CA1047686A - Polyurethane prepolymers, rebonded polyurethane foams and methods of forming rebonded polyurethane foams - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

This invention relates to novel polyurethane prepolymers which consist essentially of the reaction product of polyoxyalkylene polyol having a critical oxyethylene content and an isocyanate con-stituent, the reaction product having a defined level of free NCO.
Particularly useful prepolymers are produced using a tolylene diisocyanate residue. The prepolymers provided have outstanding utility for rebonding polyurethane foams for applications such as, for example, carpet underlays and allow significant reductions in the adhesive level used in forming such rebonded foams and in the demolding cure times in comparison with presently used prepolymer adhesives. The prepolymers are also useful for applications in which polyurethane prepolymers are used presently such as, for example, in hydrophilic foams.

Description

- (~
~ D-9912-1 BACXGROUND OF TH~ INVENTION

A substantial amount of the materials used for carpet underlay are formed from, what is termed, rebonded urethane foam. Rebonded urethane foam is the product obtained when small, shredded particles, e.g. ~ one-half inch cube in size, of a flexibIe urethane foam are coated with a thin layer of a prepolymer adhesive and compressed until the adhesive cures ` ~ sufficiently to maintain the particles of urethane foam i.n the compressed state, i.e. - the product has dimensional integrity or stability.
In manufacturing rebonded urethane foam, typically, the shredded, small par~icle urethane foam is placed in a suitable mixiny container, such as a ribbon blender, where the foam particles are subjected to vigorous mixing. As the shredded foam particles are being agitated, the prepolymer adhesive is sprayed into the mixing chamber where it coats the particles of scrap, flexible urethane foam. Water may also be added to the mixing chamber before the prepolymer is added, at about the same time the prepolymer is added, or after addition of the prepolymer. The water may or may not contain a catalyst to promote the curing of the prepolymer adhesive. After the shredded foam and prepolymer mixture are thoroughly blended, the mixture is transferred from the mixer to a mold and compressed (if a batch process is being used) or to continuously moving compression conveyors (when the process is "continuous").
In either case, the mixture is held in the compressed state ~until the shredded foam/prepolymer block achieves dimensional ., . .:
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D-9~12~1 , stability. It is this compressed block of shredded`foam/
reacted prepolymer which is identified as "rebonded urethane foam". This rebonded urethane foam may then be fabricated into whatever shape is required for the particular intended end use application~
Typically, the prepolymers which have been used ~or such rebonded foam applications comprise the reaction product of an isocyanate such as tolylene diisocyanate with a polyol such as a polyoxypropylene polyol which may contain mi.nor amounts of ethylene oxide on the order of about 15% or less.
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Prepolymers of this type suitably function to yield the desired rebonded urethane foam product~ However, the economy of the -manufacture of the rebonded foam product is dependent to a significant extent upon the amount of the prepolymer adhesive which must be used, the time needed to cure the prepolymer ;~ adhesive and the time before the rebonded polyurethane foam can ,I be "demolded" (i.e. - removed from the mold).
.! : ;I OBJECTS ~
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It is an object of the present invention to provide ~; ,, .
¦ 20 novel prepolymer compositions which allow economies in the ~`
~' manufacture of rebonded urethane foam.
A further and more specific object provides prepolymer ; compositions which may be formed from tolylene diisocyanate ``
, re~idue blended with tolylene dii~ocyana~e, l~ ~ A still further object lies in the provlsion of prepolymer compositions which can be cured in relatively shor~ -. ..
' periods of time.
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' '' :' Yet another object of this invention is to provide prepolymer compositions which allow rebonded urethane oam to be made with relatively small amounts of the prepolymer composition.
Still another object of the present: invention provides prepolymer compositions that minimize the demolding time required in the manufacture of rebonded urethane foam.
Another object of this invention is to provide ~ prepolymer compositions which exhibit improved stability upon '10 storage.
A further object provides prepolymer compositions which are h,omogeneous solutions which minimize processing problems.
A stlll further object lies in the provision of ~ prepolymer compositions which allow the manufacture of lower :! density rebonded urethane foams from a particular starting foam ~ ,, ~! source. , ", ""
Yet another object of this invention is to provide novel rebonded urethane foams and a method of preparation ' ~'20 thereof.
' , Other ob~ects and advantages of the present invention ~,' ~` will become apparent in the following description. '~,~
'. ',' '. ' . .
SUMMARY OF THE INVEWTION .
i ,~ In general, the present invention is predicated on the discovery that prepolymer compositions exhibiting outstanding properties for applications such as an adhesive for rebonding ., - : ~
polyurethane foams axe provided by the reaction product of an , ~, ~,~ ~4 ,' ', . ' ~ ~: . ~ ' . ~:

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~qL76~6 isocyanate constituen~ consisting of tolylene diisocyanate residueJ tolylene di~socyanate, diphenylmet~ane diisocyanate, polymethylene poly(phenyleneisocyanate), and blends thereof, with a polyoxyalkylerle polyol containing between about 30 to 100 percent by weight of oxyethylene and a free NC0 content in the range of from about 2 to about 20 percent by weight, with the proviso that when the oxyethylene content of the polyol is 100 percent by weight ~ :
the isocyanate is other than tolyIene diisocyanate or diphenylmethane diisocyanate, Particularly useful and :
preferred prepvlymer compositions are formed when tolylene diisocyanate residue blended with tolylene diisocyanate : ~:
is employed. The novel prepolymer compositions of this invention, except when diphenylmethane diiocyanate is used, ; ~-are homogeneous solutions. .
This invention further provides rebonded polyure- ~
thane foams utilizing certain prepolymer compositions ~:
as well as a method for forming such rebonded urethane :~
: - ~
foams. More particularly, this invention also provides a ~.
rebonded polyurethane foam comprising a block of foam -. particles having dimensional stability and said particles .
being bonded together by a cured polyurethane prapolymer, saîd prepolymer consîsting of the reaction product of (a) an îsocyanate selected from the group consisting of .

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tolylene diisocyanate, tolylene diisocyanate residue, diphenylmethane diisocyanate, polymethylene poly(pheny-leneisocyanates), and blends thereof and (b) a~.
.~; polyoxalkylene polyol having an oxyethylene content . . . . .
of from about 30 to 100 percent by weight, said prepolymer .; having a free NCO content prîor to curing, of from about .
',! 2 to 20 percent by weight. . .
.. ..

DETAILED DESCRIPTION ..
, . .
, i The polyoxyalkylene polyol constituent should :~
~, contain a range of oxyethylene content which yie~ds a .. :
;, 10 homogeneous prepolymer solu~ion. By a homogeneous ~ . . . ...
~.............. prepolymer solutian, it is meant that, by visual inspee- ~ :
.. ~ tion, the prepolymer compositions are clear and solids .~. .
.l free or contain so little solid content that homogeneous , solutions can be obtained by conventional filtration, as .:.
.l' will be hereinafter described. The homogeneity is .:
~ generally determined at ambient or room temperature .~ conditions since, if:the prepolymer solution i:s not homogeneous at such conditions, it will not be homogeneous ~ at~elevated temperatures, However, as will be pointed 1 20~ out hereinafter, when t~e prepolymer is a solid at ambient . ~ :
: temperatures, it is suf~icient if the prepolymer is : homogeneous at the temperatares at which it is a liquid.
~;-'. : In the manufacture of rebonded foam, it appears .~ , . .

~ 5a-~L~`4~ 6 that the rate of prepolymer cure is directly proportional to the oxyethylene content of the polyol utilized in preparing the prepolymer composition. Thus, the higher the oxyethylene content of the polyol, the faster the rate oE prepolymer cure that has been o~served.
The range of the polyol oxyethylene content that can --~; appropriately be utilized depends upon w~ether the prepolymer composition is formed at room temperature or an elevated temperature. When room or ambient temperatures are employed ~10 to form the prepolymer compositions of this invention, it has been found desirable to maintain the oxyethylene content in the range of from about 30 to about 80 per cent to provide homogeneous prepolymer solutions. As the oxyethylene content is decreased below 30 per cent, the prepolymers begin to lose their homogeneous character after short storage periods. Indeed, when polyols having oxyethylene contents of 20 per cent are used, the prepolymers formed are non-homog~neous from the outset. In high molecular weight polyether polyols, (e.g. ~ having hydroxyl , numbers in the range of 30-60), which may typically be used for the manufacture of these prepolymer compositions for rebonded foam applications, oxyethylene contents above about 70 per cent tend to provide prepolymer compositions which are hazy or solid at ~, .
room temperature and have high freezing point values, making the materials undesirable for storage and use in cold winter , ~ .
temperatures. Accordingly, the preerred range of polyol ~oxyethylene content~or room temperature prepolymer preparation lies in the range of rom about 40 to about 70 per cent.

