Note: Descriptions are shown in the official language in which they were submitted.
1 71 ~ Z~ Mo-2550-CIP
~ tJJ / PU-169 CIP
STABLE DISPERSIONS, PROCESS FOR PRODUCTION T~EREOF
AND USE IN THE MANUFACTURE OF POLYURET~ANES
BACKGROUND OF THE INVENTIO~
Stable dispersions for use in manufacturing
polyurethanes are known in the art. One particular
family of said dispersions which have met with
substantial commercial success are those prepared by a
continuous process of reacting an organic polyisocyanate
with polyamines containing primary and/or secondary
amino groups and/or hydrazines and/or hydrazides in the
presence of a hydroxyl-group containing material. 5ee, -
e.g. U.S. Patents 4,042,537 and 4,089,835. While these
commercially available dispersions yield polyurethane
foams having excellent physical properties, it would be
desirable if even further improvements could be
realized.
It is also known to conduct the above-noted
reaction in the present of more than 4% by weight of
water in order to prepare dispersions having viscosities
of up to 80,000 cP and preferably up to 40,000 cP at
25C. See, e.g. U.S. Patents 4,093,569 and 4,305,857.
The present invention is directed to an
improvement of the process disclosed in U.S. 4,089,835
and is more particularly directed to novel stable
dispersions, the method of manufacture thereof, and
their use in the manufacture of polyurethane foams. The
dispersions of the invention are characterized by
relatively low~viscosities. The resultant foams are
generally characterized by significantly improved
: ;~ Mo-2550-CIP
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physical properties. Foams characterized by improved
elongation and/or improved tensile strength are re~dily
obtained.
DETAILED DESCRIPTION OF THFJ INVENTION
The present invention is more particularly
: directed to an improved process for ~he in situ
production of stable dispersions of polyureas and/or
polyhydrazodicarbonamides in a hydroxy group containing
material selec~ed from the group consisting of
polyethers, polyesters, polye~ter amides, poly-
carbonates, and mixtures thereof by reacting
(a) organic polyisocyanates with
(b) a member selected from the group consisting of (i)
polyamines containing primary and/or secondary amino
groups~ (ii) hydrazines, (iii) hydrazides, or (iv)
mixtures thereof in
(c) said hydroxyl group containing material, wherein
said components (a), (b), and (c) are continuously
introduced into a flow mixer in such a quantity that
the average residence time in the mixer is less than
10 minutes and the reaction produc~ issuing from the
flow mixer is subsequently collected in a receiver,
the improvement wherein
: 25 (A) said polyisocyanate (a) is a liquid reaction
product of an organic di- and/or polyisocyanate
and a compound containing at least 1 hydroxy
:~ group, said reaction product having an
isocyanate group content of from about 5 to
~ about 45% by weight, and preferably from about
: 30 25 to 35% by weight,
(B) said liquid reaction product and said component
(b) are reacted in an isocyanate to amine
: equivalent ratio of from 0.8:1 to 1.35:1, and
~ Mo-2550-CIP
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1 31 4339
-3-
(C) wherein the reaction of component (a) 9 (b), and
(c) is conducted in the pre~ence of no more
than 4% by weight, and preferably no more than
2% by weight, of water based on the quantity of
reaction mixture including water.
In the case where 50% or more of the hydroxyl
groups of component (c) are secondary, it is preferred
that the above-noted equivalent ratio be from 1:1 to
`~ 1.35:1 to achieve products having relatively low
viscosities. Furthermore, in this case, it is preferred
that the dispersion contain from 20 to 40 percent by
weight solids.
The present invention, as noted above, is also
directed to a dispersion produced by the above-described
- 15 process, and the use of such disperslon in producing
polyurethane, either in cellular or non-cellular form.
Dispersions con~.aining from 1 to 45 percent by
weight of solids (in the form of polyureas and/or poly-
hydrazodicarbonamides) are preferred. In most cases,
the viscosities of the dispersions of the present
invention are less than 30,000 mPa.s at 25~C and are
preferably less than about 5000 mPa.s at 25C.
In preparing the liquid reaction product (A)
substantially any di- and/or polyisocyanate may be used.
Suitable isocyanates include aliphatic, cycloaliphatic,
araliphatic, aromatic and heterocyclic polyisocyanates
of the type described, for example, by W. Siefken in
~;~ Justus Liebigs Annalen der Chemie, 562, pages 75 to 136.
Specific examples include ethylene diisocyanate;
1,4-tetramethylene diisocyanate; 1,6-hexamethylene
diisocyanate; 1,12-dodecane diisocvanate;
cyclobutane-1,3-diisocyanate; cyclohexane-1,3- and
;~; 1,4 diisocyanate, and mixtures of these isomers;
.
Mo-2550-CIP
.
-4_ l 3~ J-133q
l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl
cyclohexane (see, e.g. German Auslegeschrift No.
1,202,785 and l~.S. Patent No. 3,401,190); 2,4- and
2,6-hexahydrotolylene diisocyanate and mixtures of these
isomers; hexahydro-1,3- and/or 1,4-phenylene
diisocyanate; perhydro-2,4'- and/or 4,4'-diphenyl
methane diisocyanate; 1,3~ and 1,4-phenylene
diisocyanate; 2,4- and 2,6-tolylene diisocyanate and
mixtures of these isomers; diphenyl methane-2,4'- and/or
4,4'-diisocyanate; naphthylene-1,5-diisocyanate;
triphenyl methane-4,4',4"-triisocyanate; polyphenyl
polymethylene polyisocyanates of the type which may be
obtained by condensing aniline with formaldehyde,
followed by phosgenation, and which are described, for
example, in British Patent Nos. 878,43n and 848,671; m-
: and p-isocyanatophenyl sulphonyl isocyanates of the type
described in U.S. Patent No. 3,454,606; perchlorinated
~:~ aryl polyisocyanates of the type described, for example,
in U.S. Patent No. 3,227,138; polyisocyanates containlng
20 carbodiimide groups of the type described in U.S. Patent
No. 3,152,162; diisocyanates of the type described in
U.S. Patent No. 3,492,330; polyisocyanates containing
~: allophanate groups of the type described, for example,
. in British Patent No 994,890, Belgian Patent No.
