Preparation of cellular polyurethane elastomers using polyether carbonate diols as a starting component

A process for the preparation of cellular polyurethane elastomers involves reacting PA1 a) an organic and/or modified organic polyisocyanate with PA1 b) a polyether polycarbonate diol which contains bonded polyoxytetramethylene glycol radicals having a mean molecular weight Mn (number average) of from 150 to 500, and, if desired, PA1 c) a low-molecular-weight chain extender and/or crosslinking agent, in the presence of PA1 d) a blowing agent, PA1 e) a catalyst and PA1 f) if desired additives and/or assistants.

The present invention relates to a process for the preparation of cellular 
polyurethane elastomers, also abbreviated to PU elastomers below, using a 
polyether polycarbonate diol which contains bonded polyoxytetramethylene 
glycol radicals having a mean molecular weight Mn (number average) of from 
150 to 500. 
The preparation of cellular PU elastomers by reacting organic 
polyisocyanates with organic polyhydroxyl compounds in the presence of 
catalysts and possibly chain extenders and/or crosslinking agents and 
blowing agents, assistants and/or additives is known. A suitable choice of 
the hydroxyl-containing polyesters, polyethers, polyester amides, inter 
alia, and organic polyisocyanates and the additional use of chain 
extenders, for example glycols, trihydric alcohols and/or diamines, allows 
both elastic and rigid, cellular PU elastomers and all modifications 
between the two to be prepared by this method. 
The preparation of PU elastomers, their mechanical properties and their use 
are described, for example, in High Polymers, Volume XVI, Polyurethanes, 
parts I and II, by I. H. Saunders and K. C. Frisch (Interscience 
Publishers, New York, 1962 and 1964 respectively) and in 
Kunststoff-Handbuch, Volume VII, Polyurethane, 1966 and 1983 by Dr. R. 
Vieweg and Dr. A. Hochtlen, and Dr. G. Oertel respectively 
(Carl-Hanser-Verlag, Munich). 
Cellular PU elastomers, due to their excellent vibration- and 
shock-absorbing properties, are used, for example, in the automotive 
industry to improve the driving stability of motor vehicles and in the 
shoe industry as a sole material or as shoe cores. It is desired that the 
good mechanical properties of PU elastomers of this type can be used over 
a very wide temperature range and are also retained as the temperature 
drops. 
Hitherto, the soft phase used in cellular PU elastomers was usually a 
polyether-polyol or a polyesterpolyol. Thus, U.S. Pat. No. 4,423,205 and 
U.S. Pat. No. 4,456,745 describe the preparation of polyurethanes using 
RIM technology, in which polycarbonate diols made from cyclic carbonates 
are employed. Polyurethanes prepared from poly(tetramethylene ether) 
glycol having a narrow molecular weight distribution are described in 
EP-A-167,292. Although polyurethanes which contain, as diol component, a 
polyether polycarbonate diol are described in U.S. Pat. No. 4,463,141, the 
mean molecular weight Mn (number average) of the polyoxytetramethylene 
diol employed is, however, greater than 500. Polyether polycarbonate diols 
which contain aromatic structural units are mentioned in DE-A-2 726 416. 
EP-A-335 416 describes a carbonate-modified polyoxytetramethylene glycol 
and its preparation. 
PU elastomers based on polyesters polyols are usually not resistant to 
microorganisms. Replacement of polyester-polyols by microbe-resistant 
polyether-polyols results in impairment of the mechanical properties, in 
particular at low temperatures. 
It is an object of the present invention to develop cellular PU elastomers 
which have improved mechanical properties, in particular significantly 
increased elongation at break, at room temperature and at lower 
temperatures. 
We have found that, surprisingly, this object is achieved by using specific 
polyether polycarbonate diols as the soft phase for the preparation of 
cellular PU elastomers. 