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i: , . ' ,.. :' When elevated reaction temperatures are used in the - preparation of the prepolymer compositions, the range of the oxyethylene content of the polyol which will yield homogeneous prepolymer solutions at the reaction temperature utilized lies in the range of from about 30 to about 100 per cent. The preferred range for elevated temperature preparation is from about 40 to about 70 per cent, however, for the reasons discussed herein in connection with room temperature prepared prepolymers.
Thus, polyoxyethylene polyols that are solid at room temperature L0 may be utilized and will form homogeneous prepolymer solut:ions at the elevated reaction temperatures employed. These are not .
preferred since the resulting prepolymers will become solid~upon storage at room temperature.
j The positioning of the oxyethylene units in the polyol is not believed to be critical. Accordingly, the ~ -polyoxyalkylene polyol can contain either internal ethylene oxide or the polyol can be capped with the necessary ethylene ;~ oxide content.
The hydroxyl number of the polyol constituent can vary Z0 within wide limits, depending upon the specific end use application contemplated. Suitably, the hydroxyl number may ranse from about 25 or perhaps 20 to about 650. For most applications, including rebonding urethane foams, it is preferred to maintain a hydroxyl number range of from 30 to 60, and most preferably from 30-40.
As can be appreciated, lower hydroxyl numbers are preferred since the amount of the isocyanate constLtuent needed for the prepolymer will correspondingly be reduced, resulting in a more economical operation.

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The functionality and molecular weigh-t of the polyol are not critical and may be selected so as to provide the polyol with the desired hydroxyl number. With respect to the polyol funckionality, diols and triols will be typi~ally employed but functionalities up to six and even higher certainly may be used if desired. With the hydroxyl number desired and the functionality selected, tne needed molecular weight will, as is known, be set.
In rebonded foam applications, with typical hydroxyl numbers desired, the polyols used will have molecular weights ranging ~rom

2,000 to 5,000, depending upon whether a diol or triol is involved.
The polyoxyalkylene polyol constituent may be prepared using conventional procedures which, as is known, include reacting either a mixture o an alkylene oxide such as propylene oxide and ethylene oxide or sequentially feeding the subject oxides to a hydroxyl containing starter in the presence of a catalyst, such as potassium hydroxide. This crude product may then be refined ; ;
by any method, principally to remove the catalyst. Suitably, for example, the crude polyol can be treated with magnesium silicate, stabilized with 2,6-di-tert-butyl-4-methylphenol, filtered~ and then stripped free of volatiles. For optimum prepolymer reaction characteristics, is has been found desirable to maintain the ~` water content less than about 0.4 weight per cent, preferably below about 0.1 weight per cent. Whi}e higher water contents in ;, .
the polyoI do not prevent the formation of a satisfactory ~` prepolymer, such higher water contents can result in the formation ;
; of a significant amount of carbon dioxide and urea which may cause ;
handling problems during the manufacture of the prepolymer compositions. While propylene oxide is preferred for use in forming . .
the polyol ~onstituent, other alkylene oxides such as butylene .
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' ;~.O~L7~ Ei; -oxide could be employed if desired.
The isocyanate constituent employed in forming the novel prepolymers of this invention can range, in one embodiment, from tolylene diisocyanate residue to pure tolylene diisocyanate.
As is known, tolylene diisocyanate is commerclally made by reacting toluene and nitric acid to form the 2,4- ancL 2,6-dinitrotoluene isomers, hydrogenating and then phosgenating, typically in a solvent such as dichlorobenzene, to provide the conventional mixture of 80 per cent 2,4-tolylene diisocyanate and 20 per cent 2,6-tolylene diisocyanate. After removal of the solvent, the crude product undergoes a further evaporation in a still, with the refined or puxe tolylene diisocyanate coming over. The evaporatox tails remaining are black in color and extremely viscous, even often solid, materials. It is the evaporator tail material which is defined by the terminology used herein, as a tolylene diisocyanate res~due.
If desired, and while not preferred, the tolylene diisocyanate residue may be employed, as has been discussed, as the isocyanate constituent for the novel prepolymers. When employed, due to processing problems, it may be desirable to reduce the viscosity by incorporating a suitable solvent such as methylene chloride. The tolylene diisocyanate residue should be allowed to age before usage by storage for an extended period of time, e.g. - up to about one month or even longer. During this storage period, as is known, some chemical rearrangement is believed to occur; and the visc05ity initially increases rather significantly.
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; Sufficient ~ging is achieved when the increment of the viscosity ;~

' increase begins to level off.

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it~47~ ~ ~ D-9912-1 The preferred isocyanate constituent is formed by blending the aged tolylene diisocyanate resiclue with commercially pure tolylene diisocyanate in varying amounts. Prepolymers formed rom such blends provide both economy as wel] as outstanding properties in rebonded foam applications as compared with pure tolylene diisocyanate. Suitable blends are commercially available;
and, for purposes of forming the prepolymersv the amount of pure tolylene diisocyanate used is not critical. While the weight per cent of the tolylene diisocyanate in the blend can, of course, be varied as desired, particularly useful blends are formed when the tolylene diisocyanate used is from about 33 to 67 weight per cent.
As should be appreciated, somewhat differing results are achieved depending upon the character of the tolylene diisocyanate residue used. It is preferred to employ residues that are homogeneous in character, as visually evidenced by the lack of solids present. Residues containing some solids can be used but result i~ prepolymiers which retain these solids. Homogeneous prepolymer solutions can, however, sometimes be provided by ; flltering the resulting prepolymers; and the solids content of such prepolymers should be distinguished from the extent of solids in prepolymers formed from residues and polyols not within the scope of this invention which cannot be easily and economically filtered to provide homogeneous prepolymer solutions. ,Thus, as is known, -it is ccnventional in connercial operations to employ filters such . : .
as, for example, cone filters. To be useful in such applications, the prepolymers should plug or foul the filters. Whether appropriate fil~ration can provide a satisfactorily homogeneous !
~olution can ~e determined by using a conventional laboratory p filter. If the prepolymer containing solids can be processed through ;

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1~47~i86 D--9 912--1 such a pressure filter to remove the solids, the resulting prepolymer can be considered to be within the present invention.
In addition, the isocyanate constituent may also be diphenylmethane diisocyanate (MDI) or poly~phlenyleneisocyanates~
(polymeric MDI). When polymeric MDI is utilized, the resulting prepolymer is not homogeneous. Conventional filtration of the polymeric MDI before the prepolymer is made (i.e. - pre-filtration) allows preparation of a prepolymer which, when first prepared, is essentially free of solids; but solids or sediment develop upon ~10 standing at room temperature. If, however, the prepolymer is filtered after being made (i.e. - post-filtration) the filtered prepolymer remains a clear, black homogeneous liquid, even when stored at room temperature for three weeks. Accordingly, when polymeric MDI is employed, at least a post-filtration should desirably be employed. However, the other isocyana~e constituents are generally preferred in relation to polymeric MDI due to the superior performance in rebonding polyurethane foams.
MDI may also be suitably employed as the isocyana~e constituent and is unique in that a homogeneous prepolymer solution 20 does not result, regardless of whether filtration is employed.
The character of MDI-prepolymers remains essentially the same ; regardless of the oxyethylene content, i.e. - a white slush which is relatively stable insofar as phase separation is concerned.
MDI prepolymers made with polyols having oxyethylene contents less ' than 30% are not preferred, however, since such prepolymers are

3 --relatively inferior when employed (as an adhesive for rebonding foams) Because of the lack of homogeneity of MDI prepolymers, their use is not preferred in applications where fouling of rebonding ~ , .

-11- ; ' .

- . .. .

