CA1159599A - Polyurethane compositions derived from polyols containing a controlled distribution of carboxamide groups - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Polyols containing at least one carboxamide group, -(NHC=O)-, in the polyol backbone impart to polyurethane resin-forming systems a unique combination of normal pot life and accelerated curing characteristics without sacrifice of final physical proper-ties. Methods are given for preparation of such polyols which enable incorporation of a small, predetermined number of such carboxamide groups, not exceeding in number the hydroxyl function-ality of the polyol, into each and every individual polyol mole-cule. The rapid-curing/property-development characteristics of derived polyurethane resin-forming systems are especially valu-able in molding operations, where both mold cycle times and curing energy requirements are substantially reduced in compari-son with conventional polyurethane resin-forming systems having similar final physical properties.

Description

FP.BPlD'~,~--2-ChN
1 :lS95~9 YOLYURETHANE COMPOSITXO~S DERIVE3 FROM
POLYOLS CONTAINING A COMTROLLED DISTP~BUTIOM
OF CARBOX~MIDE GROUPS

FIELD OF INVENTION AND PRIOR ART
The invention relates to polyurethane resin-lorming systems comprising a polyol res.in and a polyurethane-forming amoun~ of a polyisocyanate and to proc~sses in which th~ two components are mixed together, formed while the mixture is unset J and then allowed to cure and set up into the desired formad body. The invention is particularly directed to polyurethane resin-forming systems and processes of the above character in which ~here is at least one carboxamide group~ -[NHC=O]-, in the polyol resin back~one thereo~,up to not more than one such group per each hydroxyl group.

BA~CKG~OUND OF THE INVENTION

Polyurethane systems u.sed in the manu~ac~re of finished polyuxethane resin bodies or articles can ~e c1assified in many ways, according to both chemical derivation and to type of fina~
- fabrication process~ For example, a given polyurethane system may b classified according to the type of backbone teOg , poly-ether or polyester), type of isocyana~e e~ployed ~aromatic or ~aliphatic), type o~ chain extender (e.g~, polyol, polyamine,water, etc~) and according to many ot'ner reactive components, additives, solvents, etc., that may be employea a~ one poin~ or another, if not in the final processing step. Moreover, under each principal category there may be, and generallY clre, two or more su~classifications which are o~ co~mercial importance. For example, two important subclasses o~ polyether urethanes are t~e polyoxypropylene/ethylene cl~ss and the polyoxytetramethylene 29 class.

F~BRIDYNE-~-CAN
l 15~599 With respect to type oE final fabrication process, poly-urethane resin-forming systems may be cl~ssified as belonging to one of two principal groups- (1) the gro~p in ~7hich a chemical reaction of the polyurethane resin-forming system occurs in the final processing step to provide a polyurethane resin with mature physical properties, as is usually the case in polyurethane foam systems an~ castable elastomer-forming systems, for example; and, (2) the group in which there is essentially no chemical reaction in the final processing step, as in ~he case of polyurethane ~her~oplastic resi~s which are employed în thermoforming operations and in certain adhesive a~d coating applications.
In sy~tem~ of group ~1), that is, polyurethane resin-forming system~ in which a high molecular weight polymer resin with mature physical properties i s first obtained in the ~orming step in which the end~use article is produced, it is generally desirable that the reacti~e polyurethane resin-~orming system have a pot life sufficiently long to enable convenient handling, such as ~he filling of a mold with the reacti~e system in a liauid state~ together with rapid curing character-istics which require a minimum of heat input to supplement the natural heat of reaction of the system. Such curing character-is~ics are desixable in ~he interest of energy conserva~ion an~
minimum demold time and/or curing time, which factors relate to the ultimate manufactuxed cost of the finished polyurethane resin bodies.
In recent years, as energy costs and labor and production overhead costs have increased sharply, great attention has heen given new techniques for reduction of curing energy requiremen~s and the combined production time and investment factors as they relate to the costs of finished articles. For example, new F~BE~ID~NE-2-CAN
9~9 manufacturing techniques such as reaction injection mol~ing (RIM) have been developed fox the manuEacture of molde~ poly-urethane resin bodies as well as for molded bodies d~rived from other types o~ reactive polymer systems Amon~ the a~vant-ages o~ the RIM molding technique is the facile employment o~
highly reactive systems with short pot lives. ~lot only can these systems be demolded more rapidly than systems used in tradi~ional molding operations but, as a result of the greater reacti~ity, post-curing time and energy requirements o~ten are sharply reduce~
as wellO
Also~ especiall~ in the manufacture of polyurethane ~oams, there is a trend toward utilization of systems which offer im-pro~ed curing characteristics even thoug'n the purchase~ cos~s o~
the chemicals are greater than the costs of alternate sys~ems which provide adequate ~inal physical proper~ies. In many cases the "premium" systems provide the lower ~inal manufacture~ costs by means of increased production rates an~or reduced ~ime~temp-erature post-cure requirements. Moreover, the polymer resin physical properties provided by the premium systems generally are superior to those of s~andard systems and, in the en~-use application, an additiona~ cost~performance advantage may be realized which complement~ the original manufacured cost a~ant-age of the finished polyurethane article~
The advantages of RIM and other advancea polyurethane resin fabricatio~ techniques notwithstanding, there is a con-tinuing search for polyurethane resin-forming systems of group (1) with improved pot li~e/curing reauirement charactexistics.
If pot life can be increased without increasing d~mold time and/or post-curing time/temperature requirements, it is gener-ally the case in a giv~n system that catalysis can be employe~so as to further xeduce post~cure reauirements while keeping the FABRID'~rE:--2--CAN
~ `` l 159599 pot life above the minimum acceptable level~ Therefore new systems which, without catalysis, provide improved combinations of pot li-fe and curing characteristics, are of great general interes-t. As a great variety of catalysts ~or urethane systems is commercially available, and in view of the f~ct that catal~fsis in this field has been exte~sively studied (see, for example, J. H.
Saunders and K~ C. Frisch, "Polyurethanes: Chemistry and Tech-nclogy," PartI, Interscience, New York-London (1962) Pp. 1~9-211~, it is then a comparatively straightforward matter to ~atalyze any such inherently improved polyurethane resin-forming system ~so as to optimize its pot-life/curing characteristics for a given applicatiQn .
If a given polyurethane resin-forming system is considered as a reference point with respect to the combination of po~ life and curing characteristics which it provides, there are a number of independent variables which can generally be manipul~ted for the purpose of improving-that combination of properties. Tha~
is, for the purpose of extending the pot life without increasi~g-the cure requirements of time and/or temperature; for the purpose of reducing the cuxe requirements without shorteninq the pot 7ife;
or, hopefully, for the purpose of simultaneously ex~endins ~he pot life while reducing the cure requirements. Such independent variables include, among others, the starting temperature o~
the reactants when they are ~irst mixed to provide the reactive polyurethane resin-~orming system; external heat input to the reactio~ mixture; the choice of catalys~ and concentration there-of; and, the choice of reactants and their relative propor~ions.
Although variation of all of the above independent variables is necessary in general in the process of optimizing a polyure-thane resin-forming system for a given application, the choice of reactants provides -the greatest opportunity for adjustment F~PI~E-~-CAN
595~
o~ the charac-texistics o~ the reac-ting pol~urethane resin-fo~ning system as well as of the physical properties ~7hich it ~7ill exhi~it in its final cured state. Even though at the present time tnere are doæens of polyisocyanate products ana hundreds o~ polyols and other reactive hydrogen compounds commercially availa~le ana eco-nomically feasihle for use in formulation of new po~yurethane resin forming systems, khere is a continuing effort to develop new reactants which impart improved combinations of pot lie an~
curing characteristics and/or final pnysical proper~ies. These development efforts are directed toward all three principal types of reactive intermediates employed in polyurethane resin-~o~ming systems: the polyisocyanates, the polyol resins, an~ the low~
molecular-weight intermediates commonly termed "chain extend~rsl'~
For example, in the case of polyol resins, there has been a major efort in recen~ years to develop new types of "capped" polyether polyo}s; these are starting polyoxypropylene polyols which ha~e been further reacted with ethylene oxide, principally ~or ~he purpose of providing a higher ratio of primary to secondary hydroxyl groups in the inished polyether polyol. Primzry hy-droxyl groups are substantially more reactive with isocyanatesthan are secondary hydroxyl groups, an~ the "cappe~" polyether polyols therefore offer~ among other features, impro~ed curing characteristics in polyurethane resin-forming systems. Such polyols are particularly useful in polyure~hane foam-forming systems.
Since, on a weigh-t basis, the polyoL resin component is typically the principal component of polyurethane resin-~orming systemsf o~ten accounting ~or more than halE the total wei~h~ o~
reactive components, it is particularly ~esirable to improve individual reactivity character.istics o~ the polyol component, if at al~ possible,in any e~fort to improve the overall reac~i-F'~LBPID~ 2-CAN
~ 1~95~
vity and curing cha-racteristics of the polyur~thane resin-forming s~stem. Ho~ever, wi-th the notable ~xception o~ the aforementioned capped polyether polyols, it is generally diffi-cult to makè such improvements without bringing into play accom-panying performance and/or economic disad~anta~es. For example, if the hydroxyl unc~ionality of the polyol is increased so as ~o shorten demold time, many physical properties of the finished polyurethane resin product w i 1 1 b e affected a n d t h e overall resul~ generally is undesirable; the optimum polyol resin func-tionality usually is predetermined on the basis of final physicalproper~y consiaerations rather than pot life and/or curing charac-teristic considerations. Similarly, i~ some or all of the hy-droxyl groups of the polyol resin are replaced by other reactive hydrogen groups (lea~ing aside the ~uestion of whëther such modi fication is economi.cally and/or technically feasible) the pot life and curing characteristics can indeed b~ significantly changed; butD in general where thexe is an improvement in one characteristic, th~ other will be adversely affected. If some or all of the hydroxyl groups of a polyol resin are replaced ~y primary amino groups~ for example t the curing time and curing ~nergy requirements of a given derived polyure,hane resin-~orming sys~em will ~e sharply reducedO However, the pot life of ~he system also will be sharply reduced, and there will be other be-havioral changes in both the xeac~ing system and the finai, cured product, which other changes will generally n o t be accept-able~