The invention accordingly provides a process for the preparation of a 
cellular polyurethane elastomer by reacting 
a) an organic and/or modified organic polyisocyanate with 
b) at least one relatively high-molecular-weight polyhydroxyl compound and, 
if desired, 
c) a low-molecular-weight chain extender and/or crosslinking agent, 
in the presence of 
d) a blowing agent, 
e) a catalyst and 
f) if desired additives and/or assistants, 
wherein the relatively high-molecular-weight polyhydroxyl compound (b) is a 
polyether polycarbonate diol prepared by polycondensing 
b1) a polyoxytetramethylene glycol having a mean molecular weight Mn 
(number average) of from 150 to 500 or 
b2) a mixture comprising 
b2i) at least 10 mol-%, preferably from 50 to 95 mol-%, of the 
polyoxytetramethylene glycol (b1) and 
b2ii) less than 90 mol-%, preferably from 5 to 50 mol-%, of at least one 
polyoxyalkylene diol, other than (b1), comprising an alkylene oxide having 
2 to 4 carbon atoms in the alkylene radical, at least one linear or 
branched alkanediol having 2 to 14 carbon atoms or at least one cyclic 
alkanediol having 3 to 15 carbon atoms or a mixture of at least two of 
said diols (b2ii) 
with 
b3) phosgene, diphenyl carbonate or a dialkyl carbonate containing C.sub.1 
- to C.sub.4 -alkyl groups. 
The invention furthermore provides a process for the production of PU 
elastomer moldings, preferably shock absorbers, by a process as claimed in 
claim 1. 
The cellular PU elastomers prepared by the process according to the 
invention have improved mechanical properties, in particular very good 
elongation at break. The good processing properties of the PU formulations 
in low-pressure processes is furthermore noteworthy. 
The following applies to the starting components (a), (b), (d), (e) and, if 
used, (c) and (f) which can be used for the process according to the 
invention for the preparation of cellular PU elastomers: 
a) Suitable organic polyisocyanates are conventional aliphatic, 
cycloaliphatic, araliphatic and preferably aromatic polyisocyanates. 
The following may be mentioned as specific examples: alkylene diisocyanates 
having 4 to 12 carbon atoms in the alkylene moiety, such as 1,12-dodecane 
diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate, 
2-methylpentamethylene 1,5-diisocyanate, tetramethylene 1,4-diisocyanate 
and preferably hexamethylene 1,6-diisocyanate; cycloaliphatic 
diisocyanates, such as cyclohexane 1,3- and 1,4-diisocyanate and any 
desired mixtures of these isomers, 
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone 
diisocyanate), 2,4- and 2,6-hexahydrotolylene diisocyanate and 
corresponding isomer mixtures, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane 
diisocyanate and the corresponding isomer mixtures, and preferably 
aromatic diisocyanates, for example 2,4- and 2,6-tolylene diisocyanate and 
the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-diphenylmethane 
diisocyanate and the corresponding isomer mixtures, mixtures of 4,4'- and 
2,4'-diphenylmethane diisocyanates and in particular 4,4'-diphenylmethane 
diisocyanate and 1,5-naphthylene diisocyanate. The organic diisocyanates 
may be employed individually or in the form of mixtures. 
Suitable organic polyisocyanates are also modified polyisocyanates, i.e. 
products obtained by chemical reaction of organic polyisocyanates. Mention 
may be made, for example, of ester-, urea-, biuret-, allophanate-, 
carbodiimide- and/or urethane-containing diisocyanates and/or 
polyisocyanates. Specific examples are the following: urethane-containing 
organic, preferably aromatic, polyisocyanates containing from 33.6 to 14% 
by weight, preferably from 28 to 16% by weight, based on the total weight, 
of NCO, for example 4,4'-diphenylmethane diisocyanate or 2,4- or 
2,6-tolylene diisocyanate modified by means of low-molecular-weight diols, 
triols, dialkylene glycols, trialkylene glycols or polyoxyalkylene glycols 
having molecular weights of up to 3000, specific examples of di- and 
polyoxyalkylene glycols, which may be employed individually or as 
mixtures, being diethylene glycol, dipropylene glycol, dibutylene glycol, 
polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene 
glycol and polyoxypropylene polyoxyethylene glycol. Also suitable are 
NCO-containing prepolymers containing from 14 to 2.5% by weight, 
preferably from 9 to 3.0 % by weight, based on the total weight, of NCO 
and prepared from the polyoxyalkylene glycols mentioned above preferably 
from the polyether polycarbonate diols which can be used according to the 
invention and are described below and 4,4'-diphenylmethane diisocyanate, 
mixtures of 2,4'- and 4,4'-diphenylmethane diisocyante, 2,4- and 
2,6-tolylene diisocyanates or 1,5-naphthylene diisocyanates. Furthermore, 
liquid carbodiimide-containing polyisocyanates containing from 33.6 to 15% 
by weight, preferably from 31 to 21% by weight, based on the total weight, 
of NCO, for example based on 4,4'-, 2,4'- and/or 2,2'-diphenylmethane 
diisocyanate and/or 2,4- and 2,6-tolylene diisocyanate, have proven 
successful. 