~ D-9912-l apparatus can readily occur, e.g. - in apparatus which includes filtering means. However, in applications where fouling will no~
present a problem, MDI prepolymers can be employed and possess outstanding utility for rebonding polyurethane foams.
Blends of any of the isocyanate constituents may also be employed if desired. In addition to blends of tolylene diisocyanate and tolylene diisocyanate residue, particularly useful blends include blends of tolylene diisocyanate and ,, .
polymeric MDI with tolylene diisocyanate contents of from 40 to 60 weight per cent, based upon the total weight of the blend. As will be apparent from the prior discussion, depending upon the blend utilized, filtration may be desirable to provide homogeneity for the resulting prepolymer or use may preferably be restricted to non-fouling applications when significant amounts of MDI are employed., To form the prepolymer compositions of the present invention, the polyol and isocyanate constituents can be mixed -together in a reaction vessel at either room or el vated temperatures, and with or without a catalyst. Suitably, for example, when elevated temperatures are employed, the isocyanate constituent can be charged to the reaction vessel and heated; and the polyol ; may then be thereafter ~ed at a rate to maintain the desired reaction temperature. Suitable catalysts include any of the many known catalysts for catalyzing isocyanate-polyol reactions such as organotin compounds such as dialkyltin salts of carboxylic acids, e.g. - dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, .. ` , . ~ .
and the like. Stannous octoate and the like and tertlary amines such as bistdimethylaminoethyl)ether are further suitable ~ representative examples. Typically, the catalyst may suitably .' :
-12-. .
'; " ' `' ... ,, . ~ ~. ' be employed in small amounts, for example, from about 0.0001 per cent to about 5 per cent based upon the weight of the reaction mixture, most typically O.OQl to 0.020. If a catalyst is to be used, it may be blended with the polyol or alternatively, added to the reaction mixture in the reaction vessel. After all the constituents are completely mixed, the reaction is allowed to proceed until the generation of prepolymer is complete, as is evidenced by the visual prepolymer ~larity or stabilized viscosity or free isocyanate ~NCO) content characteristics.
At room temperatures, the reaction time may vary from about 3 days when no catalyst is employed to about 1 day when a catalyst is employed. At elevated reaction temperatures, e.g. - 50C., the prepolymer generation reaction will typically be complete in less than about 5 hours when no catalyst is present. As will be appreciated, elevated temperature should -~
be employed when the polyol constituent is normally solid at - ;~
ambient temperatures. Also, when ambient or room temperatures :, are used, it is necessary to utilize intimate or vigorous mixing, such as can be achieved by conventional mixing apparatus providing high shear.
With respect to the relative amounts of the polyol and isocyanate constituents, the ratio employed should, from . ' i . .
the functional standpoint, provide a prepolymer with the lowest ; ~ ree NCO content that will perform satisfactorily in the . ~ . .
-~ intended end use application. Typically, the free NCO content ., .
l can suitably vary from about 2 to about 20 per cent. As the ;l free NCO content of the prepolymer~ of this invention is ` decreased to approach the minimum, the prepolymers tend to.
; become unstable, as evidenced by significant viscosity increases .

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D-9912-1 ~
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in storage. Prepolymers employing free NCO contents approaching the upper limit of the range tend to allow formation of undesirable lower molecular weight compounds such as ureas which adversely affects the adhesive properties of the prepolymers. Most preferably, when the prepoiymer co~position is to be used for rebonding urethane foam, the free NCO content will be in the range of from about ;~ 5 to 10 per cent. The optimum content tha~ has been observed L for this application is about 10 per cent because of the faster curing times achieved in comparison to prepolymers containing lower free NCO content. While higher free NCO content prepolymers than those set forth herein can perhaps suitably be ; used, it should be appreciated that this is generally undesirable due to the loss of more free isocyanate into the atmosphere.
If desired, a diluent may be added ~o the prepolymer - -in amounts necessary to reduce the viscosity to whatever level is required. Any diluent may be utilized so long as, of course, no significant adverse effects are caused in the particular end ~20 use application. As an illustrative example, methylene chloride has been found to be a satisfactory diluent.
In forming the novel rebonded urethane foams of this i~vention, the process described hereinbefore may be utilized.
Thus, the polyurethane foam, generally scrap, is comminuted or shredded into relatively small particles in conventional apparatus`such as a grinder. The particle size of ~he shredded foam is not critical and will vary depending upon the type of , ` grinding used. Uniformity of particle size is not needed, and a typical shredded foam may contain particles smaller than 1/16 i : ~ .
~ 14 ~- -:.

of an inch or smaller up to particles having at least one dimension perhaps 2 inches or more. The shredded foam may also contain in commercial practice minor amounts of a wide variety of other scrap materials ranging from, for example, string to polyethylene film.
The shredded foam is then transported to a mixing container such as a ribbon blender; and, while the foam particles are being agitated, the prepolymer is added, typically by spraying. Water is typlcally added to the mixing container before addition of prepolymer, at the same time, or after.
After thorough blending of the shredded foam and prepolymer is achieved, the mixture is transferred to a means for compressing the foam to provide the desired product, thickness and density. In the case of a batch process, the mixture is transferred to a mold; and, in the case of a continuous : process r the mixture is fed into continuously moving compression conveyors. In the case of a continuous process, the mixture may first be transferred to a second ribbon blender to insure that adequate blending is obtained.
The shredded foam/prepolymer blend is held in the compressed state, as is well known in the rebonding art, until ; dimensional stability is achieved, i.e. - there is little or no tendency for the compressed product to expand. More -par~icularly, and as is known in this field, the lack of tendency for the compressed~product to expand is a relative term. The term dimensional stabLlity refers to the stability provided by curing the rebonded foa~ as is conven~ionally carried out in this .
field, and the slight expansion which may occur is to be contrasted to the significant expansion tendencies when jns~;ci~n~
curing is used. Curing of the blend can be carried out at either ~ `, ' '' '' ' ' .

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room temperature or at elevated temperatures by injecting hot fluids such as steam or hot dry air or by subjecting the compression container to a conventional radiant heat source.
; With room temperature curing, it may be desirable to use minor amounts of a catalyst. Suitable catalysts and amounts have been described in connection with the formation of the prepolymers.
The resulting block can then be further fabricated as desired.
, The utilization of the prepolymers of the present L0 invention present no processing problems, achieve faster curing times, require lesser amounts of -the prepolymer adhesive and allow shorter demolding times in comparison to the presently used prepolymers.
The resulting rebonded polyurethane product can be characterized as a dimensionally stable block of varying size depending upon the intended application. The block comprises ~ ;
discrete foam particles bonded together by an amount of cured prepolymer sufficient to provide the block with dimensional stability. While larger amounts can be used, it will generally be suitable to use no more than about 4 to 6% of prepolymer, based upon the total weight of the block constituents and including the prepolymer. This is in contrast to the ~ to 12%
often used with the prepolymers in present practice.
I For a given product density, the rebonded foam products of this invention exhibit tensile strengths, tear strength and compression load deflections comparable to products using conventional prepolymers. An added advantage of the present invention, however, resides in the ability to make useful lower density products from shredded foam of a partlcular density than , ~, ~7 ~ D-991~
~.
can be achieved using conventional prepolymers. As an example, with a foam source of 1.5 lbs.tft.3, rebonded foam products having a density of about 2.6 lbs./ft3 acc:ording to the present invention can be achieved in contrast to foams using conventional prepolymers that generally result in foam densities no lower than 3 lbs./ft.3, typically 3.5.
The prepolymer compositions of the present invention and the use of such compositions in forming rebonded urethane foams may be further illustrated by means of the following examples. It should be understood, however, that these examples are intended to be merely illustrative, but not in . .
; limitation of, the scope of this invention. ~
, .
DEFINITIQNS
As used in the Examples appearing hereinafter, the following symbols, terms and abbreviations have the indicated meanings:
::
"Cookoutl' denotes the period a reaction mixture is -heated after all starting materials have been added. ~;
"Ionol" denotes 2,6-di-tert-butyl-4-methylphenol.
"Max." denotes maximum.
"Stripped" denotes removal of volatile materials by heating at reduced pressure.
"Crude hydroxyl number" denotes the hydroxyl number of the stripped, unrefined polyol, corrected for alkalinity.
"Mixed" ~ln relati~on to type of feed) denotes that !
that alkylene oxides used are mixed prior to introduction into the reaction vessel.
"SequentiaI" (in relation to type of feed) denotes that the alkylene oxides used are introduced into the reaction vessel in discrete units.
-.~

"Psig" denotes pounds per square inch gauge pressure.
"Wt." denotes weight.
"Ion Exchanye" (in relation to refining) denotes removal of the catalyst from the crude polyol by employing appropriate ion exchange resins.
"Gm" denotes grams.
- "Cks." d~notes viscosity in centistokes at 25C.
"NCO" or "free NCO" denotes the free isocyanate content ~ in weight per cent.
! "Not homogeneous" denotes a prepolymer containing visible solids.
"Homogeneous" denotes a clear prepolymer solution ~ree of visiblé solids.