In polyurethane resin-orming systems, particularly in those where the polyol xesin component is d -functional (the function-ality being predetermined or purposes of achieving certain final polyurethane physical properties), curing to a demoldable or handleable state often involves some degree of secondary, FABRIDYN~-2 CANADA
1 ~9~9 network-forming reactions of resi~ual isocyanate such as the reaction of residual isocyanate with carbamate N-~ groups formed in an earlier stage of the polymerization process.
Other reactive hydrogen-containing groups, when present, also are involved in like reactions wi~h residual isocyanate.
The carboxamide group, - [N~IC-O]-, for example, has been incorporated in polyol resins as a reactivity and final physical property modifier, but not in the proportions and distribution, or for the purposes contemplated by this invention.
For example, polyester polyol resins generally are manufactured by means of condensation polymerization reactions in which it is not possible to control the distribu-tion of carboxamide groups among individual polyester molecules. In such reactions, an average of one or two carboxamide groups per polyester polyol molecule can be built in by inclusion of the appropriate amounts of, for example, monoethanolamine or hexamethylenediamine, respectively, but the actual polyester polyol product will be comprised of a significant proportion of molecules with no carboxamide groups, some molecules with the desired number (one or two) carboxamide groups, and another significant proportion of molecules with a surplus of carboxamide groups. While such mixtures are capable of offering some improvement in pot life/curing characteristics without undue sacrifice of other desirable behavioral characteristics, the overall improvements by these means are not as great as might be desired. While some polyester polyols containing a molecularly-uniform distribution of the carboxamide group have been disclosed in the prior art in connection with various polymer applications, including pol~urethane resins (see, for example, U. S.

F~BI~IDYNE-2 C~NADA

1 1~9~99 Patents 2j933,477; 2,933,~78; 2,990,379; 3,169,945; and, 3,186,971), there has heretofore been no recognition of the surprising and unexpected behavior obtained in accordance with the invention by the incorporation of such special carboxamide-modified polyols in a polyurethane resin-forming system.
OBJECTS OF THE INVENTION
It is an object of the invention to provide an improved polyurethane resin-forming system. It is a further object of the invention to provide improved pot life/curing characteristics of polyurethane resin-forming systems.
Further objects of the invention are to avoid the disadvantages of the prior art and to obtain such advantages as will appear as the description proceeds.
BRIEF DESCRIPTION OF THE INVENTION
It has now been found that these ob~ects are accomplished, according to the present invention, in a polyurethane resin-forming system which comprises a polyol, each molecule of which has at least one carboxamide group, -[NHC-0]-, in the backbone thereof, up to and not more than one such group per hydroxyl group, and a polyurethane resin-forming amount of a polyisocyanate. It has been found in accordance with the invention that, when these two components, alone or in admixture with other components, such as chain extenders, are mixed and the mix-ture formed while still in the fluid unset state and then allowed to set up while in the formed condition to form a polyurethane resin body, accelerated curing characteristics are obtained without sacrifice of physical properties and without adversely affecting the pot life of the system.

.~

Fl~E~RI DYNE- 2 CA~JADi!~

Polyols, each molecule of which has a-t least one unsubstituted carboxami.de group in the backbone thereof, up to not more than one such group per hydroxyl group, can be prepared conveniently by means of certain addition polymerization procedures, and also by means of certain condensation polymerization procedures where the polymer is of the "head-to-tail" type, as opposed to the "head-to-head, tail-to-tail" type which includes most conventional polyol resins employed industrially in polyurethane systems.
lO - If just one carboxamide group -[NHC=0]-, is incorporated into each molecule of a polyol resin, the curing time/temp-erature requirements of derived polyurethane reaction systems can be drastically reduced without significant loss of pot life and without deleterious change of final polymer physical properties. Similarly, good results are obtained where up to one such carboxamide group is incorporated in each molecule of a polyol resin per each hydroxyl group thereof. However, precisely one carboxamide group per polyol molecule o~ten is the most preferred number of such groups where the object is reduction of curing requirements without appreciable change of other properties of the system.
Polyester polyol resins, each molecule of which has at least one carboxamide group, -[NHC=0]-, in the backbone thereof, up to not more than one such group per hydroxyl group, can be prepared, among other ways, by :reaction of a suitable primary-amino-containiny "initiator" with (l) a suitable lactone or mixture of lactones; or, with (2) a suitable hydroxyl~substituted carboxylic acid or ester thereof; or, (3) a mixture of such lactone(s), hydroxyl-Fl~13RIDYNE 2 CANADA
l 159~9 substituted carboxylic acid(s) and/or ester(s). For example:
rHO-A-NH2 ¦ o=C-(CH2)x-O Polyesterdiols containing (Ia) l or one (from Ia) or two (from or ¦ ~ RO2C-(CH2)x-OH -> Ib) carboxamide groups, H2N-A-NH2¦ or -[O=C-NH]-, in each poly-(Ib) ~ Ho2c-(cH2)x-oH ester molecule . ~here "A" is ~ divalent hydr~ )carb~ )n radical or suitably inert substituted divalent hydrocarbon radical, preferably a divalent aliphatic hydrocarbon radical~ By "suitably inert"
is meant that the moiety "A" contains no sites which are reactive under the conditions of preparation of the carbox-amide containing polyols of the invention or which are reactive toward isocyanates in subsequent applicat.ions of the polyols.
If the initiator is an aminoalcohol of type Ia, the product is a polyesterdiol containing one [MH-C=O] group in each and every hydroxyl-terminated polyester molecule;
if the initiator is a diamine of type Ib, the product is a polyesterdiol containing two carboxamide groups in each polyester molecule, one per each hydroxyl group. If a : primary aminodiol is employed as initiator, the product is a polyestertriol containing one carboxamide group in each polyester molecule; and, if the initiator is a di(primary amino) monohydroxy compound, the product will be a polyester-triol containing two carboxamide groups in each molecule, etc.
Another type of addition polymerization procedure which is applicable to preparation of urethane-grade polyester polyol resins containing the desired molecula~ly-uniform distribution of unsubstituted carboxamide groups involves the reaction of a suitable primary-amino~containing ~'~B~IDYNE-~ C~NA~A
1 1595~9 initiator as above with the cyclic anhydrides of certain dicarboxylic acids, and subsequent reaction of the thus-produced carboxylic acid terminated carboxami~e-containing moiety wtih a mixture o~ additional cyclic anhydride of a dicarboxylic acid and an epoxide~ which mixture con-tains a molar excess of epoxide:
HO-A-N~2 ~ 2 O-C~B~ =O - > HOOC-B-COO-A-NH-CO-B-COOH