The modified polyisocyanates can, if desired, be mixed with one another or 
with unmodified organic polyisocyanates, for example 2,4'- and/or 
4,4'-diphenylmethane diisocyanate and/or 2,4- and/or 2,6-tolylene 
diisocyanate, but the functionality of the polyisocyanate mixture obtained 
is at most 3, preferably from 2 to 2.6, in particular from 2.0 to 2.4. 
Organic polyisocyanates which have proven particularly successful and are 
therefore preferred are 1,6-hexamethylene diisocyanate, isophorone 
diisocyanate and in particular 4,4'-diphenylmethane diisocyanate and 
1,5-naphthylene diisocyanate, and liquid urethane-, carbodiimide- or 
urethane- and carbodiimide-modified polyisocyanates based on mixtures of 
4,4'- and 2,4'-diphenylmethane diisocyantes and in particular on 
4,4'-diphenylmethane diisocyanate. 
b) The relatively high-molecular-weight polyhydroxyl compound (b) comprises 
at least one polyether polycarbonate diol prepared by polycondensing 
b1) a polyoxytetramethylene glycol having a mean molecular weight Mn 
(number average) of from 150 to 500, preferably from 150 to 400, in 
particular from 200 to 350, or 
b2) a mixture comprising 
b2i) at least one polyoxytetramethylene glycol (b1) and 
b2ii) at least one polyoxyalkylene diol, other than (b1), having a 
molecular weight of from 150 to 2000, preferably from 500 to 2000, 
prepared, for example, by anionic polymerization in the presence of an 
alkali metal hydroxide or alkoxide as basic catalyst and with addition of 
at least one difunctional initiator molecular or by cationic 
polymerization using a Lewis acid or bleaching earth as catalyst from one 
or more alkylene oxides having 2 to 4 carbon atoms in the alkylene moiety, 
for example 1,3-propylene oxide, 1,2- or 2,3-butylene oxide or preferably 
ethylene oxide, 1,2-propylene oxide or tetrahydrofuran, 
at least one linear or branched alkanediol having 2 to 14 carbon atoms, 
preferably 2 to 6 carbon atoms, or 
at least one cyclic alkanediol having 3 to 15 carbon atoms, preferably 5 
to 8 carbon atoms, or a mixture of at least two of said diols (b2ii) in 
the abovementioned (b2i):(b2ii) mixing ratios, with 
b3) phosgene, diphenyl carbonate or a dialkyl carbonate containing C.sub.1 
- to C.sub.4 -alkyl groups. 
The polyoxytetramethylene glycol (b1) can be prepared by conventional 
methods, for example by cationic polymerization of tetrahydrofuran. 
In order to modify the mechanical properties of the PU elastomers and the 
polyether polycarbonate diols, they can also be prepared using mixtures of 
(b2i) and the diols (b2ii). 
The polyoxyalkylene diol which is different from (b1) is preferably a 
polyoxytetramethylene glycol having a molecular weight of greater than 
500, in particular from 650 to 2000. However, suitable compounds are also 
polyoxyethylene glycol, polyoxypropylene glycol, 
polyoxypropylenepolyoxyethylene glycol, 
polyoxytetramethylenepolyoxypropylene glycol and 
polyoxytetramethylenepolyoxyethylene glycol. 
Examples of suitable linear or branched alkanediols are ethanediol, 1,3- 
and 1,2-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3- and 
1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 
1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol. Furthermore, cyclic 
alkanediols, for example 1,4-dihydroxycyclohexane, 
1,4-di(hydroxymethyl)cyclohexane and 4,4'-dihydroxydicyclohexylmethane, 
have proven suitable. 
The diols (b2ii) can be used individually or in the form of mixtures. 
The polyether polycarbonate diol is preferably prepared using a 
polyoxytetramethylene diol (b1). However, if mixtures of (b1) and (b2ii) 
are used as described above, they contain at least 10 mol-%, preferably 
from 50 to 95 mol-%, in particular from 60 to 90 mol-%, of (b1), based on 
(b1) and (b2ii). 
