parts by weight of a base polyether ~ polyol selecte~ from a group consisting of ~`~
`~ (i) a polyether triol containing at least 40 m~le ~ercent primary hydroxyl groups and `~
having a molecular weight in the range of 2,000 to 8,ooo grams per mole and (ii) a mixture of (i) and an additional ., ,,, . .
-3- -;
: " :
, .. . . .
9 ~ ~ ~
polye-ther polyol havi.ng an average of at least two : .
hydroxyl groupsJ wherein said polyether poly~l is :
present in the mixture (li) to at least 40 weigh-t percent of the total polyether polyol content of (ii), -~ ;
(B) a sufficient amount of organic polyiso-cyanate to give from 90-120 percent, on a stoichiometric basis, of isocyanate radicals for each hydroxyl radical in the composition, - ,; .~, (C) a catalytic amount of a catalyst for ::~
: 10 the production of the high resilient polyurethane foam, ,: .
(D) 1-10 parts by weight of a blowing agent, .~ -~
.` (E) a foam stabilizing amount of a siloxane-; oxyalkylene copolymer selected from a group consisting . ~:
.: . . , of (1), (2), (3), (4) ~r mixtures thereof wherein (1) ` ~:
has the general f~rmula . ;;:~
RaSi{(OSiMe2)eOSiMe2G3~a 3 . in which formula R is a hydrocarbon ~`~
.~ radical free ~f aliphatic unsaturation and contains ;
from 1-10 carbon atoms, a is 0-~
, .. Me is a Methyl ra~ical, G is a radical selected from a group con~
sisting ~f -D(0R")mA and -L-D(oR1')mA wherein L is an oxygen or sulrur atom, D is a divalent linking radical selected :: from the group consisting of , ~
~ (i) al`kylene radi.cals, ; 30 (ii) radicals composed of carbon, hydrogen and oxygen atoms, the oxygen atoms being present as ether, ester or hydroxy groups, and _L~_ / .. : ~ .... . . .
: . ,~ , :. .. . . . .
~0~649 (;ii) radicals composed ~f carbon, hydrogen ; and sulfur atoms, the sulfur atoms being present as thioether, thioester ~r thlol groups, th~re being no more than 8 carbon a-toms in D, and L is bonded to a carb~n atom of the D radical, ;~
R" is comp~sed of propylene radicals and radicals selected from the gr~up consisting of ethylene ~ .:
and butylene radicals wherein the amount of ethylene -and butylene ra~icals is less than 35 weight percent of the total (OR") ra~ical, .j;
m has an average value of 1-15~
A is a radical selected from the group c~nsisting of the -OR', OOCR', and OCQO~' radicals '~
wherein R' is a radical free 3f aliphatic unsaturati~n :~
selecte~ from the group consisting of hydr~carbon and . hydrocarboxy radicals, the A radical contalning a t~tal ~ of less than eleven atoms, in which formula when a = O, then e is 0, 1 or 2; when a = 1, then e is 0, 1, 2 ~r 3;
when a = 2, then e is 0-5, and when a = ~, then e is 0-7;
(2) has the general formula GMezSi(OSiMe2)f(0SiMeG)bOSiMe2G, in which formula when b = O, then f is 0-7 when b = 1, then f is 0-7; when b = 2, then f is 0-5; ~:~
when b = 3~ then f is 0-4 and when b = 4, f is 0-2; ..
(3) has the general formula RaSi{(OSiMe2)g(0SiMeG)cOSiMe3~ 4 - a ' ~:;; - , in which formula when a = O, g = O, then c = 1; when a = 1, g = O, then c = l; when a = 2, g = O, then c = 1 or 2; when a = 3, g = O, then c = 1-5; :
., , ~ : .
-5- ~ ~
., .
.. , `` 1~69~6g~9 when a -- 1, g = 1, then c = 1; when a = 2, c = 1, then g = 1 or 2,
: " :
, .. . . .
9 ~ ~ ~
polye-ther polyol havi.ng an average of at least two : .
hydroxyl groupsJ wherein said polyether poly~l is :
present in the mixture (li) to at least 40 weigh-t percent of the total polyether polyol content of (ii), -~ ;
(B) a sufficient amount of organic polyiso-cyanate to give from 90-120 percent, on a stoichiometric basis, of isocyanate radicals for each hydroxyl radical in the composition, - ,; .~, (C) a catalytic amount of a catalyst for ::~
: 10 the production of the high resilient polyurethane foam, ,: .
(D) 1-10 parts by weight of a blowing agent, .~ -~
.` (E) a foam stabilizing amount of a siloxane-; oxyalkylene copolymer selected from a group consisting . ~:
.: . . , of (1), (2), (3), (4) ~r mixtures thereof wherein (1) ` ~:
has the general f~rmula . ;;:~
RaSi{(OSiMe2)eOSiMe2G3~a 3 . in which formula R is a hydrocarbon ~`~
.~ radical free ~f aliphatic unsaturation and contains ;
from 1-10 carbon atoms, a is 0-~
, .. Me is a Methyl ra~ical, G is a radical selected from a group con~
sisting ~f -D(0R")mA and -L-D(oR1')mA wherein L is an oxygen or sulrur atom, D is a divalent linking radical selected :: from the group consisting of , ~
~ (i) al`kylene radi.cals, ; 30 (ii) radicals composed of carbon, hydrogen and oxygen atoms, the oxygen atoms being present as ether, ester or hydroxy groups, and _L~_ / .. : ~ .... . . .
: . ,~ , :. .. . . . .
~0~649 (;ii) radicals composed ~f carbon, hydrogen ; and sulfur atoms, the sulfur atoms being present as thioether, thioester ~r thlol groups, th~re being no more than 8 carbon a-toms in D, and L is bonded to a carb~n atom of the D radical, ;~
R" is comp~sed of propylene radicals and radicals selected from the gr~up consisting of ethylene ~ .:
and butylene radicals wherein the amount of ethylene -and butylene ra~icals is less than 35 weight percent of the total (OR") ra~ical, .j;
m has an average value of 1-15~
A is a radical selected from the group c~nsisting of the -OR', OOCR', and OCQO~' radicals '~
wherein R' is a radical free 3f aliphatic unsaturati~n :~
selecte~ from the group consisting of hydr~carbon and . hydrocarboxy radicals, the A radical contalning a t~tal ~ of less than eleven atoms, in which formula when a = O, then e is 0, 1 or 2; when a = 1, then e is 0, 1, 2 ~r 3;
when a = 2, then e is 0-5, and when a = ~, then e is 0-7;
(2) has the general formula GMezSi(OSiMe2)f(0SiMeG)bOSiMe2G, in which formula when b = O, then f is 0-7 when b = 1, then f is 0-7; when b = 2, then f is 0-5; ~:~
when b = 3~ then f is 0-4 and when b = 4, f is 0-2; ..
(3) has the general formula RaSi{(OSiMe2)g(0SiMeG)cOSiMe3~ 4 - a ' ~:;; - , in which formula when a = O, g = O, then c = 1; when a = 1, g = O, then c = l; when a = 2, g = O, then c = 1 or 2; when a = 3, g = O, then c = 1-5; :
., , ~ : .
-5- ~ ~
., .
.. , `` 1~69~6g~9 when a -- 1, g = 1, then c = 1; when a = 2, c = 1, then g = 1 or 2,
(4) has the general formula Me3Si(OSiMe2)h(OSiMeG)dOSiMe3, in which formula h has an average value of 0-7, _ has an average value of 1-5 and when = O, d = 1-5;
when _ = 1 or 2, then _ is 1-4; when _ = 3 or 4, then _ is 1-3; when h is 5, then d is 1-2; and when- _ is 6 or 7, then 1 r CII~ thereafter allowing the mixture to foam, and curing the foamed composition.
Thus, in accordance with the more specific teaching of the present concept a method is provided of pre~
paring a one-shot polyether based, high resilient polyurethane ` -`
foam. The method includes the steps of (I) preparing a homogeneous mixture consisting essentially of (A) 100 parts by weight of a base polyether ,~ ~, , .
polyol selected from the group consisting of (i) a polyether triol containing at least 40 ~ ~ ~
mole percent primary hydroxyl groups and having ~ ;
a molecular weight in the range of 2,000 to 8,000 grams per mole, and (ii) a mixture of ci~ and an additional polyether -polyol having an average of at least two hydroxyl groups, wherein said polyether polyol is present ~
in the mixture (ii) to at least 40 weight percent ~ ;
of the total polyether polyol content of (ii), (B~ a sufficient amount of organic polyisocyanate ~i 3Q to give from 90 to 120 percent, on a stoichio~ --metric basis, of isocyanate radicals for each hydroxyl radical in the composition, ~ kC -6-16~6~ g (C) a catalytic amount of a catalys~ for the ~ ~
production of the high resilient polyurethane ~ ;
foam, (D) 1 to 10 parts by ~eight of a blowing agent, ~ ;
(E) a foam stabiliz;ng amount of a copolymer of the general formula Me3Si(OSiMe2~h(0SiMeG)~OSiMe3 where _ has an average value of about 0, 1 or 3, d has an average value of about 1 or 2, Me is the Methyl radical and G is ~CH2)3(0CH2CCHHt20 3 ~CH2)3(0CH2cH~20ccH3 or ~CH2)3(0CH2CH)2 50CH3 The usual method of this invention is to combine ingredients tA), (C), (D), and (E) in any suitable container and ;~
., . . j: . , homogenize them using any suitable-means such as a commercial mixer or the likeO The component (B) is then added, the mixture again f '~
homogenized and the foam allowed to rise in the container. The foam can then be cured at room temperature (cold cured) or at O : . ~
elevated temperatures (usually 107 C) and then removed from the container for use later. In another method, the components can be metered and mixed automatically so that the separate step of adding component (B) can be eliminated. Both of these methods are generally known in the art with the exception~of the use of i ', component (E) of the present invention. The above modes of mix~
ing are not the only methods by which the foaming composition can be prepared. For instance, it is well within the scope of the ;
instant invention to mix the ingredients in any order in which it ' ~`
is desirable. The only exception is that component (B) '~
' "'""~':' :' -6a~
::
(~
^ 1~64~4~ ~
canno-t be mixed with any poly~l or similarly reactive component until the foaming is to begin The polyether p~lyols employed in -this inven-tion as component I(A) can be any p~]yether triol containing ; at least 40 mole percent of primary hydroxyl groups and having a molecular weight from about 2,000 to a~ut 8,ooo grams/mole. Preferably, said polyether poly~ls contain about 60-go mole percent of primary hydroxyl groups and have a m~lecular weight from about 4,000 to 7,oO0 grams/mole.
The preferred polyether poly~ls ~f this inventi~n are polyether triols obtained by chemical ';~
- addition of alkylene oxides to trihydroxyl organic containing materials such as glycerol, 1,2,~-hexane~
triol, l,l,l-trimethylolethane, 1,1,1 trimethylolpr~pane, - `
3-(2-hydr~xyeth~xy)-1,2 propanedi~l, 3,-(2-hydr~xypro-poxy)-1,2 propanediol and the like, as well as mixtures there~f, i~
Alternatively, the ~olyether ~olyols can be mixtures c~nsisting essentially ~f the above p~ly-ether tri~ls and other p~lyether polyols having an ;
- average of at least two hydroxyl radicals per molecule, said trisls constituting at least 40, ~referably 50 ~r ; m~re weight percent of the t~tal poly~l content of the mixture. Such other polyether p~lyols having an average ~f at least tw~ hydr~xyl radicals per molecule are triols outsi~e the scope of this inventi~n, diols, tetraols, and polymer/polyols as well as mixtures thereof. - ~
Examples of such polyether polyols containing ~ ?
at least two hydroxyl grou~s per molecule are 1,2-alkylene ; ~
.,` ':
-7- ;
:: ~
, ~ .