761,626 and published Dutch Patent Application No.
7,102,524, polyisocyanates containing isocyanurate
:- groups of the type described, for example, in U.S.
:~ Patent No. 3,002,973, in German Paten~ Nos. 1,022,789;
1,222,067 and 1,027,394, and in German Offenlegungs-
schriften Nos 1,929,034 and 2,004,048; polyisocyanates
containing urea groups of the type described in German
Patent No. 1,230,778; polyisocyanates containing biuret
groups of the type described, for example, in German
Patent No. 1,101,394; U.S. Patent Nos. 3,124,605 and
3,201,372 and in British Patent No. 889,050; poly-
Mo-2550-CIP
' ...
.,
1 ~ 3 9
--5--
isocyanates obtained by telomerization reactions of the
type described, for example, in U.S. Patent No.
3,654,106; polyisocyanates containing ester groups of
the type described, for example, in British Patent Nos.
965,474 and 1,072,956, in U.S. Patent No. 3,567,763 and
in German Patent No. 1,231,688; reaction products o the
above-mentioned isocyanates with acetals as described in
German Patent No. 1,072,385; and polyisocyanates
containing polymeric fatty acid radicals of the type
described in U.S. Patent No. 3,455,883.
It is also possible to use the isocyanate-
group-containing distillation residues accumulating in
the production of isocyanates on a commercial scale,
optionally in solution in one or more of the afore-
mentioned polyisocyanates. It is also possible to usemixtures of the aforementioned polyisocyanates.
In general, it is particularly preferred to use
readily available polyisocyanates, such as 2,4- and
2,6-tolylene diisocyanates and mixtures of these isomers
("TDI"); polyphenyl polymethylene polyisocyanates of the
type obtained by condensing aniline with formaldehyde,
followed by phosgenation ("crude MDI"); and, polyiso-
cyanates containing carbodiimide groups, allophanate
groups, isocyanurate groups; urea groups or biuret
groups ("modi~ied polyisocyanates"). TDI is presently
the most preferred.
The di- andlor polyisocyanates are reacted with
a compound containing at least one hydroxyl group, the
- resultant liquid reaction product containing from about
5 to about 45 percent bv weight isocyanate groups and
preferably from about 25 to about 35 percent by weight.
The hydroxyl-group containing compounds are preferably
selected from the group consisting of polyethers,
polyesters, polyester amides, polycarbonates and
mixtures thereof.
Mo-2550-CIP
-6- l 3l 43~q
Polyethers are preferred for use in making the
liquid reaction product and they preferably contain from
1 to 8 and more preferably from 2 to 6 primary and/or
secondary hydroxyl groups. The polyethers preferably
have molecular weights of from 200 to 16,000 and most
preferably from 500 to 12,000. Polyethers of this type
may be obtained in known manner bv reacting starter
compounds containing reactive hydrogen atoms with
alkylene oxides, such as ethylene oxide, propylene
lO oxide, butylene oxide, styrene oxide, tetrahvdrofuran or
epichlorohydrin, or with mixtures of these alkylene
oY~ides. In many cases, it is preferred to use
polyethers of the type which contain predominant amounts
of primary OY~-groups.
Suitable starter compounds containing reactive
hydrogen atoms include water, methanol, ethanol,
ethylene glycol, 1,2- or 1,3-propylene glycol, 1,4- or
2,3-butylene glycol, 1,6-hexane diol, 1,8-octane diol,
neopentyl glycol, 1,4-bis-hydroxymethyl cyclohexane,
2-methyl-1,3-propane diol, glycerol, trimethylol-
propane, 1,2,6-hexane triol, 1,2,4-butane triol,
trimethylolethane, pentaerythritol, mannitol, sorbitol,
methylglyocoside, cane sugar, phenol, isononylphenol,
resorcinol, hydroquinone, 1,2,2- and 1,1,3-tris
(hydroxyphenyl)-ethane, ammonia, methylamine, ethylene
diamine, tetra- or hexamethylene diamine, diethylene
triamine, ethanolamine, diethanolamine, triethanolamine,
aniline, phenylene diamine, 2,4- and 2,6-diaminotoluene
and polyphenyl-polymethylene-polyamines of the type
obtained by condensing aniline with formaldehyde. In
addition, resin-like materials of the phenol and resol
type may also be used as starters. Polyethers modified
with vinyl polymers, e.g., the compounds obtained by
polymerizing styrene and acrylonitri]e in the presence
Mo-2550-CIP
,
_7_ l 31 ~339
of polyethers (U.S. P~tent Nos. 3,383,151, 3,304,273,
3,523,093 and 3,110,695 and German Patent Specification
No~ 1,142,536) and polybutadienes which contain
OH-groups are also suitable.
The polyesters containing hydroxyl groups which
can be used to prepare the liquid reaction product
generally have molecular weights of :Erom 400 to 16,000
and preferably from 500 to 12,000, include reaction
products of polyhydric (preferably dihydric and,
optionally, trihydric) alcohols with polybasic
(preferably dibasic) carboxylic acids. Instead of using
free polycarboxylic acids, it is also possible to use
the corresponding polycarboxylic acid esters of lower
alcohols or mixtures thereo for producing the
polyesters. The polycarboxylic acids may be aliphatic,
cycloaliphatic, aromatic and/or heterocyclic and may be
substituted (for example by halogen atoms) and/or
unsaturated. Eæamples of suitable polycarboxylic acids
-~ include succinic acid, adipic acid, suberic acid,
azelaic acid, sebacic acid, phthalic acid, isophthalic
acid, trimellitic acid 5 phthalic acid anhydride, te~ra-
hydrophthalic acid anhvdride, hexahydrophthalic acid
anhydride, tetrachlorophthalic acid anhydride,
endomethylene tetrahydrophthalic acid anhydride,
glutaric acid anhydride, maleic acid, maleic acid
anhydride, fumaric acid, dimeric and trimeric fatty
acids, such as oleic acid, optionally in admixture with
monomeric fatty acids, terephthalic acid dimethyl ester
and terephthalic acid-bis-glycol ester. Examples of
suitable polyhydric alcohols include ethylene glycol,
1,2- and 1,3-propylene glycol, 1,4- and 2,3-butylene
glycol, 1,6-hexane diol, 1,8-octane diol, neopentyl
glycol, cyclohexane dimethanol (1,4-bis-hydroxymethyl-
:
Mo-2550-CIP
-8- 131~339
cyclohexane), 2-methyl-1,3-propane diol~ glycerol,
trimethylol propane, 1,2,6-hexane triol, 1,2,4-butane
triol, trimethylol ethane, triethylene glycol,
tetraethylene glycol, polyethylene glycols, dipropylene
glycol, polypropylene glycols, dibutylene glycol an~
polybutylene glycoLs. The polyesters may also contain
terminal carboxyl groups. Polyesters of lactones, such
as s-caprolactam, or hydroxy carboxylic acids, such as
: ~-hydroxy caproic acid, may also be used.
