Note: Descriptions are shown in the official language in which they were submitted.
21225~2
~: Mo-4056
LeA29,sg7-us
PROCESSFORTHE MANUFACTUREOFPOLYURETHANEFOAMS
BACKGROUND OFTHEINVENTION
This inven~ion relates to a novel process for the manufacture of
water-blown polyurethane foams from starting materials which are known
per se, in the presence of a catalyst comprising at least one carboxylic
acid containing ether groups, and which is present at least partially in the
form of alkali metal salt. These foams are useful in the manufacture of
composite bodies by back-foaming plas~ic sheets with reaction mixtures
containing these catalysts, which react fully to polyurethane foam. The
invention also relates to the composite bodies thus obtained.
Water-blown foams, in particular sheet composite bodies, which
~ 10 are manufactured by back-foamin~ a plastic sheet with a reaction mixture
-~; which reacts fully to form a sof~ or semi-rigid polyurethane foam, are of
great importance industrially. These are widely used, for example, for
interior fiffings for motor vehicles, aircraft or in the manufacture of
upholstered furniture. It is essential in the majority of these fields of
application that, in addition to good mechanical propcrties, influence on
thermal ageing of the skin by the foams should be nil or only minimal.
~` The thermal ageing characteristics of the known back-charged
foam~ (i.e. the tendency of the PVC skin toward embrittlement and crack
formation) in particular constitute a problem in need of a solution.
Poor thermal stabllity results from certain constituents of the
reaction mixture which reacts fully to polyurethane foam. For example,
there have been attempts to replace the tertiary amines which are
frequently utilized as catalysts, for example, with alkali metal salts of
carboxylic acids such as, for example, potassium acetate. The use of
such catalysts alone to catalyze the reaction is, however, associated with
~, ~
:`j
. s:~ksl~D80213
-.. : ~ : . . ,
,.. ;~ ' : :
2 12 ?~
- 2 -
- the disadvantage of an excessively long mold removal time or, in the
case of elevated catalyst concentration, too short an initiation time.
Admittedly, the use of organic tin compounds generally leads to improved
ageing characteristics, but the hydrolytic stability of the organic tin
5 compounds in water-containing polyol makes it difficult to ensure that
activation of the polyol component remains constant over an extended
storage period. In addition to improving thermal stability, compounds
known as "amine trapping agents" are added to the foam system.
However, these result only to a degree of improvement, and they cannot
10 be used in amine-catalyzed systems.
U.S. Patent 4,868,043 recommends using catalysts comprising
ester carboxylic acids, present in the form of alkali metal salts, of
(i~ intramolecular carboxylic acid anhydrides and (ii) monohydric alcohols
having no ether groups; and, in particular, of semi-esters, present in the
15 alkali metal salt form, of (i) intramolecular carboxylic acid anhydrides and
long-chain diols. The compatibility of the hydroxyl and ester carboxylic
~ acid salts having no ether groups with the other partners in the reaction
;, is unsatisfactory. Finally, a feature common to both catalyst types of
this patent is that their use leads to reaction mixtures which sUII fall short
20 of the optimum in terms of the practical requirement regarding the
relationship between a desirably, long initiation time and a desirably,
short mold removal time.
It has now been found that the problems described hereinabove
can be resolved in optimal manner using the catalysts described
25 hereinbelow which are essential to the invention. The essential point of
the process according to the invention, hereinafter described in greater
detail, using as catalysts comprising ether carboxylates which are
` sufficiently compatible with the other constituents of the reaction mixture
because of their ether group content, and which do not affect reaction
Mo4056
. .
.
. `
. ~ -.
.~ ' ' : "
`,'- ~ '
.
~;. 21~"~j~2
:
- 3 -
mixture reactivity as a result of hydrolytic decomposition of the catalysts,
because ester groups, which are known to be susceptible to hydrolysis,
are absent. In particular, the reaction mixtures containing the catalysts
according to the invention show a favorable relationship between long
, -~ 5 initiation times and satisfactorily short mold rernoval times.
DESCRIPTION OF THE INVENTION
The present invention relates to a process for the manufacture of
polyurethane foams by reacting a reaction mixture comprising:
a) a polyisocyanate component,
10 b) a polyol component having no salt groups,
:.;
- c~ at least one blowing agent, and
d) at least one catalyst.
wherein the catalyst comprises at least one carboxylic acid salt
containing ether groups and no ester groups, and containing (as a
.i statistical average) less than 0.3 or more than 1.3 hydroxyl groups per
molecule, and is present in an amount of from 0.01 to 100 wt-%, based
on the weight of component b).