1~6~4~
oxides such as ethylene oxide, epichlorohydrin, ],2-propylene oxide~ 1,2 butylene oxide and 2,3-bu-tylene oxide, oxacyclobutane and substituted oxacyclobutanes and tetrafuran.
They may be linear polyether glycols as are prepared, for example, by the polymerization of an - alkylene oxide in the presence of a basic catalyst~
such as potassium hydroxide, and a glycol as a primary mon~amine. Alternatively there may be used branched polyether prepared, for example, by the polymerization of an alkylene oxide in the presence of a hasic catalyst and a substance having more than tw~ active hydrogen atoms per molecule, for example, ammonia and p~lyhydroxy compounds such as glycerol, hexanetriols, trimethylol-pro~ane and ethane, triethanolamine, ~entaerythritol, sorbitol, sucrose an~ phenol-f~rmaldehyde reaction products, aminoalcohols such as monoethanolamine and diethan~lamine and polyamines such as ethylene diamine, hexamethylenediamine, diethylene triamine, tolylene diamine an~ di~minodi~henylmethane. ~ranched p~lyethers ,., ,.. ~
may also be ~roduced by copolymerizing a cyclic oxide of the type already mentioned with cyclic oxides having a functionality greater than two, for example, ~ie~oxides, glycidols and 3-hydroxymethyloxacycl~butanes. ;;~
Another ty~e of polyether ~olyol that can be mixéd with the above defined polyether triols and used as starting materials are graft polymer in polyether compositions obtained by polymeriæing ethylenically ~ ;
unsaturated monomers in a polyether as ~escribed in ~ .
3G U.S. Patent 3,383,351. Suitable monomers for producing ~
: .
::,. .
such compositions include~ for example, acrylonitrile, vinyl chloride, styreneJ butadiene~ vinylidene chloride3 and the like. The most preferred is acrylonitrile at this time. Suitable polyethers for producing such compositions include, f~r example, those polyethers described above. The graft polymer in ~olyether comp~siti~ns can contain fr~m about 1 to about 70 weight percent, preferably about 5-50 weight percent and most preferably ab~ut 10 t~ 40 weight percent of the m~ncmer polymerized in the polyether. Such compositions are conveniently prepared by polymerizing the monomers in the selecte~ ~lyether at a temperature of 40C to 150C in the presence ~f a free radical p~lymerization catalyst, such as per~xides, persulfates, ~ercarbonates, perb~rate and azo compounds. The resulting compositiorls may c~ntain some unreacted polyether, m~nomer and free ~-~olymer as well as the graft p~lymer in polyether reacted :
species.
The ~ase p~lyethers are ncrmally used in the amount of 100 parts by weight and the remainder of the com~onents are based upon the ~ase poly~ls.
' Com~onent I(B), ~rganic polyis~cyanates, which - are suitable in this inventi~n, include aliphatic diis~cy-anates such as hexamethylene diis~cyanate, ar~matic diis~cyanates such as toluene-2,4-diisocyanate, toluene~2 , -,,,~ ~
6-diis~cyanate and the familiar 8a 20 isomeric mixtures of the 2,4 and 2,6 t~luene diis~cyanate, diphenyl-methane-4,4-diis~cyanate, 3 methyldiphenylmethane -4,4'diisocyanate, m- and p-phenylene diisocyanate. ~-Other suitahle is~cyanates comprise the reaction , " _ g_ .
~- ;
1~i4~49 , products of an excess of the diisocyana-te with poly-hydric alc~hols such as trimethylolpropane. Still other isvcyanates are blends of the above isocyanates - ;
such as to]uene diisocyanate and p~ly aromatic poly-isocyanates and crude or residual polyisocyanates from -~
the pr~duction of purer species of polyisocyanates The is~cyanates can be employed in the inventi~n on a stoichiometric basis, that is, ~ne isocyanate ra~ical for every hydroxyl radical. The usual employment, however, is to utilize the-isocyanates s~ as to give from 10% less than stoichiometric quantities ~-~f is~cyanate radical to hydroxyl radical, t~ 20% greater `
than ~toichiometric quantities of isocyanate radical t~
hydroxyl in the system. Most ~referre~ for this inventi~n ~-~
is 5% in excess ~f the is~cyanate radicals over the ~ available hydr~xyl radicals.
;~ C0m~0nent I(C), a catalyst f~r the producti~n of the high resilient f0am includes ~oth ~rior art amines ,~
and soluble 0rganic c~mpounds~of heavy metals either -~
singly ~r in various combinations. Exam~les-~f amines useful in this invention include triethylenediamine and N-ethylmorph~line and examples of ~rganic comp~unds `~
of heavy metals are dibutyltindilaurate and~stannous octoate, Mixtures of catalysts may be advantage~us at times. The catalysts are used in the amounts ranging from ~.01-5.5 parts based on 100 ~arts ~f the base polyol, Compcnent I(D)g the blowing agent, is water ~--,:
or a low-b~iling ~rganic liquid. The bl~wing agent can be a mixture of water and a low-boiling organic liquid ~, . --10--' ~
, ' ,~ ~
,, . :
1~64~49 - ~
. The Low-boiling organic l~qui.d should be chemically .
inert towards the 1socyanates and water and have a boili.ng point less than -that of water. Preferably much lower as for instance 75C or lessO
Low-boiling organic liquids include halogenated alkanes such as monofluorotrichloromethane and methylene chlorideO ";
: The blowing agent is used in the amount of ~:~
l-lO parts per l~O parts of the base polyetherO When lO water is the sole blowing agent it is preferred to use :
from 200-~.5 parts per lOO parts of base polyether and :; - when halogenated alkanes are the sole blowing agent it ~ :~
is preferred to use from l-lO parts per lOO parts ~f .. ,., ~ .:~:
; base polyetherO Mixtures of halogenated alkanes are also useful in this inventionO
The final major comp~nent I(E), is the siloxane~
oxyalkylene copolymer foam stabilizerO ~hen used in this :: ::
. . .
invention, the foam stabilizer when used without dilution ~ is utilized in the amounts ranging from 0002-200 parts . 2Q ~er lOO parts of base ~olyether polyolO Most preferably it is used in the range of 00 5-lo 0 parts per lOO parts of polyether polyol The essence of the present method is the use ~
of the nove] siloxane~oxyalkylene c~olymers, comp3nent : --(E), in the f~aming systemO ~
It is the certain siloxane-oxyalkylene - :
copolymers, when used as foam stabilizers, that allow the cured foam to consist of fine-uniform cells. It . ~ :
; is the certain siloxane-oxyalkylene copolymers, when ~ ;
used as foam stabilizers, that allow the cured foam ::
., .
., 1~6~
to be clear of voids, spli-ts and holes and to be free from slab shrinkage. It is the certain siloxane-oxyalkylene copolymers, when used as fQam stabilizers, that allow the cured foam t~ exhibit. physical properties -which make it useful for molded foam applications.
Presently used polyurethane foam additives found in the art and which fall outside the scope of - -this invention, do not allow one skilled in the art to produce polyurethane foams with the above listed -advantagesO Further, the normal polyurethane foam additives do not give the processor the latitu~e tc ;~
produce foams fr~m the two polyurethane foam systems, heretofore mentioned, without s~me major change~in the foam stabilizer from one system t~ the other.
It is to be understood that the siloxane~
oxyalkylene copolymers ~f this invention are specific materialsO It is also to be understood that whenever ` --,. ~
, the symb~l = SiO is used in this s~ecification, it can : G
~ 20 have two meaningsO It can be (MeGSiO3 or it can be ,-, , , (Me2GSiO) depending on the type of basic formula of the siloxanes utilized as outlined in formulas (1) to ,, (4) aboveO In addition, the siloxane portlon of the siloxane-oxyalkylene co@olymer must contain from 0-7 (MezSiO) units and from 1-5 (MeGSiO) when the formula ~ ;
is that of (4) aboveO ;~ -When the basic formula is (2) above, the ,: ., (Me2SiO) units are 0-7 and khe (MeGSiO) units are , ~ ::, :~
0-4 and when formula (1) is used, the (Me2SiO) units are 0-7 and the (MeGSiO) units are 0.
_12-.
. , -. ., , . , ~
'~' ' .
' , , :': ' `:
3L~ 4~ :
`. -. , .-~,. When the basic formula is ~3) above, the `;`~ (Me2SiO~ un.its are 0-2 and the (MeGSiO) units are 1-5.
~ This automatically allows a molecular wei.ght range :. for the basic siloxanes of this invention to be .:~. (1) from 148 to 2340;
. ,.~,". : .
.. `. (2) from 134 to 952; ~.
~ : (3) from 221 to 2176 and .. `~ (4) from 221 to 990. . ~.
In most cases, the preferred molecular weight ~. 10 range of the siloxanes is from 221 to 1000.
-............. The siloxane portion of the siloxane- .: oxyalkylene copolymer is represented by the four following formulae which are siloxane precursors. ~ ~
(1) Ra~(OSiMez)eOSiMezZ}~_a - -(2) ZMe2si(oslMe2)f(osiMez)bosiMe2z -~
(3) RaSi{(OSiMe2)g(0S~iMeZ¦cOSiMe9~}4 a ; (4) Me3Si(OSiMe2)h(0SiMeZ)dOSiMe3 ~, e,.a, f, b~ g, c, h, d all have the meanings define~ above and Z represents the appropriate . 20 reactive group including -OR~', OC~ R~', H3 X, where X-is chlorine, bromine or ~luorine;
.l OH, -(CHa)30CHzC~-CH2J alkylhalide such as ,(~Hz)3Cl, :
:,x ;, ~ ~
i:~'3 alkyl hydroxide such as -CHzCH20H and alkyl mercaptan .
uch as -(CHz)3SHo ~ ;~
. Any of the siloxanes or mixtures of the :~
,:: ".~
~:~.:; siloxanes containing the same reactive group can be ~::
,:..s.~
::~ utilized, which give rise to a copolymer when reacted .. ~ 30 with the appropriate glycol.
" ,.,'.",~ , ' .....
,.. ..... .
. ,;,........... .
i.: .. ~ ;
:: .~,, ,:: :.
.... .. . . .. .
~6~49 -.
The siloxanes can be prepared in a number of ways but the preferred method is to hydrolyze the appr~priate silanes as for ins-tance in (1) above, a mixture of silanes such as RaSiX4-a with dimethyldichloro-silane, dimethylmonochlorosilane and thereafter equil-ibrating the cohydrolyzate with an acid catalyst such :;
as H2S04. (2) is prepared by cohydrolyzing the silanes in proportion of f moles of dimethyldichlorosilane, two mols of dimethylm~nochlorosilane, and b mols of methyl-dichlorosilaneO Once again the hydrolyzate is H2SO4 `~
equilibrated. (~) is prepared by cohydrolyzing one mol ;
: ,:, ,J , of silane of the formula ~aSiX4-a with _ mols of ~ dimethyldichl~rosilane~ c mols of methyldichlorosiIane - and at least 4~a mols of trimethylchlorosilane and ~I thereafter e~uilibrating with H2S~4o (4) is prepared by cohydrolyzing the silanes in the~pr~portion of h ~;
mols of dimethyldichlorosilane, two mols of trimethyl-monochlorasilane an~ d m~ls of methyldichlorosilaneO
The cohydrolyzate is equilibrated with H2SO40 It is t~
2~ be understood that if the resulting cohydrolyzates have m~lecular weights in excess of those within the scope of this inventi~n, the cohydrolyzates can be distilled t0 give the specific c~mpounds or average structures antici~ated by the claims 0f this inventionO In each case ab~ve, R and X are the same as defined ab~ve.
