Urethane-filled, polyether polyols are prepared by reacting (1) a hexamethylene diisocyanate residue from the phosgenation of hexamethylene diamine with contains less than 10% by weight monomeric hexamethylene diisocyanate and has a total isocyanate group content of at least 25% with (2) an alcohol containing at least four ether linkages in amounts such that the equivalent ratio of isocyanate groups in (1) to hydroxyl groups in (2) is from about 0.9:1.0 to about 1.0:0.9 and subsequently dissolving this reaction product in a polyether polyol.

BACKGROUND OF THE INVENTION 
The present invention relates to a hexamethylene diisocyanate ("HDI") 
residue-filled polyether polyol, to a process for the production of a 
polyether polyol filled with an HDI residue-based urethane, to 
polyurethane prepolymers produced from these urethane filled polyether 
polyols and to polyurethanes produced from polyether polyols filled with 
HDI residue-based urethanes. 
HDI is generally produced by phosgenating hexamethylene diamine ("HDA"). In 
the course of producing HDI by this process, a non-distillable by-product 
which is commonly referred to as "HDI residue" or "HDI bottoms" is 
generated. One of the major concerns in the production of HDI is, 
therefore, the amount of HDI residue generated and whether such HDI 
residue is useful in other applications. 
It would therefore be advantageous to develop a method for converting HDI 
distillation residue to a urethane filler in which no HDI monomer remains. 
This urethane filler would be particularly advantageous if it could be 
dissolved in a polyether polyol to produce a clear liquid product useful 
for the production of polyurethanes. 
SUMMARY OF THE INVENTION 
It is an object of the present invention to provide a polyether polyol 
filled with an HDI residue-based urethane which is storage stable at 
ambient temperature. 
It is also an object of the present invention to provide a method for 
producing a liquid HDI residue-based urethane filled polyether polyol. 
It is another object of the present invention to provide a liquid, clear, 
urethane-filled polyether polyol which has been produced from HDI residue. 
It is a further object of the present invention to provide a process for 
producing polyurethanes, particularly polyurethane foams, from a liquid, 
clear, urethane-filled polyether polyol that has been produced from HDI 
residue. 
These and other objects which will be apparent to those skilled in the art 
are accomplished by selecting an HDI residue satisfying specific criteria. 
The HDI residue to be used in the present invention contains less than 10% 
by weight monomeric HDI and has a total NCO content (i.e., total NCO 
content of monomeric HDI plus any other isocyanate group containing 
material present in the residue) of at least 25%. HDI residue satisfying 
these criteria and an alcohol containing at least four ether linkages, 
preferably from 4 to 18 ether linkages, most preferably from 4 to 8 ether 
linkages are reacted in amounts such that the equivalent ratio of 
isocyanate groups to hydroxyl groups is from about 0.9:1.0 to about 
1.0:0.9, preferably about 1:1. This reaction product is then dissolved in 
a polyether polyol to produce a urethane-filled polyether polyol. This 
urethane-filled polyether polyol may then be used to produce 
polyurethanes. 
DETAILED DESCRIPTION OF THE INVENTION 
The present invention relates to an HDI residue-based urethane filled 
polyether polyol, to a process for producing such polyether polyol, and to 
a process for the production of a polyurethane from such urethane-filled 
polyether polyol. The urethane filled polyether polyols of the present 
invention are made by reacting an alcohol containing at least four ether 
linkages, preferably from 4 to 18 ether linkages and most preferably from 
4 to 8 ether linkages and an HDI residue satisfying specific criteria in 
amounts such that the equivalent ratio of isocyanate groups to hydroxyl 
groups is from about 0.9:1 to about 1:0.9, preferably about 1:1. This 
reaction product is then dissolved in a polyether polyol to produce a 
urethane-filled polyether polyol. This urethane-filled polyether polyol 
may then be, reacted with an isocyanate to produce polyurethanes. 
The HDI residues useful in the practice of the present invention must 
satisfy the following criteria: (1) the residue must have been generated 
by the phosgenation of hexamethylene diamine; (2) the monomeric HDI 
content of the HDI residue must be less than 10% by weight; and (3) the 
total isocyanate group content of the monomeric HDI plus any other 
isocyanate group containing material in the residue must be at least 25%. 
The phosgenation of HDA may be carried out by any of the methods known to 
those skilled in the art. Upon completion of that phosgenation, monomeric 
HDI is generally removed from the reaction mixture by distillation. In 
accordance with the present invention, the reaction mixture may be 
distilled until the monomeric HDI content has been reduced to less than 
10% by weight of the total weight of the residue, preferably less than 5% 
by weight monomeric HDI, and most preferably from about 1 to about 4% by 
weight monomeric HDI. The residue has a total NCO content (i.e., the total 
NCO content of monomeric HDI plus any other isocyanate group containing 
material in the residue) of at least 25%, preferably from about 25 to 
about 30%, most preferably from about 28 to about 30%, is suitable as a 
starting material for the process of the present invention. It is 
preferred, but not required, that any solvent employed in the phosgenation 
process be removed prior to use of the HDI residue in accordance with the 
present invention. 