Suitable polycarbonates containing hydroxyl
groups which can be used to prepare the liquid reaction
product are those known compounds which may be obtained,
for example, by reacting diols, such as 1,3-propane
diol, 1,4-butane diol and/or 1,6-hexane diol, diethylene
15 glycol, triethylene glycol or tetraethylene glycol, with
diaryl carbonates, such as, diphenyl carbonate, or
~:~; phosgene.
: The polyester amides useful to prepare the
:, liquid reaction products include, for example, the
20 predominantly linear condensates obtained from poly-
~; basic saturated and unsaturated carboxylic acids or
:~ their anhydrides and polyhydric saturated and
unsaturated amino alcohols, diamines, polyamines and
mixtures thereof.
; 25 The molecular weight ranges for both the poly-
carbonates and polyester amides are generally from 400
to 16,000 and preferably from 500 to 12,000,
As noted above, the isocyanate and hydroxyl
~, containing materials are reacted in such a ratio that
30 the resultant product has an isocyanate group content of
from about 5 to about 45 percent by weight and
; preferably from about 25 to about 35 percent by weight.
The product is then reacted with a member selected from
the group consisting of polyamines containing primary
Mo-2550-CIP
''' ,,
_9_ 131~'39
and/or secondary amino groups, hydrazines, hvdrazides
and mixtures thereof in the presence of one or more
hydroxyl group containing material. The hydroxyl group
containing material used to produce the dispersion of
the present invention is selected from the group
consis~ing of polyethers, polyesters, polyester amides,
polycarbonates and mixtures thereof. The materials
described above for producing the liquid reaction
products are useful for producing the dispersion. They
can be the same or different from the hydroxyl material
used to produce the liquid reaction product.
Although in the reaction of the liquid reaction
product (A) in the presence of the hydroxyl
group-containing material, the NCO-groups react
preferentially with the -NH and/or NH2~groups, the
O~-groups also play their part in the reaction. This
reaction results in the ormation of polvurea and/or
polyhydra~odicarbonamide chains which are chemically
attached to molecules of the hydroxyl containing
20 material. Molecules of ~his type presumably have a
dispersing effect upon th'e resinous particles. The
extent to which the OH-groups take part in the reaction '`
~' is governed by the course of the reaction. If too many
hydroxyl functional molecules react with the reaction
product (A), highly viscous dispersions are obtained.
If, on the other hand, the proportion of co-reacting
hydroxyl functional molecules is too small, the
dispersions formed are in danger of being unstable. By
following the process of the instant invention, it is
30 possible to control the NCO/OH reaction to such a degree
that finely divided dispersions ~ith the low viscosity
required are formed. Additionally, the dispersions are
still so stable that they do not sediment even after
prolonged storage and even after storage at elevated
temperatures.
Mo-2550-CIP
.~. . . .
-lo- 1 31 4339
The dispersions of the present invention are
prepared using the techniques described in U.S. Patents
4,042,537 and 4,089,835.
Suitable polyamines useful in the instant
invention include: divalent and/or higher polyvalent,
primary and/or secondary, aliphatic, araliphatic,
cycloaliphatic or aromatic amines. Specific examples
include ethylene diamine, 1,2- and 1,3-propylene
10 diamine, tetramethylene diamine, hexamethylene diamine,
dodecamethylene diamine, trimethyl diaminohexane,
N,N'-dimethyl ethylene diamine, 2,2'~bis-aminopropyl
me~hylamine, higher homologues of ethylene diamine, such
as diethylene triamine, triethylene tetramine and ~etra-
15 ethylene pentamine, homologues of propylene diamine,such as dipropylene triamine, piperazine, N,N'-bis-
aminoethyl-piperazine, triazine, 4-amino-benzylamine,
4-amino-phenylethylamine, 1-amino-3,3,5-trimethyl-
5-amino-ethyl cyclohexane, 4,4'-diaminodicyclo-
20 hexylmethane and propane, 1,4-diaminocyclohexane,
phenylene diamines, naphthylene diamines, condensates of
aniline and formaldehyde, tolylene diamin~s,
bis-aminomethylbenzenes and the derivatives of the
above-mentioned aromatic amines monoalkylated on one or
25 both nitrogen atoms. The polyamines useable will
generally have molecular weights of from about 60 to
about 10,000 and preferably from 60 to 3000 wi~h the
molecular weight range of from 60 to 1000 being
particularly preferred.
Sui~able hydrazines include hydrazine itself
and mono- or N,N' disubstituted hydrazines, the
substituents being, e.g., Cl-C6-alkyl groups, cyclohexyl
groups or phenyl groups. The hydrazines generally have
a molecular weight of from 32 to 500. It is generally
35 preferred to use hydrazine itself.
Mo-2550-CIP
~, ,.