The reaction mixture may additionally comprise:
e) further auxiliary substances and additives known per se in
polyurethane chemistry.
The present invention also relates to the manufacture of composite
bodies by back-foaming a plastics sheet as a skin with a reaction mixture
~, of the aforementioned type which reacts fully to a polyurethane foam,
' 25 and to the composite bodies thus obtained.
Suitable polyisocyanates to be utilized as component a) in the
process according to the invention include any diisocyanates or
polyisocyanates, and in particular those having aromatically bonded
isocyanate groups. Suitable compounds include, for example,
Mo4û56
I
.~
,,,
~22~2
- 4 -
2,4-diisocyanatotoluene, industrial mixtures thereof with 2,6-diisocyanato-
toluene ~TDI), and, in particular, polyisocyanate mixtures of the diphenyl-
methane series (MDI) which are liquid at room temperature, are
preferably utilized. Of particular interest are the polyisocyanate mixtures
5 such as, for example, those obtained by reacting aniline formaldehyde
condensates with phosgene, or distiliation fractions or distillation residues
prepared from such products of phosgenation, or such modification
products of such polyisocyanates or polyisocyanate mixtures of the
diphenyimethane series such as those containing, for example, urethane,
10 carbodiimide and/or uretdione groups. The preferred, optionally
chemically modified polyisocyanate mixtures of the diphenylmethane
series generally exhibit an NCO content of from about 25 to 33 wt-%.
~ Component b) includes, for example, polyether polyols or mixtures
`, of polyether polyols having a (average) molecular weight, calculatable
15 from the hydroxyl group content and the hydroxyl functionality, of from
.
~ ! 400 to 12,000, preferably from 2,000 to 6,000, and a (average3 hydroxyl
`~ functionality of from 2 to 8, preferably from 2 to 4. Suitable compounds
for component b) also include mixtures of such polyether polyols with
polyhydric alcohols having molecular weights below 400, which may be
20 optionally used in addition to the polyether poiyols, in a quantity of up to
25 wt-%, based on the weight of the polyether polyols.
The suitable polyether polyols include, for example, those of the
type known per se, such as are obtainable by alkoxylation of suitable
starter molecules in a manner which is known per se. Some examples of
25 suitable starter moiecules include ethylene glycol, propylene glycol,
` trimethylolpropane, glycerol, sorbitol, pentaerythritol or saccharose, and
mixtures of such polyhydric alcohols. Utilization of polyether polyols
which have been prepared by alkoxylation of trifunctional starter ~ :
molecules, in particular, trimethylolpropane and/or glycerol, is most
Mo4056
.
;'''
;. ~ ~: .,
. ~ . .
,'s'~ ~ : ~ '
~.. ~ ,. . : ,
.,.,, : .
.; .
.:- 21~2~2
- 5 -
particuiarly preferred. Some of the suitable alkylene oxides for the
alkoxylation reaction include, for example, propylene oxide, ethylene
oxide, and mixtures of the latter two alkylene oxides. The specific
alkylene oxides mentioned hereinabove may also be used sequentially in
5 the alkoxylation reaction. Additional polyols suitable for component b)
-~ include those described in, for example, in ~uropean Patent 380,993, the
. disclosure of which is herein incorporated by reference.
~;~ Some suitable examples of low-molecular weight polyhydric
alcohols having a molecular weight below 400 include ethylene glycol,
10 propylene glycol, diethylene glycol, dipropylene glycol, glycerol,
trimethylolpropane, mixtures thereof, etc.
.~ Water is the preferred blowing agent for the presently claimed
; invention. However, other blowing agents may be used too. Some
examples of suitable b!owing agents include, for example, halogenated
15 hydrocarbons such as trifluorochloromethane, fluoridated hydrocarbons,
highly volatile organic solvents such as pentane, scetone or diethylether,
, ~,...
etc. It is less preferred to use another blowing agents in addition to
'`iJ water.
.