.
, PREPARATION PROCEDURES
.
The polyols, prepolymer compositions and the laboratory formed rebonded polyurethane foams described in the Examples presented hereinafter were prepared according to the following procedures:
A. Polyols ~
.. . - . .
Because of reactor geometry, when the procedure indicates multiple steps were used, the indicated amount of the crude polyol product from the particular step was used as the starter for the following step.
B. Prepolymer Composition ~
At room temperature, the procedure involved consisted of weighing the isocyanate constituent into a reaction bottle, ;l : ..
weighing the polyol constituent containing 0.03 parts stannous octoate per 100 parts polyol into the reaction bottle with the `' isocyanate and mixing the isocyanate and polyol by vigorously :' ' i. :~.' .;
'~ .' 1~4~i86 D-9gl2-l shaking the reaction bottle at ambient temperature. The reaction blend is then allowed to react without further agitation. After all the ingredients are completely mixed, the reaction mixture is allowed to react until the generation of the prepolvmer is complete, as visually evidenced by prepolymer clarity. The followi~g Examples were made by this room temperature technique~ 12, 15-24, 39, 41 and 43.
Examples 13 and 14 were formed using the same procedure except that the reaction mixture was maintained at 60C. Examples 39, `1~ 41 and 43 were agitated during their preparation.
ALl other prepolymer compositions were formed by the following procedure:
The isocyanate was charged to the agitated rèaction flask and heated to 65C. under an inert atmosphere. The polyol was fed to the isocyanate at a rate to keep the temperature between 65 and 70C. After all the polyol has been fed, the temperature is increased to a cookout temperature of 80C.
Analyses of the prepolymer free NCO content and viscosity were performed at various intervals, and the reaction was considered complete when the free NCO content and viscosity became stabilized.
C. Laborator~ Rebonded Urethane ~oam Preparation One hundred forty-~hree grams of shredded, flexible urethane oam are weighed using a Mettler balance (Type K7T, maximum capacity 800 grams); and the weighted foam is then poured into a five-gallon open top bucket. While stirring the shredded foam in the~bucket, 15 cubic centimeters of water are slowly added to the shredded foam. Fifteen grams of prepolymer, aged for at least 24 hours after formation, are placed in a 20 - ~
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cubic centimeter hypodermic syringe. While vigorously stirring the shredded foam/water mixture by handj the 15 gxams of prepolymer from the syringe are slowly sprayed into the shredded foam/water mixture. The vigoxous stirring of the shredded foam/
water/prepolymer mixture is continued for 30 seconds after addition of the prepolymer to the foam/water mix. A 10 inch high metal cylinder, having an 8 inch inside d1ameter perforated with 3/32 inch holes in the lower 2-inches of the cylinder, is placed on a metal plate, approximately 1/2 inch in thickness, 20 inches long and 20 inches wide, with the perforated cylinder end down. The perforations are in two rows with one row being `
1/2 inch from the bottom of the cylinder and the other row 1-1/2 inches rom the bo~tom of the cylinder, the holes being spaced 1 inch apart both horizontally and vertically. The shredded foam/water/prepolymer blend is then poured into the cylinder. A
solid wooden cylinder (7-3/4 inch diameter by 2 inches high) , , with three metal nails extending 2 inches from one end of the wooden cylinder is placed on top of the foam/water/prepolymer mixture with the metal nails extending downward into the foam.
Four 5-pound lead weights approximately 3 inches in diameter are then placed on top of the wooden cylinder, forcing the wooden cylinder down into the metal cylinder until the nails are solidly in contact with the metal plate under thè cylinder. The ~ ...................................................................... . .
metal plate with the metal cylinder, wooden cylinder, lead weights, an~ compressed foam mixture is then placed in a circulating, forced air oven which is preheated and preset to maintain a constant temperature of 150C. The entire assembly is kept in the hot air oven for 15 minutes, or other cure time deemed 1~Si~Q~I9 ~ `
to determine differences in the prepolymer reaction rates. At the '.' .'~

.^. ' '"' ~:`-~4768~ D-9912-1 , end of the cure time, the block of rebonded urethane oam is xemoved from the cylinder and subjectively evaluated to determine the relative degree of cure of the prepolymer composition.

STARTING MATERIALS
, In the Examples appearlng hereinafter, the following designations are used to denote the indicated starting materials:
A. Polyols "PEG 4000~' denotes a commercial:Ly available l'Carbowax"
polyethylene glycol having a number average molecular weight in the range from 3000 to 3700.
"PEG 1000" denotes a commercially available "Carbowax"
polyethylene glycol having a number average molecular weight in the range of from about 950 to about 1050. .~ .
"PPG" 425" denotes a polyoxypropylene glycol having an ' average hydroxyl number of 265. .~ .
:~ B. Isocyanates ; "TDI" and "TDI-P" denote a mixture of 80 per cent 2,4-tolylene diisocyanate and~20 per cent 2,6-tolylene diisocyanate.
; "TDR" denotes a commercially available product conslsting ~:
of a blend of TDI and residue, the product having an average free NCO content of 39.6%. . ~
C. Catalysts : . :
"Polycat 12" denotes a commercially available dicyclohexylmethylamine catalyst. .::
.
, , POLYOL PROPERTIES .:

A. Hydroxyl Number ~ The hydroxyl number of a polyol is the nu~er of milligrams o potassium hydroxide required for the complete ~ .' ..
. -21-,:
., .

~ ~ 4 ~ ~5 D-9912-1 hydrolysis of the fully acylated derivative prepared from 1 gram of polyol~ The hydroxyl number can also be defined by the equation: OH - 56.1 x lOOO x f where:
m.w.
OH is the hydroxyl number of the polyol, f is the functionality, that is, average number of hydroxvl groups per molecule of polyol and m.w. is the molecular weight , .. ., .. - -.
of the polyol.
C. Oxyethylene Content Measured by either Nuclear Magnetic Resonance -("~MR") or calculated from the ratios of the alkylene oxides used.
D. Oxypropylene Content . . .
~` Calculated as the difference from 100% in view of the polyol oxyethylene content.

PREPOLYMER PROPERTIES
Free NCO Content ,i ~ .
.`~'! ASTM D1638.
FILTRATION :
In all instances, the filtering of the isocyanate .. . . . .
reactant or the resulting prepolymer was carried out by emplo~ring a conventional l-liter, stainless steel pressure filter. A coarse grade commercial filter paper was used, and pressure application was achieved by nitrogen at 90 , psig.
'~'1 . . .
`¦ EXAMPLES 1 TO 7 .~ Examples 1 through 7 illustrate the preparation, ~-l using a mixed oxide feed, of polyoxalkylene polyols having ~, oxyethylene contents varying from 20 to 100 per cent.
The details of the preparation and the analyses of the crude and refined products are set forth in Table I:

.~, ~7~8~i D
_I ~
~t N C) ~ O ; .
U7 ' ~ . O
CO rl O CJ~ ~ O
'X

O ~ O ~ ~
~ ~ ~' X ~O ~ U~ ~ .
i ~ ~ oC~ ~ I rl O ~ O ~
I tn u~ O u~ ~ O O
'~ ~ O

. ~ O ` ~ ~ `
C ~ O C~ 1 0 ~

;~ ~~ 0 ~ O
.~ ~ 1~
_~ o ~ ~ ~ ' I I I O C~
.C U~ :
~:` 3 ~ ~:
a) 3 O ~ ' ~ ~ ~ -I O . . , :
o o ~--~ ~ `
U l U~ ~ I X ~ 0~ I -- ~ O O t~ r C~
~ h '` ~: U
P~ U~
. P U ~ ~ C

o ~ C r ~ _, c~ c~ e O , :

~' ~o ~
. ~ V g~ COO U~ o) p ~
., u p~ ~ o ,~ ~ e ~ :

e ~ ~ r o 3 ~ x ~ ~ ~ a, o ~ ~
a~ ~ ~ v ~ ~ JJ v v ~
O OD ~ 1 c~ e ~:
~1 ) S~i Xo Xi ri S ~ X~ ii i v v ~ v o ~ ~ r , . . 'v ~ .r e ~ r i D

~ .- _ û 'n ~ o ~ ~ .r. ~ a .~ .r. . ~ V ~ ~ O ~ ~
X u ~ r~~ ~ ~ 2 C~ O ~ i r-i ~ ~ 3 ~ i ~ V
s~ iJ~ i3~

:

~t~6 ~rl x x ~ o o ~
o g o~ ~ o g ~1 ~ o _I o ~o oo X ~ a~ o ~
^~o ~: o o , , H
'~' ' ~ ~ O
a~ o P~ o x ~ e~
,~ o o r I o ~ . O t.- .
,~: ~ : .' v~ ~ ~ XCJ~ 1 O .11 ~. O ~
~ ~ ~ , x æ ~ r~ z O ~ ~ ~ ~ ~
,. ~ P~
~ _~
~0 ~ r~
a~ la ~ a ¦~ ~n .~ ~ ~ r o ~ ~ oO
X r o ~r ~ ' :~
t: ~` .''~
a "

V ~ _ ~ ~ O ~ r~ ~ r ~ C . ~ .
o ~ I ,~ ~ n ~ r u 0 ~ e ~ 0 ~ e c v~ 5~sae~0~0~

,; ; ., : ; ~

, .

