Polymer/polyol composition, processes for making the same and polyurethane therefrom

Polymer/polyol compositions, obtained by polymerizing an ethylenically unsaturated monomer in situ in a polyol in the presence of inner-olefin containing at least 5 carbon atoms, are of lower viscosity and can provide polyurethanes having improved properties. Polymer/polyol compositions, obtained by polymerizing an ethylenically unsaturated monomer, in situ in a polyol in the presence of an azo compound and a peroxide having a 10 hours half-life period temperature which is lower by at least 10.degree. C. than that of the azo compound, have improved stability even at higher styrene content.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to polymer/polyol compositions that are suitable for 
producing polyurethanes. The invention also relates to methods for making 
such compositions and polyurethanes therefrom. 
2. Description of the Prior Art 
It is known to produce polyurethanes by reacting an organic polyisocyanate 
with a polymer/polyol composition, obtained by polymerizing one or more 
ethylenically unsaturated monomers (such as acrylonitrile and/or styrene) 
in situ in a polyol (such as polyether polyol). 
The viscosity of known polymer/polyol compositions increases in accordance 
with an increase in polymer content. The increased polymer content is 
required in order to produce polyurethanes of improved properties, such as 
compressive hardness. Additionally, in polymer/polyol compositions 
containing higher styrene content, the dispersibility is adversely 
affected, while higher styrene content is desirable in order to inhibit 
scorching of polyurethanes. 
SUMMARY OF THE INVENTION 
It is an object of the present invention to provide polymer/polyol 
compositions, which are of lower viscosity, even at a higher polymer 
content. 
It is another object of this invention to provide polymer/polyol 
compositions, capable of providing polyurethanes having improved 
properties, such as compressive hardness. 
It is still another object of this invention to provide polymer/polyol 
compositions of improved dispersibility even at higher styrene content. 
It is yet another object of the invention to provide polymer/polyol 
compositions capable of producing polyurethanes without scorching. 
Briefly, these and other objects of the present invention, which describes 
hereinafter will become more readily apparent, have been attained broadly 
by providing a polymer/polyol composition, obtained by polymerizing an 
ethylenically unsaturated monomer in situ in a polyol in the presence of 
an inner-olefin containing at least 5 carbon atoms, or by polymerizing an 
ethylenically unsaturated monomer in situ in a polyol in the presence of 
initiators comprising an azo compound and a peroxide having a 10 hours 
half-life period temperature which is at least 10.degree. C. lower than 
that of the azo compound.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
As an embodiment of this invention, polymer/polyol compositions can be 
produced by polymerizing (1) an ethylenically unsaturated monomer in situ 
in (2) a polyol in the presence of (3) an inner-olefin containing at least 
5 carbon atoms. 
Suitable inner-olefins (3) include straight-chain and branched ones, 
containing usually at least 5, preferably 6-30, more preferably 8-20, 
particularly 9-18 carbon atoms and having a double bond (C.dbd.C) at 
non-alpha-position (2-, 3-, 4-position and so on). Branched olefins are 
preferred. Olefins containing less than 5 carbon atoms have boiling points 
which are too low; while olefins containing carbon atoms exceeding 30 
result in solidification. Illustrative of suitable inner-olefins are 2-, 
3- and 4- hexenes, octenes, nonenes, decenes, dodecenes, tetradecenes, 
hexadecenes, octadecenes, eicosenes, heneicosenes, docosenes, tricosenes, 
tetracosenes, pentacosenes, hexacosenes, and the like, as well as mixtures 
of two or more of them. Among these, preferred are octenes, nonenes, 
decenes, dodecenes, tetradecenes, hexadecene and octadecenes; and 
particularly preferred are nonenes. 
Suitable ethylenically unsaturated monomers (1) include, for example, 
aromatic hydrocarbon monomers, such as styrene, alpha-methyl styrene, and 
the like; unsaturated nitriles, such as (meth)acrylonitrile [acrylonitrile 
and methacrylonitrile; similar expressions are used hereinafter]; and 
(meth)acrylate esters, including alkyl (meth)acrylates containing 1-30 or 
more carbon atoms in the alkyl group, such as methyl, butyl, nonyl, decyl, 
undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, 
eicosyl and docohyl (meth)acrylates. 
Other examples of suitable ethylenically unsaturated monomers are 
alpha-olefins containing usually at least 5 carbon atoms, preferably 6-30, 
more preferably 8-20, particularly 11-18 carbon atoms; and include, for 
example, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 
1-hexadecene, 1-octadecene, 1-eicosene, 1-heneicosene, 1-docosene, 
1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, and the like, as 
well as mixtures of two or more of them. 
One or more monomers other than above may also be used if necessary. 
Suitable examples of such monomers include ethylenically unsaturated 
carboxylic acids and derivatives thereof, such as (meth)acrylic acids, and 
(meth)acrylamides; aliphatic hydrocarbon monomers, such as ethylene, 
propylene and iso-butylene; fluorine-containing vinyl monomers, such as 
perfluorooctylethyl (meth)acrylates; nitrogen-containing vinyl monomers, 
such as dialkylaminoethyl (meth)acrylates and morpholinoethyl 
(meth)acrylates; vinyl-terminated silicones, and the like. 
Among these ethylenically unsaturated monomers (1), preferred are (i) 
combinations of alpha-olefin with one or more other monomers, and (ii) at 
least one monomer selected from the group consisting of aromatic 
hydrocarbon monomers, unsaturated nitriles and (meth)acrylate esters. More 
preferred are combinations of alpha-olefin with at least one monomer 
selected from the group consisting of aromatic hydrocarbon monomers, 
unsaturated nitriles and (meth)acrylate esters. 
In producing polymer/polyols by polymerizing one or more ethylenically 
unsaturated monomers (1), the content of aromatic hydrocarbon monomer is 
generally 0-90%, preferably 0-80%, based on the total weight of the 
monomers (1). Polymer/polyols, obtained by using more than 90% of styrene, 
provide polyurethanes of poor rigidity. The content of unsaturated nitrile 
is usually 0-99.5%, preferably 20-55%. Weight ratio of aromatic 
hydrocarbon monomer/unsaturated nitrile is usually 0/100-80/20, preferably 
44/55-70/30. The content of (meth)acrylate esters is generally 0-50%, 
preferably 0-30%. Use of more than 50% of (meth)acrylate esters results in 
viscous polymer/polyols at higher polymer content. The amount of monomers 
other than above is usually 0-30%, preferably 0-10%. The content of 
alpha-olefin containing at least 5 carbon atoms is usually 0.5-50%, 
preferably 1-20%, based on the total weight of the monomers. When the 
content of alpha-olefin is less than 0.5%, the resulting polymer/polyols 
become viscous at higher polymer content; and use of more than 50% causes 
difficulties in producing polyurethane foams. In the above-mentioned 
compositions and hereinafter, % represents percent by weight (wt %) unless 
otherwise specified. 