~ 3 1 433q
Suitable hydrazines and hvdrazides useful in
accordance with the instant invention include hydrazine,
methyl hydrazine, ethyl hydraæine, hydrazine hydrate,
propyl hydrazine, isopropyl hydrazine, n-butyl
hydrazine, isobutyl hydrazine, tert.-blltyl hydrazine,
butenyl hydrazine, dodecyl hydrazine, phenyl hydrazi.ne,
tolyl hydrazine, benzyl hydrazine, 2-phenvlethyl
hydrazine, cyclohexyl hydrazine, cyclopentyl hydrazine,
~-cyanoethyl hydrazine, 1,2-dimethyl hydrazine,
1,2-diethyl hydrazine, 1,2-diisobutyl hydrazine,
l-butyl-2 methyl hydrazine, hydrazobenzene, 1-benzyl-2-
phenyl hydrazine, oxallyl dihydrazide, semicarbazide,
carbohydrazide, 4-methyl semicarbazide, 4-phenyl semi-
carbazide, isophthalic acid dihydrazide,~-hydrazino-
propionic acid hydrazide, thiosemicarbazide, thio-
carbohydrazide, aminoguanidine, l-amino-piperazine and
1,4-diaminopiperazine.
The hydrazides useable are generally the
hydrazides of divalent or higher polyvalent carboxylic
acid, such as carbonic acid, oxalic acid, malonic acid,
: succinic acid, adipic acid, sebacic acid, azelaic acid,
; maleic acid, fumaric acid, phthalic acid, isophthalic
acid, and terephthalic acid; the esters of hydrazino-
monocarboxylic acid with dihydric or higher polyhydric
alcohols and phenols, such as ethane diol, 1,2-propane
diol, 1,2-butane diol, 19 3-butane diol and 1,4-butane
diol, hexane diol, diethylene glycol, triethylene
glycol, tetraethylene glycol, dipropylene glycol,
tripropylene glycol and hydroquinone; and the amines of
hydrazinomonocarboxylic acid (semicarbazides) with, for
example, the above-mentioned diamines and polyamines.
The hydrazides generally have molecular wei~hts of from
90 to 10,000, preferably from 90 to 3000 and, with
particular preference, from 90 to 1000.
Mo-2550-CIP
- 1 31 4339
-12-
The above-nentioned amines and hydrazines are
optionally used in the form of ~heir standard
commercial~grade aqueous solutions.
The invention enables isocyanates and amines,
hydrazines or hydrazides with a functionality of more
than two to be proportionately or exclusively used. The
reaction of compounds of such relatively high
functionality in hydroxyl group-containing materials
does not result in the formation of solid, or at the
least, very highly viscous reaction products. Rather
the reaction results once again in the fonnation of
; finely divided dispersions.
The polyaddition products obtained by the
process according to the invention, dispersed in the
hydroxyl group~containing material, may also he modified
by the propor~ionate use of monofunctional isocyanates,
amines, hydrazine derivatives or ammonia. For exampl~,
the average molecular weight of the polyaddition
products may ~e adjusted by incorporating monofunctional
compounds of this type. In cases where alkanolamines
with primary or secondary amino groups are used, it is
possible to synthesize polyureas and polyurea
; polyhydrazo-dicarbonamides containing free hydroxyl
groups. It is also possible to introduce other groups,
such as ester groups, relatively long aliphatic radical,
tertiary amino groups, and active dou~le bonds, by
utilizing correspondingly substituted monoamines or
diamines and/or isocyanates.
According to the invention, the monofunctional
compounds may generally be used in proportions of up to
40 mol % and more preferably in proportions of up to 25
mol % (based on total isocyanate, amine, hydrazine and
hydrazide content).
.
Mo-2550-CIP
131~339
-13-
Suitable monofunctional isocyanates include:
alkyl isocyanates, such as methyl, ethyl, isopropyl,
isobutyl, hexyl, lauryl and stearyl isocyanate;
chlorohexyl isocyanate; cyclohexyl isocyanate; phenyl
isocyanate; to]yl isocyanate, 4-chlorophenyl isocyanate,
and diisopropyl phenyl isocyanate.
Examples of suitable monoamines include alkyl
and dialkyl amines ~ith Cl-C18 alkyl groups,
cycloaliphatic amines, such as cyclohexyl amine and
homologues thereof; aniline and N-alkyl anilines;
aniline derivati~7es substituted on the benzene nucleus,
alkanolamines, such as ethanolamine, diethanolamine,
propanolamine, dipropanolamine, butanolamine and
dibutanolamine; diamines with one tertiary and one
primary or secondary amino groups, such as N,N-di-
methyl ethylene diamine and ~-methYl-piperazine.
Suitable monofunctional hydrazine derivatives and
hydrazides o~ monocarboxylic acids, hydrazine
monocarboxylic acid esters of monofunctional alcohols or
~:~ 20 phenols, and semi-carbazides, such as methyl, ethyl,
propyl, butyl, hexyl, dodecyl, stearyl, phenyl and
cyclohexyl semicarbazide.
It is also possible to include in the hydroxyl
group-containing material used to produce the dispersion
herein, relatively low molecular weight glycols and
~ polyols, having molecular weights up to 400. Suitable
; low molecular weight polyols are the diols and triols
~ generally known from polyurethane chemistry as chain
: extenders and crosslinkers, such as 1,2- and
1,3-propylene glycol, 1,4- and 2,3-butylene glycol,
1,6-hexane diol, 1,8 octane diol, neopentyl glycol,
cyclohexane dimethanol, 2-methyl-1,3-propane diol,
glycerol, trimethylol propane, 1,2,6-hexane triol,
1,2,4-butane triol or trimethylol ethane, but glycols
Mo-2550-ClP
1 31 ~339
-14-
with hydrophilic character, such as ethylene glycol,
diethylene glycol, triethylene glycol and dipropylene
glycol are preferred. In addition, however, it is also
possible to use compounds, such as dibutylene glycol,
thiodiglycol an~ castor oil, in component (c). ~ster
diols corresponding to one of the following general
formulae are also useful:
HO-(cH2)x-cO-o-(c~2)y OH
HO-(CH2)x-O-CO-R-CO-O-(CH2)x-OH
wherein
R represents an alkylene or arylene radlcal having
from 1 to 10 carbon atoms and preferably having from
2 to 6 carbon atoms,
x= from 2 to 6 and
y= from 23 to 5. Specific examples include ~-hydroxy
butyl-E-hydroxy caproic acid ester, ~-hydroxy
hexyl-~-hydroxy butvric acid ester, adipic
acid~bis-( ~-hydroxy-ethyl)-ester and terephthalic
acid-bis-( ~-hydroxy-ethyl)-ester. Diol urethanes
corresponding to the following general formula are
also useful:
HO-(cH2)x-o-co-NH-Rl-NH-co-o-(cH2)x-oH
wherein
R' represents an alkylene, cycloalkylene or arylene
radical having from 2 to 15 carbon atoms and
preferably having from 2 to 6 carbon atoms, and
x is an integer of from 2 to 6. Examples include
1,6-hexamethylene-bis-( ~-hydroxyethyl urethane) or
4,4'-diphenyl methane-bis-(~-hydroxybutyl urethane).