} Another method of preparing the siloxanes is to equilibrate siloxanes that have already been hydrolyzed.
Such a method f0r instance would involve the equilibration at tem~eratures (usually in excess of 50C), a mixture of ~0 units of (Me2SiQ) in the form of octamethylcyclotetra- ~
.,:
s~ ~ , .. .... .
~' :,, , , - : "
4~g siloxane, b units o~ (MeZS10) in the form of (MéZSiO)4 and 1 unit o~` (ZMe2Si)z0 (i:~` applicable) in the ;~
presence of an equllibrating catalyst. Such equili- ;
brating catalysts are known in the ar-t and consist of ~. :
acid clays~ acid treated melamine type resins and fluorinated alkanes with sulfonic acid groups~ For those unfamiliar with such preparations, they can be found in detail in United Sta-tes Patent 3,4~2,192~
Because of the desirable low m~lecular weight - ~::
of the siloxanes in this inventiong it is within the .
scope of the invention to use siloxanes which have been .
~ prepared by re-equilibrati~n from higher molecular weight .~ siloxanes of the same general formulae as set out aboveO
The glycol portion of the siloxane oxyalkylene copolymer must be predominantly poly~ropyleneO It is to be understood that the glycol portion must contain ~.
less than 35 weight percent of oxyethylene or oxybuty-lene if they are used at allO The ~referred glycol is ~;
100 ~ercent propylene glycolO The molecular weight of the glycol ~or-tion is 103-500 grams/moleO The ~referred range is 150-350 grams/moleO
The glycols useful in the siloxane-oxyalkylene copolymer can be copolymers of pro~ylene oxide and -.
oxides sele~Gted from a group consisting of ethylene and butylene oxides wherein the amount of ethylene or :~ ~
butylene radicals is less than 35 weight percent of ;
~ the total alkylene oxide in the copolymerO When ~.
siloxane-oxya].kylene copolymers are desired that contain .
the ~Si-D- linking grou~, the polyalkylene glyCQl should ~:
contain a monoalkenyl ether endblock~ The monoalkenyl .
;
: , : .
: , . , . ., , ,,, ,:, : , , 64~
ether endb]ocked p~lyal~ylene gLycols can be copo].ymers of propylene oxide and ethylene oxide or copolymers of propylene oxide and butylene oxide or can be copolymers of all three oxides provided the total ethylene and :~:
bu-tylene oxides, either singly or combined, do not exceed 35 weight percent of the total alkylene oxide : of the polyalkyleneoxide glycolO In addition~ the ~ ends of the polyglycol chain not attached to the siloxane ! moiety have a group A wherein A is defined above 10 These glycol copolymers can be linear or branched and the molecular weight of the glycols is ~ . ;
103-500. The preferred range is 150-350 One method of preparing the glycol copolymers -.
.~ is to dissolve sodium metal in the appropriate alcohol, ; i.e. allyl alcohol or ethanol, in a mole ratio of one to one and reacting the resulting product with the ;~.
appropriate alkylene oxides at elevated temperatures and under pressureO The resulting product, after `~.
purification by removal of low boilers, is then capped with the appr~priate group A
The siloxane-oxyalkylene copolymer is then prepared by reacting the appropriate siloxane precursor r and the appropriate polyglycol at elevated temperaturesO ~ .;;
The siloxane-oxyalkylene copolymer is ~.
prepared by reacting a monoalkylene ether, preferably . ~ :
the allyl ether, of the desired polyalkylene glycol with a siloxane conta:ining SiH groupO When siloxane- .
oxyalkylene co~olymers are used that contain the Si-0-C
bonded copolymer, io eO where the linking radical is -0-D, -the preferred method of preparing the siloxane-oxyalkylene -16~ -,, .
, 4~
copolymer îs by reacting the correspondlng alkoxy functional siloxane with the appropriate glycol~, i.e.
_SiOQ ~ HOC_ ~ SiO~ ~ QOFf ; ~ in -this instance is a hydrocarbon radical .~-~' .
free of aliphatic unsaturation and containing 1-10 ,, carbon atoms.
When the siloxane-oxyalkylene copolymer :.
~ contains a sulfur atom, the preferred method is to :, ::,:
~; react a siloxane, which contains the mercaptan group, with a monoalkylene ether, preferably the allyl ether of the desired polyalkylene glycol using a free radical type of catalyst such as ultraviolet light or azobisiso-~` butyrolnitrile me first of these preferred methods is the reaction of an allyl ether endblocked glycol with SiH
containing siloxanesO The reaction is carried out by , ~
heating a mixture of the two reactants in the presence ~-, of a pIatinum catalyst such as chloropla-tinic acid dissolved in a small amount of isopropyl alcohol, at :... ., ~ 20 temperatures of from 100-200C.
;~s The second reaction is carried out by combining j~ the reactants and heating in a solvent solution at reflux ,::"~.. , ~, ! temperatures The preferred solvent is xylene. The . presence of a catalytic amount of concentrated hydro-::.
chloric acid facilitates the reaction. ~;~
~ The third type of reaction is carried out by .~ combining the reactants, heating to the decomposition .~ temperature of the catalyst and allowing the reaction : .
~.~ to proceed for 1-3 hours. A sample of the material is : ~, then titrated to determine the amount of mercaptan that : ,' ~' ': , ":
:' : ,:
: ~ "
, '' ,, ~ ,:
.
~ ~46~9 has reacted The normal reactants would be a mercapto containing siloxane and an alLyl ether endblocked glycol as in -the first method above.
The siloxane-oxyalkylene copolymer is then ~; used neat, or optionally with a glycol diluent~ in the i:
foam formulation. Such a diluent, for example, can be ., .:
dipropylene glycol.
~` Because of the discovery -that these certain siloxane-oxyalkylene copolymers, having the specific , properties defined above, give superior high resilient `~ foams, we have advanced the art beyond that which was -;:::
known concerning high resilience polyurethane foams ;;i Furthermore, we have overcome a prejudice in the art by .:~ ,;, our inventionO In United States Patent 3,741,917, the : . .
inventors describe their invention as a process which ~ i ., ~ .
~ utilizes siloxane-oxyalkylene copolymers. They state,~ ~
..~ .
however, that the glycol portion of the siloxane~
oxyalkylene copolymer must contain at least 35 weight ~ ~ p@rcent of oxyethylene in order ~or suitable foams ': `.- ' -~ 20 to be producedO
We have discovered that suitable foams can ` be produced by utilizing siloxane-oxyalkylene copolymers as foam stabilizers that contain much less than 35 ~; weight percent of oxyethylene~ Moreovér, we have found ;: -. :::
that our siloxane-oxyalkylene copolymer gives more ~
. j: :,: ~
~ consistant foams and further, the foam stabilizer can .,. . ,,~ . , be used in both of the recognized foam systems in use today, It is to be understood that the composition of this invention can contain small amounts of other :,,:
,:,~,.~ .:., i. ~
~:". :':
, ~:
`~ '', '~, .
, :'':`
/ ~
`~
`., . .
," ' . ` ' ' , : ' .
. , : : : ~ :. : .
64~9 ingredien-ts normally founcl in poLyurethane foam systems such as solvents, flame retardants and low molecular ~
weight siloxane oils. ~`
The following examples are lllustrative only and should not be construed as limiting the invention.
For those unfamiliar wlth such preparations, they can be found in detail in UOS. Patent 3,402,192.
The properties taken on the final cured foam were obtained in the following manner unless otherwise indicated.
Cell structure is a subjective test and consists of taking a vertical cut with a band saw through the standing cured foam while the foam is still in the mold, observing the cell structure and counting the number of cells per 2~54 cm A numerical rating is placed on the cell structure ranging from 1-5 wherein 1 is fine and 5 is coarseO It can also be rated -~
as fine, medium, or coarse wherein 1-2 is fine, ~-4 is medium and 5+ is coarseO -The air flow of a small sample cut from the heart of the foam bun is taken on a standard breath-ability apparatusO A slice of foam is removed to give a flat surface from which the foam and mold are subjected to cutting at 1804 cm. and 20096 cm. from and parallel to the bottom of the mold~ A 50 o8 cmO square 2.54 cm~ thick `~
slice is cut from the center of this 2054 cm. cross section The air flow is taken on the apparatus at lo 27 cmO of waterO
The air flow is reported in liters/min and values are taken ;;
on crushed and non-crushed foam samples and reported below ;~
~0 as 00/00 i,e o42/408 ~.
-19- ,~.
, , ' , ,. , ,: ., . :
", , , , ., .. , . , .. ., ~ ~ , , , ~ 469L~ ~
In the exampl.e~ and the claims, Me is employed :~
as an abbrevia-tion for the C~.13- radical, IPA is iso- -propyl alcohol and all viscosities and refractive indices :~
were measured at 25C unless otherwise specified.
Example l This example illus-trates the preparation c)f a siloxane precurso:r for the polyurethane foam stabilizer. ..
Into a twelve liter, three-necked flask equipped with a stirrer, heating apparatus, temperature controller and a reflux condenser surmounted with a :~
CaCl2 tube, was added 1620 gms of (Me3Si)20, 740 gms of .- ~ .
dimethyl cyclics, 600 gms of a 1QW molecular weight methylhydrogen fluid and an equilibration catalyst for the mixtureO The mixture was heated at 65C :~or .; ~ ~.
16 hours and then allowed to coolO It was treated with NaHC03 to neutralize the catalyst and then it was vacuum ~. ;;
filteredO The resulting fluid was clear and colorless .~ ~
The analytical data showed there was present oO336% of ~.
: SiH which correspon~s to a molecular weight o~ 29705.
. . . ~
. Theoretical was 00338% and 2960 The viscosity was 129 cs at 25C, refràctive index = 103848 ancl the speci:fic gravlty . ; -~ ~ ?
was o.848. The formula corresponds roughly to the structure :~ -.
. Me3SiO(Me2SiO) l O ~, (MeHSiO) l O OSiMe3 ~ ' ' Example 2 The preparation of a siloxane-oxyalkylene copolymer use~ul as a f~am stabilizer in this inventionO ~ h.~.:
: , :
Into a l liter, 3-necked glass flask equipped with a thermometerJ air motor, heating apparatus and a reflux condenser surmounted by a CaCl2 tube, was placed :.
200 gms of the si.loxane from Example l, 280 gms of ::
-20- .~
64g MeO(C3H6O)3H and 50 gms of dry xylene. The mixture was hea~ed to 100C. and 3 ml. of H2PtC16 H2O in solvent (30 ppm Pt was added). The reaction was refluxed for 6 hrs. at 152C. and a test was run for residual SiH
which indicated a small amount was present. A small amount of stannous octoate was added to remove the residual SiH and the mixture was heated for an additional hourO The fluid was stripped to remoVe low boiling materials. The material had the general ormula 10Me3SiO(~3e2Sio~l O~MeSiO)l.OSiMe3 (OCH2CH)30CH3 ~-Example 3 Evaluation of Bxample 2 material in a foam system utilizing a commercial foam stabilizer as a comparison.
This is a polymer in polyol system.
Preparation of a premix:
a) Pluracol 5811 40.0 pts 4080.0 gms b~ Dow CP47O1260.0 pts 6120.0 gms ..... .
c~ water 2.6 pts 265.2 gms d) triethylene- 0.04 pts 4.0 gms diamine .
e) Houdry X-Dm3 0.80 pts 81.6 gms A grafted polyglycol having a hydroxyl number of 26 MgKOH/gm and a viscosity o 2800 cps at 770F.