Any of the known monofunctional alcohols containing 4 or more ether 
linkages (i.e., compounds containing one alcoholic hydroxyl group and at 
least four ether linkages) may be reacted with an HDI residue satisfying 
the criteria of the present invention. 
Examples of suitable monofunctional alcohols containing four or more ether 
linkages include those obtained in known manner by reacting one or more 
starting compounds containing an active hydrogen atom with one or more 
alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, 
styrene oxide, tetrahydrofuran, epichlorohydrin and mixtures of these 
alkylene oxides. Polyethers obtained by addition of ethylene oxide and/or 
propylene oxide are most preferred. Suitable starting compounds containing 
one reactive hydrogen atom include: 1-methoxy-2-propanol, diethylene 
glycol monobutylether, any of the isomers of butanol, any of the isomers 
of pentanol, and any of the other known carbon backbone alcohols. 
The monofunctional alcohols containing four or more ether linkages which 
are useful in the practice of the present invention generally have a 
molecular weight (number average determined by end group analysis) of from 
about 200 to about 1100, preferably from about 200 to about 400. Suitable 
alcohols may also contain groups such as chlorine, bromine, tertiary amine 
groups and other groups which are not reactive with respect to isocyanate 
groups. Mixtures of such alcohols may also be used. 
In addition to the monofunctional alcohol containing at least four ether 
groups, alcohols containing less than 4 ether groups or no ether groups at 
all and polyhydroxyl compounds such as diols and polyether polyols may 
also be reacted with the HDI residue to form urethane groups. However, any 
polyhydroxyl compounds and alcohols containing less than four ether groups 
should not be used in an amount such that they represent more than 20% of 
the total number of hydroxyl groups to be reacted with the HDI residue to 
form the urethane filler. 
Polyether polyols useful in the practice of the present invention both for 
preparing the HDI urethane-capped residue and dissolving the HDI 
urethane-capped residue, typically have hydroxyl functionalities of from 
about 2 to about 6, preferably from about 2 to about 3, and molecular 
weights (number average determined by end group analysis) of from about 
400 to about 6,000, preferably from about 500 to about 2,000 and at least 
4, preferably from about 9 to about 130 ether linkages. Examples of such 
polyether polyols include those obtained in known manner by reacting one 
or more starting compounds which contain at least one reactive hydrogen 
atom with an alkylene oxide such as ethylene oxide, propylene oxide, 
butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin and 
mixtures of these alkylene oxides. Polyethers obtained by the addition of 
ethylene oxide and/or propylene oxide are most preferred. Suitable 
starting compounds containing reactive hydrogen atoms include polyhydric 
alcohols such as ethylene glycol, 1,2- and 1,3-propylene glycol, 1,3- and 
1,4-butylene glycol, 1,6-hexanediol, 1,8- octanediol, neopentyl glycol, 
cyclohexanedimethanol, (1,4-bis(hydroxy-methyl)cyclohexane), 
2-methyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, triethylene 
glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, 
polypropylene glycol, dibutylene glycol and polybutylene glycol, glycerine 
and trimethylolpropane; water; methanol; ethanol; 1,2,6-hexane triol; 
1,2,4-butane triol; trimethylol ethane; pentaerythritol; mannitol; 
sorbitol; methyl glycoside; sucrose; phenol; isononyl phenol; resorcinol; 
hydroquinone; and 1,1,1- or 1,1,2-tris-(hydroxylphenyl )-ethane. 
Diols useful for producing HDI-based urethane filler in accordance with the 
present invention typically have hydroxyl functionalities of from about 2 
to about 3. Diols described above as being useful starting compounds for 
the preparation of polyethers are examples of suitable diols. 
The HDI residue satisfying the criteria of the present invention, an 
alcohol containing at least four ether linkages and any optional polyol 
are reacted in amounts such that the equivalent ratio of isocyanate groups 
to hydroxyl groups is from about 0.9:1 to about 1:0.9, preferably about 
1:1. This reaction may be carried out at temperatures of from about 
30.degree. to about 120.degree. C., preferably from about 60.degree. to 
about 90.degree. C., at ambient pressure. 
The reaction product is a urethane group containing HDI residue-based 
composition which is soluble in most of the commonly used organic solvents 
(e.g., toluene, methylene chloride and tetrahydrofuran) and in polyether 
polyols at ambient temperature. This reaction product may then be 
dissolved in a polyether polyol to produce an HDI residue based 
urethane-filled polyether. 