(Ia) (II) (III) (III) ~ n (II) + n+2 R-CH-CH~R' - -\o/

. (IV) HO-[(CHRCHR')-OOC-B-COO] a~( CHRCHR')-X-(CHRCHR')-[OOC-B-COO-(R'CHRCH)]b-OH, (V) where "B" is a divalent hydrocarbon radical, the dicarboxylic acid derivative of which is capable of forming a cyclic anhydride; "X" is the diester moiety derived from the dicarboxylic acid, ~II; and a~b = n. Both a and b can be zero. As a modification of this approach to preparation of the carboxamide-containing urethane-grade polyols of the invention, it is sometimes possible to combine lactone polymerization, hydroxyacid polymerization or hydroxyacid ester polymerization, as described above, with the primary-amino-containing initiator/cyclic anhydride/epoxide reaction.
Still another type of addition polymerization procedure for preparation of the polyols of the invention, which is applicable to preparation of urethane-grade polyether polyol resins containing a predetermined and molecularly uniform distribution of carboxamide groups, involves the addition-polymerization of an epoxide, using as initiator a compound F1~ I DYI~E- 2 CI~NADA
l 159~9~

containing a suitable carboxamide group as defined herein-above together with two or more epoxide-reactive hydroyen atoms such as are provided by primary and secondary amino or hydroxyl groups, carboxylic acid yroups, etc. It is of course necessary to employ reaction conditions which will not bring about attack on the carboxamide groups~ Suitable such carboxamide-containing initiators include, for example, among many other compositions, the afore-mentioned reaction products of primary-amino-containing initiators with lactones and/or hydroxyacids and/or hydroxyacid esters, which reaction products are polyols containing the carboxamide group, -[NHC=O]-; and, polycarboxylic acids containing the -[NHC=0]
-group, such as those included broadly under Structure III
hereinabove.
In every case except certain instances where epoxides are employed, the combined number of arnino (except tertiary amino) and hydroxyl groups in the initiator determines and will be equal to the hydroxyl functionality of the polyol product, and the ratio of initiator to other reactants determines the number average molecular weight of the polyol product. In general, there will be a measurable residuum of primary amine unelss epoxide reactants are employed;
in the case of diamine initiators, any such residuum will be small and, in the case of monoamine initiators, negligible for practical purposes. It is believed that any residuum of amine occurs as amino end groups on polyester molecules, with only a tiny fraction of the residuum remaining as unreacted initiator.

~;

~ RI~JE-2 t~ 9 Where epoxides are employed as reactants, the products of course will be properly classified as polyether polyols or as polyether-ester polyols or as polyester polyols depending upon what types o~ epoxide reactions occur and upon whether there are polyether or polyester moieties in the primary-amino-containing initiator. Also, if there are primary amino groups in the initiator which are available for reaction with the epoxide, the hydroxyl functionality of the final polyol product will be greater than in reaction systems involving no epoxide-primary amine reactions. These relationships are familiar to those skilled in preparation of conventional urethane-grade polyether polyols and polyester polyols. Some convenient general approaches to the preparation of carboxamide-containing polyether polyols of the invention are as follows:
(Ia) + (II) ~ HO-A-NHCO-B-COOH
n ~IV) + (III) or (VI) -- 3-rPolyetherdiol containing one -[NHC=O]- group in each molecule _ (Ib) + 2 (II) HOOC-B-CONH-A-NHCO-B-COOH
(VII) (Ib) + 2 O=Ci-(CH2)x-Ol - ~ HO-(CH2)X-CONH-A-NHCO(CH2)x-OH
(VIII) (VII) or (VIII) + n (IV) ~ Polyetherdiol containing two -[NHC=O]- groups in each molecule The carboxamide-modified polyols of the invention are employed essentially as replacements ~or conventional polyester polyols or polyether polyols, as the case may be, in urethane systems in which the polyol is a reactant in the final reaction step and in which systems it is desired FABF~I DYNE- 2 1 1~;95g9 to obtain improved curing behavior without appreciable loss of pot life. Alternatively, these polyols may be employed in other types of urethane systems. Still other applica~ions, including non-urethane-related applications of polyols, will now be apparent to those skilled in the art.
The types of urethane systems in which carboxamide-modified polyols of the invention may be employed to particular advantage for the purpose of securing improved curing characteristics without appreciable loss of pot life include castable elastomer systems; two-component/ polyol-cure caulk, binder and adhesive systems; rigid, semi-rigid and flexible foam systems providing foams of all densities;
microcellular elastomer systems; and two-component, polyol-cure coating systems. In order to realize the benefits, relative to conventional systems, of accelerated cure without sacrifice of pot life, it is essential that the system in each case employ a carboxamide-modified polyol of the invention as a partial or complete replacement for a conventional polyol in the formulation, and that the system be of a type in which the carboxamide-modified polyol reacts with isocyanate in the final reaction step in which the finished polyurethane article is produced.
The carboxamide-modified polyols of the invention also may be employed in urethane systems in which the carboxamide-modified polyols are reacted with isocyanate prior to the final reaction step in which a polyurethane article is produced. However, in such systems it must be taken into account that the carboxamide groups, -[NHC=O]-, are isocyanate-reactive, even though not so reactive as primary or secondary hydroxyl groups. In general, where normal '~

F~J3~IDYNE-2 l 1$9~9 reaction temperatures and/or storage periods are employed in the manufacture of urethane intermediates involving reaction of isocyanate with the carboxamide-modified polyols of the invention, there will be a measurable degree of reaction of isocyanate with the carboxamide moiety. Where a strictly linear polyurethane intermediate or end product is desired, as, for example, in the cases of many polyurethane thermo-plastics, it often is not feasible ~o employ a carboxamide-containing diol of the invention in place of a conventional polyetherdiol or polyesterdiol in view of the branching which will occur at some of the carboxamide moieties. In other cases, where branching can be tolerated, or where it is desired, advantageous formulations based upon urethane intermediates derived from the carboxamide-modified polyols of the invention generally can be devised. Opportunities for employing such carboxamide-modified polyols in poly-urethane intermediates and, subsequently, in polyurethane systems will be apparent to those skilled in the art, judgement in such cases being based upon predetermination of the extent of reaction of any carboxamide groups present under the conditions employed in preparation and storage of the intermediates. If unreacted carboxamide groups are presènt in a polyurethane intermediate derived from a carboxamide-modified polyol of the invention at the onset of a final polyurethane-producing reaction employing such an intermediate, the carboxamide groups will, of course, be available for reaction with isocyanate and can serve to accelerate curing of the polyurethane article thus produced.
However, the relative improvement in curing characteristics generally will not be as great as in systems where a F~B~IDYNE-2 ~ ~5~5~
carboxamide-containing polyol of the invention has replaced a conventional polyol in the final polyurethane-producing step.
In polyurethane systems of the type to which the polyols of the invention are particularly directed, that is, systems in which a polyol resin is reacted with isocyanate in the final polyurethane-producing step, there are generally one or more other isocyanate-reactive compounds present besides the polyol resin itself. Usually, one or more chain extenders, ~ e.g., low molecular weight polyols, polyamines, aminoalcohols, or other low molecular weight compounds having at least two isocyanate-reactive groups, are present in the formulation so as to provide a finished polyurethane with the desired content and distribution of additional urethane and/or urea groups.
The content and distribution of urethane and urea groups in the polymer in turn are major factors determining final polymer properties, such as hardness, tensile and compression properties, and elasticity.
Suitable such low molecular weight diol chain extenders include poly(methylene) glycols of the general formula HO(C~2)nOH where n equals two to about twelve; lower poly(oxy-alkylene~ glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and tripro-pylene glycol; cycloaliphatic diols such as cyclobutane-1,3-diol, cyclopentanediols, cyclohexanediols, 1,3-bis(hydroxy-methyl)cyclobutane, bis(hydroxymethyl)cyclopentanes, bis(hy-droxymethyl)cyclohexanes, 4,4'-methylenebis(cyclohexylmethanol), and lower alkylene oxide adducts thereof containing up to about four oxyalkylene residues; 1,3-butanediol and 1,2-butanediol; other alkanediols of up to about 15 carbon atoms F~BRIDYNE-2 1 15g59~