47~

EXAMPLES 8 To 10 Examples 8 to 10 illustrate the preparation of three polyols using sequential feed and having oxyethylene : contents within the range used to form the prepolymer compositions of the present invention.
The preparation details and the analyses of the . crude and refined polyols are set forth in Table II:

.. . ' , ". . '. '~ .
' , ' ' . ', ~' .
' , ' ' -', , . "
.. .. ..

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, ~: : , :
:., ~ : l:. .
` ~' . . ;
.
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.~ ., ;, ~: .

TABLE II
Se~uentail Oxide Polyol Preparation Example No. 8 9 10 Starter Data Starter PPG 425 Special Special Starter(b) Starter(d) Weight, grams 542 580 633 Potassium hydroxide, gram5 5.5 5 6 Feed Data - Ratio of ethylene oxide/
; propylene oxide 40/60 38/62 41/59 Propylene oxide, grams 6~3 610 660 Ethylene oxide, grams 874 398 926 Propylene oxide, grams 693 610 669 Ethylene oxide, grams 882 398 926 Propylene oxide, grams 693 610 660 Temperature, C. 114 114 114 Pressure, psig 60 60 60 Feed time, hours 4 3.5 5 Cookout time, hours 2.75 3.25 2.75 Crude hydroxyl number 37.5 40.51(c) 38.70 Refining (a) (b) (c) Analysis of Refined Product Hydroxyl number 37.0 37.01 37.8 ;~ Acid number - 0.005 Water, per cent 0.026 0.026 0.36 `~ Total alkalinity - 0.00007 -.
~:
.
______ (a) Refined by treating with 2 per cent by weight magnesium silicate, stabilized with 500 ppm Ionol~ filtered and stripped.
(b) Special starter made by reacting 76.1 grams of propylene glycol with 533 grams of ethylene oxide.
(c) Adjusted hydroxyl number by feeding an additional 248 grams of propylene oxide.
:. , , ~d) Special starter made by reacting 758 grams of a product formed ~y reacting 3 moles of propylene oxide with one mole of glycerine in the p~esence of KOH catalyst with 1246 grams of propylene oxide.
. I :

~Q ~~C~
: . .
.:, : ...

.

~ ~:

~7~ D-9912-1 . EXAMPLES 11 TO 24 Examples 11 to 24 show the preparation of prepolymer compositions using polyols having oxyethy].ene contents ranging from 14 to 100 per cent and TDR, with the exception of Examples 16 and 17 which used TDI.
The prepolymer compositions prepared were evaluated from the standpoint of appearance and were then twith the ~- exception of Examples 23 and 24~ used~to form laboratory rebonded urethane foams as has been described herein.
The results are set forth in Table III:

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26- .

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.,,~ ~ o o 4~ o ,~
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rC a~ O '~:1 U
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E ~ ,lo~ ~ c) o ~ o ~J ~r~O ~ o O ~ JJ O ~ ~ O
OO ~ r-lo o ~ o r~ 00 h ~ u ) p~ U C~
~ r~D ~D ~ Fi ~ O ~ O D ::~ O ~ ~ O
o~ ~rd O ~~ D O r~ ~ JJ r~ 1 O O LO
r--l r~r~ a r~ r~ U ~ r-~
v ~ O a~ n O ~
o~ ~~ r,~ ~~ O ~ 0 1~ ~ D ~ rl V U ~ D o O ~rl rl F~ ~~ O JJ~ d D ~ O v ~.J O UO ,~
r-l ~r~ D ~r~ 'O JJ ~ D S~ D r-l u~
C~ Y ~ e ~
a~ ~ ~ O O O C~ ~ U ~ O ~ ~ a\ O O ~
11 0X O ~X O ~1) ? O r l u) O _l rl X O LO O O ~ ~ O r-l rl p~ D~ ~u r~D rrl O C~ D r~ O ~ ~ E3 ,- u7 . ::

~ s~ ~s 0.
Q~ i~s~ h ~ 3 _sO --I :1 ~SO
~ O O ra v I S 0 0 v V O rs ¢~ ~~ . s ~rl ~J 0J a~~rl ~J 0 5~0 I
S-~~ O~ ~O~ S ~ S ~'S ~ 0 Q~
Cs ~ S-~ V 0~ 0~ 0 U ~ O ~ r-l s~
~ ~S~/r; ~S r-l e ~ e "~O, o ~ ~ ~ ~ ~ v v JJ r~ E ~, ,~, r, h ~L ~rs ~ ~rS 3 ~rl 5~; V ~s ~rS e V ~ ,,, j2 ~r~S 0 ~rs 0 ' ' O,s r-lO r~S O r-l O r-!S O r-s o r-s O ~.~ O r I Os r-l s?i ~LS O O s ~ D U~ X D ~n O rt~ O
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c) ¢ ~ ~ ~o ?~ e 1 0 ,~ O
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au ,~ g U a o ~ o~ g ~ ~ a ~) ~n C ~ 1 ~ o ~ D~ C IU Q~
o a~ ^ ~: ~,1 c ~ c ~n u~
~ ~ .J e ~ o u c ~ o o r~ P E ~ c ~ e a) C O o ~ D e ~ ta JJ a) o O ~ ~
o O ~ U~ t t ~ ~ . h ta ~c ~ u a ~o ~ Z Z
tu tu tc~ u e ~ u u 8 ~
tt~ ~ tU ~~ C f~ ~ D ~0 n ~a ,D ~ ~a V ~ ~ V r~
¢ ~ ~ tn tU ~ tu ~ tl~ ~ tl~ 1~ 0 C tt) tU o ~ tn ~ o o ~u o ~u o ~u o ~u o o ~u ~u o ~ u~ c ~ ~ 4 v ~
~ ~r~ c ~ o~ o~ o ~ o ~ rl c P ~ ta t~tu tu o ~ ~ ra O O ~c) 1~ ~ C ~n ~ tU r ~ P~ ta U ~rl 3 ~ rl ~ C O ,1 P~ C ~a C~ ~ X ~U ~U ~ O~ Or~ O,~ 0 ~1 ~U U ~ U ~U
~ ~ e u ~ v~ D u~ D cn ~ ~
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1~ O ,~ r~~O `D ~O ~O r~ :
O ~L ~U ~
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~O O ~o O GOo 0~
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: ............. P~ ~ ~a C
o æl ~ ~ ~~ 'N ~ '') `t '~

:

~7~ D-9912-1 ' :
As can be seen, by maintaining the oxyethylene ~ :
co~nt of the polyol within the range of from 30.to 100 per - cent, the laboratory rebonded foam blocks formed from the prepolymers usin~ such polyols can be satisfactorily cured ~: in 15 minutes.