Suitable polyols (2) employed for producing polymer/polyol compositions 
according to this invention include, for example, polyether polyols, 
polyester polyols, and mixtures of them, both of which polyols are usually 
used as raw materials for producing polyurethanes. 
Illustrative of such polyether polyols are those obtainable by addition of 
alkylene oxide to compounds containing at least two (preferably two to 
eight) active hydrogen atoms [such as polyhydric alcohols, polyhydric 
phenols, amines, polycarboxylic acids, phosphoric acids and the like] and 
mixtures of two or more of such adducts. 
Suitable examples of polyhydric alcohols include diols, for example, 
alkylene glycols, such as ethylene glycol, propylene glycol, 1,3- and 
1,4-butane diols, 1,6-hexane diol, neopentyl glycol, diethylene glycol and 
the like, and cyclic group-containing diols, as written in JPN Patent 
Publication No. 1474/1970, such as bis(hydroxymethyl) cyclohexane, 
bis(hydroxyethyl)benzene, and the like; trihydric alcohols, such as 
glycerol, trimethylolpropane, trimethylolethane, hexane triol, triethanol 
amine, and the like; tetrahydric alcohols, such as pentaerythritol, 
alpha-methylglucoside, diglycerol, and the like; and polyols having higher 
functionality (5-8 or higher), for example, sugar alcohols, including 
pentitols (such as adnitol, arabitol and xylitol) and hexitols (such as 
sorbitol, mannitol, iditol, talitol and dulcitol), saccharides, including 
monosaccharides (such as glucose, mannose, fructose, galactose, allose, 
altrose, talose, gulose, idose, sorbose, psicose and tagatose), di- or 
oligo-saccharides (such as sucrose, trehalose, cellobiose, lactose and 
raffinose), glycosides, such as glucosides of polyols (for instance, 
glycols, such as ethylene glycol and propylene glycols, alkane polyols, 
such as glycerol, trimethylolpropane, hexane triol and pentaerythritol); 
poly(alkane polyol)s (polyglycerols, such as triglycerol and 
tetraglycerol, and polypentaerythritols, such as dipentaerythritol and 
tripentaerithritol), and cycloalkane polyols, such as 
tetrakis(hydroxymethyl)cyclohexanol. 
Exemplary of suitable polyhydric phenols are mono-nuclear phenols, such as 
hydroquinone, catechol, resorcin, pyrogallol and phloroglucinol, and 
poly-nuclear phenols, for example, bisphenols, such as bisphenol A, 
bisphenol F, bisphenol sulfon and the like, as well as phenol-formaldehyde 
condensation products (novolaks), such as polyphenols as disclosed in U.S. 
Pat. No. 3,265,641. 
Suitable amines are inclusive of ammonia; alkanol amines, such as mono-, 
di- and tri- ethanol amines and isopropanol amines, and 
aminoethylethanolamine and the like; aliphatic, aromatic, araliphatic and 
alicyclic monoamines, for example, C.sub.1 -C.sub.20 alkyl amines (such as 
methyl, ethyl, isopropyl, butyl, octyl and lauryl amines, and the like), 
aniline, toluidine, naphthyl amines, benzyl amine, cyclohexyl amine and 
the like; aliphatic, aromatic, araliphatic and alicyclic polyamines, such 
as C.sub.2 -C.sub.6 alkylene diamines (such as ethylene diamine, propylene 
diamine, hexamethylene diamine and the like), polyalkylene polyamines 
(such as diethylene triamine, triethylene tetramine and the like), 
aromatic diamines (such as tolylene diamines, phenylene diamines, xylylene 
diamines, methylene dianilines, diphenylether diamines and other aromatic 
polyamines), alicyclic diamines (such as isophorone diamine, cyclohexylene 
diamines, dicyclo-hexylmethane diamines and the like); and heterocyclic 
polyamines, such as piperazine, N-aminoethylpiperazine, and other 
hetero-cyclic polyamines, written in JPN Patent Publication No. 
21044/1980. 
Two or more of these active hydrogen atom-containing compounds may also be 
used in conjunction. 
Among these active hydrogen atom-containing compounds, preferred are 
polyhydric alcolhols. Among polyhydric alcohols, preferred are ethylene 
glycol, propylene glycol, glycerol, trimethylol propane, hexane triol, 
pentaerythritol, methylglucoside, sorbitol and sucrose. 
Suitable alkylene oxides (hereinafter referred to as AO), employed for 
producing polyether polyols, include, for example, ethylene oxide 
(hereinafter referred to as EO), propylene oxide (hereinafter referred to 
as PO), 1,2-, 2,3- , 1,3- and 1,4-butylene oxides, styrene oxide, 
epichlorohydrin and the like, as well as combinations of two or more of 
them (block and/or random addition). Among these, preferred are EO and/or 
PO, and combination thereof with smaller amount (such as up to 5% based on 
the total weight of AO) of other AO. More preferred are PO and combination 
of PO with EO. 
Addition of AO to active hydrogen atom-containing compounds can be carried 
out in the usual way, with or without catalysts such as alkaline 
catalysts, amine catalysts and acidic catalysts, under normal or elevated 
pressure, in a single step or multi-stages. 
In general, among polyether polyols, preferred are those containing 
polyoxypropylene chain, and those containing both polyoxypropylene and 
polyoxyethylene chains. Such polyether polyols, include those obtained by 
addition of PO to active hydrogen atom-containing compound(s) as stated 
above; block adducts obtained by adding PO and EO to active hydrogen 
atom-containing compound(s), in such manners as (1) adding PO followed by 
EO (tipped), (2) adding PO-EO-PO-EO in this order (balanced), (3) adding 
EO-PO-EO in this order, and (4) adding PO-EO-PO in this order (activated 
secondary); random adducts, such as (5) mixed-adding EO/PO; and 
random/block adducts, such as (6) adding PO-EO/PO-optionally PO-EO in this 
order, as written in JPN Lay-open Patent No. 209920/1982, and (7) adding 
EO/PO followed by EO, as described in JPN Lay-open Patent No. 13700/1978. 
(In the above, EO/PO means a mixture of EO and PO.) Smaller amount (for 
instance, up to 5% based on the total weight of AO) of other AO (such as 
butylene oxides, styrene oxide) may be contained in any of PO and/or EO in 
the above. 