where the hydroxyl groups may be primary or secondary hydroxyl groups, such as neopentyl glycol and 2,2,4-trimethylpentane-1, 5-diol; N-alkyl- and N-aryl-substituted alkanolamines, such as N-methyldiethanolamine and N-phenyldietha olamine; and, other aromatic-aliphatic diols such as 1,4-bis(2-hydroxyethoxy) benzene, 1,3- and 1,4-bis(hydroxymethyl)benzene, and 4,4'-methylenebis[N-methyl-N-(2-hydr~xyethyl)aniline]; and, other lower diols containing primary and/or secondary hydroxyl groups and optionally containing other functional groups which are non-interfering when said diols are employed in polyurethane formulations. Common examples of such non-interfering groups are carboxylic acid ester groups and ether groups.
Useful triols and higher-functionality polyol chain extenders include such compounds as glycerol; l,l,l-trir,lethyl-olpropane and l,l,l-trimethylolethane; 1,2,4-butanetriol and 1,2,6-hexanetriol; trialkanolamines such as triethanolamine and triisopropanolamine; alkylene oxide adducts of polyamines containing three or more epoxide-reactive hydrogen atoms, such as N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine and N-(2-hydroxyethyl)-N'-[2-bis(2-hydroxyethyl)amino ethyl]piperazine; and alkylene oxide adducts of these and other compounds containing three or more epoxide-reactive hydrogen atoms such as pentaerythritol, sorbitol, sucrose, a-methylglucoside, phenolic resins and aromatic amine-- formaldehyde resins, said alkylene oxide adducts containing up to about three oxyalkylene residues per epoxide-reactive hydrogen atom of the parent compound. Other useful lower molecular weight polyols will be apparent to those skilled in the art.

~ DYNE-2 ~ 1595'~9 Useful aminoalcohol chain extenders include monoethanol-amine; die~hanolamine; monoisopropanolamine and diisopropanol-amine; diglycolamine; N-(2-hydroxyethyl)piperazine; hydroxy-methylcyclohexyl amines and aminomethylcyclohexanols; 3-amino propanol-l and 6-aminohexanol-1; and, oxyalkylated polyamines in which one or more, but not all, of the epoxide-reactive hydrogen atoms have been reacted with an alkylene oxide, such as N,N'-bis~2-hydroxyethyl)1,3-propanediamine and N,N'-bis(2-hydroxypropyl)-4,4'-methylenedianiline. Many other such useful aminoalcohols are known to those skilled in the art.
Useful polyamine chain extenders include a variety of aliphatic, cycloaliphatic and aromatic diamines and higher-functionality polyamines bearing primary and/or secondary amino groups, such as ethylene diamine; propylene diamine;
1,3-diaminopropane; hexamethylene diamine; cyclohexanediamines;
piperazine; 4,4'-oxydianiline; 4,4'-methylenedianiline;
4,4'-methylenebis(2-chloroaniline); 3,3'-dichlorobenzidine;
the phenylene and tolylene diamines; aromatic amine-formaldehyde resins; diethylene triamine; triethylene tetramine; 4,4'-methylenebis(N-methylaniline); 4,4'-methylenebis(methyl anthranilate); 1,5-naphthalene diamine; and, lower poly(oxy-alkylene)diamines. Still other useful polyamino compounds will be apparent to those skilled in the art.
Another low molecular weight, isocyanate-reactive compound which deserves special mention in this connection is water, which, upon reaction in a polyurethane formulation, ultimately provides one urea group plus one molecule of carbon dioxide per molecule of water reacted. The use of the carbon dioxide gas thus produced as a blowing agent in the preparation of polyurethane microcellular elastomers and foams of all densities is well known to those skilled in the l 159~g~

art, as are applications of other less commonly used types of low molecular weight, isocyanate-reactive compounds which can be employed, together with the polyols of the invention, to provide special effects and/or ultimate physical properties.
The ratio of lower molecular weight, isocyanate-reactive compound(s) to the carboxamide-modified polyol(s) of the invention which may be employed to produce the polyurethanes of the invention varies widely, depending upon the type of polyurethane end product which it is desired to produce. Generally speaking, the percentage of total reactive hydrogen equivalents in the polyurethane formulation which is accounted for by low molecular weight isocyanate-reactive components may range from zero, inl the case of such poly-urethanes as very soft castable elastomers, to upwards of 90 percent, in the case of very hard castable elastomers and other hard compositions; the remaining reactive hydrogen equivalents are comprised by the polyol(s) of the invention together with any conventional polyol resin(s) or other high molecular weight reactive hydrogen compounds which are employed in a given formulation. For example, an intermediate-hardness (80 Shore A) one-shot castable elastomer composition derived from 4,4'-diphenylmethane diisocyanate, 1,4-butanediol and a 2000 molecular weight carboxamide-modified polyesterdiol of the invention will require a butanediol/polyesterdiol mixture in which butanediol accounts for about 67 percent of the total reactive hydrogen equivalents of the mixture.
For purposes of simplifying this discussion and of relating to systems based upon conventional polyol resins, the potential equivalents of reactive hydrogen represented by the carboxamide groups of the polyol resin are not here taken into account.
Such basis for discussion is employed because the carboxamide ~ABRIDYNE 2 ~ ~5~9 ~roups mainly represent alternate sites for reaction of isocyanate as the supply of available reactive hydrogen atoms on hydroxyl or amino groups is depleted in advanced stages of polyurethane formation. Moreover, as already has been pointed out, and as will be illustrated in the examples hereinbelow, the carboxamide-containing polyol resins of the invention often can be substituted mole for mole for conventional polyol resins of similar structure and like molecular weight and hydroxyl functionality without causing appreciable chanyes in lO- such basic polyurethane properties as hardness.
In the polyurethane formulations to which the invention is particularly directed, that is, formulations in which a carboxamide-modified polyol resin reacts with isocyanate in the final polyurethane-producing reaction step, the ratio of isocyanate equivalents to total reactive hydrogen equivalents (again discounting the equivalents of potentially reactive hydrogen contained in the carboxamide groups) most often is unity + lO percent; however, in certain types of polyurethane end product formulations, the ratio o~ NCO equivalents to non-carboxamide reactive hydrogen equivalents may range from 0.50, and lower, to about 1.50, or even higher. Products employing extremely low ratios are exemplified by polyester-polyol-tolylene diisocyanate one-shot castable elastomers of low hardness, while certain two-component polyol/moisture-cure reactive coating formulations, for example, employ very high ratios of isocyanate equivalents to total reacti.ve hydrogen equivalents.
Where the carboxamide-containing polyols of the invention are employed in the manufacture of urethane intermediates such as prepolymers, which may be ei-ther reactive-hydrogen-terminated (generally hydroxyl-terminated) or isocyanate-terminated, there FA~:IDYNE~2 1 ~5g~

are essentially two ratio ranges: for reactive-hydrogen-terminated intermediates, the ratio of isocyanate equivalents to reactive hydrogen equivalents generally is in the range of from about 0.2 to 0.8; for isocyanate-terminated intermediates, the ratio usually is in the range of from about 1.3 to about 10. Intermediates containing unreacted NCO groups may have limited storage life and/or require storage at low temperature in view of the possibility of reaction of the isocyanate with carboxamide groups~ Although the invention is not particularly directed to such u~e~hane intermediates, they may, however, often be employed to advantage as replacements for conventional intermediates so as to obtain some relative improvement in curing characteristics, as well as in physical properties, in a wide variety of polyurethane systems.
The polyisocyanates which are useful in the polyurethane systems of the invention, as well as in preparation of urethane intermediates from the carboxamide-containing polyol resins of the invention, include many aromatic, aliphatic and aromatic-aliphatic polyisocyanates, some of which are listed by Siefken ~Analen 562, pages 122-135 (1949)]. Worthy of particular mention are 4,4'-methylenebis(phenyl isocyanate) and its 2,4'-and 2,2'-isomers; 2,4- and 2,6-tolylene diisocyanate; 1,3- and 1,4-phenylene diisocyante; ~
diisocyanatoxylene-1,3 and -1,4; 4,4',4"-tris(isocyanatophenyl) methane; 1,5-naphthalene diisocyanate; polyisocyanates obtained by phosgenation of aniline-formaldehyde resins; 3,3'-dimethyl-4,4'-diisocyanatobiphenyl; 3,3'-dimethoxy-4,4'-diisocyanatobi-phenyl; 4,4'-methylerlebis(2-methoxyphenyl isocyanate);
~ hexamethylene diisocyanate and the triisocyanate formed by reaction of three moles of it w.ith one mole of water;

-20a-FABRIDYN~-2 95~9 isophorone diisocyanate; krimethylhexamethylene diisocyanate, methyl-2,4-diisocyanatocyclohexane; 4,4'-methylenebis(cyclo-hexyl isocyanate); and, the triisocyanate obtained by reaction of three moles of tolylene diisocyanate with one mole of l,l,l-trimethylolpropane. Other useful polyisocyanates will be apparent to those skilled in the art.