Component b3) may be phosgene in pure or technical-grade form or diluted 
with a gas which is inert under the condensation conditions. Preferred 
carbonates are dialkyl carbonates containing C.sub.1 - to C.sub.4 - alkyl 
groups, in particular dimethyl carbonate, diethyl carbonate and dipropyl 
carbonate. Diphenyl carbonate is also suitable. It is also possible to use 
mixtures of the carbonates. 
The mixing ratio between the polyoxytetramethylene diol b2i), with, if 
used, further diols b2ii), and the carbonate component b3) depends on the 
desired molecular weight of the polyether polycarbonate diol and on the 
carbonate component employed. 
In some cases, losses of the carbonate employed occur during the reaction, 
and this must thus be employed in relatively large amounts. In the case of 
phosgene, the excess depends on the amount of phosgene expelled with the 
hydrochloric acid formed and in the particularly preferred case of dialkyl 
carbonates on whether the carbonate employed forms an azeotrope with the 
alcohol produced on transesterification, the excess being from 0.5 to 50 
mol-%, preferably from 5 to 35 mol-%. 
The reaction of b1), if desired mixed with b2ii), with the carbonate 
component is preferably carried out in the presence of a catalyst. 
Catalysts which can be used are conventional transesterification catalysts, 
for example tetraisopropyl orthotitanate, dibutyltin oxide, dibutyltin 
dilaurate and zirconium(IV) acetylacetonate, and alkali metal alkoxides, 
for example sodium methoxide, sodium ethoxide and potassium ethoxide. The 
amount of catalyst is from 0.001 to 2%, preferably from 0.01 to 0.5%, 
based on the total amount of starting materials. 
The reaction components are preferably heated to the boil with the 
catalyst. If a dialkyl carbonate is used, the corresponding alcohol or 
carbonate/alcohol azeotrope formed during the reaction can be removed by 
distillation. The transesterification is generally carried out at from 
20.degree. to 250.degree. C., preferably at from 40.degree. to 200.degree. 
C. If phosgene is used, the reaction can be carried out at from 0.degree. 
to 100.degree. C., preferably at from 20.degree. to 80.degree. C. In this 
case, a base, for example pyridine or triethylamine, is preferably added 
to the reaction mixture in order to neutralize the hydrochloric acid 
formed. 
If the catalyst used is an alkali metal alkoxide, a reaction temperature of 
from 20.degree. to 150.degree. C., in particular from 40.degree. to 
80.degree. C., is preferred, and the catalyst is removed by neutralization 
with an acid, such as phosphoric acid, and removal of the precipitated 
alkali metal salt of the particular acid. 
If the catalyst used is tetraisopropyl orthotitanate, a reaction 
temperature of from 40.degree. to 250.degree. C., in particular from 
100.degree. to 200.degree. C., is preferred, and the excess catalyst can 
be deactivated when the reaction is complete, for example by adding 
phosphoric acid. 
Thee reaction can be carried out at atmospheric pressure, under reduced 
pressure or under superatmospheric pressure. A reduced pressure of from 
0.1 to 5 mbar is usually applied at the end of the reaction in order to 
remove the final residues of low-boiling components. The reaction is 
complete when no further low-boiling components distil over. 
The polyether polycarbonate diol produced has a mean molecular weight Mn 
(number average) of from 800 to 8000, preferably from 1200 to 6000, in 
particular from 1800 to 4200. 
c) The cellular PU elastomer can be prepared in the presence or absence of 
a chain extender and/or crosslinking agent. However, to modify the 
mechanical properties, for example the hardness, elasticity, inter alia, 
the addition of a chain extender, crosslinking agent or if desired a 
mixture of the two may prove advantageous. The chain extender and/or 
crosslinking agent used is a diol and/or triol having a molecular weight 
of less than 400, preferably from 60 to 300. Examples of suitable 
compounds are aliphatic, cycloaliphatic and/or araliphatic diols having 2 
to 14, preferably 4 to 10, carbon atoms, for example ethylene glycol, 
1,3-propanediol, 1,10-decanediol, o-, m- and p-dihydroxycyclohexane, 
diethylene glycol, dipropylene glycol and preferably 1,4-butanediol, 
1,6-hexanediol and bis(2-hydroxyethyl)hydroquinone, triols, such as 1,2,4- 
and 1,3,5-trihydroxycyclohexane, glycerol and trimethylolpropane, and 
low-molecular-weight hydroxyl-containing polyalkylene oxides based on 
ethylene oxide and/or 1,2-propylene oxide, and the abovementioned diols 
and/or triols as initiator molecules. 