The content of polyoxyethylene chains (hereinafter referred to as EO 
content) may be varied widely. 
When moderate or slow curability is desirable, EO content is generally 25% 
or less, based on the total weight of AO. In case where rapid curability 
is required, EO content is usually at least 5%, preferably 7-50%, more 
preferably 10-40%, in view of reactivity, curing characteristics, initial 
physical properties, compatibility and unform reaction with isocyanates, 
and workability. There may be used polyether polyols of EO content less 
than 5% in combination with ones of EO content more than 5%, or ones of EO 
content more than 50% with ones of EO content less than 50%, so as to 
provide an average EO content within the above range. 
For rapid curability, particularly preferred are polyols containing 
terminal polyoxyethylene chains. Terminal EO content is usually at least 
5%, preferably at least 7, more preferably 7-30%. Internal EO content is 
generally at most 50%, preferably 10-40%. The primary hydroxyl content of 
such polyols is usually at least 20%, preferably at least 30%, more 
preferably at least 50%, most preferably at least 70%. 
Suitable polyester polyols are inclusive of condensation products of 
polyols dihydric alcohols (such as ethylene glycol, propylene glycol, 1,3- 
and 1,4-butane diols, 1,6-hexane diol, neopentyl glycol, and diethylene 
glycol) or combinations thereof with trihydric or higher functional 
polyhydric alcohols (such as glycerol, trimethylolpropane and the like) 
and/or polyether polyols (such as those described above) with dicarboxylic 
acids (for example, aliphatic or aromatic dicarboxylic acids, such as 
glutaric, adipic, sebacic, fumaric, maleic, phthalic and terephthalic 
acids) or ester-forming derivatives thereof (anhydrides and lower alkyl 
esters, such as maleic and phthalic anhydrides, dimethyl terephtharate, 
and the like); and ring-opening polymerization products of lactones (such 
as epsilon-caprolactone). 
Instead of or in combination with these polyols (polyether polyols and/or 
polyester polyols), modified polyols, for example, urethane-modified 
polyols (OH-terminated urethane prepolymers) prepared from organic 
polyisocyanates and excess of these polyols, and polyols containing 
polymerizable unsaturated bonds in the molecules (such as maleic 
anhydride-modified polyols) may also be employed for producing 
polymer/polyol compositions in accordance with this invention. 
Among these polyols (2), preferred are polyether polyols. 
These polyols (polyether polyols or other high molecular weight polyols), 
used for producing polymer/polyol compositions according to the invention, 
have usually 2-8 hydroxyl groups, preferably 2.3-4 hydroxyl groups 
(average). Hydroxyl number (hereinafter referred to as OHV) of these 
polyols is usually 200 or less, preferably 15-100, more preferably 20-70. 
Polyols having OHV more than 200 cause difficulty in foaming and result in 
too rigid and brittle polyurethanes. Molecular weight of these polyols is 
usually 2000-30000 or higher, preferably 2500-10000. 
These polyols (polyether polyols or other high molecular weight polyols) 
can be used as a mixture of those having different OHV, for instance, a 
mixture of a major amount (usually at least 50%) of those having OHV of 70 
or less and those having OHV of 80-500. These high molecular weight 
polyols may also be used in combination with a minor amount (for example, 
20% or less, particularly 5% or less) of low molecular weight polyols 
having high OHV (such as 700 or more). Examples of such low molecular 
weight polyols include polyhydric alcohols, as mentioned above as the raw 
materials for polyether polyols, as well as low mole AO (such as EO and/or 
PO) adducts of active hydrogen atom-containing compounds (such as 
polyhydric alcohols, amines and so on, as described above). 
In producing polymer/polyol composition, in accordance with this invention, 
the amount of said ethylenically unsaturated monomer (1) is generally 1-80 
parts, preferably 5-60 parts, per 100 parts of the total amount of said 
polyol (2) and said monomer (1). Using said monomer above 80 parts results 
in phase separation into polyol and polymer phases. Amounts lower than 1 
part leads to polyurethanes of poor physical properties, such as 
compressive hardness. In the above-mentioned compositions and hereinafter, 
"parts" represents parts by weight unless otherwise specified. The amount 
of said inner-olefins (3) contain usually at least 5 carbon atoms is 
usually 0.5-50%, preferably 1-20%, based on the total weight of (1), (2) 
and (3). 
Preparation of polymer/polyol compositions according to this invention can 
be carried out in the usual way. Suitable methods include, for example, 
those by polymerizing monomer in polyol in the presence of polymerization 
initiator (such as radical generators), as described in U.S. Pat. No. 
3,383,351, JPN Patent Publication Nos. 24737/1964 and 47999/1972 and JPN 
Lay-open Patent No. 15894/1975; and those by grafting polymer, prepared 
from monomer beforehand, to polyol in the presence of radical generator, 
as described in JPN Patent Publication No. 47597/1972. Preferred is the 
former method. 
Polymerization is usually carried out in the presence of polymerization 
initiators. Suitable initiators are free radical generators, for example, 
azo compounds, peroxides and others. Examples of suitable azo compounds 
include 2,2'-azobisisobutyro-nitrile (hereinafter referred to as AIBN) 
{65.degree. C.}, 2,2'-azobis(2,4-dimethylvaleronitrile) (hereinafter 
referred to as AVN) {51.degree. C.}, 2,2'-azobis(2-methylbutyronitrile 
{67.degree. C.}, 1,1'-azobis(cyclohexane-1-carbonitrile) (hereinafter 
referred to as ACCN) {88.degree. C.}, 
2-phenyl-azo-4-methoxy-2,4-dimethylvaleronitrile {122.degree. C.}, 
1-[(1-cyano-1methylethyl)azo] formimido(2-carbamoylazo) iso-butyronitrile 
{104.degree. C.}, 2,2'-azobis(2,4,4-trimethylpentane) azodi-t-octane 
{110.degree. C.}, 2,2'-azobis(2methylpropane)azodi-t-butane {160.degree. 