These Examples illustra~e the effect on the homogeneity of the prepolymer composition due to varying the oxyethylene content in the polyol constituent.
The various prepolymer compositions were maintained at a cookout temperature of about 80C., and analyses of the free NCO content, viscosity and visual appearance of the prepolymers were made after cookout times of 1, 3 and 5 hours as well as after varying days of storage at room temperature.
~ ~he results are set forth in Table IV:

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N ~ D 0~1 1 1 ~ 0 I I ~ u) I I

O O O O

N 0 E b~ N 0 ~ o 0 ~1 u~ O O d' o ~ O
N ~ S 0~1 ~I,I S 0~I~I S Lf) I I S
. ' ' .
~ tg u~ u~
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: i O O o a~
" ~ 0 b~ o ~0Q b~ bo ~, ~1 ~-- ~ILt) ~ Ln ~o N N o ~ ~:) o o O N [' ~ ~1 ~ DS 0 ~t ~1 ~1,~ 0 ~1 ~I S L~

O
~' ~0 o O

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N ~S) ~ ~I N ~D S 0 r-l t--I ~I S 0~1 ~I S Ir.t ~1 'I S : ;
O
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o ~ 0 S S o , ) N ~ ~O ~1 ~1 U:) ~ 0 ~ I I C ~'7 1 I C ~ I I ~ -~ ~:
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U ~ X~ a ~ O E

o(~ S ~ s ~ s - ~ :~ V ~ ~ ~ ~ V ^~ >, t .:
E E rl ~ E r~ o Z ~ o ~ +, a) ~ o ~ ~ O h O
tQ b~ ~ O ~ aQ~ ~$t~ $'t ~o o~ td Z ~ ~ ~O (~) Z '~ t ~ $ `
S ~ o E~ Q, o Oo ~ o ~ O ~ o ; :~
V E~ ¢ V V -~ V
29 - ~

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C
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o ~

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oo ~ z ~

- 29 a~-',',', ' ~ :
. .~ -( ~

~ 7~ ~ ~ D-9912-1 In contrast to the prepolymers formed rom polyols having oxyethylene contents of 14% (Ex. 29) and 20~ (Ex. 25), the prepolymers formed from polyols having oxyethylene contents in the range of 30 to 50% exhibit homogeneity upon formation and have stability which allows storage at room temperature for a number of days without losing the homogeneous characteristic.

~ EXAMPLES 30 TO 33 :~
- Examples 30 to 33 illustrate the effect of varying the amount of free NCO content of prepolymers formed from TDR. ~:
and a polyoxyalkylene glycol having an oxyethylene content of 43 per cent and which is described in Ex. 6. .
i The ree NCO content was varied from 3 to 10 per :
cent, and a cookout temperature of 80C. was used. After periods of 1, 3 and 5 hours as well as after storage for a number of days at room temperature, analyses of the NCO content and the viscosity were measured.
The results are set forth in Table V: :
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".

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8 ~
ai ~~ I o ~ ~3 ~I tr) ~ O t~
. r ~ C~

'~ : ' : ' ' '~' ~ . ~ ,': ' ~ . . .

~ f ' ' ~: ' , .' : ~ L U~ h Ln O h ~ O h ~ O $ ~ ~ -: o ~- ~:o ~ h ~ R ~ ~ ~ ~ U

f' l~ ' X ~ ~ ga ~! . 3 1 ~ ~ `
, .. . .

D-9912-l 61~

As can be seen, the viscosity of the prepolymer ~decreases in a linear fashion with increasing free NCO
content. However, upon storage, the prepolymer having 3% free NCO content are less stable.

These Examples compare t~e properties of prepolymers : made from both TDI-P and TDR and with a conventional poly-oxypropylene triol containing 14 per cent ethylene oxicle and having a hydroxyl number of 46 to prepolymers made with the polyol of Example 6 (oxyethylene content of about 43 per cent).
~ cookout temperature of 80C. was maintained in all : instances, and analyses of various samples-at certain times of .
cookout were made for the NCO content, the viscosity and the :::~
. -.
appearance of the prepolymer~ ~.

The results are set forth in Table IV: ;
:: . .
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: .-, ,:

' ,.';; ', ' , - ' ; :
: -32- ~:

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~476~6 o o o o,) ~ ~, o ~ ~ ~
LO t' o ~ o ~ o o o 0 H 11~ 0 I Ei ~ E~
1' ~ ~ u~ ~ Lr) o o o ~ o o o o o o :

o o o :: ~, o 0 ~ ou~ ~ o ~ o o o H t\l ~ ) Eu~
o oo o o o u~ o o ~D .' ~ E~ ' ~ S 0 ~ ~1 ~ S ~ ~ ~ S U~

.,~
P ~ ~ ~
~ o o o C~ .~
~ oE Eo E
o o s s s Q X O
h u~ s) o o o O
~:: ~ :
Q

,~ O ' ~o ~ ' ~! ¦ O O b~ b~ r ! O ~) ~ O ~ OD O ~1 ~O O
. .'~ v p ~ O E~
.1 ~ ~I N 11') 0 u) O O 00 0 O ~1 0 ~1 (~ D U~ S0 ~1 ~Ir l S ~~I N S Lr) O V ~ .

(li r,J) O ~
~H r,~ -H O O N N

O b~
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X ~ ~ h ~ ' tt l . ~ ~ ~ tdQ~ U >~
rr~ ~ ~ tH Il) ~ 3 0 ~ r~ Q ~ ~ rl rl td rl tn r.
~ Z ~d ~ ~ J ~ r~n ~d ~n O
r ~ ~ ~ ~ td ~ td td td ~ ~ rJ~ O td ~ ~ ~ U ~ U, ~rlr~ ~ ~1 td a~ - U r~ ~, rJ~ o U~ ~ O u~
~r~ ~ ~ $ ~ td td O O ~ O r,r~ Ql O ~ V c~ V
X ( td O td F~ Q~ O O td 'Z ~ ~ O td O
1~ I` X ~rJ S a~ O h O ~ O O ~ O ::; O
r~ ~ ~ 1 V E~ ;L~ ~ E~ ¢ V V ¢ V ~[; V

~; ~~33~ .~ -.~ " , : :.
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~ 4~68~

o o , O N~J) N b~ o 0 8 0 C ~ ' ~ t" ~o 01~ ~ E03 d' __ __----------------~ ~ ~I S '~ S
b~21 hrs. ~:
o I :
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: .
~ 0~ 80C
rl O ~ a 21 hrs.
Q b~ b~
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o G 0 . : .
:
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o P ~ o P o ~ e ~ o $ ¢ ~ V "", ..
: :' . . -.
!

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~ V ~ ~ - U ~ ~ ~ U ~ V ~ ~ ~ 0 . :, O O ~ O , ~ ~ O ? E3 ? O O ~ ~

~;., ` , :
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~i.
~ 4~ D-9912-1 The prepolymers of Examples 34 and 37 exhibit superior stability in contrast to the prepolymers of Examples 35 and 36, which were made with a polyol having a low oxyethylene content.

Examples 38 to 43 illustrate the effect of reaction temperature and polyol water content on the reaction rate of prepolymers formed from TDR and the polyol constituent prepared in Example 6. The-water content of the polyol of Example 6 was increased for Examples 40 and 41 by water addition. The water content for Examples 42 and 43 was decreased by stripping.
A cookout temperature of 80C. was compared with a temperature of 25-30~C., and analyses were periodically made of the viscosity and the free NCO content. After storage at room temperature for a number of daysl the prepolymers were also evaluated vlsually for appea~ance. The results are set forth in Table VII~

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`,' ' : ' ~' ' -'': ' ' ~i . ' ' ': ' "

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~47~6 o, O .-~ O i ~ ~ ~ 0 ~1 ~ a O H N ~\10 11 O r I O O ~~ I 0 a~
N 0~ L() It) LO O ~ ' Ln 1 0 ~D 0~1 0 ~
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O O ~ ~1 1 0 ~ ~ O ~ ~ O
I ~1 0 ~ 1 ~1 00 ~I 0 ~1 ~ 0 ~1 ~ 0 ~1 If~ 0 O
.,., ~ ., ,; O
0~1 ~1 1' 0Il') U~
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~ 01~ t' N t' U) O
:` 0 ~10 I t' N 1(') ~') ~ ttl ~ t' d' ~ ) C~ 1~ 10 In O O ~ t' 0 :` 1~ 0 d1 ~ ~1 0~D 0 ~ ~ N t~l t' N 0 . ~ N ~ t' N
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o ~ ,J ~ Q ~ ,1 u~ Q ~ .,~, ~o , ;Z; bl~ :~ b~ ) ~ Q ~ Q ~rl 1-7 ~ Q) +~ 3 ~ (1~ I,qU~ ~ Ul (1~ ~ U~U~ ~ Ul N IJ~
:~ o -~d: ~` t~i ~ +' a) ~ ~ o ~ ~, o ~ ~ o ~ ~ o ~) ~ .
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: ' : X S 1~ O ~ ~
V V ~ ~ v V

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:::` . ;Z;,1 h ,~ v ,, , U~ +'O C , o ` o a) oo: ^ u rd ~V ~ U~ ^ rV U~
. ` : A~al :~ o o~ ~, O
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3 ~ ~ ~ ~ C ~
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s ~ ,.
.
i....