The cellular PU elastomer can also be prepared using secondary aromatic 
diamines, primary aromatic diamines, 3,3'-di- and/or 
3,3',5,5'-tetraalkyl-substituted diaminodiphenylmethanes in addition to 
the abovementioned diols and/or triols or mixed with these as chain 
extender or crosslinking agent. 
Examples of secondary aromatic diamines are N,N'-dialkyl-substituted 
aromatic diamines, which may also be substituted on the aromatic ring by 
alkyl radicals, having 1 to 20, preferably 1 to 4, carbon atoms in the 
N-alkyl radical, such as N,N'-diethyl-, N,N'-di-sec-pentyl-, 
N,N'-di-sec-hexyl-, N,N'-di-sec-decyl-, N,N'- dicyclohexyl-p- or 
-m-phenylenediamine, N,N'-dimethyl-, N,N'-diethyl-, 
N,N'-diisopropyl-,N,N'-di-sec-butyl-, 
N,N'-dicyclohexyl-4,4'-diaminodiphenylmethane and 
N,N'-di-secbutylbenzidine. 
The aromatic diamines used are expediently those which contain at least one 
alkyl substituent in the ortho-position to the amino groups, are liquid at 
room temperature and are miscible with the polyether polycarbonate diols. 
Furthermore, alkyl-substituted meta-phenylenediamines of the formulae 
##STR1## 
where R.sup.3 and R.sup.2 are identical or different methyl, ethyl, propyl 
or isopropyl radicals, and R.sup.1 is linear or branched alkyl having 1 to 
10, preferably 4 to 6, carbon atoms have proved successful. 
Particular success has been achieved using alkyl radicals R.sup.1 in which 
the branching point is on the C.sup.1 carbon atom. Examples of radicals 
R.sup.1 are methyl, ethyl, isopropyl, 1-methyloctyl, 2-ethyloctyl, 
1-methylhexyl, 1,1-dimethylpentyl, 1,3,3-trimethylhexyl, 1-ethylpentyl, 
2-ethylpentyl and preferably cyclohexyl, 1-methyl-n-propyl, tert-butyl, 
1-ethyl-n-propyl, 1-methyl-n-butyl and 1,1-dimethyl-n-propyl. 
Examples of suitable alkyl-substituted m-phenylenediamines are 
2,4-dimethyl-6-cyclohexyl-, 2-cyclohexyl-4,6-diethyl-, 
2-cyclohexyl-2,6-isopropyl-, 2,4-dimethyl-6-(1-ethyl-n-propyl)-, 
2,4-dimethyl-6-(1,1-dimethyl-n-propyl)- and 
2-(1-methyl-n-butyl)4,6-dimethyl-1,3-phenylenediamine. Preference is given 
to 1-methyl-3,5-diethyl-2,4- and -2,6-phenylenediamines, 
2,4-dimethyl-6-tert-butyl-, 2,4-dimethyl-6-isooctyl- and 
2,4-dimethyl-6-cyclohexyl-1,3-m-phenylenediamine. 
Examples of suitable 3,3'-di- and 3,3',5,5'-tetra-n-alkyl-substituted 
4,4'-diaminodiphenylmethanes are 3,3'-di-, 3,3',5,5'-tetramethyl-, 
3,3'-di-, 3,3',5,5'-tetraethyl-, 3,3'-di- and 
3,3',5,5'-tetra-n-propyl-4,4'-diaminodiphenylmethane. 
Preference is given to diaminodiphenylmethanes of the formula 
##STR2## 
where R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are identical or different and 
are methyl, ethyl, propyl, isopropyl, sec-butyl or tert-butyl, but where 
at least one of the radicals must be isopropyl or sec-butyl. 
4,4'-Diaminodiphenylmethanes can also be used mixed with isomers of the 
formulae 
##STR3## 
where R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as defined above. 
Preference is given to 3,5-dimethyl-3',5'-diisopropyl- and 
3,3',5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane. The 
diaminodiphenylmethanes can be employed individually or in the form of 
mixtures. 