; Even diol ureas corresponding to the following
general for~ula are useful:
Mo-2550-CIP
-1S- 1 31 ~33~
. .
HO- ( CH2 ) x-N-CO-NH-R" -NH-CO-N- ( CH2 ) X-OH
R"' R"'
where in
R" represents an alkylene, cycloalkylene or arylene
radical having from 2 to 15 carbon atoms and
:: preferably having from 2 to 9 carbon atoms.
R"' represents H or CH3 and
x= 2 or 3. Examples include 4,4'-diphenyl
methane-bis-(~-hydroxyethyl urea) or the compound
FH3
HQ-C~2-CH2-N~-CO-NI~
~7'..
CH CH2-N~-CO-NH-CH2-CH2 OH
: ,
~, Particularly suitable low molecular weight
:: dihydric and trihydric alcohols are those which, in
admixture with the relatively high molecular weight
polyethers, give a dispersant ~component (c) in the
process according to the present invention) which is
::~` liquid below 50C. The viscosity of the reaction
: mixture in the through-flow mixers at the reaction
temperature is generally below 2000 cP, preferably below
1000 cP and most preferably in the range of from 100 to
5~0 cP.
1 : The molecular weight of the products ~ormed in
:~ dispersion in hydroxyl containing material is determined
by the quantitative ratio between polyamine, hydrazine
or hydraæide on the one hand and the isocyanate content
of the reaction product (A) on the other hand (and by
. the monofunctional compounds used, if any). It is
,
Mo-2550-CIP
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i
-16- ~ 3 1 ~t339
particuarly preferred to react substantially equivalent
quantities of isocyanates and NH-functional compounds in
the hydroxyl group-containing material. ~owever, it is
also possible to use an excess of isocyanate. In
; 5 general, an NCO:NH ratio of from 0.80 to 1.35, more
preferably from 0.90 to 1.35, and most preferably from
1.051 to 1.30, is maintained.
The concentration of the polyaddition products
in the hydroxyl group-containing material may vary
within wide limits, although it is generally, from 1 to
45% by weight, more preferably from ~0 to 40~ by weight
In general, the reaction components are
introduced into a flow mixer of the tvpe generally known
in the art at room temperature. If desired, the
hydroxyl containing material may be introduced at a
slightly elevated temperature (for example 40 to 50C)
to reduce the viscosity for ease of pumping and more
efficient mixing. The reaction temperature may rise to
from 50 to 150C under the effect of the shear forces
generated in cases where a d~namic mixer is used and
under the effect of the heat of the polyaddition
- reaction generated depending upon the quantity of
resinous solids. In general, however, it is best to
keep the temperature below 110C (optionally by cooling
the mixer), because otherwise any water which may be
present evaporates and can give rise to disturbances as
a result of bubble formation. In cases where hydrazine
is used, it is important to ensure that the
decomposition temperature of hydrazine is not exceeded.
The polyaddition reaction or polyisocyanates
and polyamines, hydrazines or hydrazides can be carried
out in higher-performance continuous flow mi~e~s with
average residence times of from abo~t 1 second up to 10
minutes and preferably from 2 seconds to 3 minutes.
Mo-2550 CIP
-17- ~ 3 1 ~339
The homogenization or dispersion time 0 should
only amount to at most 10% of the average residence
time, in order to obtain thorough admixture of the
5 components It is possible, although not essential, to
arrange two or even more flow mixers one behind the
other. The times quoted above then apply logically to
the mixer system as a whole.
FLow mixers are known and divided into two
10 groups, namely static mixers with fixed fittings, and
dynamic mixers with movable fittings operating on the
rotor-stator principle. They may optionally be heated
or cooled. In the case of static mixers, the mixing
energy required is applied through pumps, whereas in the
15 case of dynamic mixers a separate motor drives the
rotor.
In every case, the dispersing effect and, hence
; the particle size in the dispersion is governed by the
energy applied and the shear forces correspondingly
20 generated.
Static mixers may be divided into the following
groups:
(a) Mixers with simple fittings (see e.g., U.S.
Patent No. 3,286,992, German Offenlegungs-
schrift No. 2,119, 293 and U.S. Patent
- No.3,704,006).
(b) Multi-channel mixers tfor example, the
AMK-Ross-ISG Mixers manufactured by Aachener
Misch-und Knetmaschinen-Fabrik, West Germany).
(c) So-called packing mixers, for example, the
static mixers manufactured by Sulzer AG
~Winterthur, Switzerland) and the BKM-Mixers
manufactured by Bayer AG (West Germany~. (See
e.g., U.S. Patents 3,785,620 and 4,062,524,
respectively).
Mo-2S50-CIP
'~ 1
c~i
-18- 1 31 ~339
(d) Further variants of static mixers are mixing
;~ nozzlPs, for example3 those manufactured by the
Lechler Company (Stuttgart, West Germany) or
the mixing chambers in the HK-machines
manufactured by the Hennecke Company
(Birlinghofen, West Germany) into which the
starting products are injected under high
pressure (counter-current injection).
Dynamic mixers suitable for use in the process
according ~o the invention include the flow mixers
manufactured by the companies Ekato RMT (Schopfheim,
West Germany), Lightnin (Neu-Isenburg, West Germany) and
Hennecke (toothed stirrer) which, like the known
impeller-type homogenizing machines, operates on the
stator-rotor principle, but cannot be used to perform
feed or delivery functionsO The energy required for
dispersion in general amounts to from 1 to more than
lOkW per liter of mixer volume depending upon the
required particle size, the type of mixer used and the
viscosity of the starting materials.