. .
Polypropylene glycol triol of 4700 molecular weight and having 50% Ethylene oxide end blocking.
Isocyanate containing 80/20 toluene diisocyanate and 30polymeric isocyanates . ;, ~.
.~' ' '~ ' ": .
: ' , . . . .
~,, , :
.
~4~
This mixture was mixed for 4 hours to homogenize.
To 103.44 gms of -the ab~ve premix, the following was added~
f) 10% in Dioctylphthalate of stannous octoate .03 pts -~
g) WUC-3051-T (isocyanate) 34.2 pts Larger quantities of the above materials ~
were joined to have enough material to run on a foam ~--machine, i.e. 517 gms ~f premix and 1.5 gms of f), and ;~
.- .:; ~....
171 gms o~ g).
Running the machine at 12~0 R~PoM~ mix time 20 seconds for the premix and 5 seconds for final mixO ;~
Results ;~
Approx.
Surfactant Conc ~ roup Structure ;` `~
commercial 0.1 pts MeO Si-C ':~ ~
Example 2 0.5 pts MeO Si-O-C i~ - -Example 2 0.1 pts Me~ Si-O-C `
Cells Air flow Shrink ' i . ., ,~ -medium 11.89/1~509 none fine severe ;j i-, .;: .:, me~ium 11.3~/127.4 none Example 4 This example illustrates the preparati~n of Me3SiO(Me2SiO)1.O(MeSiO)l.~SiMe3 ~ ~
(CH2) 3 :., ~ ~ .
(OCH2CH2CH2)~OCH
to a glass three-necked, round bottomed flask equipped `~
with the equipment as f~und in Example 2, was added -22- ;
,' .~ :
, ' ~ ''~ ' `:
.:: ~: , . . . . . : "~. - : . .
69L~
296 grams of the siloxane of Example 1. To this was added 286 grams of CH2=cHcH2~ocH2cH)4ocH3~ The mixture was heated to 110C. and catalyzed with 0.3 cc of chloro- ~
platinic acid in isopropyl alcohol. The pot exothermed ~ -to 148C. and when it cooled to 120C., it was heated fOT
4 hours. The product when cooled was clear and dark amber in color with a slight platinum precipitate.
.. . .
% SiH was found to be 0.011~ or a residual amount. ;
This product was diluted with CP-4701 to give approximately ` --12.5% of the sur-factant in the glycol. ~hen evaluated as ~ ~ ~
a foam stabilizer, the following properties were found. `
Using the stabilizer at 1.0 pts per hundred gave a foam `
rise of 13.55 cm., cells with a rating of 2. (1 - fine, ; 5 = coarse?, air flow = 0.7/5.6 and there were no voids or ;
.-. ,, splits. ~ commercial material gave the following properties at 1.0 pph. Rise = 5 1/4, cells = 1.5, air flow = 21.5/169.9, no voids and no splits. It is, therefore, observed that the material of the present invention gives equivalent results.
; :. . , ~;, 20The system used in evaluation was that as shown in Example 3 `~
above.
~ ~ -Example 5 This example illustrates the preparation of a siloxane. To a 3-liter, 3-necked round bottomed glass flask, there was added 1620 gms of (Me3Si)20, 2220 gms of dimethyl-siloxane cyclics, 600 gms of a trimethylsiloxy-endblocked methylhydrogen fluid having approximately 1.6% SiH and 4.0 gms of a sulfonic acid catalyst.
This material was heated for 7-8 hours at 65C. The material was cooled and enough NaHCO3 was E~ ~
~6~649 ~ ,:
added to neutralize the catalyst. The material was filtered to give a clear, colorless product. Analysis gave 0.222% SiH, Calc was 0.225, Viscosity was 2.43 cs at 25C. Refractive Index was 1.3903 and Specific Cravity was 0.889.
Example 6 This example represents the preparation of ~-an Si-C bonded surfactant using the siloxane of ~xample 5.
In a l-liter, 3-necked flask was placed 400 gms of the siloxane rom Example 5, 257 gms of CH2=CHCH2 -(OCH2CH)2 20CH3. The mix~ure was heated to 110C. -and 0.3 cc platinum catalyst solution was added : ,~
~3 ppm pt). The mixture exothermed to 147C. and was heated at 140C. for 1 hour, then 120C. for 3 hours~
The product was filtered and gave a light yellow~ clear -~
solution. The residual SiH was .012%.
The surfactant was diluted to 2.5 weight percent ` -~-in CP-4701 polyglycol and evaluated in a foam system as follows.
; A premix was prepared as a polymer in polyol system. `
~ ' .,; ~ .
; 30 :
,. ,~ :
., .
, ., , ~' 3~6~6~
Ingredient A~ount gms Parts (a) ~(CH3)2NCH2CH2}20 2.l~ o.8 (b) NEM (n-Ethyl morpholine) 24~V 0,8 (c) Triethylenediamine 2~4 oO8 ; (d) Distilled wa-ter 84,o 2.~
(e) Niax~ polyol ll-341 18000060,0 (f) Niax~ polyol 34-281 120000 4 light colored~ low viscosity polyols produced ;-by in-situ polymerization of a vinyl monomer in the presence of conventional polyols. 11-34 has a viscosity of 1050 cs at 20C and a hydroxyl number o-f 3205 to 3505 mg. KOH/gm, Nia~3 polyol 34-2B has a viscosity of 2550 cps at 25C by a Brookfield viscometer.
This material was mixed on a roller for four ; ;~
hours to assure complete dispersion of' the ingredients.
~o the premix was added the following for every -103.76 gms of premix- ` -(a) surfactant -, -(b) 003 gm dibutyltindilaurate, mixed thoroughly and added (c) 3402 gms of isocyanate blend composed of 80 parts of 80/20 toluene diisocyanate and 20 parts of polymethylene polyphenylisocyanatso Carried out the additions in the following manner:
(1) Added the surfactant and the tin catalyst to ~
; the premix; I ;
(2) Mixed at 750 rO pom~ for 20 seconds using a commercial mixer;
(3) Added the isocyanate (4) Mixed at 1250 rOp.mO for 4 seconds;
,, ::', ' ' :, .: . ., :. .
~64649 ~
.
when _ = 1 or 2, then _ is 1-4; when _ = 3 or 4, then _ is 1-3; when h is 5, then d is 1-2; and when- _ is 6 or 7, then 1 r CII~ thereafter allowing the mixture to foam, and curing the foamed composition.
Thus, in accordance with the more specific teaching of the present concept a method is provided of pre~
paring a one-shot polyether based, high resilient polyurethane ` -`
foam. The method includes the steps of (I) preparing a homogeneous mixture consisting essentially of (A) 100 parts by weight of a base polyether ,~ ~, , .
polyol selected from the group consisting of (i) a polyether triol containing at least 40 ~ ~ ~
mole percent primary hydroxyl groups and having ~ ;
a molecular weight in the range of 2,000 to 8,000 grams per mole, and (ii) a mixture of ci~ and an additional polyether -polyol having an average of at least two hydroxyl groups, wherein said polyether polyol is present ~
in the mixture (ii) to at least 40 weight percent ~ ;
of the total polyether polyol content of (ii), (B~ a sufficient amount of organic polyisocyanate ~i 3Q to give from 90 to 120 percent, on a stoichio~ --metric basis, of isocyanate radicals for each hydroxyl radical in the composition, ~ kC -6-16~6~ g (C) a catalytic amount of a catalys~ for the ~ ~
production of the high resilient polyurethane ~ ;
foam, (D) 1 to 10 parts by ~eight of a blowing agent, ~ ;
(E) a foam stabiliz;ng amount of a copolymer of the general formula Me3Si(OSiMe2~h(0SiMeG)~OSiMe3 where _ has an average value of about 0, 1 or 3, d has an average value of about 1 or 2, Me is the Methyl radical and G is ~CH2)3(0CH2CCHHt20 3 ~CH2)3(0CH2cH~20ccH3 or ~CH2)3(0CH2CH)2 50CH3 The usual method of this invention is to combine ingredients tA), (C), (D), and (E) in any suitable container and ;~
., . . j: . , homogenize them using any suitable-means such as a commercial mixer or the likeO The component (B) is then added, the mixture again f '~
homogenized and the foam allowed to rise in the container. The foam can then be cured at room temperature (cold cured) or at O : . ~
elevated temperatures (usually 107 C) and then removed from the container for use later. In another method, the components can be metered and mixed automatically so that the separate step of adding component (B) can be eliminated. Both of these methods are generally known in the art with the exception~of the use of i ', component (E) of the present invention. The above modes of mix~
ing are not the only methods by which the foaming composition can be prepared. For instance, it is well within the scope of the ;
instant invention to mix the ingredients in any order in which it ' ~`
is desirable. The only exception is that component (B) '~
' "'""~':' :' -6a~
::
(~
^ 1~64~4~ ~
canno-t be mixed with any poly~l or similarly reactive component until the foaming is to begin The polyether p~lyols employed in -this inven-tion as component I(A) can be any p~]yether triol containing ; at least 40 mole percent of primary hydroxyl groups and having a molecular weight from about 2,000 to a~ut 8,ooo grams/mole. Preferably, said polyether poly~ls contain about 60-go mole percent of primary hydroxyl groups and have a m~lecular weight from about 4,000 to 7,oO0 grams/mole.
The preferred polyether poly~ls ~f this inventi~n are polyether triols obtained by chemical ';~
- addition of alkylene oxides to trihydroxyl organic containing materials such as glycerol, 1,2,~-hexane~
triol, l,l,l-trimethylolethane, 1,1,1 trimethylolpr~pane, - `
3-(2-hydr~xyeth~xy)-1,2 propanedi~l, 3,-(2-hydr~xypro-poxy)-1,2 propanediol and the like, as well as mixtures there~f, i~
Alternatively, the ~olyether ~olyols can be mixtures c~nsisting essentially ~f the above p~ly-ether tri~ls and other p~lyether polyols having an ;
- average of at least two hydroxyl radicals per molecule, said trisls constituting at least 40, ~referably 50 ~r ; m~re weight percent of the t~tal poly~l content of the mixture. Such other polyether p~lyols having an average ~f at least tw~ hydr~xyl radicals per molecule are triols outsi~e the scope of this inventi~n, diols, tetraols, and polymer/polyols as well as mixtures thereof. - ~
Examples of such polyether polyols containing ~ ?
at least two hydroxyl grou~s per molecule are 1,2-alkylene ; ~
.,` ':
-7- ;
:: ~
, ~ .
1~6~4~
oxides such as ethylene oxide, epichlorohydrin, ],2-propylene oxide~ 1,2 butylene oxide and 2,3-bu-tylene oxide, oxacyclobutane and substituted oxacyclobutanes and tetrafuran.
They may be linear polyether glycols as are prepared, for example, by the polymerization of an - alkylene oxide in the presence of a basic catalyst~
such as potassium hydroxide, and a glycol as a primary mon~amine. Alternatively there may be used branched polyether prepared, for example, by the polymerization of an alkylene oxide in the presence of a hasic catalyst and a substance having more than tw~ active hydrogen atoms per molecule, for example, ammonia and p~lyhydroxy compounds such as glycerol, hexanetriols, trimethylol-pro~ane and ethane, triethanolamine, ~entaerythritol, sorbitol, sucrose an~ phenol-f~rmaldehyde reaction products, aminoalcohols such as monoethanolamine and diethan~lamine and polyamines such as ethylene diamine, hexamethylenediamine, diethylene triamine, tolylene diamine an~ di~minodi~henylmethane. ~ranched p~lyethers ,., ,.. ~
may also be ~roduced by copolymerizing a cyclic oxide of the type already mentioned with cyclic oxides having a functionality greater than two, for example, ~ie~oxides, glycidols and 3-hydroxymethyloxacycl~butanes. ;;~
Another ty~e of polyether ~olyol that can be mixéd with the above defined polyether triols and used as starting materials are graft polymer in polyether compositions obtained by polymeriæing ethylenically ~ ;
unsaturated monomers in a polyether as ~escribed in ~ .