C.}, dimethyl 2,2-azobis(2-methylpropionate) {66.degree. C.}, 
2,2'-azobis[2-(hydroxymethyl)] propionitrile {77.degree. C.}, and the 
like. Illustrative of suitable peroxides are percarbonates, for example 
bis(4-t-butylcyclohexyl) peroxydicarbonate (hereinafter referred to as 
TCP) {44.degree. C.}, di-3-methoxybutyl peroxydicarbonate {43.degree. C.}, 
di-sec-butyl peroxydicarbonate {45.degree. C.}, di-isopropyl 
peroxydicarbonate, t-butyl peroxyiso-propylcarbonate, and the like; diacyl 
peroxides, such as iso-butyryl peroxide (hereinafter referred to as IBP) 
{33.degree. C.}, 2,4-dichlorobenzoyl peroxide {54.degree. C.}, lauroyl 
peroxide {61.degree. C.}, dibenzoyl peroxide, di-t-butyl peroxide, dicumyl 
peroxide, and the like; alkyl peresters, such as t-butyl 
peroxyneodecanoate (hereinafter referred to as BPND) {47.degree. C.}, 
t-butyl peroxypivalate { 45.degree. C.}, 
2,5-dimethyl-hexane-d2,5-diper-2-ethylhexoate, t-butyl 
peroxy(2-ethyl-hexanoate), t-butyl percrotonate, t-butyl perisobutyrate, 
di-t-butyl perphthalate and the like; methyl isobutyl ketone peroxide, 
t-butyl hydroperoxide, 1,1-di-t-butyl peroxy-3,3,5-trimethylcyclohexane 
and so on; and peroxides other than above, as written in JPN Ptent 
Lay-open No. 76517/1986. In the above, the numerical value within braces { 
} represents a 10 hours half-life period temperature, that is the 
temperature providing half-life period of 10 hours. 
Other initiators include, for instance, persulfates, perborates, 
persuccinates and so on. Among these initiators, preferred are azo 
compounds (especially AIBN and AVN), peroxides (especially TCP and BPND), 
and particularly combinations of them described bellow. 
As another embodiment of the present invention, polymer/polyol compositions 
are produced by polymerizing said monomer (1) in situ in said polyol (2) 
in the presence of initiators comprising (A) an azo compound and (B) a 
peroxide having a 10 hours half-life period temperature which is lower by 
at least 10.degree. C. than that of the azo compound. Peroxides preferably 
have half-life period temperature not more than 10 seconds. Illustrative 
examples of such combinations of initiators are as follows: 
__________________________________________________________________________ 
(A) AIBN 
AIBN 
AIBN 
ACCN 
ACCN 
ACCN 
AVN ACCN 
ACCN 
ACCN 
AIBN 
AIBN 
AVN 
AIBN 
AIBN 
AVN AVN AVN 
(B) BPND 
TCP IBP BPND 
TCP IBP IBP BPND 
BPND 
IBP BPND 
BPND 
BPND 
IBP TCP IBP 
*, .degree.C. 
17 21 32 41 44 55 18 41 55 55 17 21 18 
__________________________________________________________________________ 
*difference of 10 hours halflife period temperatures 
The initiators in this invention usually comprises 10-90% preferably 20-80% 
of the azo compound, and 10-90% preferably 20-80% of said peroxide. 
In producing polymer/polyol compositions, in accordance with the invention, 
the amount of polymerization initiator is usually 0.05-20%, preferably 
0.1-15%, more preferably 0.2-10%, based on the weight of the monomer (1). 
Polymerization can be performed in the absence of solvent or alternatively 
in the presence of one or more solvents (particularly in case of producing 
polymer/polyol compositions of high polymer content). Suitable solvents 
include, for example, benzene, toluene, xylene, acetonitrile, ethyl 
acetate, hexane, heptane, dioxane, N,N-dimethylformamide, 
N,N-dimethylacetoamide, iso-propanol, n-butanol and the like. 
Polymerization may also be carried out in the presence of known chain 
transfer agents, if necessary. Illustrative of suitable chain transfer 
agents are halogenated hydrocarbons, such as carbon tetrachloride, carbon 
tetrabromide and chloroform; alcohols, such as iso-propanol, methanol, 
2-butanol and allyl alcohol; alkyl mercaptans, such as dodecyl mercaptan 
and mercaptoethanol; and enolethers as described in JPN Lay-open Patent 
No. 31,880/1980. 
Polymerization may be performed continuously or batchwise. Polymerization 
is carried out at temperature above the decomposition temperature of the 
polymerization initiator, usually at 60.degree.-180.degree. C., preferably 
at 90.degree.-160.degree. C., more preferably at 100.degree.-150.degree. 
C., under atmospheric pressure, under pressure or under increased reduced 
pressure. 
Polymer/polyol compositions obtained after polymerization may be used as 
raw materials for polyurethane, as such without any after-treatment; but 
it is desirable to remove impurities such as decomposition products of 
polymerization initiators, unreacted monomers, organic solvents and so on, 
by conventional means. 
Polymer/polyol compositions thus obtained are translucent or opaque, white 
or brownish yellow dispersions, in which all the polymerized monomers 
(namely, polymers) are stably dispersed in polyols. 
Polymer content of said polymer/polyol compositions is generally 1-80%, 
preferably 3-60%, more preferably 5-20%. 
OHV of polymer/polyol compositions is generally 5-100, preferably 7-90, 
more preferably 15-80, most preferably 20-70 mgKOH/g. 
In producing polyurethanes from polymer/polyol composition (a), according 
to the present invention, one or more other active hydrogen 
atom-containing compounds may be used in combination, if desired. Such 
compounds include, for example, high molecular polyols (b) and low 
molecular weight active hydrogen atom containing compounds (c), and 
combinations of (b) and (c). 
Examples of suitable high molecular weight polyols (b) are polyether 
polyols, polyester polyols, urethane-modified polyols, and vinyl-modified 
polyols or polymer/polyols other than (a). Suitable polyether polyols and 
polyester polyols include the same ones as described as the raw materials 
for polymer/polyol compositions. Examples of polymer/polyols other than 
(a) are those obtainable by polymerizing ethylenically unsaturated 
monomers such as those described above (i.e., acrylonitrile and styrene) 
in situ in these polyols (such as polyether polyols and/or polyester 
polyols, and the like) without using inner-olefins and without using the 
particular combinations of initiators as mentioned above, for instance, 
those written in JPN Lay-open Patents No. 101899/ 1979 and No. 
122396/1979. Polyols from natural oils such as castor oil, modified 
polyols as mentioned above, polybutadiene polyols and hydroxyl-containing 
vinyl polymers (such as acrylic polyols), as described in JPN Lay-open 
Patents No. 57413/1983 and No. 57414/1983, for instance, may also be used. 
Such high molecular weight polyols (b) usually contain 2-8 or more 
hydroxyl groups and have OH equivalent weight of 200-4000, preferably 3-8 
hydroxyl groups and have OH equivalent weight of 400-3000. Among these 
polyols (b), preferred are polyether polyols. 