Said chain extenders and/or crosslinking agents (c) can be used 
individually or as mixtures of identical or different types of compound. 
The chain extender, crosslinking agent or mixture thereof is expediently 
used, if at all, in an amount of from 2 to 60% by weight, preferably from 
8 to 50% by weight, in particular from 10 to 40% by weight, based on the 
weight of the polyether polycarbonate diol (b) plus (c). 
d) The preferred blowing agent (d) is water, which reacts with the organic, 
modified or unmodified polyisocyanates (a) to form carbon dioxide and urea 
groups, thus affecting the compressive strength of the end product. The 
water is usually used in an amount of from 0.05 to 6% by weight, 
preferably from 0.1 to 4% by weight, in particular from 0.15 to 2.5% by 
weight, based on the weight of components (a), (b) and, if used, (c). 
The blowing agent (d) may alternatively be, instead of, or preferably in 
combination with, water, a low-boiling liquid which evaporates under the 
conditions of the exothermic polyaddition reaction and advantageously has 
a boiling point of from -40.degree. to 120.degree. C., preferably from 10 
to 90.degree. C., at atmospheric pressure, or a gas. 
The liquids of the abovementioned type and gases which are suitable as 
blowing agents may be selected, for example, from the group comprising the 
alkanes, which advantageously have 3 to 5 carbon atoms, e.g. propane, n- 
and isobutane, n- and isopentane and preferably technical-grade pentane 
mixtures, cycloalkanes, which advantageously have 4 to 6 carbon atoms, 
e.g. cyclobutane, cyclopentene, cyclohexene and preferably cyclopentane 
and/or cyclohexane, dialkyl ethers, e.g. dimethyl ether, methyl ethyl 
ether and diethyl ether, cycloalkylene ethers, e.g. furan, ketones, e.g. 
acetone and methyl ethyl ketone, carboxylic acid esters, such as methyl 
formate, fluoroalkanes which are degraded in the troposphere and therefore 
do not damage the ozone layer, e.g. trifluoromethane, difluoromethane, 
difluoroethane, tetrafluoroethane and heptafluoroethane, and gases, e.g. 
nitrogen, carbon monoxide and noble gases, e.g. helium, neon and krypton. 
It is furthermore possible to use chlorofluorohydrocarbons, e.g. 
trichlorofluoromethane and trichlorotrifluoroethane. 
The most expedient amount of low-boiling liquid or gas, which can in each 
case be employed individually or as a mixture of liquids or a mixture of 
gases or as a mixture of gases and liquids, depends on the desired density 
and the amount of water employed. The necessary amount can easily be 
determined by simple preliminary experiments. Satisfactory results are 
usually given by amounts of from 0.5 to 20 parts by weight, preferably 
from 2 to 10 parts by weight, of liquid and from 0.01 to 30 parts by 
weight, preferably from 2 to 20 parts by weight, of gas, in each case 
based on 100 parts by weight of components (a), (b) and, if used, (c). 
e) The catalyst (e) used for the preparation of the PU elastomer is, in 
particular, a compound which greatly accelerates the reaction of the 
hydroxyl-containing compounds of component (b) and, if used, (c) with the 
organic, modified or unmodified polyisocyanates (a). Suitable catalysts 
are organometallic compounds, preferably organotin compounds, such as 
tin(II) salts of organic carboxylic acids, e.g. tin(II) diacetate, tin(II) 
dioctanoate, tin(II) diethylhexanoate and tin(II) dilaurate, and the 
dialkyltin(IV) salts of organic carboxylic acids, e.g. dibutyltin 
diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin 
diacetate. The organometallic compounds are employed individually or 
preferably in combination with highly basic amines. Examples are amidines, 
such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines, such 
as triethylamine, tributylamine , dimethylbenzylamine, N-methyl-, N-ethyl- 
and N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine, 
N,N,N',N'-tetramethylbutanediamine, pentamethyldiethylenetriamine, 
tetramethyldiaminoethyl ether, bis(dimethylaminopropyl)urea, 
dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo[3.3.0]octane and 
preferably 1,4-diazabicyclo[2.2.2]octane, and alkanolamine compounds, such 
as triethanolamine, triisopropanolamine, N-methyl- and 
N-ethyldiethanolamine and dimethylethanolamine. 
f) The cellular PU elastomer may also be prepared in the presence of 
additives and/or assistants (f). 