3G U.S. Patent 3,383,351. Suitable monomers for producing ~
: .
::,. .
such compositions include~ for example, acrylonitrile, vinyl chloride, styreneJ butadiene~ vinylidene chloride3 and the like. The most preferred is acrylonitrile at this time. Suitable polyethers for producing such compositions include, f~r example, those polyethers described above. The graft polymer in ~olyether comp~siti~ns can contain fr~m about 1 to about 70 weight percent, preferably about 5-50 weight percent and most preferably ab~ut 10 t~ 40 weight percent of the m~ncmer polymerized in the polyether. Such compositions are conveniently prepared by polymerizing the monomers in the selecte~ ~lyether at a temperature of 40C to 150C in the presence ~f a free radical p~lymerization catalyst, such as per~xides, persulfates, ~ercarbonates, perb~rate and azo compounds. The resulting compositiorls may c~ntain some unreacted polyether, m~nomer and free ~-~olymer as well as the graft p~lymer in polyether reacted :
species.
The ~ase p~lyethers are ncrmally used in the amount of 100 parts by weight and the remainder of the com~onents are based upon the ~ase poly~ls.
' Com~onent I(B), ~rganic polyis~cyanates, which - are suitable in this inventi~n, include aliphatic diis~cy-anates such as hexamethylene diis~cyanate, ar~matic diis~cyanates such as toluene-2,4-diisocyanate, toluene~2 , -,,,~ ~
6-diis~cyanate and the familiar 8a 20 isomeric mixtures of the 2,4 and 2,6 t~luene diis~cyanate, diphenyl-methane-4,4-diis~cyanate, 3 methyldiphenylmethane -4,4'diisocyanate, m- and p-phenylene diisocyanate. ~-Other suitahle is~cyanates comprise the reaction , " _ g_ .
~- ;
1~i4~49 , products of an excess of the diisocyana-te with poly-hydric alc~hols such as trimethylolpropane. Still other isvcyanates are blends of the above isocyanates - ;
such as to]uene diisocyanate and p~ly aromatic poly-isocyanates and crude or residual polyisocyanates from -~
the pr~duction of purer species of polyisocyanates The is~cyanates can be employed in the inventi~n on a stoichiometric basis, that is, ~ne isocyanate ra~ical for every hydroxyl radical. The usual employment, however, is to utilize the-isocyanates s~ as to give from 10% less than stoichiometric quantities ~-~f is~cyanate radical to hydroxyl radical, t~ 20% greater `
than ~toichiometric quantities of isocyanate radical t~
hydroxyl in the system. Most ~referre~ for this inventi~n ~-~
is 5% in excess ~f the is~cyanate radicals over the ~ available hydr~xyl radicals.
;~ C0m~0nent I(C), a catalyst f~r the producti~n of the high resilient f0am includes ~oth ~rior art amines ,~
and soluble 0rganic c~mpounds~of heavy metals either -~
singly ~r in various combinations. Exam~les-~f amines useful in this invention include triethylenediamine and N-ethylmorph~line and examples of ~rganic comp~unds `~
of heavy metals are dibutyltindilaurate and~stannous octoate, Mixtures of catalysts may be advantage~us at times. The catalysts are used in the amounts ranging from ~.01-5.5 parts based on 100 ~arts ~f the base polyol, Compcnent I(D)g the blowing agent, is water ~--,:
or a low-b~iling ~rganic liquid. The bl~wing agent can be a mixture of water and a low-boiling organic liquid ~, . --10--' ~
, ' ,~ ~
,, . :
1~64~49 - ~
. The Low-boiling organic l~qui.d should be chemically .
inert towards the 1socyanates and water and have a boili.ng point less than -that of water. Preferably much lower as for instance 75C or lessO
Low-boiling organic liquids include halogenated alkanes such as monofluorotrichloromethane and methylene chlorideO ";
: The blowing agent is used in the amount of ~:~
l-lO parts per l~O parts of the base polyetherO When lO water is the sole blowing agent it is preferred to use :
from 200-~.5 parts per lOO parts of base polyether and :; - when halogenated alkanes are the sole blowing agent it ~ :~
is preferred to use from l-lO parts per lOO parts ~f .. ,., ~ .:~:
; base polyetherO Mixtures of halogenated alkanes are also useful in this inventionO
The final major comp~nent I(E), is the siloxane~
oxyalkylene copolymer foam stabilizerO ~hen used in this :: ::
. . .
invention, the foam stabilizer when used without dilution ~ is utilized in the amounts ranging from 0002-200 parts . 2Q ~er lOO parts of base ~olyether polyolO Most preferably it is used in the range of 00 5-lo 0 parts per lOO parts of polyether polyol The essence of the present method is the use ~
of the nove] siloxane~oxyalkylene c~olymers, comp3nent : --(E), in the f~aming systemO ~
It is the certain siloxane-oxyalkylene - :
copolymers, when used as foam stabilizers, that allow the cured foam to consist of fine-uniform cells. It . ~ :
; is the certain siloxane-oxyalkylene copolymers, when ~ ;
used as foam stabilizers, that allow the cured foam ::
., .
., 1~6~
to be clear of voids, spli-ts and holes and to be free from slab shrinkage. It is the certain siloxane-oxyalkylene copolymers, when used as fQam stabilizers, that allow the cured foam t~ exhibit. physical properties -which make it useful for molded foam applications.
Presently used polyurethane foam additives found in the art and which fall outside the scope of - -this invention, do not allow one skilled in the art to produce polyurethane foams with the above listed -advantagesO Further, the normal polyurethane foam additives do not give the processor the latitu~e tc ;~
produce foams fr~m the two polyurethane foam systems, heretofore mentioned, without s~me major change~in the foam stabilizer from one system t~ the other.
It is to be understood that the siloxane~
oxyalkylene copolymers ~f this invention are specific materialsO It is also to be understood that whenever ` --,. ~
, the symb~l = SiO is used in this s~ecification, it can : G
~ 20 have two meaningsO It can be (MeGSiO3 or it can be ,-, , , (Me2GSiO) depending on the type of basic formula of the siloxanes utilized as outlined in formulas (1) to ,, (4) aboveO In addition, the siloxane portlon of the siloxane-oxyalkylene co@olymer must contain from 0-7 (MezSiO) units and from 1-5 (MeGSiO) when the formula ~ ;
is that of (4) aboveO ;~ -When the basic formula is (2) above, the ,: ., (Me2SiO) units are 0-7 and khe (MeGSiO) units are , ~ ::, :~
0-4 and when formula (1) is used, the (Me2SiO) units are 0-7 and the (MeGSiO) units are 0.
_12-.
. , -. ., , . , ~
'~' ' .
' , , :': ' `:
3L~ 4~ :
`. -. , .-~,. When the basic formula is ~3) above, the `;`~ (Me2SiO~ un.its are 0-2 and the (MeGSiO) units are 1-5.
~ This automatically allows a molecular wei.ght range :. for the basic siloxanes of this invention to be .:~. (1) from 148 to 2340;
. ,.~,". : .
.. `. (2) from 134 to 952; ~.
~ : (3) from 221 to 2176 and .. `~ (4) from 221 to 990. . ~.
In most cases, the preferred molecular weight ~. 10 range of the siloxanes is from 221 to 1000.
-............. The siloxane portion of the siloxane- .: oxyalkylene copolymer is represented by the four following formulae which are siloxane precursors. ~ ~
(1) Ra~(OSiMez)eOSiMezZ}~_a - -(2) ZMe2si(oslMe2)f(osiMez)bosiMe2z -~
(3) RaSi{(OSiMe2)g(0S~iMeZ¦cOSiMe9~}4 a ; (4) Me3Si(OSiMe2)h(0SiMeZ)dOSiMe3 ~, e,.a, f, b~ g, c, h, d all have the meanings define~ above and Z represents the appropriate . 20 reactive group including -OR~', OC~ R~', H3 X, where X-is chlorine, bromine or ~luorine;
.l OH, -(CHa)30CHzC~-CH2J alkylhalide such as ,(~Hz)3Cl, :
:,x ;, ~ ~
i:~'3 alkyl hydroxide such as -CHzCH20H and alkyl mercaptan .
uch as -(CHz)3SHo ~ ;~
. Any of the siloxanes or mixtures of the :~
,:: ".~
~:~.:; siloxanes containing the same reactive group can be ~::
,:..s.~
::~ utilized, which give rise to a copolymer when reacted .. ~ 30 with the appropriate glycol.
" ,.,'.",~ , ' .....
,.. ..... .
. ,;,........... .
i.: .. ~ ;
:: .~,, ,:: :.
.... .. . . .. .
~6~49 -.
The siloxanes can be prepared in a number of ways but the preferred method is to hydrolyze the appr~priate silanes as for ins-tance in (1) above, a mixture of silanes such as RaSiX4-a with dimethyldichloro-silane, dimethylmonochlorosilane and thereafter equil-ibrating the cohydrolyzate with an acid catalyst such :;
as H2S04. (2) is prepared by cohydrolyzing the silanes in proportion of f moles of dimethyldichlorosilane, two mols of dimethylm~nochlorosilane, and b mols of methyl-dichlorosilaneO Once again the hydrolyzate is H2SO4 `~
equilibrated. (~) is prepared by cohydrolyzing one mol ;
: ,:, ,J , of silane of the formula ~aSiX4-a with _ mols of ~ dimethyldichl~rosilane~ c mols of methyldichlorosiIane - and at least 4~a mols of trimethylchlorosilane and ~I thereafter e~uilibrating with H2S~4o (4) is prepared by cohydrolyzing the silanes in the~pr~portion of h ~;
mols of dimethyldichlorosilane, two mols of trimethyl-monochlorasilane an~ d m~ls of methyldichlorosilaneO
The cohydrolyzate is equilibrated with H2SO40 It is t~
2~ be understood that if the resulting cohydrolyzates have m~lecular weights in excess of those within the scope of this inventi~n, the cohydrolyzates can be distilled t0 give the specific c~mpounds or average structures antici~ated by the claims 0f this inventionO In each case ab~ve, R and X are the same as defined ab~ve.
} Another method of preparing the siloxanes is to equilibrate siloxanes that have already been hydrolyzed.
Such a method f0r instance would involve the equilibration at tem~eratures (usually in excess of 50C), a mixture of ~0 units of (Me2SiQ) in the form of octamethylcyclotetra- ~
.,:
s~ ~ , .. .... .
~' :,, , , - : "
4~g siloxane, b units o~ (MeZS10) in the form of (MéZSiO)4 and 1 unit o~` (ZMe2Si)z0 (i:~` applicable) in the ;~
presence of an equllibrating catalyst. Such equili- ;
brating catalysts are known in the ar-t and consist of ~. :
acid clays~ acid treated melamine type resins and fluorinated alkanes with sulfonic acid groups~ For those unfamiliar with such preparations, they can be found in detail in United Sta-tes Patent 3,4~2,192~
Because of the desirable low m~lecular weight - ~::
of the siloxanes in this inventiong it is within the .
scope of the invention to use siloxanes which have been .