Suitable catalysts for the invention include any organic carboxylic ~ -
20 acids having no ester groups and containing ether groups, which are
present at least partially in the form of salt, preferably in the form of alkalimetal salt, and which contain (as a statistical average) less than 0.3 or
~ .,
more than 1.3 hydroxyl groups per molecule. Preferred salts include
compounds such as, for example, ether carboxylic acids present to the .
25 extent of ~rom 20 to 100% in the form of an alkali metal salt, preferably
the sodium or potassium salt, which conform in terms of hydroxyl group
content to the conditions mentioned; and have a molecular weight of from
~;~ 250 to 8,000, preferably from 300 to 1,000; and which (as a statistical
average) contain at least 2 ether bridges per molecule; from 0 to 5,
Mo4056
`!
x
- ~;~ - ~ .
~ 2~62~2
- preferably from 2 to 3, hydroxyl groups per molecule; and from 1 to 6,
:~ preferably from 1 to 3, carboxyl groups, per molecule, present at ieast
partially in the form of a salt. The molecular weights set forth
hereinabove are calculated on the free, unneutralized acid. The
5 particularly preferred catalysts are those which either exhibit no free
hydroxyl groups or (as a statistical average) exhibit at least 2 hydroxyl
groups, so that, in terms of the isocyanate addition reaction, they do not
under any circumstances bring about chain scission but preferably extend
chain length.
The suitable oatalysts d) according to the invention which are
particularly preferred include, for example, acids corresponding to the
general formula:
R' R"
I I
. (HO)m R(O--CH--CH--COOH)n
15 which meet the requirements set forth hereinabove and are present at
` least partially in the form of alkali metal salt,
` wherein in the formula: ~ :
.~
R represents a radical such as is obtained by removal of the
. hydroxyl groups from a (m+n)hydric pGlyether alcohol which is .
:'! 20 free from ester groups and which has a molecular weight of ~om 300 to 1000,
R' represents a hydrogen atom or a carboxyl group, -
~'!`j R" represents a hydrogen atom or a methyl group when R' =
hydrogen, and represents a hydrogen atom when R' =
-COOH,
25 m represents an integer or (as a statistical average) a
; fractional number from 0 to 5, with exclusion of the range
~. 0.3 to 1.3, and
~ .
Mo4056
~: 2~22~2
- 7 -
n stands for an integer or (as a statistical average) a
~ fractional number from 1 to 6,
- wherein the sum of m+n results in a value of from 1 to 6.
The suitable catalysts for the present invention are prepared, for
5 example, by reacting (i) alcohols of the type hereinafter mentioned in
greater detail, with (ii) derivatives of unsaturated carboxylic acids, in the
presence of (iii) basic catalysts, with concurrent or subsequent
conversion of the reaction products formed from (i) and (ii) into the
; corresponding salts for use in the invention.
Suitable alcohols (i) include compounds such as, for example,
polyether alcohols having molecular weights of from 200 to 4,000,
preferably 300 to 1,000, and having from 1 to 6, preferably from 2 to 3
hydroxyl groups per molecule. Mixtures of these polyether alcohols are
5~i also suitable. All data relative to molecular weight given in this context
r ~
.~ 15 are calculated on the (where mixtures are used, average) rnolecular
.
weight calculatable from OH content and OH functionality.
The suitable polyether alcohols include the alkoxylation products of
alcohols having no ethergroups, such as, forexample, methanol,
ethanol, the propanol isorners, the butanol isomers, the hexanol isomers,
~: 20 the octanol isomers, ethylene glycol, propylene glycol, glycerol,
trimethylolpropane, sorbitol, pentaerythritol or mixtures of such starter
, ,,~
molecules, wherein ethylene oxide and/or propylene oxide, optionally in
mixture or in any sequence, islare used for the alkoxyiation.
The carboxylic acid dérivatives (ii) include any derivatives of a"B-
~,~ 25 unsaturated carboxylic acids such as, for example, acrylic acid,
methacrylic acid, maleic acid or fumaric acid, which can be easily
converted in a simple manner into the corresponding free acids. Some
examples of derivatives of the acids, which are suitable according to the
invention, include the amides, nitriles and, in particular, the C1-C6-alkyl
i
,~ Mo4056
, .
21225~2
.
'~ esters of the acids. Preferred carboxylic acid derivatives (ii) are C1-C6-
~ alkyl esters of acrylic acid, with t-butyl acrylate being most preferred.