Examples of additives and assistants which may be mentioned are 
surfactants, foam stabilizers, cell regulators, lubricants, fillers, dyes, 
pigments, crystalline, microporous molecular sieves, flameproofing agents, 
hydrolysis stabilizers, and fungistatic and bacteriostatic substances. 
Examples of surfactants are compounds which support homogenization of the 
starting materials and may also be suitable for regulating the cell 
structure. Examples which may be mentioned are emulsifiers, such as the 
sodium salts of castor oil sulfates or of fatty acids, and salts of fatty 
acids with amines, e.g. diethylamine oleate, diethanolamine stearate and 
diethanolamine ricinoleate, salts of sulfonic acids, e.g. alkali metal 
salts or ammonium salts of dodecylbenzene- or dinaphthylmethanedisulfonic 
acid and ricinoleic acid; foam stabilizers, such as siloxane-oxyalkylene 
copolymers and other organopolysiloxanes, oxyethylated alkylphenols, 
oxyethylated fatty alcohols, paraffin oils, castor oil esters, ricinoleic 
acid esters, Turkey red oil and groundnut oil, and cell regulators, such 
as paraffins, fatty alcohols and dimethylpolysiloxanes. Suitable compounds 
for improving the emulsification action and the cell structure and/or for 
stabilizing the foam are furthermore oligomeric polyacrylates containing 
polyoxyalkylene and fluoroalkane radicals as side groups. The surfactants 
are usually used in amounts of from 0.01 to 5 parts by weight, based on 
100 parts by weight of component (b). 
A particularly successful lubricant is a ricinoleic acid polyester having a 
molecular weight of from 1500 to 3500, preferably from 2000 to 3000, which 
is expediently employed in an amount of from 0.5 to 10% by weight, 
preferably from 5 to 8% by weight, based on the weight of component (b) or 
of components (b) and (c). 
For the purposes of the present invention, fillers, in particular 
reinforcing fillers, are conventional organic or inorganic fillers, 
reinforcing agents, weighting agents, agents for improving the abrasion 
behavior in paints, coating agents, etc. Specific examples are inorganic 
fillers, such as silicate minerals, for example phyllosilicates, such as 
antigorite, serpentine, hornblends, amphiboles, chrysotile, and talc; 
metal oxides, such as kaolin, aluminum oxides, aluminum silicate, titanium 
oxides and iron oxides, metal salts, such as chalk, baryte and inorganic 
pigments, such as cadmium sulfide, zinc sulfide and glass particles. 
Examples of suitable organic fillers are carbon black, melamine, 
colophony, cyclopentadienyl resins and graft polymers. 
The inorganic or organic fillers may be used individually or as mixtures 
and are advantageously introduced into the reaction mixture in amounts of 
from 0.5 to 50 % by weight, preferably from 1 to 40% by weight, based on 
the weight of components (a) to (c). 
In order to produce PU elastomer moldings having an essentially pore-free, 
smooth surface when water or a water-containing physical blowing agent is 
used, it has proven particularly expedient to add a crystalline, 
microporous molecular sieve having a cavity diameter of less than 1.3 nm, 
preferably less than 0.7 nm, and comprising a metal oxide or metal 
phosphate. Molecular sieves of this type are described in the literature. 
Suitable metal oxides essentially comprise aluminum silicon oxide, boron 
silicon oxide, iron(III) silicon oxide, gallium silicon oxide, 
chromium(III) silicon oxide, beryllium silicon oxide, vanadium silicon 
oxide, antimony(V) silicon oxide, arsenic(III) silicon oxide, titanium(IV) 
silicon oxide, aluminum germanium oxide, boron germanium oxide, aluminum 
zirconium oxide and aluminum hafnium oxide. Specific examples are 
aluminosilicate, borosilicate, iron silicate or gallium silicate zeolites 
having a pentasil structure. Preference is given to mordenite in the H 
form, Na form or ammonium form, offretite in the H form, K form, Na form 
or ammonium form, zeolite ZSM-5 in the H form, Na form or ammonium form, 
zeolite ZSM-11, zeolite ZSM-12, betazeolite, clinopthilolite, ferrierite, 
ultrastable Y-zeolite, ultrastable mordenite or silicalites or mixtures of 
at least 2 of said zeolites. 