~ prepared by re-equilibrati~n from higher molecular weight .~ siloxanes of the same general formulae as set out aboveO
The glycol portion of the siloxane oxyalkylene copolymer must be predominantly poly~ropyleneO It is to be understood that the glycol portion must contain ~.
less than 35 weight percent of oxyethylene or oxybuty-lene if they are used at allO The ~referred glycol is ~;
100 ~ercent propylene glycolO The molecular weight of the glycol ~or-tion is 103-500 grams/moleO The ~referred range is 150-350 grams/moleO
The glycols useful in the siloxane-oxyalkylene copolymer can be copolymers of pro~ylene oxide and -.
oxides sele~Gted from a group consisting of ethylene and butylene oxides wherein the amount of ethylene or :~ ~
butylene radicals is less than 35 weight percent of ;
~ the total alkylene oxide in the copolymerO When ~.
siloxane-oxya].kylene copolymers are desired that contain .
the ~Si-D- linking grou~, the polyalkylene glyCQl should ~:
contain a monoalkenyl ether endblock~ The monoalkenyl .
;
: , : .
: , . , . ., , ,,, ,:, : , , 64~
ether endb]ocked p~lyal~ylene gLycols can be copo].ymers of propylene oxide and ethylene oxide or copolymers of propylene oxide and butylene oxide or can be copolymers of all three oxides provided the total ethylene and :~:
bu-tylene oxides, either singly or combined, do not exceed 35 weight percent of the total alkylene oxide : of the polyalkyleneoxide glycolO In addition~ the ~ ends of the polyglycol chain not attached to the siloxane ! moiety have a group A wherein A is defined above 10 These glycol copolymers can be linear or branched and the molecular weight of the glycols is ~ . ;
103-500. The preferred range is 150-350 One method of preparing the glycol copolymers -.
.~ is to dissolve sodium metal in the appropriate alcohol, ; i.e. allyl alcohol or ethanol, in a mole ratio of one to one and reacting the resulting product with the ;~.
appropriate alkylene oxides at elevated temperatures and under pressureO The resulting product, after `~.
purification by removal of low boilers, is then capped with the appr~priate group A
The siloxane-oxyalkylene copolymer is then prepared by reacting the appropriate siloxane precursor r and the appropriate polyglycol at elevated temperaturesO ~ .;;
The siloxane-oxyalkylene copolymer is ~.
prepared by reacting a monoalkylene ether, preferably . ~ :
the allyl ether, of the desired polyalkylene glycol with a siloxane conta:ining SiH groupO When siloxane- .
oxyalkylene co~olymers are used that contain the Si-0-C
bonded copolymer, io eO where the linking radical is -0-D, -the preferred method of preparing the siloxane-oxyalkylene -16~ -,, .
, 4~
copolymer îs by reacting the correspondlng alkoxy functional siloxane with the appropriate glycol~, i.e.
_SiOQ ~ HOC_ ~ SiO~ ~ QOFf ; ~ in -this instance is a hydrocarbon radical .~-~' .
free of aliphatic unsaturation and containing 1-10 ,, carbon atoms.
When the siloxane-oxyalkylene copolymer :.
~ contains a sulfur atom, the preferred method is to :, ::,:
~; react a siloxane, which contains the mercaptan group, with a monoalkylene ether, preferably the allyl ether of the desired polyalkylene glycol using a free radical type of catalyst such as ultraviolet light or azobisiso-~` butyrolnitrile me first of these preferred methods is the reaction of an allyl ether endblocked glycol with SiH
containing siloxanesO The reaction is carried out by , ~
heating a mixture of the two reactants in the presence ~-, of a pIatinum catalyst such as chloropla-tinic acid dissolved in a small amount of isopropyl alcohol, at :... ., ~ 20 temperatures of from 100-200C.
;~s The second reaction is carried out by combining j~ the reactants and heating in a solvent solution at reflux ,::"~.. , ~, ! temperatures The preferred solvent is xylene. The . presence of a catalytic amount of concentrated hydro-::.
chloric acid facilitates the reaction. ~;~
~ The third type of reaction is carried out by .~ combining the reactants, heating to the decomposition .~ temperature of the catalyst and allowing the reaction : .
~.~ to proceed for 1-3 hours. A sample of the material is : ~, then titrated to determine the amount of mercaptan that : ,' ~' ': , ":
:' : ,:
: ~ "
, '' ,, ~ ,:
.
~ ~46~9 has reacted The normal reactants would be a mercapto containing siloxane and an alLyl ether endblocked glycol as in -the first method above.
The siloxane-oxyalkylene copolymer is then ~; used neat, or optionally with a glycol diluent~ in the i:
foam formulation. Such a diluent, for example, can be ., .:
dipropylene glycol.
~` Because of the discovery -that these certain siloxane-oxyalkylene copolymers, having the specific , properties defined above, give superior high resilient `~ foams, we have advanced the art beyond that which was -;:::
known concerning high resilience polyurethane foams ;;i Furthermore, we have overcome a prejudice in the art by .:~ ,;, our inventionO In United States Patent 3,741,917, the : . .
inventors describe their invention as a process which ~ i ., ~ .
~ utilizes siloxane-oxyalkylene copolymers. They state,~ ~
..~ .
however, that the glycol portion of the siloxane~
oxyalkylene copolymer must contain at least 35 weight ~ ~ p@rcent of oxyethylene in order ~or suitable foams ': `.- ' -~ 20 to be producedO
We have discovered that suitable foams can ` be produced by utilizing siloxane-oxyalkylene copolymers as foam stabilizers that contain much less than 35 ~; weight percent of oxyethylene~ Moreovér, we have found ;: -. :::
that our siloxane-oxyalkylene copolymer gives more ~
. j: :,: ~
~ consistant foams and further, the foam stabilizer can .,. . ,,~ . , be used in both of the recognized foam systems in use today, It is to be understood that the composition of this invention can contain small amounts of other :,,:
,:,~,.~ .:., i. ~
~:". :':
, ~:
`~ '', '~, .
, :'':`
/ ~
`~
`., . .
," ' . ` ' ' , : ' .
. , : : : ~ :. : .
64~9 ingredien-ts normally founcl in poLyurethane foam systems such as solvents, flame retardants and low molecular ~
weight siloxane oils. ~`
The following examples are lllustrative only and should not be construed as limiting the invention.
For those unfamiliar wlth such preparations, they can be found in detail in UOS. Patent 3,402,192.
The properties taken on the final cured foam were obtained in the following manner unless otherwise indicated.
Cell structure is a subjective test and consists of taking a vertical cut with a band saw through the standing cured foam while the foam is still in the mold, observing the cell structure and counting the number of cells per 2~54 cm A numerical rating is placed on the cell structure ranging from 1-5 wherein 1 is fine and 5 is coarseO It can also be rated -~
as fine, medium, or coarse wherein 1-2 is fine, ~-4 is medium and 5+ is coarseO -The air flow of a small sample cut from the heart of the foam bun is taken on a standard breath-ability apparatusO A slice of foam is removed to give a flat surface from which the foam and mold are subjected to cutting at 1804 cm. and 20096 cm. from and parallel to the bottom of the mold~ A 50 o8 cmO square 2.54 cm~ thick `~
slice is cut from the center of this 2054 cm. cross section The air flow is taken on the apparatus at lo 27 cmO of waterO
The air flow is reported in liters/min and values are taken ;;
on crushed and non-crushed foam samples and reported below ;~
~0 as 00/00 i,e o42/408 ~.
-19- ,~.
, , ' , ,. , ,: ., . :
", , , , ., .. , . , .. ., ~ ~ , , , ~ 469L~ ~
In the exampl.e~ and the claims, Me is employed :~
as an abbrevia-tion for the C~.13- radical, IPA is iso- -propyl alcohol and all viscosities and refractive indices :~
were measured at 25C unless otherwise specified.
Example l This example illus-trates the preparation c)f a siloxane precurso:r for the polyurethane foam stabilizer. ..
Into a twelve liter, three-necked flask equipped with a stirrer, heating apparatus, temperature controller and a reflux condenser surmounted with a :~
CaCl2 tube, was added 1620 gms of (Me3Si)20, 740 gms of .- ~ .
dimethyl cyclics, 600 gms of a 1QW molecular weight methylhydrogen fluid and an equilibration catalyst for the mixtureO The mixture was heated at 65C :~or .; ~ ~.
16 hours and then allowed to coolO It was treated with NaHC03 to neutralize the catalyst and then it was vacuum ~. ;;
filteredO The resulting fluid was clear and colorless .~ ~
The analytical data showed there was present oO336% of ~.
: SiH which correspon~s to a molecular weight o~ 29705.
. . . ~
. Theoretical was 00338% and 2960 The viscosity was 129 cs at 25C, refràctive index = 103848 ancl the speci:fic gravlty . ; -~ ~ ?
was o.848. The formula corresponds roughly to the structure :~ -.
. Me3SiO(Me2SiO) l O ~, (MeHSiO) l O OSiMe3 ~ ' ' Example 2 The preparation of a siloxane-oxyalkylene copolymer use~ul as a f~am stabilizer in this inventionO ~ h.~.:
: , :
Into a l liter, 3-necked glass flask equipped with a thermometerJ air motor, heating apparatus and a reflux condenser surmounted by a CaCl2 tube, was placed :.
200 gms of the si.loxane from Example l, 280 gms of ::
-20- .~
64g MeO(C3H6O)3H and 50 gms of dry xylene. The mixture was hea~ed to 100C. and 3 ml. of H2PtC16 H2O in solvent (30 ppm Pt was added). The reaction was refluxed for 6 hrs. at 152C. and a test was run for residual SiH
which indicated a small amount was present. A small amount of stannous octoate was added to remove the residual SiH and the mixture was heated for an additional hourO The fluid was stripped to remoVe low boiling materials. The material had the general ormula 10Me3SiO(~3e2Sio~l O~MeSiO)l.OSiMe3 (OCH2CH)30CH3 ~-Example 3 Evaluation of Bxample 2 material in a foam system utilizing a commercial foam stabilizer as a comparison.
This is a polymer in polyol system.
Preparation of a premix:
a) Pluracol 5811 40.0 pts 4080.0 gms b~ Dow CP47O1260.0 pts 6120.0 gms ..... .
c~ water 2.6 pts 265.2 gms d) triethylene- 0.04 pts 4.0 gms diamine .
e) Houdry X-Dm3 0.80 pts 81.6 gms A grafted polyglycol having a hydroxyl number of 26 MgKOH/gm and a viscosity o 2800 cps at 770F.
. .
Polypropylene glycol triol of 4700 molecular weight and having 50% Ethylene oxide end blocking.
Isocyanate containing 80/20 toluene diisocyanate and 30polymeric isocyanates . ;, ~.
.~' ' '~ ' ": .
: ' , . . . .
~,, , :
.
~4~
This mixture was mixed for 4 hours to homogenize.
To 103.44 gms of -the ab~ve premix, the following was added~
f) 10% in Dioctylphthalate of stannous octoate .03 pts -~
g) WUC-3051-T (isocyanate) 34.2 pts Larger quantities of the above materials ~
were joined to have enough material to run on a foam ~--machine, i.e. 517 gms ~f premix and 1.5 gms of f), and ;~
.- .:; ~....
171 gms o~ g).
Running the machine at 12~0 R~PoM~ mix time 20 seconds for the premix and 5 seconds for final mixO ;~
Results ;~
Approx.
Surfactant Conc ~ roup Structure ;` `~
commercial 0.1 pts MeO Si-C ':~ ~
Example 2 0.5 pts MeO Si-O-C i~ - -Example 2 0.1 pts Me~ Si-O-C `
Cells Air flow Shrink ' i . ., ,~ -medium 11.89/1~509 none fine severe ;j i-, .;: .:, me~ium 11.3~/127.4 none Example 4 This example illustrates the preparati~n of Me3SiO(Me2SiO)1.O(MeSiO)l.~SiMe3 ~ ~
(CH2) 3 :., ~ ~ .