Some examples of suitable catalysts (iii) which accelerate the
addition of hydroxyl groups of component (i) to the olefinic double bonds
5 of the components (ii) include alkali megal organyls such as phenyllithium,
- butyllithium; Grignard reagents such as ethylmagnesium bromide,
ammonium hydroxide; alkali metal hydroxides such as sodium hydroxide
or potassium hydroxide; alkali metal alcoholates and alkali metal
phenolates; alkali metal hydrides such as sodium hydride; amines such
10 as, for example, guanidine; phosphines such as, for example,
~- tributylphosphine; ion exchangers present in the OH form such as nickel
acetylacetonate; and dialkyl tin oxides such as dibutyl oxide. Powdered
. potassium hydroxide or potassium t-butanolate are preferred catalysts
If basic alkali metal compounds of the type mentioned hereinabove
by way of example are used as catalysts (iii), these not only accelerate
the reaction of hydroxyl group addition to the olefinic double bonds, but
also the saponification reaction with formation of the corresponding free
carboxylic acids. It is frequently expedient to consider the saponification
20 reaction taking- place in situ contemporaneo.usly with the addition reaction
with formation of addition compounds from the starting components (i)
~ and (ii), by either adding additional catalyst during the reaction or by
: using a correspondingly greater quantity of catalyst from the outset in
order to make up the quantity of catalyst consumed during the
25 saponification reaction with formation of salts. Accordingly, during the
reaction of the starting components (i) and (ii), the quantity of the catalyst
(iii) used may vary over a broad range of from 0.05 to 10, preferably from
, 0.5 to 5, mole-%, based on the OH equivalents contained in the starting
component (i).
Mo4056
.~ . .
~ ~ , ' ? . '
;~
9 2~22~2
The starting materials (i) and (ii) in the presence of the catalysts
(iii) react in a manner which is known per se in a solvent or preferably in
substance within the temperature range of 0 to 100C, until the
theoretical hydroxyl number of the reaction product is reached. If a
5 deficiency of the a"B-unsaturated carboxylic acid derivatives (ii) is used,
calculated on the quantity of hydroxyl groups contained in the alcohol
component (i), products are obtained which still exhibit free hydroxyl
groups and which are hence incorporated in the process products when
~: ~ the process according to the invention is carried out. if an excess of
10 component (ii) is used in order to ensure complete reaction with the
, ~, hydroxyl groups of the alcohols (i), the excess can be removed from the :
~` reaction mixture, for example by distillation, after the reaction has taken
place, and may then be used again.
. The quantitative ratios of the starting components (i) and (ii) are
`i 15 generally selected such that a molar ratio of alcoholic OH groups of
component (i) to olefinic compounds of component (ii) of from 5:1 to
0.6:1 is present in the reaction rnixture. In accordance with the details set
forth hereinabove, it is preferably ensured that the final hydroxyl
functionality of the reaction products is beiow 0.3 or above 1.3.
Suitable solvents for this reaction include those solvents that are
inert under the reaction conditions. Some examples of those solvents
include diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran,
dioxane, t-butanol, benzene, toluene, chlorobenzene, dimethylformamide,
' dimethyl sulphoxide, N-methylpyrrolidone and acetonitrile. It is preferred
`' 25 that the reaction occurs in the absence of solvent.
The ether carboxylic acid derivatives which are obtained as an
intermediate stage are hydrolyzed using processes which are known per
~it
se. This includes, for example, by reaction with aqueous acids such as,
for example, hydrohalic acids, sulfuric acid, phosphoric acid, sulfonic
.
~ Mo4056
,.jl
.
3 ~
: 1 :
21225~2
- 10-
acids and halocarboxylic acids. Hydrochloric acid is preferred. It is in
some cases advantageous to effect the hydrolysis in the presence of a
solvent which can be removed again by distillation after the reaction is
completed, and be used again. Suitable solvents include those solvents
5 that are inert under the reaction conditions, i.e. solvents which do not
themselves undergo hydro~ysis or protonization. Some examples include
diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane,
t-butanol, benzene, toluene, chlorobenzene, dimethylformamide, dimethyl
sulphoxide, N-methylpyrrolidone and acetonitrile. The ether carboxylic
10 acid derivatives are generally hydrolyzed within the temperature range
50 to 11 0C.