In cases where anhydrous amines, hydrazines and
hydrazides are used, there is no need ~or any further
working-up on completion of the polyaddition reactions.
However, in cases~where aqueous amines (for example,
aqueous ethylene diamine solution or hydrazine hydrate)
are used, it is advisable in some cases to remove the
water from the dispersion in vacuo.
~; In general, the process according to the
invention is carried out by introducing the three
components hydroxyl group-containing material,
NH-component and liquid reaction product from separate
supply vessels through metering pumps into ~he flow
mixer in which they are thoroughly mi~ed and in which,
at the same time, most of the polyaddition reaction
Mo-2550-CIP
:
;:
, . . : .
,
.
-19- ~ 339
takes place. However, it is also possible to combine
the amine component with the hydroxyl group~containing
component before introduction into the flow mixer. The
substantially reacted product is then introduced into a
receiver in which it is optionally stirred to complete
the reaction, optionally with heating to form 50 to
150C. In cases where aqueous amines are used, the end
products are, if desired, freed in vacuo from the water
present in them.
Additives, such as activators, stabilizers,
water, blowing agents, flameproofing agents and pigment
pastes, may be added to the dispersions prepared by the
process according to the invention either during or
after the reaction.
The dispersions prepared by the process
according to the invention may be processed, for
example, into soft, semi-hard and hard polyurethane
foams with improved properties, such as increased
tensile strength and elongation. The dispersions are
also suitable for the production of, for example,
elastomers, coverings and coatings based on
polyurethanes.
Other starting components suitable according to
the invention for use in the production of the foams are
- 25 aliphatic, cycloaliphatic, araliphatic, aromatic and
heterocyclic polyisocyanates of the type previously
described.
According to the inventior, water and/or
; readily volatile organic substances are used as blowing
agents. Organic blowing agents include acetone, ethyl
acetate, halogen-substituted alkanes, such as methylene
chloride, chloroform, ethylidene chloride, vinylidene
chloride, monofluorotrichloromethane, chloridifluoro-
Mo-2550-CIP
-20- l 31 ~33~
methane, and dichlorodifluoromethane; butane, hexane,
heptane, diethyl ether and the like. A blowing effect
may also be obtained by addlng compounds such as azo-
compounds which decompose at temperatures above room
temperature giving off gases (such as nitrogen). A
suitable azo-compound is a~oisobutyronitrile. Further
examples of blowing agents and information on the use of
blowing agents may be found in Kunststoff-Handbuch-
Vol. VII, Vieweg and Hochtlen, Carl-Hanser-Verlag,
Munich, 1966 pages 108 and 109, 453 to 455 and 507-510.
In many cases t catalysts are also used in
producing the foams in accordance with the invention.
Suitable known catalysts include tertiary amines, such
as triethylamine, tributylamine, N-methyl morpholine,
N-ethyl morpholine, N-coco-morpholine, N,N,N',N'-
tetramethyl ethylene diamine, 1,4 diaza-bicyclo-(2,2,2)-
octane, N-methyl-N'-dimethyl amino ethyl piperazine,
N,N-dimethyl benzylamine, bis-(N,N-diethylamino-
ethyl)-adipate, N,N-diethyl benzylamine, pentamethyl
diethylene triamine, N,N'-dimethyl cyclohexylamine,
N,N,N',Ni-tetramethyI-1,3-butane diamine, `~`
N,N-dimethyl-~-phenylethYlamine, 1,2-dimethyl imidazole
and 2-methyl-imidazole. Other suitable catalysts are
known Mannich bases of secondary amines, such as
dimethyl amine, and aldehydes, preferably formaldehyde,
or ketones, such as acetone, methylethyl ketone,
cyclohexanone, and phenols, such as phenol, nonyl phenol
and bis-phenol.
Tertiary amines containing isocyanate-reactive
hydrogen atoms may also be used as catalysts and include
triethanolamine, triisopropanolamine, N,N-dimethyl
ethanolamine, also their reaction products with alkylene
oxides, such as propylene oxide and/or ethylene oxide.
Mo-2550-CIP
', ~ ,
,i ~ , ,. . j~
-21- l 31 4339
Other suitable catalysts are sila-amines with
carbon-silicon bonds of the type described, for example,
in U.S, Patent No. 3,620,984. Specific examples include
2,2,4-trimethyl-2-silamorpholine and 1,3-diethylamino-
methyl tetramethyl disiloxane.
It is also possible to use catalysts and
nitrogen-containing bases, such as tetraalkyl ammonium
hydroxides; alkali metal kydroxides, such as sodium
hydroxide, alkali metal phenolates, such as sodium
~` 10 phenolates, or alkali metal alcoholates, such as sodium
methylate. Hexahydrotriazines may also be used as
catalysts.
According to the invention, organometallic
compounds and more especially organo tin compounds may
also be used as catalysts.
Preferred organotin compounds include tin (II)
salts of carboxylic acids, such as tin (II) acetate, tin
(II) octoate, tin (II~ ethyl hexoate and tin (II)
laurate) and tin (IV) compounds such as dibutyl tin
oxide, dibutyl tin dichloride, dibutyl tin diacetate,
dibutyl tin dilaurate, dibutyl tin maleate or dioctyl
tin diacetate Tt is of course, possible to use any of
the above-mentioned catalysts in the for~ of mixtures.
, Further representati~es of ca~alysts suitable
~- 25 for use in accordance with the invention and information
~ on the way in which they work may be found in
;~ Kunststoff-Handbuch, Vol. VII, by Vieweg and Hochtlen,
Carl-Hanser-Verlag, M~nich, 1966 for example on pages 96
to 102.
The catalysts are generally used in a quantity
of from 0.001 to 10% by weight, bas~d on the quantity of
the high molecular weight compound according to the
invention.