DETAILED DESCRIPTION OF THE LNVENTION
The invention may be more fully understood by reference to the following examples in which parts and percentages are by weight unless otherwise specified.

-20b-l 1S95'~

Preparation of Polyols Con-taininy the _ Carboxamide Gr~up, -~NHC=O~-Example la A 5,000 ml Pyrex~ reaction flask was fitted with an electric heating mantle, ground glass agitator with Teflon~ blade, ther-mometer, nitrogen inlet, reflux condenser, and distillation column with vacuum distilla-tion ~rain. In the reaction fl~sk we~e.placed 117 g 6~aminohexanol-1 and 1,883 g ~-caprolactone.
The mixture was stirred and heated over a one-hour period to 105C whlle a slow stream o~ dry nitroge~ was bubbled throu~h the liquid and vented through the reflux condenser. Then, 0.05 g stannous 2-ethylhexanoate was added, and the temperature o~ ~he reaction mixture was increased gradually over a two-hour perioa to 170C~ The temperature then was held between 170 ana 185C
for 16 hours longer~ at which time an additional 0.05 g stann~us

2 ethylhexanoate was added. ~fter ~our hours more at 170-180C
with continued slow e~ullition of nitrogen gas through the pr~-duct, it was cooled to room temperature an~ analyzed. The hy-. ~ . , .
droxyl number was found to be 57~3 and the acid number, 0.74.
Upon standing at room temperature the viscous yellow liqui~
cxystalliz~d to a waxy solid.

Example Za :
To the reaetion vessel of Example la were charged 12~ g N-(2-aminoethyl~piperazine and 2,071 g ~-caprolactone. Using the gene~al procedure of Example 1, the reaction mixture was heated to 115~C over a n.inety-minute period. Then, 0.06 ~ ai-butyltin diacetate was added and the temperature was increased to 175C over the next two hours, and then maintained at 175-185 for 20 hours more~ An additional 0.06 g dibutyltin diacetate was added, and the reaction mixture was held at 175-190C with 1 ~59~9 continued nitrogen ebullition four hours longer. It then was allowed ~o cool, under nitrogen, to room temperature, whereupon the hydroxyl numher was determined to be 50.8 and the acid number, 0.68. Upon standing at room temperature the product set to a waxy~ crystalline solidO
Example 3a The apparatus o~ Example la was purged with nitrogen, and 116 ~ molten l;~-hexanedi~mine was added, followed by 1,884 g ~-caprolactone. The mixture was stirred with gentle heating t~
dis~nlve the diamine, which had partially solidi~ied on the bottom of the flask. A~ter two hours the temperature reached 110C, at which time 0~02 g tetraisopropy~ titanate was added Over the next two hours, ~ith continued slow nitrogen ebullition as in Example la, the temperature was increased to 170C, and then was held in the range o 170-180C for 16 hours. The heat .
. the~ was turned off and, after the product had caoled to 140~
vacuum was applied and the pressure was held at 1-2 mm Hg until the stirred product had cooled to 70C. A sample was remo~ed for analysi~ and found to have a hydrox~l number of 54.9 an~ an a~id num~er of 0.40. Upon cooling to room temperature~ the ligh~
yellow viscous li~uid crystallized to a waxy solid.
Example 4a The water~cooled reflux condenser of the apparatus of Example la was replaced with a dry ice/acetone condenser vented to the atmosphere, ar;d the fractional distillation column ana distillation head were replaced with a dropping funnel. Glutaric anhydride (1,368 g) was charged to the flask and blankete~ with nitrogen; 284 g 4-aminometh~lcyclohexylcarbinol was added dropwlse with rapid stirring over a one-hour period, and the warm mixture was heated to 140C and stirred at 140-1~5C for one hour. Then 0.5 g anhydrous stannous chloride dissolved in 10 ml tetrahydro-FABkID~E-2-CAN

1 15~5~

furan was added slowly from the dropping funnel ~nd the reac-tion mixture was heated to 160C. While keeping the tempera-ture in the range, 160-175C, 770 g propylene oxide was added dropwis2 from the dropping funnel at a rate just suf~icient to maintain a slight reflux in the dry ice condenser. During this perio~, a very slow ebullition of dry nitrogen ~hrough the reaction mixture was employed to exclude oxyyen. Af~er six hours, ~he propylene oxide feed was complete. The reaction mixture ~as held at 160-170C for one hour longex, and then ~he ary }ce condenser was repalced with an air condenser. ~he nitrogen was turned of~ and vacuum slowly appliea at the top o~ the air condenser so as to evaporate any low boiling residual componen~s.
The yellow brown liquid was cooled to room temperature un~er 5 m~
Hg, and then was analyzedO The hydroxyl num~er was 95.6 and ~he acid number, 1.4. The dark, viscous polyester did not solidify while standin~ at room temperature ~or se~eral weeks.
Example 5a - To the reaction apparatus of Example1a was charged 1~5 g 2-(2-aminoethoxy)etha~l (diglycolamine~ an~ 2,195 g o cru~e 6-hydroxyhexanoic acid ~comprised of 6-hydroxyhexanoic aci~ to-gether wi~h lower oligom~rs and water o condensation forme~
upon storag~ of the hydroxyacidl. The reflux condenser was removed and replaced by a stopper. The mixture then was ~eate~
over a three-hour period to 210C, during which time polye~ter-ification proceeded and water of condensation was distillea at atmospheric pressure. Then the pressure was reduced gradual}y to 25 mm Hg while holding the reaction mixture ak 210~15C an~
additional water was collected in an ice-cooled vacuum recei~er.
The receiver was emptied of water and 0~05 g stannous 2-ethylhex-anoate was added from a syxinge to the reaction mixture. The ~ABRIDYME-2-CAM
1 1595~9 pressure then was further reduced over the nex~ hour to 8-10 m~
Hg while water vapor produced by the reactiorl was exhausted in-to the vacuum pump, without condensation in the receiver. The temperature then was allowed to fall to 190C; 0.05 g adaitiona~
stannous 2-e-thylhexanoate was added and the temperature maintained at 190-195C or seven hours with the pressure at 7-10 mm Hg.
The system then was brought to atmospheric pressure by admitting nitrogen to the flask, and the product was allowed to cool. The polyesterdiol was found ~o have a hydroxyl ~umber of 55.9 and an acid number of 0~25. Upon cooling to room ~emperature, the pale yellow viscous l.iquid se~ to a waxy crys~alline solid.
Exam~le 6a To the reaction apparatus of Ex~nple 5a was charged 89 g 4-aminohutanol 1 and 2,511 g methyl 6-hydroxyhexanoate. The xeaction mixture was heated rapidly to 14~C while a slow stream of nitrogen was bubbled through the liquid and vented through the distillation train~ Then 0.10 g stannous 2-ethylhexanoate was addea and the reaction mixkure was heated~ over a three-hour period, to 210C, during which time methanol ~istilled at atm~s-pheric pressureO When distillation of methanol had nearly ceasedafter 15 mi~utes at 210~C, 0.05 ~ additlonal stannous catal~st was added and the pressure was reduced gradually while methanol continued to be collected in a vacuurn receiver cooled in a dry ice/acetone bath. When methanol could no longer be s~en collec-tins in the vacuum receiver with the system at 210-215~C and 40-50 n~Q
Hg, the recei~er was emptied and the pressure ~urther reduced, gradually, to 10 mm Hg. The pressure was kept at 8-11 mm Hg f~r ive hours more while the xeaction mixture was stirred rapialy at 210-215C. Then the product was allowed to cool, while stirring under vacuum, to 150C, whereupon the system was ~rough~ to ~2~