Examples of suitable low molecular weight active hydrogen atom-containing 
compounds (c) include compounds containing at least two (preferably 2-3, 
particularly 2) active hydrogen atoms (such as hydroxyl, amino and 
mercapto, preferably hydroxyl) and having a molecular weight of 500 or 
less (preferably 60-400) or an equivalent weight (molecular weight per 
active hydrogen atom-containing groups) of at least 30 and less than 200, 
which compounds are generally called chain-extenders or crosslinkers. Such 
compounds include, for instance, low molecular weight polyols and 
aminoalcohols. Illustrative examples of such polyols are dihydric 
alcohols, such as ethylene glycol, diethylene glycol, propylene glycols, 
dipropylene glycol, 1,3- and 1,4-butane diols, neopentyl glycol and 
1,6-hexane diol; alcohols containing three or more hydroxyl groups, such 
as glycerol, trimethylol propane, pentaerythritol, diglycerol, 
alpha-methylglucoside, sorbitol, xylitol, mannitol, dipentaerythritol, 
glucose, fructose, sucrose and the like; polyhydroxyl componds having 
molecular weight of 200-400, obtainable by adding a smaller amount of one 
or more AO (such as EO and/or PO) to active hydrogen atom-containing 
compounds (such as polyhydric alcohols as mentioned above), for example 
polyethylene glycols and polypropylene glycols; cyclic group-containing 
diols, as disclosed in JPN Patent Publication No.1474/1970, for example, 
AO (such as EO and/or PO) adducts of polyhydric phenols (such as bisphenol 
A, hydroquinone and the like; tertiary or quaternary nitrogen 
atom-containing polyols, for instance, those as written in JPN Lay-open 
Patent No.130699/1979, N-alkyldialkanol amines (such as N-methyldiethanol 
amine, N-butyldiethanol amine and the like and quaternarized products of 
these amines), and trialkanol amines (such as triethanol amine, 
tripropanol amines and the like); and sulfur-containing polyols, such as 
thiodiglycol. Suitable aminoalcohols inculude, for example, mono- and 
di-alkanolamines, such as mono- and di- ethanol amines and propanol 
amines. Among these, preferred are low molecular weight polyols 
(especially diols). More preferred are ethylene glycol, 1,4-butane diol, 
neopentyl glycol, 1,6-hexane diol, and mixtures of two or more of them. 
Other high molecular weight polyols (b) and/or low molecular weight active 
hydrogen atom-containing compounds (c) may be added to raw materials 
(polyether polyols) of polymer/polyol compositions (a) according to this 
invention, during production of (a), or after production of (a). 
In producing polyurethanes, using, as active-hydrogen atom-containing 
components, polymer/polyol compositions (a) according to this invention, 
with or without other high molecular weight polyols (b) and/or low 
molecular weight active hydrogen atom-containing compounds (c), the amount 
of (a) is usually at least 5%, preferably at least 10%, more preferably at 
least 50%, the amount of (b) is generally 0-95%, preferably 0-80%, more 
preferably 0-50%, and the amount of (c) is usually 0-30%, preferably 
0-25%, more preferably 0-10%, based on the total weight of the 
active-hydrogen atom-containing components such as (a) and optionally (b) 
and/or (c). Use of lower amount of (a) results in polyurethanes of poor 
physical properties, such as compressive hardness. Using larger amount of 
(c) causes high exotherm, and results in scorching, or molded articles 
having a tendency to form blister in the vicinity of the inlet and being 
too rigid and brittle. 
In producing polyurethanes according to the invention, there can be used 
any of organic polyisocyanates, conventionally employed for production of 
polyurethanes. Suitable polyisocyanates include aromatic polyisocyanates 
containing 6-20 carbon atoms (except carbon atoms in NCO groups), 
aliphatic polyisocyanates containing 2-18 carbon atoms, alicyclic 
polyisocyanates containing 4-15 carbon atoms, araliphatic polyisocyanates 
containing 8-15 carbon atoms, and modified polyisocyanates of these 
polyisocyanates containing urethane, carbodiimide, allophanate, urea, 
biuret, urethdione, urethonimine, isocyanurate and/or oxazolidone groups. 
Illustrative examples of polyisocyanates are: aromatic polyisocyanates, 
such as 1,3- and/or 1,4-phenylenediisocyanates, 2,4- and/or 
2,6-tolylenediisocyanates (TDI), crude TDI, diphenylmethane-2,4'-and/or 
4,4'-diisocyanates (MDI), crude MDI or 
polymethylene-polyphenylenepolyisocyanates (PAPI) obtained by phosgenation 
of crude diamino-diphenyl methane, condensation products of formaldehyde 
with aromatic amine such as aniline, or a mixture thereof; mixtures of 
diamino-diphenyl methane and minor amount (such as 2-20%) of polyamine of 
3 or higher functionality; naphthalene-1,5-diisocyanate, 
triphenylmethane-4,4',4"-triisocyanate, m-and p-isocyanato-phenyl sulfonyl 
isocyanate, and the like; aliphatic polyisocyanates, such as 
ethylenediisocyanate, tetramethylenediisocyanate, 
hexamethylenediisocyanate, dodecamethylenediisocyanate, 
1,6,11-undecanediisocyanate, 2,2,4-trimethylhexanediisocyanate, lysine 
diisocyanate, 2,6-diisocyanato-methyl caproate, bis(2-isocyanato-ethyl 
fumarate, bis(2-isocyanato-ethyl) carbonate, 
2-isocyanatoethyl-2,6-diisocyanato-hexanoate, and the like; alicyclic 
polyisocyanates, such as isophorone diisocyanate, dicyclohexylmethane 
diisocyanates (hydrogenated MDI), cyclohexylene diisocyanates, 
methylcyclohexylene diisocyanates (hydrogenated TDI), 
bis(2-isocyanato-ethyl) 4-cyclohexene-1,2-dicarboxylate, and the like; 
araliphatic polyisocyanates, such as xylylene diisocyanates, 
diethylbenzene diisocyanates, and the like; and modified polyisocyanates 
of these polyisocyanates, containing urethane, carbodimide, allophanate, 
urea, biuret, urethdione, urethimine, isocyanurate and/or oxazolidone 
groups, such as urethane-modified TDI, carbodiimide-modified MDI, 
urethane-modified MDI, trihydrocarbyl phosphate-modified MDI, and the 
like; as well as mixtures of two or more of them, such as combination of 
modified MDI with urethane-modified TDI (isocyanate-terminated 
prepolymer). Examples of suitable polyols, used for producing 
urethane-modified polyisocyanates (isocyanate-terminated prepolymer 
obtained from a polyol with excess polyisocyanate, such as TDI, MDI), are 
polyols having equivalent weight of 30-200, for example, glycols, such as 
ethylene glycol, propylene glycol, diethylene glycol and dipropylene 
glycol; triols, such as trimethylol propane and glycerol, polyols of 
higher functionality, such as pentaerythritol and sorbitol; and AO (EO 
and/or PO) adducts of them. Among these, preferred are those having a 
functionality of 2-3. Free isocyanatecontent of these modified 
polyisocyanates and prepolymers are generally 8-33%, preferably 10-30%, 
more preferably 12-29%. Among these polyisocyanates, preferred are 
aromatic polyisocyanates and modified ones therefrom. More preferred are 
TDI (including 2,4- and 2,6-isomers, mixtures of them and crude TDI) and 
MDI (including 4,4'- and 2,4'-isomers, mixtures of them and crude MDI or 
PAPI), and modified polyisocyanates containing urethane, carbodiimide, 
allophanate, urea, biuret and/or isocyanurate groups, derived from these 
polyisocyanates (TDI and/or MDI). The most preferred are TDI, crude MDI 
and modified MDI. 