Mo~2550-CIP
1 31 ~339
-22-
According to the invention, it is also possible
to use surface-active additives, such as emulsi~iers and
foam stabilizers. Examples of suitable emulsifiers
include sodium salts of castor oil sulphonates or salts
s of fatty acids with amines, such as diethylamine oleate
or diethanolamine stearate. Alkali metal or ammonium
salts of sulphonic acids, for example, of dodecyl
benzene sulphonic acid or dinaphthyl methane disulphonic
acid, or of fatty acids, such as ricinoleic acid or of
polymeric fatty acids may also be used as surface-active
additives.
Suitable foam stabilizers include polyether
siloxanes, especially those which are water-soluble.
The compounds are generally synthesized in such a way
that a copolymer of ethylene oxide and propvlene oxide
is attached to a polydimethyl siloxane radical. Foam
stabilizers of this type are described, for example, in
U.S. Patent Nos. 2,834t748; 2,917,480 and 3,629,30~.
According to the invention, it is also possible
; 20 to use reaction retarders such as acid-reacting
substances (e.g. hydrochloric acid or organic acid
~; halides), cell regulators, such as paraffins, fatty
alcohols or dimethyl polysiloxanes; pigments, dyes,
flame-proofing agents, such as tris-chloroethyl
phosphate, tricresyl phosphate or a~monium phosphate and
polyphosphates; stabilizers against ageing and
weathering, plasticizers, fungistatic and bacteriostatic
compounds and fillers, such as barium sulphate,
kieselguhr, carbon black or whiting.
Other examples of surface-active additives,
~oam stabilizers, cell regulators, reaction retarders,
stabilizers, flameproo~ing agents, plasticizers, dyes,
fillers, and fungistatic and bacteriostatic compounds,
optionally used in accordance with the invention, and
Mo-2550-CIP
1 31 4339
-23-
also details on the way additives of this type are used
and the way in which they work may be found in
Kunststoff-Handbuch, ~ol. VII, Vieweg and Hochtlen,
Carl-Hanser-Verlag, Munich, 1966 pages 103-113.
According to the invention, the reaction
components may be reacted by the known one-stage
process, by the prepolymer process or by the semi-
prepolymer process, in many cases using machines, for
example, those of the type described in U.S. Patent No.
2,764,565. Particulars o~ processing machines which m~y
also be used in accordance with the invention may be
found in Kunststoff-Handbuch, Vol. VII, Vieweg and
Hochtlen, Carl-Hanser-Verlag, Munich 1966, pages 121 to
205.
According to the invention, the foams are often
produced by ~oaming in molds. To this end, the reaction
mixture is introduced into a mold. Suitable mold
materials include metals (for example, aluminum) or
- plastics (for example, epoxide resin). In the mold, the
; 20 foamable reaction mixture foams and forms the molding.
In-mold foaming may also be carried out in such a way
that the molding has a compact skin and a cellular core.
According to the invention, it is possible in this
connection to introduce into the mold such a quantity of
foa~able reaction mixtures that the foam formed just
fills the mold. However, it is also possible to
introduce into the mold more foamable reaction mixture
than is required to fill the interior of the mold with
foam. This technique is known as "over-charging" and is
described, for example, in U.S. Patent Nos. 3,178,490
and 3,182,104.
In many cases, "external release agents" such
as silicone oils, are used during in-mold ~oaming.
However, it is also possible to use so-called "internal
~o-2550-CIP
1 31 433~
24-
release agents", optionally in admixture with external
release agents, as known, for example, from German
Offenlegungsschriften 2,121,670 and 2,307,589.
Cold-hardening foams may also be produced in
accordance with the invention (cf~ British Patent No.
1,162,517, German Offenlegungsschrift No. ~,153,086).
It is further possible to prodllce foams by
block foaming or by the known double conveyor belt
process.
The foams produced by the process according to
the invention may be used, for exam~le, as upholstery
materials, mattresses, packaging materials,
shock-absorbing motor-vehicle components, films for
laminating purposes and as insulating materials. The
highly flexible foams produced by the process according
to the invention are particularly suitable for flame
lamination with films, woven fabrics and knitted fabrics
of natural and synthetic materials. Films of these
foams may also be effectively welded by high-freauency
and ultrasonic welding. ~he hard polyurethane foams
produced are also suitable for the production of
articles with an integral structure or for the
production of sandwich elements. The foams may either
be produced by the in-mold foaming process or may be
obtained by fabrication from block-foamed materials.
They may be processed by deep-drawing, stamping or
hot-forming.
The invention is further illustrated, but is
not intended to be limited by the following examples in
which all parts and percentages are by weight unless
otherwise specified.
EXAMPLES
In the examples which follow, the following
materials were used:
Mo-2550-CIP
~,
:.
.
-25- 1314339
Polyether (A) A glycerine-started polvether of
propylene oxide and ethylene oxide with
an OH number of 35 and a primary OH group
content of approximately 80% based on the
total OH content of the polyether.
Polyether (B) A trimethylolpropane-started polyether of
propylene oxide and ethylene oxide with
an OX number of 45 and a primary OH
content of less than 5% based on the
total OH content of the polyether.
; Polyether (C) A glycerine and propylene glycol-started
polyether of propylene oxide and ethylene
oxide with an OH number of 56 and a
primary OH content of less than 5% based
on the totaI OH content of the polyether.
Polyether (D) Same as Polyether (A) but with an OH
number OI 46 and a primary OH content of
approximately 50% based on the total OH
content-of the polyether.
Polyether (E) A linear polypropylene glycol terminally
modified with ethylene oxide. (OH number
28; approximately 80~ by weight of the OH
~; groups are primary OH groups.)
Polyether (F) A linear polypropylene glycol (O~ number
56).
Polyether (G) Same as Polyether (E) but with an O~
number 150.
Polyether (H) A linear polypropylene glycol (OH number
112).
Polyether (I) A trimethylol propane-started polyether
of propylene oxide with an OH number of
660.
TDI Mixture of 80% 2,4- and 20% of
2,6-toluene diisocyanate.
Mo-2550-CIP
,
,
,~ .
-26- 1314339
MDI 4,4'-diphenylmeth~.ne diisocyanate.