The amount of polyether in which the urethane group containing HDI residue 
is dissolved is generally determined on the basis of handling and 
processing considerations (e.g., viscosity). For most applications, 
however, the amount of polyether polyol used is selected so that the 
dissolved urethane-group containing HDI residue will be present in a 
quantity of from about 10 to about 50% by weight of the solution. 
The urethane filled polyethers of the present invention are characterized 
by their clarity and low viscosity when compared to other filled 
polyethers. 
The urethane filled polyethers of the present invention may be used to 
produce polyurethanes by reacting them with any of the known isocyanates. 
These filled polyethers are preferably reacted with polyisocyanates having 
functionalities of from about 2 to about 4 and molecular weights of from 
about 100 to about 400 in amounts such that the NCO/OH ratio is from about 
0.8 to about 1.2 to produce polyurethanes. 
The preferred polyisocyanates include toluene diisocyanate, diphenylmethane 
diisocyanate and polyphenyl polymethylene polyisocyanate. 
Catalysts, blowing agents and solvents may be used to aid the 
polyurethane-forming reaction. Examples of catalysts useful for promoting 
urethane reactions include di-n-butyl tin dichloride, di-n-butyl tin 
diacetate, di-n-butyl tin dilaurate, triethylenediamine, bismuth nitrate. 
Examples of suitable blowing agents include methylene chloride and carbon 
dioxide. Examples of the useful solvents include toluene, tetrahydrofuran, 
and chlorobenzene.

Having thus described my invention, the following Examples are given as 
being illustrative thereof. All parts and percentages given in these 
Examples are parts by weight and percentages by weight, unless otherwise 
indicated. 
EXAMPLES 
The materials used in the Examples which follow were: 
ALCOHOL A: diethylene glycol monobutyl ether having 1 ether group. 
ALCOHOL B: 1-methoxy-2-propanol having one (1) ether group. 
ALCOHOL C: 1-butanol having no ether groups. 
ALCOHOL D: a 1-butanol started propylene oxide adduct having a molecular 
weight of 315, a hydroxyl functionality of 1 and 4 ether linkages. 
POLYETHER A: a propylene glycol/propylene oxide/ethylene oxide adduct with 
the ethylene oxide present as 20% by weight termination having a molecular 
weight of 4,000 and a hydroxyl functionality of approximately 2. 
POLYETHER B: a propylene glycol/propylene oxide adduct having a molecular 
weight of 2,000 and a functionality of approximately 2. 
POLYETHER C: a glycerine/propylene oxide/ethylene oxide adduct with the 
ethylene oxide present as 17% by weight termination having a molecular 
weight of 4800 and a functionality of approximately 3. 
POLYETHER D: a glycerine/propylene glycol/propylene oxide/ethylene oxide 
adduct with the ethylene oxide present as 10% internal block having a 
molecular weight of 2860 and a functionality of approximately 2.9. 
HDI RESIDUE: residue generated by phosgenation of HDA (hexamethylene 
diamine) which contains 3.5% monomeric HDI and has a total NCO content of 
28.3% by weight. 
The procedure used in each of the Examples was as follows: 
HDI RESIDUE was introduced into a 1 liter 3-necked flask equipped with a 
stirrer and thermometer in the amount indicated in the Table. The HDI 
RESIDUE was stirred and to this stirred HDI RESIDUE was added the amount 
of alcohol and any optional polyol at 25.degree. C. in the amount(s) 
indicated in the Table. The resultant mixture was heated to 90.degree. C. 
and then held at 90.degree. C. until no NCO groups remained. The contents 
of the flask were then dissolved in the amount of POLYETHER necessary to 
obtain a product having the capped urethane residue content indicated in 
the Table. 
TABLE 
__________________________________________________________________________ 
HDI % 
Residue gms gms. Urethane Visc. 
EX. 
(gms) 
Alc. 
Alcohol 
Polyether 
Polyether 
filler 
Appearance 
mPa .multidot. s 
__________________________________________________________________________ 
1 59.0 D 125 A 736 20 clear 934 
2 59.0 D 125 C 736 20 clear 1024 
3 59.0 D 125 D 736 20 clear 522 
4* 62.4 C 31.3 C 291 24.4 turbid with 
-- 
solids 
5* 100 B 60.6 C 643 20 turbid with 
-- 
tar 
6* 100 A 109 C 627 25 turbid 
-- 
7* 100 A 109 A 627 25 turbid 
-- 
8* 100 A 109 D 627 25 turbid with 
-- 
solids 
9* 100 A 109 B 627 25 turbid with 
-- 
solids 
__________________________________________________________________________ 
*Comparative 
Although the invention has been described in detail in the foregoing for 
the purpose of illustration, it is to be understood that such detail is 
solely for that purpose and that variations can be made therein by those 
skilled in the art without departing from the spirit and scope of the 
invention except as it may be limited by the claims.