~BPIDY~E-2 -CAN
~ 159~9~

atmospheric pressure by ad~ission of nitrogen to the flas7 The yellow liquid product was analyzed and ~ound to have a hydroxyl number of 55.0 and an acid n~er o~ 0.20~ Upon cool;n~
to room temperature it set to a waxy crys-talline solid.
Example 7a -Ts the apparatus of Example la ~7as charged 2,000 g of a poly(oxypropylene) diamine o~ 2,000 molecular weiyht ~JEFFAMINE~
D-2000 and 230 g ~caprolactone. While nitrogen was ~ubbled slowly through th~ reaction mixture, it was stirred ana heatea gradually, o~er khree hours, to 170C~ Af~er stirring for three hours longer with nitrogen ebullition at 160-17QC, the heat was turned o~f and the product allowea to cool overnight to room temperature while blanketed with nitro~en. The viscous li~ui~
then was analyzed/o the hydroxyl nt~ er was 50.4 and the aci~
nt~mber ~as less than n O 20 Exam~e 8a 13y means of a proceduxe similar to tha~ of Example 8a, 2,000 g of a ~000 molecular weight poly(ox~propylene) aiamine (~EFFAMIN$~ D-1000~ and 515 g ~-enantholactone were reacted to 20 produc~ a caxboxamide~containing polyether~iol with a hydroxyl numb~r o 89. 7 and an ac:id number less t~r~ 0 . 2Q v _ithotlt:
the Carboxamide_Group for Comparative Evaluation .
Exam~le lb Using the apparatus and general procedure of Example la, 118 g 1,6-hexanediol was reactea with 1,882 g ~-caprolactone to produce a polyesterdiol with a hydroxyl number of 56.8 and an acid nt~nber of 0.45. ~he light yellow ~iscous liquid crystal-lized readily, upon cooling to near room temperature, to a waxy ~~5-~ABRIDYNE ~CAN

~ 150599 solid.
Example 2b Using the apparatus and general procedure of Example 2a, 130 g N-(2-hydroxyethyl)piperazine and 2,070 g ~-caprolactone were reacted to produce a polyesterdiol with a hydroxyl num~er of 51~4 and an acid number of 0.48. Upon cooling to room temper-ature~ the yellow viscous liquid set to a waxy solid.
Example 4b Using the apparatus and general procedure of Examp}e 4a, 1,368 g glutaric anhydride and 285 g 1,4-bis(hydro~ymethyl~cy clohexane were reacted, using a two-hour hold period at 14Q-145D.
The procedure then was continued as in Example 4a. The ~ark oranger viscous product did not solidify upon standing at room temperature for three weeks. It had a hydroxyl nu~ber o~ g4~1 and an acid number of 1~25~

~ ^ - .
: Using the procedure and apparatus of Example 5a, iO6 g o~
diethylene glycol and 2 t 195 g of the same crude 6-hydroxyhexanoic acid were reacted to produce a polyesterdiol with a hy~roxyl number of 5602 and an acid number of 0.32. The yellow, viscous liquid ~et ~o a waxy solid upon cooling to room ~emperature~

.
Using the apparatus and general pxocedure o~ Example 6a, 90 g 1,4-butanediol and 2,511 g methyl 6~hydroxyhexanoate were reacted to produce a polyesterdiol with a hydroxyl numb~r o~ 55~5 and an acid number o~ 0~26. The light yellow viscous liquid set to a waxy crystalline solid upon standing brieEly at room temperature.
Example 7b Using the apparatu5 and yeneral procedure o~ Example 7a, -26~

FA~RID~NE-~CAN
9 ~

2,000 g of a 2,000 molecular weight poly(oxypropylene) glycol (NIAX~' PolyolPPG-2025) was reacted with 230 g ~-caprolac-tone~
However, 0.05g stannous 2-ethylhexanoate was added when -the reaction mixture firs-t reached a temperature o~ 130C an~ the reaction mixture was stirred at 160-170C ~or 19 hours ra~her than three hours as in Example 7a. The hydroxyl number of the pale yellow liquid product was determined to be 51~ and the acid number was 0.27. It did not solidify aftex standing a~
room temperature for two weeks.
~
Using the apparatus and procedure of Example 7b, 2,000 g of a 1,02S molecular weight poly(oxyprop~lene~ glycol (~TAX~
Polyol PPG-1025) was reacted with 515 g ~-enantholactone to produce a pxoduct with a hydroxyl number of 87.4 and an aci~
numher of 0 ~4. The pale yellow viscous liquid did not soliaiy ~pon standing a~ room temperatuxe for ten days t although it ai~
become hazyO The haziness disappeared immedi~tely upon heating . the product to 70C while stirring moderately.
Com~arison Of PolYurethane 5YStems Basea On ~ ~
- ~ Based On Similar, Non-Carboxamide-Containin ~ols Example 9a A castable "one-shot" polyurethane elastomer was prepare~
from the carboxamide-containing polyesterdiol o~ Example la as follows: ~he polyesterdiol (400 g, 0.409 hydroxyl equivalents) was weighed into a clean, open-top two-quart can and heated to 80C while degassing in a vacuum oven~ Then 50.2 g anh~drous 1,4~butanediol was added, the mixture stirred briefly, and the can returned to the vacuum oven until the temperature of the FABRI~YNE-2-CAN
l 1~95~9 liquid returned to ~0~C. The can was .removed from ~he oven and stirred brie1y wi-th a stainless steel spatula; while stirring briskly with the spatula in such a manner as to avoi~ whip2ing air bubbles into the liquid, 200 g (1.599 isocyanate equiYalents~
of 4,4'-diphen~lmethane diisocyanate heated -to 60C was poured into the diol mixture and the stirring continued for 40 seconds, at which time the end of usable pot life was indicated by a rapid exotherm and first emission of visible ~apors from the reaction mixtureO It was noted, however, that ~here had not yet been a noticeabl~ increase in the viscosity of the reaction mix-ture. The liquid was immediately poured into two 6 x 6 x 0.075"
chromium plated rub~2r molds which had been previously sprayed with Teflon~ mold release and heated to 105C. Wh2n the mol~
cavities had been ~lightly overfilled, the tops were put in place and the molds were stacked on the platens of a hydraulic press which had been preheated to 105-110C. The p~aten clamping ~orGe was immediately brough~ to 60,000 pounds, held for te~ seconds, then released and immediately brought back to 60,0~0 pounas and held at this le~el ~or ten minutes. It having been noted that 2Q the flash from the rnolds had solidified to a strik~ngl~ str~n~, elastic materi l^after onl~ five minutes in the press, after ~en minutes in the pres~ ~he molds were remove~. They were opene~
without difficulty and the elastomer specimens were remavable immediately without damage. One specimen was cooled ~uickly with cold running watex for five minutes, and kwo ten5ile test specim~ns were cut ~rom it and immediately subjected to tensile testing on a Scott testing machine. Both were found to have de~elopea more than 4,500 psi ultimate ten~ile strength, this only 20 minutes after being cast. The second molded specimen was placed in,a mechanical convection oven at 100-105C and post-cured fo~ 16 FABRIDYNE-2-CA~
~ ~59~99 hours. This elastomer was opaque and pale yellow-orange in color.
Physical properties after ~wo weeks' aging at room temperatllre are yiven in Table I.
Example 9b Using the apparatus and procedure of Example 9a, a castable polyurethane elastomer was prepared from 400 g (0.4ng hydroxyl equivalents) of the polyesterdiol of Example lb together with 200 g 4,4'-diphenylmethane diisocyanate ~1.59g isocyanate equiv-alents) and 50.4 g anhydrous 1,4-butanediol (1.118 hydroxyl equi~alents)O The polyesterdiol of this example di~fered ~rom that of Example 9a essentially only in that it contained an estex moiety, -[O-C-O]-, in pl ce of the one carboxamide moiety, [NH-C=O]-, present iD. each o ~he polyesterdiol molecules of ~xample 9a. Within experimental error, the usa~le pot life of the el~stomer was the same as in ~xample 9a; vapors rising from the reaction mixture wexé first noted 45 seconds after mixing in the isocyanate7 Immediately therea-~ter the liquid was poured into the two xubber moldsF and within 20 seconds after hydraulir pressure had been applied ~he second time ~he flash had turned opa~ue and extrem~ly viscous. After five minutes in the press, the flash had the consistency of a so~t cheese. After ten minutes the molds w~re removed ~ut, upon attempting to open the firs~ one~
it was ~ound that this could not be done without damaging the test specimens, which still were soft and cheese-like. The molds were replaced in the press for another twenty minutes, at which t.ime it was found that the mold covers could be removed but that the specimen~ still were rnuch too fragile to remove from tne molds.
The open molds were placed in the mechanical convection oven and~
- after one hour the elastorner specimens could be rernoved withou~
damage, but only with great care. The specimens then were post-J ~9~9~