(OCH2CH2CH2)~OCH
to a glass three-necked, round bottomed flask equipped `~
with the equipment as f~und in Example 2, was added -22- ;
,' .~ :
, ' ~ ''~ ' `:
.:: ~: , . . . . . : "~. - : . .
69L~
296 grams of the siloxane of Example 1. To this was added 286 grams of CH2=cHcH2~ocH2cH)4ocH3~ The mixture was heated to 110C. and catalyzed with 0.3 cc of chloro- ~
platinic acid in isopropyl alcohol. The pot exothermed ~ -to 148C. and when it cooled to 120C., it was heated fOT
4 hours. The product when cooled was clear and dark amber in color with a slight platinum precipitate.
.. . .
% SiH was found to be 0.011~ or a residual amount. ;
This product was diluted with CP-4701 to give approximately ` --12.5% of the sur-factant in the glycol. ~hen evaluated as ~ ~ ~
a foam stabilizer, the following properties were found. `
Using the stabilizer at 1.0 pts per hundred gave a foam `
rise of 13.55 cm., cells with a rating of 2. (1 - fine, ; 5 = coarse?, air flow = 0.7/5.6 and there were no voids or ;
.-. ,, splits. ~ commercial material gave the following properties at 1.0 pph. Rise = 5 1/4, cells = 1.5, air flow = 21.5/169.9, no voids and no splits. It is, therefore, observed that the material of the present invention gives equivalent results.
; :. . , ~;, 20The system used in evaluation was that as shown in Example 3 `~
above.
~ ~ -Example 5 This example illustrates the preparation of a siloxane. To a 3-liter, 3-necked round bottomed glass flask, there was added 1620 gms of (Me3Si)20, 2220 gms of dimethyl-siloxane cyclics, 600 gms of a trimethylsiloxy-endblocked methylhydrogen fluid having approximately 1.6% SiH and 4.0 gms of a sulfonic acid catalyst.
This material was heated for 7-8 hours at 65C. The material was cooled and enough NaHCO3 was E~ ~
~6~649 ~ ,:
added to neutralize the catalyst. The material was filtered to give a clear, colorless product. Analysis gave 0.222% SiH, Calc was 0.225, Viscosity was 2.43 cs at 25C. Refractive Index was 1.3903 and Specific Cravity was 0.889.
Example 6 This example represents the preparation of ~-an Si-C bonded surfactant using the siloxane of ~xample 5.
In a l-liter, 3-necked flask was placed 400 gms of the siloxane rom Example 5, 257 gms of CH2=CHCH2 -(OCH2CH)2 20CH3. The mix~ure was heated to 110C. -and 0.3 cc platinum catalyst solution was added : ,~
~3 ppm pt). The mixture exothermed to 147C. and was heated at 140C. for 1 hour, then 120C. for 3 hours~
The product was filtered and gave a light yellow~ clear -~
solution. The residual SiH was .012%.
The surfactant was diluted to 2.5 weight percent ` -~-in CP-4701 polyglycol and evaluated in a foam system as follows.
; A premix was prepared as a polymer in polyol system. `
~ ' .,; ~ .
; 30 :
,. ,~ :
., .
, ., , ~' 3~6~6~
Ingredient A~ount gms Parts (a) ~(CH3)2NCH2CH2}20 2.l~ o.8 (b) NEM (n-Ethyl morpholine) 24~V 0,8 (c) Triethylenediamine 2~4 oO8 ; (d) Distilled wa-ter 84,o 2.~
(e) Niax~ polyol ll-341 18000060,0 (f) Niax~ polyol 34-281 120000 4 light colored~ low viscosity polyols produced ;-by in-situ polymerization of a vinyl monomer in the presence of conventional polyols. 11-34 has a viscosity of 1050 cs at 20C and a hydroxyl number o-f 3205 to 3505 mg. KOH/gm, Nia~3 polyol 34-2B has a viscosity of 2550 cps at 25C by a Brookfield viscometer.
This material was mixed on a roller for four ; ;~
hours to assure complete dispersion of' the ingredients.
~o the premix was added the following for every -103.76 gms of premix- ` -(a) surfactant -, -(b) 003 gm dibutyltindilaurate, mixed thoroughly and added (c) 3402 gms of isocyanate blend composed of 80 parts of 80/20 toluene diisocyanate and 20 parts of polymethylene polyphenylisocyanatso Carried out the additions in the following manner:
(1) Added the surfactant and the tin catalyst to ~
; the premix; I ;
(2) Mixed at 750 rO pom~ for 20 seconds using a commercial mixer;
(3) Added the isocyanate (4) Mixed at 1250 rOp.mO for 4 seconds;
,, ::', ' ' :, .: . ., :. .
~64649 ~
.
(5) Poured into a container (mold) and allowed to rise; -~ -
(6) After full rise, postcured for 15 minutes at 107C., if desired; ;~
(7) Cut foam sample and allow to cool to measure shrink tendency and air flow.
Using the above method, the following results ` -were obtained using the material from the above example as the foam stabilizer.
At 1.0 pph surfactant: rise - 5 1/2; cells = 1.5; ;
air flow = 15.86/172.8; NO splits or voids; NO shrinkage~
Example 7 Three surfactants within the scope of this invention and having the following formulas, were tested in the polymer in polyol system for effectiveness, s ~1) Me3sio(Me2sio)3(Melslo)2siMe3 (2) Me3SiO(Me2SiO)3(MeSiO)lSiMe3 ~ ;
G
(3) Me3SiO(~e2SiO)l(MeSiO) G
All surfactants were diluted to 7.5 welght % in CP-4701 In all cases, G was . . . :, -(CH2)3(OCH2CH)2 2OCH3. -~
CH3 --~
The following formulation for the foam was used.
(~) 60 parts CP-4701 (primary hydroxyl Dow) (b) 40 parts Pluracol 581 (Wyandotte Chem.)l .
(c) .08 parts (CH3)2NCH2cH2OcH2cH2N(cH3)2 (d) .8 parts N-ethyl morpholine (e) .08 parts Triethylenediamine ~` `
(f) 2.8 parts ~ater See Example 3 B~ -26-, . ~ ., -, , 1g~6~6~
To the premix was added surfactant and (g~ .o3 parts Dibutyltindilaurate i~
(h) 34.2 parts Isocyanate blend as in the previous example Procedure:
(1) Mix in (g) and the surfactant at 750 r,pOm. for 20 seconds; i~
(2) Add isocyanate and mix at 1250 r.p.m. for 4 seconds;
(3) Pour and allow 3 minutes before postcuring f~r 15 minutes at 107C;
(4) Cool and cut. `
The results~
Surfactant Commercial NoO 1 No. 2 No. 3 surf, ~ph surfactant 1~0 loO 1~0 1~0 Foam rise 12.38 cm. 14~29 cmO 13097 cm. 12~7 cm.
Cell size 105 loO 105 2~0 Shrinkage None Slight None N~ne -~
Voi~s None None None Slight i-~
Air fl~w ;~
lit./min at ``~
27 cm. HzO `~
Noncrushed/ 10. 2/104~8 3~96/73~6 10~ 2/102 21~5/215 Crushed Example 8 `~
The three surfactants of the ab~ve example ~-. .... . . ~ .
were evaluated in a hetr~ ~olyol system.
The fQrmulati~n for the f~am was: ~
",'' ' ''~:
, .
,, I
1~646~
.~ Premix ! (a) 96 parts CP 470 (b) .o8 parts (CH3)2NCH2CH20CH2CH2N(CH3)z ~:
(C) J8 parts N-ethyl m~rpholine ~ o8 par-ts Triethylenediamine (e) 2.8 parts Water ~f) 4.0 parts Pluracol 3552 (453 hydroxy No.) To the premix add surfactant and .
(g) .03 parts Dibutyltindilaurate (h) 35.0 parts Isocyanate blend from Example 6.
. 10 lSee Example 3. : ~:
polyglycol obtainable from Wyandotte Chemical, . Wyandotte, MichiganO ~:.
Procedure: Essentiall.y the same as Example 7.
The results .~ Surfactant No. 1 No. 2 No. 3 pph surfactant lo O 1~ 0 1~ 0 cell size loO 1~O ls5 , shrinkage severe slight none : air flow- 56.64 90.6 ~: 2~ crushed -~
~1: ? `~
voids none none none .
.
: .
~; : .
, 30 :
~, ~ -28-"
., ~,,:; ,: .. ,. : : . : .. .. :
Using the above method, the following results ` -were obtained using the material from the above example as the foam stabilizer.
At 1.0 pph surfactant: rise - 5 1/2; cells = 1.5; ;
air flow = 15.86/172.8; NO splits or voids; NO shrinkage~
Example 7 Three surfactants within the scope of this invention and having the following formulas, were tested in the polymer in polyol system for effectiveness, s ~1) Me3sio(Me2sio)3(Melslo)2siMe3 (2) Me3SiO(Me2SiO)3(MeSiO)lSiMe3 ~ ;
G
(3) Me3SiO(~e2SiO)l(MeSiO) G
All surfactants were diluted to 7.5 welght % in CP-4701 In all cases, G was . . . :, -(CH2)3(OCH2CH)2 2OCH3. -~
CH3 --~
The following formulation for the foam was used.
(~) 60 parts CP-4701 (primary hydroxyl Dow) (b) 40 parts Pluracol 581 (Wyandotte Chem.)l .
(c) .08 parts (CH3)2NCH2cH2OcH2cH2N(cH3)2 (d) .8 parts N-ethyl morpholine (e) .08 parts Triethylenediamine ~` `
(f) 2.8 parts ~ater See Example 3 B~ -26-, . ~ ., -, , 1g~6~6~
To the premix was added surfactant and (g~ .o3 parts Dibutyltindilaurate i~
(h) 34.2 parts Isocyanate blend as in the previous example Procedure:
(1) Mix in (g) and the surfactant at 750 r,pOm. for 20 seconds; i~
(2) Add isocyanate and mix at 1250 r.p.m. for 4 seconds;
(3) Pour and allow 3 minutes before postcuring f~r 15 minutes at 107C;
(4) Cool and cut. `
The results~
Surfactant Commercial NoO 1 No. 2 No. 3 surf, ~ph surfactant 1~0 loO 1~0 1~0 Foam rise 12.38 cm. 14~29 cmO 13097 cm. 12~7 cm.
Cell size 105 loO 105 2~0 Shrinkage None Slight None N~ne -~
Voi~s None None None Slight i-~
Air fl~w ;~
lit./min at ``~
27 cm. HzO `~
Noncrushed/ 10. 2/104~8 3~96/73~6 10~ 2/102 21~5/215 Crushed Example 8 `~
The three surfactants of the ab~ve example ~-. .... . . ~ .
were evaluated in a hetr~ ~olyol system.
The fQrmulati~n for the f~am was: ~
",'' ' ''~:
, .
,, I
1~646~
.~ Premix ! (a) 96 parts CP 470 (b) .o8 parts (CH3)2NCH2CH20CH2CH2N(CH3)z ~:
(C) J8 parts N-ethyl m~rpholine ~ o8 par-ts Triethylenediamine (e) 2.8 parts Water ~f) 4.0 parts Pluracol 3552 (453 hydroxy No.) To the premix add surfactant and .
(g) .03 parts Dibutyltindilaurate (h) 35.0 parts Isocyanate blend from Example 6.
. 10 lSee Example 3. : ~:
polyglycol obtainable from Wyandotte Chemical, . Wyandotte, MichiganO ~:.