In order to convert the alkoxy carboxylic acids which are formed
into the corresponding salts, hydroxides, carbonates or bicarbonates of
sodium or potassium or amine catalysts such as are conventional in
15 polyurethane chemistry are used. The bases are preferably used in the
form of aqueous solutions, so that mixtures of catalyst d) according to the
~! invention and blowing agent c) occur directly, and are then mixed down
with the remaining components b) and e). The salts which are used as
catalysts, which are prepared by neutralization of the corresponding ether
20 carboxylic acids, may also be prepared in component b) or in a portion of
the alcohols being used as component b3, so that soiutions of the
catalysts d) occur directly in the polyol component b), or in a portion
thereof.
If greater quantities of water are necessary to prepare the salts
25 than are required subsequently as blowing agent, the excess water may
naturally be removed by distillation before carrying out the process
`~ according to the invention.
~ ~.
Mo4056
.i
~' ~
21 22~12
r ~ 11 ~
The ether carboxylic acid salts which are essential to the invention
may also be prepared directly from the reaction products of the starting
components (i~ and (ii), which are obtained as intermediates, by
: saponiflcation with caustic liquor. Singie-stage preparation of the
` 5 catalysts d) is also possible if alkali metal hydroxides are used as
catalysts for reacting the starting components (i) and (ii).
Some examples of additional ways of possibly preparing the
: catalysts d) which are essential to the invention include: reacting ether
. alcohols with chloroacetic acid derivatives, followed by hydrolysis and
; 10 salting out of the alkoxy acetic acid derivatives obtained; grafting of ether
alcohols with acrylic acid derivatives, followed by hydrolysis and salting
out of the ether carboxylic acid derivatives obtained; and partial or
complete oxidation of ether alcohols using oxidants such as, for example,
chromates, permanganates, nitrates, oxygen or peroxides, followed by
salting out the ether carboxylic acids obtained.
The catalysts d) necessary to the invention are used in the
. .
process according to the invention in a quantity of from 0.01 to 100,
preferably from 0.1 to 10 wt-%, based on the weight of component b).
The reaction mixture may, in addition to the catalysts according to
the invention, also contain other catalysts which are known per se.
~ However, this is less preferable. Some examples of such catalysts
i~ include any alkali metal salts of c~rboxylic acids not conforming to the
definition of component d), such as, for example, potassium acetate, ~ ~
potassium tartrate or potassium succinate; or classic catalysts such as ~ ~ -
25 triethylenediamine, bis-(2-dimethylaminoethyl3 ether, N,N-dimethylethanol-
amine, N,N,N',N",N"-pentamethyldiethylenetriamine, N-methylmorpholine,
dimethylbenzylamine, tertiary alkyl phosphines, tin(ll) octoate, or dibutyl-
tin-(lV) dilaurate; and metal chelates, such as, for example, acetyl
acetonate chelates of magnesium, zirconium or nickel. These catalysts
,
;~
Mo4056
.~
. ': ''
212~0~
-12 -
which may be optionally used in addition to those necessary to the
invention, are considered to be part of group e) of the starting materials
; of the invention. If these catalysts are used, they are present in quantities
of a maximum of 1.0 wt-%, based on the weight of component b).
Further auxiliary agents e) which may be optionally used include
the conventional additives such as, for example, flameproofing agents,
fillers, pigments, plasticizers, antistats, or cell regulating agents.
In carrying out the process according to the invention, the starting
. materials described hereinabove are reacted together in quantitative
~ 10 ratios such as to correspond to an NCO index of from 60 to 140. The
.~ components b) to e) are generally mixed to form a "polyol component",
which is then reacted with the poiyisocyanate component using the usual
methods for manufacturing polyurethane foam.
By the term NCO index, is meant the number of NCO groups
divided by the number of NCO-reactive groups, multiplied by 100.
The process according to the invention is suitable for
manufacturing any foam. The products of the process according to the
invention are preferably, however, soft or semi-rigid polyurethane foams
.~ (i.e. having a compression hardness of 20 to 400 KPa-s at 40%
deformation) having a gross density of from 30 to 500, preferably from 30
to 200 kg/m, and of the type such as those used in known manner for
back-foaming plastics sheets for the purpose of manufacturing sheet
composite materiais for upholstery purposes or for the interior of motor
vehicles, aircraft or ships (instrument panels, inside door moldings,
armrests, headrests, etc.).