Polyurethanes, produced from polymer/polyol compositions, in accordance 
with the present invention, include foamed or cellular compositions 
(foams), and non-cellular compositions (such as elastomers, sheet 
materials and so on). 
In producing polyurethane foams, foaming can be attained by using blowing 
agents, or by introducing gases, such as air (air loading), or combination 
of them. Examples of suitable blowing agents are reactive blowing agents, 
such as water, which generates carbon dioxide by reaction with 
polyisocyanate, and the like; and volatile blowing agents, for example, 
halogen-substituted aliphatic hydrocarbons, such as methylene chloride, 
chloroform, compressive hardethylidene dichloride, vinylidene chloride, 
trichloro-fluoromethane, dichlorofluoromethane and the like; low-boiling 
hydrocarbons, such as butane, hexane, heptane and the like; and volatile 
organic solvents without halogen, such as acetone, ethyl acetate, 
diethylether and the like; as well as combinations of two or more of them. 
Among these, preferred are halogen-substituted aliphatic hydro-carbons 
(particularly freons, such as methylene chloride and 
trichlorofluoromethane), water and combinations of them. The amount of 
blowing agents can be varied according to the desired density of 
polyurethanes, which may vary widely, for instance, from 0.01 to 1.4 
g/cm.sup.3. 
In producing polyurethanes, according to this invention, organic 
polyisocyanates and active hydrogen atom-containing components such as 
(a), and optionally (b) and/or (c) and/or water are reacted in such an 
amount to provide NCO index of usually 80-140, preferably 85-120, more 
preferably 95-115, most preferably 100-110. Furthermore, drastically 
higher NCO index than the above-mentioned range, for instance 150-5000 or 
more, preferably 300-1000, may be employed to introduce isocyanurate 
linkages into polyurethanes (resins or foams). 
In producing polyurethanes according to this invention, there may be used, 
if necessary, any known materials, such as catalysts, and other 
auxiliaries, usually employed in producing polyurethanes. 
Examples of suitable catalysts are amine catalysts, including tertiary 
amines, secondary amines, alkanolamines and quaternary ammonium 
hydroxides, for example, triethylamine, tributylamine, N-methylmorpholine, 
N-ethylmorpholine, N,N,N',N'-tetramethylethylenediamine, 
pentamethyldiethylenetriamine, triethylenediamine, 
N-methyl-N'-dimethylaminoethyl-piperazine, N,N-dimethylbenzylamine, 
N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethyl-1,3-butanediamine, 
1,2-dimethylimidazole, dimethylamine, N-methyldiethanolamine, 
N-ethyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, 
tetraalkylammonium hydroxides (such as tetramethylammonium hydroxide), 
aralkyltrialkylammonium hydroxides (such as benzyltrimethylammonium 
hydroxide), diazabicycloalkenes as disclosed in U.S. Pat. No. 4,524,104 
(such as DBU), and the like; alkaline catalysts, including phenoxides, 
hydroxides, alkoxides and carboxylates of alkali metals (such as sodium 
and potassium), for example, sodium phenolate, potassium hydroxide, sodium 
methoxide, potassium acetate, sodium acetate, potassium 2-ethylhexanoate 
and the like; phosphines, such as triethylphosphine; metal chelete 
compounds, such as potassium-salicylaldehyde complex; organotin compounds, 
including Sn.sup.II and Sn.sup.IV compounds, such as stannous acetate, 
stannous octoate (stannous 2-ethylhexanoate), dibutyltin oxide, dibutyltin 
dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin 
maleate, dioctyltin diacetate and the like; other organo metal compounds, 
such as di-alkyl titanate, lead naphtenate, and so on. Catalysts for 
trimerization of NCO groups forming isocyanurate ring, such as 
tris(dimethylaminomethyl) phenol, 
N,N',N"-tris(di-methylaminopropyl)hexa-hydro-s-triazine and the like, may 
also be used. These catalysts are used in small amounts, for instance, 
from about 0.001 to about 5% based on the weight of the reaction mixture. 
Exemplary of other auxiliaries are surfactants, as emulsifiers and foam 
stabilizers, particularly silicone surfactants 
(polysiloxane-polyoxyalkylene copolymers) being important. Illustrative of 
other known additives are flame retardants (such as phosphorus compounds, 
halogen compounds, Sb.sub.2 O.sub.3 and the like), retarders (such as 
acidic compounds), colorants (pigments and dyes), internal mold release 
agents (such as hydrocarbon waxes and silicone compounds), age resistors, 
antioxidants (such as hindered phenols), plasticizers, solvents, 
thixotropants (such as colloidal silica), germicides, fillers (such as 
carbon black, titanium dioxide, diatomaceus earth, glass fiber, shattered 
glass fiber, talc, mica, silica, sand, aluminum powder, graphite, 
asbestos, and the like), and so on. 
Polyurethanes of the present invention can be produced in known manners, 
including one-shot process, semi-prepolymer process and prepolymer 
process. There may be used any known mixing or foaming machines usually 
employed in producing polyurethanes. In case where no solvent is used, 
mixing machines, such as kneaders and extruders, can be used. Production 
of various non-cellular or cellular polyurethanes may be carried out in 
closed mold or open mold, usually by mixing raw materials with low 
pressure or high pressure mixing machines. Other methods, such as spray 
method, may also be used. It is preferred to produce polyurethanes by 
mixing and reacting using high pressure machines. Furthermore, 
polyurethanes may also be produced under vacuum to eliminate gases, such 
as air dissolved or mingled in raw materials, before and/or after mixing, 
preferably before mixing, of the raw materials. 