Prepolymer reaction rates are much faster at elevated temperatures, as evidenced by the free NCO content and viscosity characteristics. Increased water contents result in increased viscosity in the resultant prepolymer.
As can be seen from a comparison of the prepolymer of Example 43 (low water content) with the prepolymers of Examples 39 and ; 41, a room temperature, uncatalyzed reaction requires a minimum water content to provide a homogeneous prepolymer.

Prepolymer compositions according to the present invention were compared to a conventionally used prepolymer composition in the formation of low density rebonded oam by batch technigues.
The prepolymer compositions evaluated are set forth in Table VIII below:

. - .: .
TABLE VIII

Prepolymer Compositions - Batch Trial E ample No. 44 45 46 Polyol, oxyethylene content~ % 14(b) 43(a) 43(a) ~20 Isocyanate TDI TDR TDR
NCO content, % 10.0 6.5 10.0 .~ . .~ .
~a) The polyol of Example 6.

(b) Sequential feed, KOH catalyzed polyol formed using a ~- glycerol starter.
In the control run, Example 44, 33 pounds of prepolymer per pound of Polycat 12 catalyst was used. The buns could be demolded after one hour, and the cure of these buns at that time was evaluated as being only fair~ In contrast, buns using the - ~ prepolymer of Example 4S (diluted with methylene chloride to ~ 30 reduce the viscosity to permit adequate spraying) containing 33 .~ . :,'. . . ' . ~ .
~ ~ -36- ~

D-9912-1 ~
~4~6~

pounds of the diluted prepolymer blend could be successfully demolded in 45 minutes, wi~h or without the addition of the catalyst~ The lowest concentration of the prepolymer/methylene chloride blend evaluated was 27 pounds of prepolymer blend per 350 pound bun of bonded foam; and, at this rate, demolding in 45 minutes was achieved without the use of the catalyst.
`~ In Example 46, the prepolymer/methylene chloride -~
blend used to form buns at a rate of 3~ pounds of the blend and one pound of catalyst allowed demolding after only 30 minutes of cure. The completeness of cure at the time of demolding was evaluated as being very good. Using the prepolymer composition of Example 46, the concentration of the prepolymer was gradually decreased and the foam bun cure evaluated after each prepolymer concentration change. The lowest prepolymer concentration .. ~ . ...
; evaluated was 17 pounds of the prepolymer/methylene chloride blend with no catalyst being added. These buns could be demolded after 40 minutes of cure; and the foam strength was evaluated as being very good.

~ These examples illustrate an evaluation on a - continuous rebonded foam machine and compare a typically ~ ~ used prepolymer composition with a prepolymer composition in - ~ accordance with the present invention. The~ prepolymer composition utilized in Example 47 is identified~in Example 46, and this is compared to a control (Example 48) utilizing a prepolymer (10 ` per cent free~NCO~ prepared from TDI and a polyoxypropylene ;
triol having a hydroxyl number of about 56. The results are set ;., .~ ~ : .
~ forth in Table IX below:

, , , ~ , . .
:

D-9912-l TABLE IX
Example No. 4'7 48 % Solids in prepolymer composition 7'7 lO0 % Methylene chloride in prepolymer composition 23 0 Pounds of shredded foam/minute 77 77 Prepolymer blend in rebonded foam at start, % 6.9 8.6 Prepolymer blend in rebonded foam at end, % - , 5.1 .6 Prepolymer solids in rebonded foam ' at start, % 5.3 8.6 Prepolymer solids in rebonded foam at end, % 3.9 8.6 Rebonded foam cure time, minutes 3 3 ' It should be appreciated that there may be inaccuracies in the data collected due to problems - encountered during the trial. Specifically, a prepolymer mix tank was inoperable, and an a,ir operated pump was used ;
to transfer the prepolymer blend through the spray nozzles and into the blender. Due to the higher viscosity of the ', prepolymer used in Example 47, high concentrations of methylene chloride had to be employed to reduce the viscosity ;
to a level which could be handled. ~, , ' The data generated do indicate that the prepolymer ' , of Example 47 can be employed at a much lower concentration ,~
' , than the control prepolymer of Example 48. The use levels ~,,, ~, shown would indicate that the prepolymer of Example 47 could allow a 41 per cent decrease in the prepolymer blend use level and a 55 per cent decrease in the prepolymer solids use level. ' ,, ', . .:

~.
x ~

.

~7~

These Examples present an evaluation similar to Examples 47 to 48, except that the prepolymer composition of Example 50 employs the prepolymer identified in Example 45 (i.e. -having a free NCO content of 6.5 per cent).
The data generated are set forth in Table X below:
TABLE X
Exam~le Mo. 49 50 ~ .
. % Solids in prepolymer composition 100 71 :
% Methylene chloride in prepolymer :
composition 0 29 Pounds of shredded foam/minute at start 36 36 Pounds o prepolymer blend/minute at start 2.47 2.28 Prepolymer blend in rebonded foam at ~ :
start, ~ . 6.4 - 6.0 Prepolymer solids in rebonded foam at .. .~.
start, % 6.4 4.3 : -~ :, ... .
Rebonded foam cure time, minutes :
(at start) 2.5 2.5 ~ :
~, . '~ ' 20 Pounds of shredded foam/minute at end ~ 45 Rebonded foam cure time, minutes (at end) 2.5 ~.5 Pounds of prepolymer blend/minute at end - 2.28 : ' .Prepolymer blend in rebonded foam at end, % - 4.8 ..
Prepolymer solids in rebonded foam at ::
end, % _ 3 4 :~Rebonded foam cure time, minutes (at end) - 2 After the completion of the Example 50 run, set forth in Table X, the prepolymer of Example 49 was again sprayed into-the shredded foam/prepolymer blender, the prepolymer concentration 0 increased to the 6.4 per cent level successfully used earlier in .
Example 49 while the rebonded foam cure time was maintained at ` . , . , :
' . :. :. : ' .:

_, =
2 minutes. The rebonded foam produced under these circumstances was inadequately cured and began to fall apart (i.e. ~ was dimensionally unstable) upon leaving the compression area of the machine.
During the trial, rebonded foam production using a cure time of about 1.7 minutes was attempted using the prepolymer composition of Example 50. The foam did not bond satisfactorily at this cure time, and the cure time was thereafter increased to 2 minutes for the remainder of the trial.

From the data, the prepolymer composition of Example 50 performed at 25~ lower prepolymer blend concentration than did the control prepolymer of Example 49. On a prepolymer solids basis, the concentration of the prepolymer of Example 50 was 47 per cent lower than the concentration of the control prepolymer used in Example 49.
' ", , These Examples demonstrate the preparation of homogeneous prepolymer solutions according to the present invention using isocyanates ranging from evaporator tails to toluene diisocyanate to blends thereof and further illustrates the necessity of maintaining the oxyethylene content of the ~
polyol within the levels previously described. -The results are set forth in Table XI:
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As can be seen, homogeneous prepolymers can be : prepared from evapoxator tails, tolylene diisocyanate and blends thereof when the polyol employed has an exyethylene content of 50%.

.

These Examples illustrate the preparation of prepolymers employing MDI and polymeric MDI with the polyol described in Example 51 and show the effects on the character of the prepolymer when a p~e- or post-filtration is utilizedO

The results are set forth in Table XII: .
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~76~

As can be seen a homogeneous prepolymer solution with polymeric MDI having storage stability is prepared when post-filtration lS utilized. However, when MDI is employed, while stable, the prepolymer is not ho~ogeneous.

; These Examples further illustrate the preparation of prepolyme , using as the isocyanate constituent TDR~
~' L polymeric MDI, ~I and various blends.
The results are set forth in Table XIII:
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u ~I N N N
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a~ O ~ ~ O ~ u~ ~ ~ ~) h ~ n U ~a ~L) e o o ~ ,~ _, O
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... . . . i ... i .. ' ... . ... .... , , ,j.. , .. ~ .. .. .. . . . .