Plastic sheets which are suitable for this particular purpose include
those sheets which are known per se, and have been used in the
manufacture of sheet composite materials by back-foaming plastic sheets
with polyurethane ~oams. Some examples include sheets of polyvinyl
Mo4056
~., .. ;~ . .. . . .
2122~02
- 13 -
chloride (PVC), polyurethane, polymer blends of PVC and ABS, or
thermoplastic polyoleflnes.
-~ The process according to the invention is preferably carried out
such that the internal walls of a mold are lined at least partially with the
. . .
plastic sheet to be back-foamed and the molding tool is then charged
, with the foamable mixture. The sheets used for lining the molds
internally may be preformed in a manner which is known per se, making
- use of the known technique of deep-drawing or "powder slush".
-- The quantity of the foamable mixture introduced into the mold is
~ 10 generally calculated so as to result in foams falling within the gross
; density range set forth hereinabove.
The following examples further illustrate details for the process of
this invention. The invention, which is set forth in the foregoing
disclosure, is not to be limited either in spirit or scope by these exampies.
- 15 Those skilled in the art will readily understand that known variations of
the conditions of the following procedures can be used. Unless otherwise
noted, all percentages are by weight and all temperatures are degrees
celsius. ~ -
i EXAMPLES
Catalvst 1: i
a) Acrylate addition
~; 1 9 powdered potassium hydroxide was dissolved or dispersed, - ~ -
with slight heating, in 1500 g (1.66 OH equivalents) dehydrated polyether ;
alcohol, OH number 62, prepared from butanol and EO. At 35 to 40C,
319 g (2.49 mole) t-butyl acrylate were added dropwise to this over a
period of 2 hours, with continuous stirring for 5 hours at 40C. After this,
.
the catalyst was neutralized with a 37%-concentration of hydrochloric
acid, and excess t-butyl acrylate was distilled in a water jet vacuum until
i the sump temperature reached 80C. The resulting intermediate product
`~ Mo4056
:!
- ~ ~
. . .
..
`~-. - -. : - - .
` - .
~ . ............................ . . .; .
,;.............................. . - :.
,. . :
;, . .
2~%25~2
- 14-
had a hydroxyl number of 6.8. This corresponded to a 90% conversion
,
of the hydroxyl groups present initially. An ester equivalent weight of
1134.4 was calculated from this. The hydroxyl functionality of the
; reaction product was around zero.
; 5 b) Hvdrolysis
1700 9 of product (1.5 ester equivalents) from 1a), 1700 ml water
and 29.6 ml (0.3 mole) 37%-concentration hydrochloric acid were stirred
at 95C until distillation of t-butanol was complete. The dilute
hydrochloric acid was then distilled off in a water jet vacuum until a
maximum sump temperature of 80C was reached. The resulting ether
acid had an acid number of 53.2. This corresponded to a carboxyl
equivaient weight of 1054.5.
c) Neutralization
1400 9 (1.33 acid equivalents) of intermediate product according
to 1b) were neutralized by drop-wise addition of 141.4 9 (1.26 mole) of a
~, 50%-concentration potassium hydroxide solution (degree of neutralization
' 95%, calculated on acid equivalents), with the intemal temperature held
- between 25 and 35C by cooling. An 80%-concentration solution was
-~, then formed by the addition of the calculated quantity of water. The
;.~ 20 resultant product had a viscosity of 130 mPa-s/25C and a base number
of 42. This gave a carboxylate equivalent weight of 1335.
CatalYst 2:
. a) Acrvlate addition
~ In a manner similar to that set forth in Example 1a), 1500 9 (7.14
!'~ 25 Otl equivalents) of polyether diol, OH number 265, was prepared from
propylene glycol and PO, and 1371 9 (10.71 mole) t-butyl acrylate were
reacted in the presence of 4 9 powdered potassium hydroxide. The
resulting intermediate product had a hydroxyl number of 23.4. This
corresponded to 87% conversion of the hydroxyl groups present initially.
',``
Mo4056
:
. ~ . . . . - .,
. .- - .
. . -
,.;.. ; , , ., . - . .
.,. .:: . , .
,',3,:,: : '
".,
,-. . ' ' , . .
~ 212~5~2
- 15-
This gave an ester equivalent weight of 370.4. The hydroxyl functionality
of the reaction product was around 0.25.