cured in the oven for 16 hours a-t 100-105C, as in Example 9a After two weeks' aging at room temperature, t'ne physical prope~r-ties were determined to be as shown in Table I.
Example lOa Using the apparatus and procedure of Example 9a, a castable polyurethane elastomer was prepared from 400 g ~0.391 hydroxyl equivalents) o~ the polyes~erdiol o~ Example 3 together with 37.3 g 1,4~butanediol ~O.B27 hyaroxyl equivalents) and 160 g .4,4'-diphenylmethane diisocyanate (1~279 isocyanate equivalents~.
Vapors were fir t noted rising from the reaction mixture 55 second~
after adding the isocyanate. The flash from the molds was etas~ic after less than fiv~ mi~utes in the hydraulic press, and the molds were opened and the elastomer specimens removed without difficult~
after ten minutes in the press. Ater the standard curing and aging cycles of Example 9ar the light yellow, opaque elastomer specimens were determined to have the physical propertie~ showm in Table I~
Example lOb Using the apparatus and proceduxe of Example lOa, a castable polyurethane e~astomer wa~ prepared from 400 g ~00405 hydro~yl equivale~ts) of ~he polyes~erdiol o Example lb together wi~h 36.6 g 1,4-butanediol (0.813 hydroxyl equivalents) and 160 g 4,4'-diphenylmetha~e diisocyanate (1.279 isocyanate equivalents).
Like the reaction of Example lOa, vapors began ris.ing ~rom the reaction mixture noticeably at about 55 seconds after the is~-cyanate had been stirred in. The ~lash from the molds turn~d extremely viscous within 30 seconds after the second application of hydraulic pressure, this indicating the gel point, which wa5, within experimental error, the same as in Example lOa. However~
a~ter ten minutes in the press, it was dete~nined that, althouyh FABRIDY~TE--2--CAN

the molds could be opened without damage to the polyurethane specimens, the specimens were still of a cheese-like consistency and could not be removed. The open molds then were placed in the mechanical convection oven at 100~105C for one hour~ after which time the specimens were ~ufficiently cured to be removea from ~he molds without damage. This being aone, the specimens were cured and aged as in Example lOa. The of-white, opaque elastomer specimens were ~ound to have the physîcal properties reported in Table I. The essential dif~erence be~wee~ the poly-esterdiol of this example and the polyesterdiol of Examp~e lOa is that the latter contains two carboxamide groups, -tNH-C=O]-~
per polyesterdiol molecule while the polyesterdiol o~ ~his example contains none~ This small compositional difference is believea to be respo~sible for the remarkable differeQce in curing rates of the two derived ~lastomer compositions.
Example lla i A castable polyurethane elastomer was prepared from the polyesterdiol of Example 5a ~400 g, 0.398 hy~roxyl equivalents~
together with 36.9 g (0.820 hydroxy~ equivalents) of 1~4-~u~ane 20 diol and 160 g (1.279 isoc~anate equiva~ents) of 4,4~-diphenyl-methane diisocyanate, using th~ apparatus and procedure of Ex-ampla 9a. The hehavior of the reactive system ~Jas closely similar to that of Example 10a; the most notable difference was tha~ the rates o~ gelation and development of e7asticity oE the mold ~lash were sl.ightly slower, this being attribu~ed to the lower content of carboxamide groups (one -[NH-~=O~- group per polyesterdiol molecule as opposed to two such groups per molecule in the poly-esterdiol o Example 10a). The final physical properties of 1:he opaque~ pale yellow elastomer specimens are given in Ta~le ~.

The specimens were slightly more opaque than those of Example ~Oa.

1 ~5~ 3g Example llb Following the procedure of Example lla, a castable poly-urethane elastomer was prepared from the polyesterdiol of Example 5b~ 1,4-butanediol (400 g, 0.398 hydroxyl equivalents and 36.8 g, 0.817 hydroxyl equivalents, respectively) and 160 g of 4,4'-diphenylmethane diisocyanate (1.279 isocyanate equivalents) In comparison with the results of Example lOb, there were no noteworthy differences in behavior of the system. This was not surprising, as theoretically the only significant compositional difference between the polyesterdiols of the two examples was the presence of one ether linkage, -0-, in the poLyesterdiol of this example as opposed to none being present in the polyesterdiol of Example lOb. At the same time it can be concluded that the different synthetic method used for preparation of the polyesterdiol in this example, with respect to the polyesterdiol employed in Example lOb, did not produce any compositional differences having a significant affect on curing behavior.

Moreover, the marked difference in curing behavior between the elastomers of Examples lla and llb once again points out the surprising effect of incorporating just one -[NH-C=O] - group per polyesterdiol molecule, as this difference was the only significant compositional distinction between the polyesterdiols employed in Examples lla and llb:

There was one such group per polyes~erdiol molecule in Example lla and none in Example llb.
Example 12a Using the apparatus of Example 9a, a castable polyurethane elastar~r was prepared from 400 g of the polyesterdiol of Example 6a (0.392 hydroxyl equivalents), 240 g 4,4'-diphenylmethane diisocyanate (1.918 isocyanate equivalents) and 134 g 1,4-bis(2-hydroxyetho~)b~nzene (1.352 hydroxyl equivalents~. The polyester FABRIDYME~CAW
1 ~59~

first was weighed into the open-top can and deg~ssed wnile heating to 75C in a ~acuum oven. Then, the molten isocyanate, at about 50C, was added and ~he mixture stirred ~or 30 seconas.
The resulting solution was placed in the vacuum oven (which was set at 120C) and degassed fuxther for twenty minutes, with brief stirring at five-minute inkervals. Each time the oven was opened for stirring, the vacuum was broken with dry nitrogen.
During this period the tempera~ure of the liquid increasea to 115C~ part o~ the heat coming from the exothermic reactio~ of -the polyeste~ al~d isocyanate~ The resul~ing quasi-prepol~mer then was removed from the oven and the 1,4-bis(~-hydroxyethoxy) benzene/ preheated to 120~C,was added imm~diately ana the reactiQn mixture stirred rapidly with a wide spatlla but in such a man~er as to avoid whipping air into the li~uid. After 70-75 seconds, vapors were noticed rising from the liquid. Stirring was con~i~ue~
for a few seconds longer, and ~he reae~ion mixture was poured into ~he ~wo rubber mold~ of Example 9a, which had been prehea~e~
to 120C~ Then the pxocedure of Example 9a was ollowea, except that the temperature of the hydraulic press plate~s was 118~C~
20 After ten minutes in the press, the flash was found to be an opa~ue, slightly resilient material ana, after ~ifteen minutes total in the press, the molds were opened and the elastomer spe-cimens remove~ without difficulty. ~hey were post-cured for 16 hours in a mechanical convecti~n oven at 115-120C, and then aged at room temperature for two weeks. The physical properties were determined to be as shown in Table I.
E mple 12b - Using the apparatus and procedure of Example 12a, a poly-urethane castable elastomer was prepared from 400 g o ~he poly-esterdiol of Example 6b (0~396 hydroxyl equivalents), 240 g o~ -F~BRI~NE-2 -CAN

1 ~595~9 4,4'-diphenylmethane diisocyanate (1.918 isocyana-te equlvalents~
and 133O6 g 1,4-bis(2-hydroxyethoxy)benzene ~1.3~8 hydroxyl e~ui~-alents~. After ten minutes in the press, the flash was a highly opaque hard material, but quite brittle. After five minutes longer the molds were removed and opened, but the elastomer specimens found ~o be ~oo frayile to remove without damage. The open molds were placed in the rnechanical con~ection o~en ~or one hour, at which time the elastomer could be removed wi~hout ~amage, although it had not ~et developed the toughness of the elastomer of Example 12a. Moreover, af~er pos~ curing for 16 hours longer in the oven~ the specimens were noted to ~e more intensely opaque than those of Example 12a, sug~esting a higher degree of crys~al-linity in the e~astomer of this example. After aging two weeks at room temperature, the physical properties were measured and found to be as shown in Table I~
Example_ 3a Using the apparatus of Example la with the distillation train replaced with a dropping funnel, 400 g of the proauct of Example 7b was added over a 90-minute period to a ~ixture of sno g 4~4'-diphenylmethane diisocyanate and 200 g Tsonate~ 143L
.
which ha~ been preheated to 60C. Th~ heating mantle was r~mo~e~
.
~rom the resin pot and the rate of addition-of the diol was ad-just~d SQ as to keep the reaction mixture at 60-70C. Fifteen minutes after the diol feed had been completed the heating mantle was replaced and the temperature maintained at 60-65C for one hour longer, while continuing the slow ebullition of nitrogen through the liquid which had begun before the addition of diol.
Then the isocyanate-texminated quasi-prepolymer was degassea ~or ten minutes at 40 mm Mg. Upon cooling ~o xoom temperature the product was analyzed and found to contain 20.32 percent free ~CO
To a waxed paper cup was charged 100 g of the product o~