As can be seen? a homogenous prepolyme~ was only formed when TDR was used, with the polyol being one containing about 50% oxyethylene contenlt. Howe~er, as set forth in Examples 56 to 60, filtration can provide homogeneous prepolymers when pol~meric l~DI is used.
,. ~
EXAMPLES 71 to 77 These Examples illustrate the preparation of laboratory rebonded urethane foams utilizing MDI and polymeric MDI prepolymers. A TDR prepolymer was also employed to provide a comparison, The polyol used in ~ -each Example was that identified in Example 51.
The procedure was the same as previously describedJ except that 120 gms. of shredded foam and 12 cubic centimeters of water and of the prepolymer were utilized. ;
The results are set forth in Table XIV:

~ABLE XIV
.
Exa~le No 71 72 73 74 75 - Prep~lymer ~1) MDI MDI Polymeric Polymeric TDRt2 tprepared tprepared MDI MDI
2 0 in Ex. 59) in Ex. 60; tPrePared tprepared post- in Ex. 57; in Ex. 5B~
filtered) post- pre-filtered) filtered) Physical Properties of Rebonded Fbam Density, lbs.~ft.3 5.17 50398 5.33 4.992 5.436 Tensile strength, 7.15 7.12 2.84 2.32 7.96 psi.
Elongation, ~ . 72 66 42 ~5 65 Ibs.~in. 1.83 2.09 0.82 0.5? l.so tl) 5wenty per cent nethylene chloride added Obased on weight of p~rpolym~r).

(2) Prepolymer msde using th2 polyol aescribed in Ex. 51; free NCO of 10~.

~46-.,~.,~ .' - .

~4~$ : ~
As seen from the above Table, the MDI and TDR
prepolymers provide the resulting rebonded foam with superior physical properties in relation to prepolymers using polymeric MDI. Also, the use of filtration does not appear to substantially increase the properties.
Because of the visual similarity of MDI prepolymers ;
made with polyols having widely varying oxyethylene contents, a laboratory rebonded foam was made with a MD~I prepolymer ~Example 76) .
and the polyol of Example 52 (oxyethylene content of 14%). For ~
L0 comparison, a prepolymer having the composition of Example 75 ~ -was also tested (Example 77).
The amounts of the shredded foam, water and prepolymer used were as set forth in Examples 71 to 75, and the results were as follows:
TABLE XV
Example No. 76 ~ 77 Prepolymer MDI TDR
i Physical Properties of~
Rebonded Foam :

Density, lbs/ft.3 5.60 5.55 Tensile Strength, psi. 3.90 8.81 Elongation, % 40 74 Tear strength, lbs./in. 1.22 2.11 The rebonded foam made with the TDR prepolymer has . . .
superior properties to those utilizing the MDI prepolymer.
Indeed, by comparing Example 77 with Examples 71 and 72, it can be seen that the MDI prepolymers made with polyols having oxyethylene contents of 50% provide rebonded foams with properties markedly superior to the rebonded foams of Example 77 wherein the polyol used had an oxyethylene content of 14%.

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Claims (21)

WHAT IS CLAIMED IS;

1, A polyurethane prepolymer consisting of the reaction product of (a) an isocyanate selected from the group consisting of tolylene diisocyanate, tolylene diisocyanate residue, diphenylmethane diisocyanate, polymethylene poly(phenyleneisocyanates), and blends thereof and (b) a polyoxyalkylene polyol having an oxyethylene content of from about 30 to 100 percent by weight, the oxyalkylene groups in the polyol being oxyethylene groups or oxyethylene groups and oxypropylene groups and said prepolymer having a free NCO content of from about 2 to 20 percent by weight, with the proviso that when the oxyethylene content of the polyol is 100 percent by weight the isocyanate is other than tolylene diisocyanate or diphenylmethane diisocyanate and with the further proviso that the prepolymer is a homogeneous solution except when the diisocyanate is diphenylmethane diisocyanate.

2. The prepolymer of claim 1 wherein the free NCO content is from about 5 to 10 percent by weight.

3. The prepolymer of claim 1 wherein the oxyethylene content of the polyol is from about 40 to 70 percent by weight.

4. The prepolymer of claim 1 wherein the isocyanate is tolylene diisocyanate.

5. The prepolymer of claim 1 wherein the isocyanate is tolylene diisocyanate residue.

6. The prepolymer of claim 1 wherein the hydroxyl number of the polyol is from about 30 to 60.

7. The prepolymer of claim 1 wherein the isocyanate is a blend of tolylene diisocyanate and tolylene diisocyanate residue.

8. The prepolymer of claim 7 wherein the free NCO content is from about 5 to 10 percent by weight.

9. The prepolymer of claim 7 wherein the free NCO content is about 10 percent by weight.

10. The prepolymer of claim 7 wherein the oxyethylene content of the polyol is from about 40 to 70 percent by weight.

11. A polyurethane prepolymer that is a homo-geneous solution consisting of the reaction product of (a) an isocyanate selected from the group consisting of tolylene diisocyanate, tolylene diisocyanate residue, polymethylene poly(phenyleneisocyanates), and blends thereof and (b) a polyoxyalkylene polyol having an oxyethylene content of from about 30 to 100 percent by weight, the oxyalkylene groups in the polyol being oxyethylene groups or oxyethylene groups and oxypro-pylene groups and said prepolymer having a free NCO
content of from about 2 to 20 percent by weight, with the proviso that, when the oxyethylene content of the polyol is 100 percent by weight, the isocyanate is other than tolylene diisocyanate.

12. A polyurethane prepolymer that is a homo-geneous solution consisting of the reaction product of (a) an isocyanate selected from the group consisting of tolylene diisocyanate residue, polymethylene poly(pheny-leneisocyanates), and blends thereof and (b) a polyoxy-alkylene polyol having an oxyethylene content of from about 30 to 100 percent by weight, the oxyalkylene groups in the polyol being oxyethylene groups or oxyethylene groups and oxypropylene groups and said prepolymer having a free NCO content of from about 2 to 20 percent by weight.

13. A polyurethane prepolymer that is a homo-geneous solution consisting of the reaction product of (a) an isocyanate selected from the group consisting of tolylene diisocyanate, tolylene diisocyanate residue, polymethylene poly(phenyleneisocyanates), and blends thereof and (b) a polyoxyalkylene polyol having an oxyethylene content of from about 30 to 70 percent by weight, the oxyalkylene groups in the polyol being oxyethylene groups and oxypropylene groups and said pre-polymer having a free NCO content of from about 2 to 20 percent by weight,

14, A rebonded polyurethane foam comprising a block of foam particles having dimensional stability and said particles being bonded together by a cured poly-urethane prepolymer, said prepolymer consisting of the reaction product of (a) an isocyanate selected from the group consisting of tolylene diisocyanate, tolylene diisocyanate residue, diphenylmethane diisocyanate, polymethylene poly(phenyleneisocyanates), and blends thereof and (b) a polyoxyalkylene polyol having an oxyethylene content of from about 30 to 100 percent by weight, the oxyalkylene groups in the polyol being oxyethylene groups or oxyethylene groups and oxypro-pylene groups and said prepolymer having a free NCO
content, prior to curing, of from about 2 to 20 percent by weight and being present in an amount of no more than about 6 percent based on the total weight of the block constituent including the prepolymer.

15. The foam of claim 14 wherein the oxyethylene content of the polyol is from about 40 to 70 percent by weight.

16. The foam of claim 14 wherein the isocyanate is tolylene diisocyanate.

17, The foam of claim 14 wherein the isocyanate is tolylene diisocyanate residue.

18. The foam of claim 14 wherein the isocyanate is a blend of tolylene diisocyanate and tolylene diiso-cyanate residue.

19. The foam of claim 18 wherein the oxyethylene content of the polyol is from about 40 to 70 percent by weight.

20. The foam of claim 18 wherein the hydroxyl number of the polyol is from about 30 to 60.

21. A method of forming a rebonded polyurethane foam having dimensional stability from foam particles which comprises blending the foam particles, introducing, during the blending, a polyurethane prepolymer consisting of the reaction product of (a) an isocyanate selected from the group consisting of tolylene diisocyanate, tolylene diisocyanate residue, diphenylmethane diisocyanate, polymethylene poly(phenyleneisocyanates), and blends thereof and (b) a polyoxyalkylene polyol having an oxy-ethylene content of from about 30 to 100 percent by weight, the oxyalkylene groups in the polyol being oxyethylene groups or oxyethylene groups and oxypropylene groups and said prepolymer having a free NCO content of from about 2 to 20 percent by weight and being present in an amount of no more than about 6 percent based on the total weight of the block constituent including the prepolymer, compress-ing the foam particles and prepolymer blend to form a block of the desired dimensions, curing the foam particles and prepolymer to the extent that said block has dimensional stability and removing the resulting block from compression.