- b~ Hydrolysis
In a manner similar to that set forth in Example 1b), 2340 g (6.32
ester equivalents) of intermediate product according to 2a), 2340 g water
and 124.6 g (1.26 mole) of 37%-concentration hydrochloric acid were
reacted with the addition of 500 ml of dioxane. The resulting etheric acid
had an acid number of 187.4. This corresponded to a carboxyl
: equivalent weight of 299.4.
c) Neutralization
1712 g (5.72 acid equivalents) of intermediate product produced
according to 2b) were neutralized with 449 g (4.01 mole) of a 50%-
concentration potassium hydroxide solution (degree of neutralization was
70%, calculated on acid equivalents), and a solids content of 80% was
1~ formed by the addition of water. The resulting product had a viscosity of
`, 360 mPa-s/25C and a base number of 102.5. This gave a carboxylate
, equivalent weight of 547.3.
~, CatalYst 3:
a) Acrylate addition ~-
9 20 In a manner similar to that set forth in Example 1a~, 1500 9 (14.71
OH equivalents3 of polyether triol, OH number 550, were prepared from
trimethylolpropane and PO, and 659 9 (5.15 mole) t-butyl acrylate were
reacted in the presence of 8.2 g powdered potassium hydroxide. The
'I resulting intermediate product had a hydroxyl number of 272.1. This
corresponded to a 31% conversion of the hydroxyl groups present
initially. This gave an ester equivalent weight of 455.2. The hydroxyl
functionality of the reaction product was around 2.07.
.
Mo4056
:
.
2 ~ 2 ~
- 16-
b) HvdrolYsis
In a manner similar to that of Example 1b), 2040 9 (4.48 ester
equivalents) of intermediate product from 3a), 2040 9 water and 88 g (0.9
- mole) of 37%-concentration hydrochloric acid were reacted. The
5 resulting etheric acid had an acid number of 104. This corresponded to
a carboxyl equivalent weight of 539.4.
c) Neutralization
1474 9 (2.73 acid equivalents) of intermediate product from 3b)
were neutralized with 307 g ~2.73 mole) of a 50%-concentration
10 potassium hydroxide solution (degree of neutralization 100%, calculated
on acid equivalents), and a solids content of 80% was formed by the
addition of water. The resulting product has a viscosity of 500
mPa~s/25C and a base number of 75.6. This gave a carboxylate
equivalent weight of 742.1.
15 CatalYst 4
. a) Acrylate addition
:.i '
~. In a manner similar to that set forth in Example 1a), 1500 9 (12
:~ OH equivalents) of polyether polyol, OH number 450 and having a
functionality of 6, prepared from sorbitol and PO, and 829 9 (6.48 mole)
20 t-butyl acrylate were reacted in the presence of 6.7 9 powdered
potassiurn hydroxide. The resulting intermediate product had a hydroxyl
number of 157. This corresponded to 48% conversion of the hydroxyl
groups present initially. This gave an ester equivalent weight of 389.1.
The hydroxyl functionality of the reaction product was around 3.12.
25 b) HYdrolysis
In a manner similar to Example 1b), 2030 g (5.22 ester
equivalents) of intermediate product according to 4a), 2030 g water and
103 g (1.04 mole) of a 37%-concentration hydrochloric acid were reacted.
Mo4056
,
,. .,,, ~ ~
~;
.- , . .
` ~
c ~
2~225~2
- 17 -
The resulting etheric acid had an acid number of 145.3. This
corresponded to a carboxyl equivalent weight of 386.1.
c) Neutralization
1569 9 (4.06 acid equivalents) of intermediate product from 4b)
were neutralized with 387.4 9 (3.45 mole) of a 50%-concentration
potassium hydroxide solution (degree of neutralization 85%, calculated
on acid equivalents~, and a solids content of 80% was formed by the
addition of water. The resulting product had a viscosity of 540
mPa-s/25C and a base number of 97.7. This gave a carboxylate -
equivalent weight of 574.2.