All prepolymers were prepared using the
ollowing method:
The polyether(s) and isocyanate(s) were charged to a
reaction vessel at room temperature. A slight
nitrogen pad was placed on the reactor and the
contents were heated to 80C. This temperature was ~-
maintained for several hours until the measured NCO
content of the prepolymer corresponded to ~he
theoretical NCO content. The material was cooled to
room temperature and discharged from the reactor.
The following specific preparation of
Prepolymer A serves as an example:
4,000 g (1 mole) of Polyether E and 6,090 g (35
moles) of TDI were charged to a reactor at room
temperature. A slight nitrogen pad was placed on
the reactor and the temperature increased to 80~C.
This temperature was maintained for 2 hours. After
this time, the NCO content was determined to be
28.1%. The product was cooled to room temperature
and discharged from the reactor.
Several prepolymers were prepared using the
procedure noted. The molar ratios and % by weight NCO
were as indicated in Table I.
TABLE I
Prepolymer Com osition (Mole Ratio) % NCO
P
A TDI-Polyether E (35/1) 28.1
B TDI~Polyether F (20/1) 29.1
C TDI-Polyether G (10/1) 30.4
D TDI-Polyether H (10/1) 27.6
E TDI-Polyether F -Polyether I
(25/1/0.5) 29.8
F TDI-MDI-Polyether F (18/5/1) 29.0
G TDI-Polyether F (15/1) 25.5
Mo-2550-CIP
1 31 4339
-27-
H TDI-Polyether H (12.5/1) 30,4
I TDI-Polyether F (30/1) 33,7
J TDI-Polyether F (25/1) 31.7
K TDI-Polyether E (30/1) 26,4
L TDI-Polyether C (40/1) 33.4
M TDI-Polyether F-Polyether I
(25/~/1) 27.6
Example 1
2,600 g/minute of Polyether A and 243 g/minute
of hydrazine hydrate were separately pumped into a
static mixer (diameter: 12.5 mm; length: 152 mm; number
of elements: 6) while 1,344 g/minute of Polyether A and
834 g/minute of TDI were synchronously pumped through a
second, identical static mixer. The mixtures leaving
the two s~atic mixers were brought together in a toothed
stirrer ~chamber volume 500 ml; 5,000 rpm). The
result;ng dispersion ~as delivered to a post reactor
where it was stirred for 30 minutes at 80-100C and
subsequently dewatered in vacuo. A stablej white,
finely divided dispersion having a solids content of
20~, an OH number of 28, and a viscosity of 3,500 mPas @
25~C was obtained.
~.
. Mo-2550-CIP
-28- 131~33q
Examples 2-29
The procedure was the same as ln Example 1
except that a variety of NCO-terminated prepolymeræ were
substituted for the toluene diisocyanate, a variety of
base polyols having different structures was used, and
isocyanate/amino equivalent ratio and solids contents
were also varied. The values of each of these
parameters for each example are shown i.n Table II.
~'
~ 20
:
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Mo-2550-CIP
131~339
--29--
. ~ U~ ,
:~: ~o. oooooLr~oooooU~ooooo
N ~ O ~D ~ ~t ~ O ~ O O O L~ O ~ N ~ O .--1 0
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:: :
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.,
OOOOOOOOOOOOOOOOOO
.. N C~l N N N N N N t~ N C~l N N N N N N ~
~ ~:.o
~ V~
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: ,: :~:
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O
:~ ~
~ O O O O O O O O ~ O O O O ~ ~ O ~ O
l, O O O O O O O C`J O O O O O O O O O O
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a~
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~ O ~-- C C~ 1.~ C~ T ~ C~ 7 Y ~
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C C Cl c~ a:l C t~ ~ O
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Mo~2550-CIP
,.,
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1 3 1 4339
~ o
U~ Ln ~ o o o o o o o o o o o
::~ ~ F ~ ~t ~ ~ r~ Lf) ~ ~ ~
~` . ~. ~ ,~ a~ r~ CD ~ Lr) ~0 ~1 ._
N ~D
:~ : ' ~'
: :
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3 ~ O O O ~ O O O O O O O
.,_ ., ~) ~) ~ C~.l ~) ~ ~1 ~ ~) ~ N
V O
c) U3
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o L~ L 7 o ~n Ln o L~ o
O: IY r-l ~ N O _I O ~1 ~I N O O
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E
: ~ o ~ s s ~ ~ ,_, ~ ,_
.~ :c
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:~ :~
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vlaJ
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LiJ ~ N C~l N C~l N N C~l N ~1 N
Mo - 2 5 5 0-CIP
,
3 ~
-31-
xamples 30-46
The experimental polyols were evaluated using
the formulations listed in the following data below.
The amount of TDI used in the formulations varied
depending on the water level and OH no. of the polyol~
but the isocyanate index was kept constant at 110.
Component PBW PBW
Polyol 100 100
Water 2.5 4.0
C-7a ca. 0.35 (varies) ca. 0.50 (varies)
p~70b 0.3 0.3
L-6202C 1.0 1.0
TDI (110 Index) (110 Index)
a 25% stannous octoate in dioctylphthalate, Witco
Chemical Co.
b Polycat 70, a tertiary amine for Abbott Laboratories
c Dimethylpolysiloxane polyalkyleneoxide copolymer
stabilizer, Union Carbide Corp.
The polyols used in Examples 30 through 46
correspond to the polyols produced in Examples 1 through
17 respectively. The properties of the resultant foam
were as indicated in Table III.
2S
Mo-2550-CIP
131~33q
-32-
TABLE III
FOAM PROPERTIES
Tensile
Density Strength Elonga~ion
E~amples ~kg/m _ _ KPa _ %
.
32.0 150 80
31 28.0 195 160
32 28.0 160 00
33 27.0 170 160
; 34 27.0 155 170
27.0 275 190
36 27.0 185 180
37 24.2 180 170
: 38 25.6 150 104
~: 39 23.4 170 185
23.7 165 145
41 24.2 160 125
42 23.2 150 130
43 25.0 140 135
44 23.4 150 130
23.5 155 160
46 24.6 155 150
~.
'~
~ Mo-2550-CIP
-33- 131~339
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
eY.cept as it may be limited by the claims.
:`
~ 20
' ;:
.,
;~ 25
Mo-2550-CIP
.