Procedure: Essentiall.y the same as Example 7.
The results .~ Surfactant No. 1 No. 2 No. 3 pph surfactant lo O 1~ 0 1~ 0 cell size loO 1~O ls5 , shrinkage severe slight none : air flow- 56.64 90.6 ~: 2~ crushed -~
~1: ? `~
voids none none none .
.
: .
~; : .
, 30 :
~, ~ -28-"
., ~,,:; ,: .. ,. : : . : .. .. :
Claims (8)
1. A method of preparing a one-shot polyether based, high resilient polyurethane foam which method includes the steps of (I) preparing a homogeneous mixture consisting essentially of (A) 100 parts by weight of a base polyether polyol selected from a group consisting of (i) a polyether triol containing at least 40 mole percent primary hydroxyl groups and having a molecular weight in the range of 2,000 to 8,000 grams per mole, and (ii) a mixture of (i) and an additional polyether polyol having an average of at least two hydroxyl groups, wherein said polyether polyol is present in the mixture (ii) to at least 40 weight percent of the total polyether polyol content of (ii), (B) a sufficient amount of organic polyisocyanate to give from 90 to 120 percent, on a stoichiometric basis, of isocyanate radicals for each hydroxyl radical in the composition, (C) a catalytic amount of a catalyst for the production of the high resilient polyurethane foam, (D) 1 to 10 parts by weight of a blowing agent, (E) a foam stabilizing amount of a copolymer of the general formula Me3Si(OSiMe2)h(0SiMeG)dOSiMe3, wherein h has an average value of about 3, d has an average value o-f about 1, and G is essentially (CH2)3(OCH2,CH)2OCH3, (II) thereafter allowing the mixture to foam, and (III) curing the foamed composition.
2. A method of preparing a one-shot polyether based, high resilient polyurethane foam which method includes the steps of (I) preparing a homogeneous mixture consisting essentially of (A) 100 parts by weight of a base polyether polyol selected from a group consisting of (i) a polyether triol containing at least 40 mole percent primary hydroxyl groups and having a molecular weight in the range of 2,000 to 8,000 grams per mole, and (ii) a mixture of (i) and an additional polyether polyol having an average of at least two hydroxyl groups, wherein said polyether polyol is present in the mixture (ii) to at least 40 weight percent of the total polyether polyol content of (ii), (B) a sufficient amount of organic polyisocyanate to give from 90 to 120 percent, on a stoichiometric basis, of isocyanate radicals for each hydroxyl radical in the composition, (C) a catalytic amount of a catalyst for the production of the high resilient polyurethane foam, (D) 1 to 10 parts by weight of a blowing agent, (E) a foam stabilizing amount of a copolymer of the general formula Me3Si(OSiMe2)h(OSiMeG)dOSiMe3, wherein h has an average value of about 1, d has an average value of about 1, and G is essentially (CH2)3(OCH2,CH)2OCH3 (II) thereafter allowing the mixture to foam, and (III) curing the foamed composition.
3. A method of preparing a one-shot polyether based, high resilient polyurethane foam which method includes the steps of (I) preparing a homogeneous mixture consisting essentially of (A) 100 parts by weight of a base polyether polyol selected from a group consisting of (i) a polyether triol containing at least 40 mole percent primary hydroxyl groups and having a molecular weight in the range of 2,000 to 8,000 grams per mole, and (ii) a mixture of (i) and an additional polyether polyol having an average of at least two hydroxyl groups wherein said polyether polyol is present in the mixture (ii) to at least 40 weight percent of the total polyether polyol content of (ii), (B) a sufficient amount of organic polyisocyanate to give from 90 to 120 percent, on a stoichiometric basis, of isocyanate radicals for each hydroxyl radical in the composition, (C) a catalytic amount of a catalyst for the production of the high resilient polyurethane foam, (D) 1 to 10 parts by weight of a blowing agent, (E) a foam stabilizing amount of a copolymer of the general formula Me3Si(OSiMe2)h(OSiMeG)dOSiMe3, wherein h has an average value of about 3, d has an average value of about 2, and G is essentially (CH2)3(OCH2,CH)2OCH3, (II) thereafter allowing the mixture to foam, and (III) curing the foamed composition.
4. A method of preparing a one-shot polyether based, high resilient polyurethane foam which method includes the steps of (I) preparing a homogeneous mixture consisting essentially of (A) 100 parts by weight of a base polyether polyol selected from a group consisting of (i) a polyether triol containing at least 40 mole percent primary hydroxyl groups and having a molecular weight in the range of 2,000 to 8,000 grams per mole, and (ii) a mixture of (i) and an additional polyether polyol having an average of at least two hydroxyl groups, wherein said polyether polyol is present in the mixture (ii) to at least 40 weight percent of the total polyether polyol content of (ii), (B) a sufficient amount of organic polyisocyanate to give from 90 to 120 percent, on a stoichiometric basis, of isocyanate radicals for: each hydroxyl radical in the composition, (C) a catalytic amount of a catalyst for the production of the high resilient polyurethane foam, (D) 1 to 10 parts by weight of a blowing agent, (E) a foam stabilizing amount of a copolymer of the general formula Me3Si(OSiMe2)h(OSiMeG)dOSiMe3, wherein h has an average value of about 1, d has an average value of about 1, and G is essentially O
(CH2)3(OCH2,CH)2.5OCCH3, (II) thereafter allowing the mixture to foam, and (III) curing the foamed composition.
(CH2)3(OCH2,CH)2.5OCCH3, (II) thereafter allowing the mixture to foam, and (III) curing the foamed composition.
5. A method of preparing a one-shot polyether based, high resilient polyurethane foam which method includes the steps of (I) preparing a homogeneous mixture consisting essentially of (A) 100 parts by weight of a base polyether polyol selected from a group consisting of (i) a polyether triol containing at least 40 mole percent primary hydroxyl groups and having a molecular weight in the range of 2,000 to 8,000 grams per mole, and (ii) a mixture of (i) and an additional polyether polyol having an average of at least two hydroxyl groups, wherein said polyether polyol is present in the mixture (ii) to at least 40 weight percent of the total polyether polyol content of (ii), (B) a sufficient amount of organic polyisocyanate to give from 90 to 120 percent, on a stoichiometric basis, of isocyanate radicals for each hydroxyl radical in the composition, (C) a catalytic amount of a catalyst for the production of the high resilient polyurethane foam, (D) 1 to 10 parts by weight of a blowing agent, (E) a foam stabilizing amount of a copolymer of the general formula Me3Si(OSiMe2)h(OSiMeG)dOSiMe3, wherein h has an average value of about 1, d has an average value of about 1, and G is essentially (CH2)3(OCH2,CH)2.5OCH3, (II) thereafter allowing the mixture to foam, and (III) curing the foamed composition.
6. A method of preparing a one-shot polyether based, high resilient polyurethane foam which method includes the steps of (I) preparing a homogeneous mixture consisting essentially of (A) 100 parts by weight of a base polyether polyol selected from a group consisting of (i) a polyether triol containing at least 40 mole percent primary hydroxyl groups and having a molecular weight in the range of 2,000 to 8,000 grams per mole, and (li) a mixture of (i) and an additional polyether polyol having an average of at least two hydroxyl groups, wherein said polyether polyol is present in the mixture (ii) to at least 40 weight percent of the total polyether polyol content of (ii), (B) a sufficient amount of organic polyisocyanate to give from 90 to 120 percent, on a stoichiometric basis, of isocyanate radicals for each hydroxyl radical in the composition, (C) a catalytic amount of a catalyst for the production of the high resilient polyurethane foam, (D) 1 to 10 parts by weight of a blowing agent, (E) a foam stabilizing amount of a copolymer of the general formula Me3Si(OSiMe2)h(OSiMeG)dOSiMe3, wherein h has an average value of about 3, d has an average value of about 2 and G is essentially (CH2)3(OCH2,CH)2.5OCH3, (II) thereafter allowing the mixture to foam, and (III) curing the foamed composition.
7. A method of preparing a one-shot polyether based, high resilient polyurethane foam which method includes the steps of (I) preparing a homogeneous mixture consisting essentially of (A) 100 parts by weight of a base polyether polyol selected from a group consisting of (i) a polyether triol containing at least 40 mole percent primary hydroxyl groups and having a molecular weight in the range of 2,000 to
8,000 grams per mole, and (ii) a mixture of (i) and an additional polyether polyol having an average of at least two hydroxyl groups, wherein said polyether polyol is present in the mixture (ii) to at least 40 weight percent of the total polyether polyol content of (ii), (B) a sufficient amount of organic polyisocyanate to give from 90 to 120 percent, on a stoichiometric basis, of isocyanate radicals for each hydroxyl radical in the composition, (C) a catalytic amount of a catalyst for the production of the high resilient polyurethane foam, (D) 1 to 10 parts by weight of a blowing agent, (E) a foam stabilizing amount of a copolymer of the general formula Me3Si(OSiMe2)h(OSiMeG)dOSiMe3, wherein h has an average value of about O,d has an average value of about 1, and G is essentially (CH2)3(OCH2,CH)2.5OCH3, (II) thereafter allowing the mixture to foam, and (III) curing the foamed composition.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US46118674A | 1974-04-15 | 1974-04-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1064649A true CA1064649A (en) | 1979-10-16 |
Family
ID=23831544
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA205,851A Expired CA1064649A (en) | 1974-04-15 | 1974-07-29 | Polyether based, high resilient polyurethane foam |
Country Status (8)
Country | Link |
---|---|
JP (1) | JPS543715B2 (en) |
AT (1) | AT340692B (en) |
BE (1) | BE821148A (en) |
CA (1) | CA1064649A (en) |
DE (1) | DE2439734A1 (en) |
FR (1) | FR2278717A1 (en) |
GB (1) | GB1453161A (en) |
IT (1) | IT1022904B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117209712A (en) * | 2023-08-15 | 2023-12-12 | 佛山市创意新材料科技有限公司 | Popcorn sole and preparation method thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS638414A (en) * | 1986-06-28 | 1988-01-14 | Somar Corp | Thermosetting powder composition |
-
1974
- 1974-07-29 CA CA205,851A patent/CA1064649A/en not_active Expired
- 1974-07-30 GB GB3355774A patent/GB1453161A/en not_active Expired
- 1974-08-19 DE DE19742439734 patent/DE2439734A1/en not_active Ceased
- 1974-08-20 AT AT679474A patent/AT340692B/en not_active IP Right Cessation
- 1974-08-20 JP JP9547774A patent/JPS543715B2/ja not_active Expired
- 1974-10-14 FR FR7434479A patent/FR2278717A1/en active Granted
- 1974-10-16 IT IT2846274A patent/IT1022904B/en active
- 1974-10-16 BE BE149601A patent/BE821148A/en not_active IP Right Cessation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117209712A (en) * | 2023-08-15 | 2023-12-12 | 佛山市创意新材料科技有限公司 | Popcorn sole and preparation method thereof |
CN117209712B (en) * | 2023-08-15 | 2024-02-27 | 佛山市创意新材料科技有限公司 | Popcorn sole and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
ATA679474A (en) | 1977-04-15 |
AT340692B (en) | 1977-12-27 |
AU7191774A (en) | 1976-02-05 |
FR2278717B1 (en) | 1979-08-03 |
GB1453161A (en) | 1976-10-20 |
DE2439734A1 (en) | 1975-10-16 |
IT1022904B (en) | 1978-04-20 |
JPS50134098A (en) | 1975-10-23 |
FR2278717A1 (en) | 1976-02-13 |
JPS543715B2 (en) | 1979-02-26 |
BE821148A (en) | 1975-04-16 |
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