;
: Catalvst 5
:, .
a) Acrvlate addition
In a manner similar to Example 1a), 224 g (1 OH equivalent) of -
polyether triol, OH number ~50, prepared from trimethylolpropane, 1.1%
PO and 98.9% EO, and 192 9 (1.5 mole) t-butyl acrylate were reacted in
~, the presence of 1.2 9 of powdered potassium hydroxide. The resulting
intermediate product had a hydroxyl number of 33.2. This corresponded
~, to a 81% conversion of the hydroxyl groups present initially. This gave
' an ester equivalent weight of 405.8. The hydroxyi functionality of the -
~`~ 20 reaction product was around 2Ø
b) Hvdrolvsis
In a manner similar to that of Example 1b), 250 9 (0.62 ester
equivalents) of intermediate product according to 5a) and 113 9 (0.31
,~ mole) of a 10%-concentration hydrochloric acid were reacted. The` 25 resulting etheric acid had an acid number of 144. This corresponded to
a carboxyl equivalent weight of 389.6.
, .
,,
. .
Mo4056
,
~.
. . .
~ 2~2~2
~ - 18-
: c) Neutralization
,~ .
190 g (0.49 acid equivalents) of intermediate product according to
5b) were neutralized with 38.1 g (0.34 mole) of 50%-concentration
potassium hydroxide solution ~degree of neutralization 69%, calculated
5 on acid equivalents), and a solids content of 80% was formed by tha
addition of water. The resulting product had a viscosity of 390
mPa-s/25C and a base number of 75.4. This gave a carboxylate
equivalent weight of 744.
~,-
preparation of polv-formu!ations accordina to the invention
.110 100 parts by weight of a polyether polyol of OH number 28,
`~ prepared by propoxylating trimethylolpropane followed by ethoxylating the
propoxylation product (weight ratio of PO: EO = 85: 15) were mixed
i~ with catalyst in two parallel experiments. In each case, these mixtures
were then mixed with water, so that the mixture contained 3.2 parts by
. 15 weight of water.
The catalyst concentrations were in all examples selected such
that approximately identical rise times resulted (i.e. 150 + 10 sec.).
PolYisocvanate component
A polyisocyanate mixture of the diphenylmethane series having a
20 viscosity (23C) of 200 rnPa.s and an NCO content of 32 wt-%
obtained by phosgenation of an aniline-forrnaldhyde-condensate
`i consisting of a mixture of 50 wt-% of monomeric MDI-isomers and
of 50 wt-% of higher horno3Ogs thereof was used in the exarnples which follow
Examples accordinq to the invent on and Comparative Examples
The foams were prepared using the hand foaming method. In this
method, all components, with the exception of the polyisocyanate
25 component, were pre-stirred (1,000 rpm) for 30 sec. The polyisocyanate
.' component was then added, and stirring continued for a further 10 sec.
at 25C. The NCO index in all examples was 100.
:
Mo4056
.. ~
- 19- 2122~0 ~
Th0 initiation, rise and setting times were determined, with the
poiyol formuiation being combined with the polyisocyanate component in
a 660 ml cardboard beaker, while stirring at 25C. The initiation time was
the time which elapsed from the ~ime of polyisocyanate addition to the
commencement of foaming; the rise time was the time which elapsed
from poiyisocyanate addition to the termination of foaming; the setting
; time was the time which elapsed from polyisocyanate addition until the
foam ceased to be tacky.
!.' Example A was according to the invention, using 8.0 parts by
weight of catalyst 1.
'; Example B was according to the invention, using 4.0 parts by
weight of catalyst 2. -
Example C was according to the invention, using 4.0 parts by
weight of catalyst 3.
~ 15 Example D was according to ~he invention, using 4.0 parts by
:~ weight of catalyst4.
Example E was acccrding to the invention, using 3.75 parts by
weight of catalyst 5.
Example F was a Comparative Example, and followed the same
procedure as Example A, except that the catalyst according to the
invention was replaced by 0.3 parts by weight of potassium acetate.
Example G is a Comparative Example, and followed the same
procedure as Example A, except that the catalyst according to the
invention was replaced by 0.3 parts by weight N,N,N',N'-tetramethyi
~ 25 hexamethylenediamine.
`.
Mo4056
-.i, '
~i
~,
~ - ~ . i -
, : ' :
.
-, . .
:
~ -20- 2~22~;~2
,- Example A B C D E F G
:
Initiation
::` time (s) 15 17 18 34 24 18 15
,. ,
Rise time
.~, 5 (s) 142 140 155 157 135 161 141
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
-: 1û the invention except as it may be limited by the claims.
~'
`~:
`:
" ,
, .,
, .
- ~ .
Mo4056
~ . ~
,
, , , ~
,~ ~, . .