l 1~9 ~o o 1-- 1- ~-CO ~. CO ~ U7 C~ ~-O O O ~ O C~ ~ 1~
I' 1--.
~o 1' W ~~ ~ cn ~D O O
o o `' g ~ ~ o ~ ~o W W 1-- ~ 1' ~ ~ ~ ~a ~, ~, Y co ~rl O W ~1 O~ ~
- o o o o o o . o o c~P n-., ~ ~ Pl ~ o O o r~ o`P ~ ~t ' ~ '~ 1~
. a~ ~1 Ul G~ ~ U~ ~ n o ~ ~ ~ u~ ~ ~ ~n o ~0o ~ 8 g ~n ~ ~, ,~ . ~D ~ .
'. ~ w ~ ~ - '^ ~ ~, , ~ ~ o~o - ~, ~, . ~
. ,,.~ Ul, ~ w ~ ~ ~ I_ ~ ~ ~ ~ ~n o ~ o o ~ 'O ,~
o N ~P N t~a N ~h ÇJ O ~;d CO O Ul ~D ~ rt o ~

-35- ~

FABRIDY~E-2-CA~
~ 15~.59~

Example 7a, 20.0 g 1,4--butanediol, 0.60 g triethanolamine, 0.30 water, 0.20 g Dabco~ 33LV, 0.20 g L-520 Silicone Sur~actan-t (Union Car~Dide) and 0.10 g dibutyltin dilaurate. This mi~ture was s~irred for abou~ one minute at high speed with an air-driven mixer with sta.inless steel propeller, which caused tiny air bub-bles to become dispexsed in the liquid. Then 122.1 g o the isocyanate prepolymer of this example was added and ~he mixture stirred at high speed for 10-12 seconds.. The reaction mixture was immediately poured into a 5 x 5 x 11' steel mold which haa been sprayed with a Teflon~ mold release and preheated to 70C.
The mola was closed and placed in a 70C oven. After 3.5 minutes from the time of p~uring the reaction mixture into the mold, it was removed from the oven, opened, and the ~.icrocellular elastomer specimen removed easily fxom the mold without damage.
In a separate experiment in which the microcellular elastomer was allQwed to rise in a one~quart waxed papex cup, the cream time~
rise time and tack-free time of this *ormulation were found to be 18, 48 and 103 seconds, respectively.
Example 13b Using the procedure of Example 13a, a molde~ microce11ular ela5to~er spee~m~ was prepared by reacting 122.3 g o the quasir pxepolymer of Exa~.ple 13a with the same polyol pre-mix ~onmula~ion - used in Example 13a except that the 100 g of aiol was replaced-by 100 g of the diol o~ Example 7b. The cover could be removed from the mold easily after 3.5 minutes in the mold, but the microcel-lular elastomer specimen still was too fragile to be removed with-out damage. In repeat experiments it was found that about 5~0 minutes in tne mold was necessary before this formulation could be removed and handled without damage in the manner of Example 13a. The cream time, rise time, and tack-~ree time of this fcrmu-lation were found to be 18, 50 and lla seconds, xespectively.

~36-5 '~ 9 The more rapid c~lrin~ characteristics, without significant change of initial reaction characteristics, of the formulation of Ex-ample 13a relative to the formulation of Example 13b is attri-buted to the presence of two carboxamide groups per molecule o~
polyol resin in Example 13a as opposed to no car~oxamide groups - in the polyol resin of ~xample 13b.
Example 14a Using the apparatus and procedure o~ Example 13a~ a quasi-prepolymer~wa~ prepared ~rom 900 g 4,4'-diphenylmethane diisocy- ..
anate and 480 g of the polyesterdiol of Example 2b. This product :
was found to have a ree NC0 content of Z0.45 percent. Then, microcellular elastomer w~s prepared from 142.0 g of the pre-polymer and a pre-mix o~ 120 g of the polyes-terdiol of Exa~ple ~ 2a, 2000 g 1,4~butane~iol, 4.0 g triethanolamine, 0.40 g waterJ
0.40 ~ DC-193 Silicone Sur~actant tDow Corning) an~ 0.10 g o~
Catalyst T-12 (Metal & Thermit). The microcellular elas~omer could be demolded easily without damage a~ter 4.2:5 minutes in the mold. The cream time~ rise and tack-free times far this fonmMlation w~re separatel~ determined to be 15, ~1 an~ 80 seconds, respectively.
.

A microc~llular elastomer was prepare~ using a procedure - -and materials identical to that of Example 14a excep~ ~ha~, in the polyol pre~mix, 120 g of the polyesterdiol of Example 2b was substituted for the polyesterdiol of Example 2a. The cream, rise and tack free times of the product. were, respectively, 15, 40 and 86 seconds. However, the product could not be demolded without damage until it had been in the closed mold for 5.8 minutesO Also, upon demolding the product was noted to be less resilient than that of Example 14a when it was fir5t demolded.
These dif~er~nce5 in curing beha~ior are attributed to the pres-FABRIDY~f E--2-CAN
l15~ 9 ence of one mono-N-substituted carboxamide group, -ENHC=03-, per molecule in the polyesterdiol resin o~ Example 14a as opposed to no mono-N-substituted carboxamide groups in the polyesterdiol resin of this example.
It is to be understood that the invention is not to be limited to the exact details of operatiun or structure sho~n and described, as obvious modifications and equivalents will be apparent to one skilled in the art.

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'' ' . ' , '': '

Claims (16)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A one-step polyurethane resin-forming system for preparing a finished polyurethane body comprising a polyisocyanate component and a polyisocyanate reactive component in which the polyiso-cyanate reactive component consists essentially of a polyol resin or a polyol resin plus a chain extender, each molecule of which polyol resin has in the backbone thereof at least one carboxamide group of the formula -[NHC=O]- in which both free valences are attached to non-aromatic carbon atoms, and not more than one such group per hydroxyl group, said polyol resin being free of urethane linkages and the proportions being such that when the polyisocyanate reactive component and the polyisocyanate com-ponent are mixed, the mixture sets up into the desired poly-urethane body.

2. The polyurethane resin-forming system according to Claim 1, in which the carboxamide group containing polyol resin comprises at least 10 percent of the polyisocyanate component.

3. The polyurethane resin-forming system according to Claim 1, in which the system is a castable elastomer system.

4. The polyurethane resin forming system according to Claim 1, in which at least one of the components is a prepolymer.

5. The polyurethane resin-forming system according to Claim 1, in which the system contains a chain extender.

6. The polyurethane resin-forming system according to Claim 5, in which the chain extender is a low molecular weight compound having at least two isocyanate-reactive groups or water.

-39- (Claims page 1)

7 . The polyurethane resin-forming system according to Claim 1, in which the carboxamide group containing polyol resin is a polyester diol.

8. The polyurethane resin-forming system according to Claim 2, in which the carboxamide group containing polyol resin is a polyetherdiol.

9. A process for making a formed polyurethane body which com-prises preparing a fluid mixture of a polyol resin, each molecule of which has at least one carboxamide group, -[NHC=O]-, in the backbone thereof, up to not more than one such group per hydroxyl group with a polyurethane resin-forming amount of polyisocyanate, forming the resulting mixture while it is still in the fluid unset state, and allowing the formed mixture to set up while in the formed condition.

10. A process for making a formed polyurethane body according to Claim 9, in which the carboxamide group containing polyol resin comprise at least 10 percent of the polyisocyanate reactive component.

11. A process for making a formed polyurethane body according to Claim 9, in which the formed polyurethane body is a castable elastomer.

12. A process for making a formed polyurethane body according to Claim 9, in which at least one of the components is a prepolymer.

-40-(Claims page 2)

13. A process for making a formed polyurethane body according to Claim 9, in which the mixture contains a chain extender.

14. A process for making a formed polyurethane body according to Claim 13, in which the chain extender is a low molecular weight compound having at least two isocyanate-reactive groups or water.

15. A process for making a formed polyurethane body according to Claim 9, in which the carboxamide group containing polyol resin is a polyesterdiol.

16. A process for making a formed polyurethane body according to Claim 9, in which the carboxamide group containing polyol resin is a polyetherdiol.

-41- (Claims page 3)