The present invention is useful for producing high-resilient and firm, 
flexible and semi-rigid polyurethane foams, suitable for energy absorbers, 
or cushioning materials of automobiles, furnitures and so on, and for 
producing cellular and non-cellular rigid polyurethanes, as well as for 
producing polyurethanes suitable for adhesives, coatings and the like. 
This invention is particularly useful for producing flexible polyurethane 
molded foams and slab foams. 
The invention is also useful for producing molded articles by RIM (reaction 
injection molding) method. Molding by RIM method can be carried out in the 
same conditions as conventional RIM method. For instance, Component A is 
prepared by mixing uniformly active hydrogen atom-containing compounds 
such as (a) and optionally (b) and/or (c), and optionally other additives 
(catalysts, surfactants and/or other additives), and then optionally 
adding thereto blowing agents (water and/or volatile blowing agents) or 
air loading. As Component B, polyisocyanate is used. These Components A 
and B are charged in the tanks A and B of the high pressure foaming 
machine. Components A and B are mixed in the mixing head and introduced 
into the mold, via the injection nozzle attached to the mold beforehand. 
Molding conditions may be the same as those in the known RIM methods. For 
example, the raw materials (2-4 components), conditioned at a temperature 
of 25.degree.-90.degree. C., are intimately mixed in an impingement 
mixhead under a pressure of 100-200 Kg/cm.sup.2 G and then injected into a 
closed mold preheated to a temperature of 30.degree.-200.degree. C. 
(preferably 60.degree.-90.degree. C.), followed by demolding within 0.1-5 
minutes. After demolding, molded articles thus obtained may be further 
after-cured or annealed. Annealing can be carried out, for instance, for 
0.3-100 hours at 60.degree.-180.degree. C., preferably 
80.degree.-160.degree. C., more preferably 100.degree.-150.degree. C., 
particularly for 1-30 hours at 120.degree.-140.degree. C. 
Polymer/polyol compositions, prepared by polymerizing a monomer in situ in 
a polyol in the presence of an inner-olefin containing at least 5 carbon 
atoms, in accordance with the present invention, are of lower viscosity 
even at a higher polymer content, and capable of providing polyurethanes 
having improved properties, such as compressive hardness. 
By polymerizing a monomer in situ in a polyol in the presence of initiators 
comprising an azo compound and a peroxide having a 10 hours half-life 
period temperature which is lower by at least 10.degree. C. than that of 
the azo compound, ratio of polymerization can be remarkably improved, and 
there be attained polymer/polyol compositions having improved 
dispersibility and are stable even at higher styrene content, and can 
provide polyurethane foams without causing scorching. 
Thus, polyurethanes formed from polymer/polyol compositions according to 
this invention are particularly useful as automotive parts, including 
interior trim and exterior trim, such as handles, sheet cushion, crash 
pads, bumpers, fenders, door panels, trunk lid and outer bodies, as well 
as elastomeric applications, and household implements, such as furnitures. 
Having generally described the invention, a more complete understanding can 
be obtained by reference to certain specific examples, which are included 
for purposes of illustration only and are not intended to be limiting 
unless otherwise specified. 
Raw materials used in the following examples are as follows: 
(1)Polyols: 
Polyol A: a polyether polyol (OHV:34), produced by addition of PO to 
glycerol. 
Polyol B: a polyether polyol (OHV: 42, EO content: 10%), produced by 
addition of PO to glycerol and sucrose (weight ratio 30/70), followed by 
tipping EO. 
Polyol C: a polyether polyol (OHV: 55), produced by addition of PO to 
glycerol. EG: ethylene glycol. 
(2) Ethylenically unsaturated monomers: 
D-124: alpha-olefin (C12/C14 weight ratio 56:44). AN: acrylonitrile, ST: 
styrene. 
(3) Inner-olefin: 
Nonene (produced by Arco Chemical). 
(4) Polyisocyanate: 
TDI-80: TDI (2,4-/2,6-ratio: 80/20) 
(6) Catalysts: 
DABCO33LV: 33% solution of triethylene diamine in dipropylene glycol 
U-28: tin catalyst (Neostan U-28, produced by Nitro Kasei K. K.) 
(7) Silicone surfactants 
L-520: polyether-polysiloxane block copolymer, produced by Nippon Uncar K. 
K. 
Dispersion stability test of polymer/polyol composition was measured as 
follows: 
Each polymer/polyol composition was centrifuged for 30 minutes at about 
18,000 rpm with a centrifugal force of about 38,000 g, followed by turning 
the centrifuge tube upside down and allowing to stand for an hour. The 
weight % of the residue remained within the centrifuge tube, based on the 
weight of the initial polymer/polyol composition, was used as index of 
dispersion stability. 
Measuring methods of properties of polyurethane foams or articles are as 
follows. 
Density (kg/m.sup.3), Tensile strength (kg/cm.sup.2), Elongation at break 
(%), and Tear strength (kg/cm): JIS K-6301. 25% and 65% ILD (kg/314 
cm.sup.2), Rebound elasticity (%), and Compression set (%): JIS K-6382. 
EXAMPLES I TO XVII, AND COMATIVE EXAMPLE i TO vii 
According to formulations (parts) and polymerization conditions 
(temperature, .degree.C., and time, hours) written in Tables 1, 2 and 3, 
polyols were charged into a reaction vessel equipped with a stirrer and 
temperature control means, and heated under stirring. Then, monomers, 
initiators and dodecyl mercaptan (hereinafter referred to as DM) were 
continuously fed by pump over 2 hours, while maintaining the temperature, 
followed by stirring at the same temperature. Finally, volatile materials 
were removed under heating to 110.degree. C. at reduced pressure of 25 
mmHg for 3 hours to obtain polymer/polyol compositions of Examples I to 
XVII and those of Comparative Examples i to vii (hereinafter referred to 
as P/Polyols I to XVII and P/Polyols i to vii, respectively). OH-V (mg 
KOH/g), viscosity (cps. at 25.degree. C.) and stability (%) of these 
polymer polyols were measured. The results were as shown in Tables 1, 2 
and 3. 
TABLE 1 
______________________________________ 
Example Example Comparative Example 
No. I II III IV i ii iii iv 
______________________________________ 
Polyol B 38.5 38.5 38.5 38.5 38.5 38.5 38.5 38.5 
Polyol C 16.5 16.5 16.5 16.5 16.5 16.5 16.5 16.5 
AN 15.8 15.8 15.8 15.8 15.8 15.8 15.8 15.8 
ST 29.2 29.2 29.2 29.2 29.2 29.2 29.2 29.2 
D-124 2.5 -- -- -- -- -- -- 2.5 
Nonene 3.0 3.0 5.0 -- -- -- -- -- 
Dodecene -- -- -- 5.0 -- -- -- -- 
Hexane -- -- -- -- -- 5.0 -- -- 
IPA -- -- -- -- -- -- 5.0 5.0 
TCP 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 
DM 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 
Temperature 
120 120 120 120 120 120 120 120 
Time 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 
Viscosity 
2900 3600 3500 4000 Solid 
7500 9000 6800 
______________________________________ 
(Note) 
IPA: isopropyl alcohol; 
DM: dodecyl mercaptan 
TABLE 2 
______________________________________ 
Comparative 
Example Example Example 
No. v vi vii V VI VII VIII IX 
______________________________________ 
Polyol A 19.5 19.5 19.5 19.5 19.5 -- -- 
Polyol B 45.5 45.5 45.5 45.5 45.5 38.5 38.5 38.5 
Polyol C -- -- -- -- -- 16.5 16.5 16.5 
AN 17.5 17.5 17.5 17.5 17.5 22.5 15.8 20.0 
ST 17.5 17.5 17.5 17.5 17.5 22.5 29.2 30.0 
D-124 -- 2.0 5.0 -- 2.0 2.5 2.5 2.5 
Nonene -- -- -- 5.0 3.0 3.0 3.0 3.0 
AIBN 0.7 0.7 0.7 0.7 0.7 0.9 1.4 2.3 
DM 0.35 0.35 0.35 
0.35 
0.35 
0.2 0.2 0.3 
Temperature 
125 125 125 125 125 120 120 120 
Time 2.5 2.5 2.5 2.5 2.5 3.5 3.5 4.0 
Viscosity 
7000 4100 2000 2100 1200 3500 3100 5000 
______________________________________ 
TABLE 3 
__________________________________________________________________________ 
Example No. 
X XI XII XIII 
XIV XV XVI XVII 
__________________________________________________________________________ 
Polyol B 56.0 
56.0 
56.0 
56.0 
56.0 
56.0 
56.0 
49.0 
Polyol C 24.0 
24.0 
24.0 
24.0 
24.0 
24.0 
24.0 
21.0 
AN 7.0 
7.0 
7.0 
7.0 
7.0 
7.0 
7.0 
10.5 
ST 13.0 
13.0 
13.0 
13.0 
13.0 
13.0 
13.0 
19.5 
Nonene 3.0 
3.0 
3.0 
3.0 
3.0 
-- -- -- 
IBP -- -- -- 0.1 
-- 0.05 
-- 0.11 
BPND -- 0.1 
-- -- 0.1 
0.05 
0.08 
-- 
TCP -- -- 0.1 
-- -- -- -- -- 
AVN -- -- -- 0.1 
0.05 
-- -- 0.06 
AIBN 1.0 
0.1 
0.1 
-- 0.05 
0.05 
0.03 
-- 
ACCN -- -- -- -- -- 0.05 
0.09 
0.14 
Temperature 
130 
120 
110 
100 
110 
100 
120 
120 
Time 1.0 
1.0 
1.0 
1.0 
1.0 
3.0 
1/4 1/4 
Ratio of 90.5 
97.5 
95.7 
96.5 
98.5 
98.5 
99.4 
99.0 
polymerization, % 
Stability 
6.3 
3.8 
4.1 
4.6 
4.4 
4.5 
2.8 
3.5 
Viscosity 
2400 
2500 
2300 
2400 
2000 
2200 
2700 
3300 
__________________________________________________________________________ 
EXAMPLES 1 to 9, AND COMATIVE EXAMPLES 1 AND 2 
Polyurethane foams were produced according to foaming formulations (parts), 
written in Tables 4 and 5. 
Properties and density (kg/m.sup.3, JIS K-6301) of the resulting foams were 
measured, and the results were shown in Tables 4 and 5. 
TABLE 4 
__________________________________________________________________________ 
Comparative 
Example Example Example 
No. 1 2 1 2 3 4 5 
__________________________________________________________________________ 
Polyol C 
100 50 500 0 50 50 50 
P/Polyol I 
0 0 50 100 0 0 0 
P/Polyol iv 
0 50 0 0 0 0 0 
P/Polyol VI 
0 0 0 0 50 0 0 
P/Polyol VII 
0 0 0 0 0 50 0 
P/Polyol VIII 
0 0 0 0 0 0 50 
Water 4.5 4.5 4.5 4.5 4.5 4.5 4.5 
DABCO 33LV 
0.3 0.3 0.3 0.3 0.3 0.3 0.3 
U-28 0.30 0.26 0.26 0.22 0.28 0.28 0.26 
L-520 1.5 1.5 1.5 1.5 1.5 1.5 1.5 
TDI-80 54.6 52.2 52.2 49.7 50.8 52.2 52.2 
Density 23.7 26.1 23.8 24.6 26.0 25.6 26.0 
25% ILD 10.6 16.4 17.0 28.9 16.8 18.0 17.1 
Tensile 1.06 1.21 1.27 1.47 1.16 1.24 1.24 
strength 
Tear 0.87 0.67 0.89 0.85 0.71 0.68 0.65 
strength 
Elongation 
174 100 103 58 106 102 100 
at break 
Rebound 40 34 34 29 35 33 34 
elasticity 
Compression 
3.2 6.4 6.5 35.0 8.7 5.9 5.8 
set 
__________________________________________________________________________ 
TABLE 5 
______________________________________ 
Example No. 6 7 8 9 
______________________________________ 
P/Polyol X 100 0 0 0 
P/Polyol XI 0 100 0 0 
P/Polyol XII 0 0 100 0 
P/Polyol XVI 0 0 0 100 
Water 4.5 4.5 4.5 4.5 
DABCO 33LV 0.3 0.3 0.3 0.3 
U-28 0.3 0.3 0.3 0.3 
L-520 1.5 1.5 1.5 1.5 
TDI-80 52.2 52.2 52.2 52.2 
Density 23.6 23.3 23.4 23.5 
25% ILD 16.8 17.9 18.5 21.0 
Tensile strength 
0.86 0.99 1.05 1.12 
Tear strength 
0.84 0.86 0.90 0.95 
Elongation at break 
120 120 125 122 
Rebound elasticity 
35 34 35 35 
Compression set 
5.8 5.8 5.9 6.2 
______________________________________