Suitable metal phosphates are aluminum phosphates or silicoaluminum 
phosphates, which may additionally contain cations of lithium, beryllium, 
boron, magnesium, gallium, germanium, arsenic, titanium, manganese, iron, 
cobalt or zinc. Examples of metal phosphates of said type are APO, SAPO, 
ELAPO, ELAPSO, MeAPO and MeAPSO. Preference is given to zirconium 
phosphates in the H form, Na form or ammonium form, zirconium phosphate 
silicates, titanium phosphates, VPI-5 and MCM-9. 
The crystalline, microporous molecular sieves having a cavity diameter of 
less than 1.3 nm comprising metal oxides or metal phosphates are usually 
used in an amount of from 1 to 30% by weight, preferably from 5 to 20% by 
weight, in particular from more than 10 to 16% by weight, based on the 
weight of components (b) and, if used, (c). 
Examples of suitable flameproofing agents are tricresyl phosphate, 
tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, 
tris(1,3-dichloropropyl) phosphate, tris(2,3-dibromopropyl) phosphate and 
tetrakis(2-chloroethyl)ethylene diphosphate. 
In addition to the abovementioned halogen-substituted phosphates, it is 
also possible to use inorganic flameproofing agents, such as red 
phosphorus, expandable graphite, aluminum oxide hydrate, antimony 
trioxide, arsenic oxide, ammonium polyphosphate or calcium sulfate, or a 
cyanuric acid derivative, e.g. melamine, or a mixture of two or more 
flameproofing agents, e.g. expandable graphite and ammonium polyphosphate, 
expandable graphite, melamine and ammonium polyphosphate, ammonium 
polyphosphates and melamine and, if desired, starch in order to flameproof 
the moldings produced according to the invention. In general, it has 
proven expedient to use from 2 to 40 parts by weight, preferably from 5 to 
25 parts by weight, of said flameproofing agents or mixtures per 100 parts 
by weight of components (a) to (c). 
Further details on the other conventional assistants and additives 
mentioned above can be obtained from the specialist literature, for 
example from the monograph by J. H. Saunders and K. C. Frisch, High 
Polymers, Volume XVI, Polyurethanes, parts 1 and 2, Interscience 
Publishers 1962 and 1964 respectively, or Kunststoff-Handbuch, 
Polyurethane, Volume VII, Carl-Hanser-Verlag, Munich, Vienna, 1st and 2nd 
editions, 1966 and 1983, respectively. 
To prepare the PU elastomer or produce moldings from a PU elastomer, the 
organic, modified or unmodified polyisocyanate (a), the relatively 
high-molecular-weight compound containing at least two reactive hydrogen 
atoms (b) and, if desired, the low-molecular-weight chain extender and/or 
crosslinking agent are reacted in such amounts that the equivalence ratio 
between the NCO groups of the polyisocyanate (a) and the total number of 
reactive hydrogen atoms in components (b) and, if used, (c) is from 1:0.3 
to 1:2, preferably from 1:0.4 to 1:1.7, in particular from 1:0.9 to 1:1.1. 
The PU elastomer can be prepared or moldings can be produced from the PU 
elastomer by known processes, e.g. by the prepolymer or semiprepolymer 
process or by the one-shot process using the high-pressure or, preferably, 
low-pressure method. Moldings are expediently produced in a closed, 
heatable mold, e.g. a metallic mold, for example made of aluminum, cast 
iron or steel, or a mold made from a fiber-reinforced polyester or epoxy 
resin molding material. Low-viscosity formulations which have good flow 
properties and therefore improved processing properties can also be 
converted into moldings by reaction injection molding (RIM). 
These procedures are described, for example, by Dr. H. Piechota and Dr. H. 
Rohr in Integralschaumstoffe, Carl-Hanser-Verlag, Munich, Vienna, 1975; D. 
J. Prepelka and J. L. Wharton in Journal of Cellular Plastics, March/April 
1975, pages 87 to 98; U. Knipp in Journal of Cellular Plastics, 
March/April 1973, pages 76 to 84, and in Kunststoff-Handbuch, Volume 7, 
Polyurethane, 2nd Edition, 1983, pages 333 ff. 
It has proven particularly advantageous to use the two-component process 
and to combine components (b), (d), (e) and, if used, (c) and (f) in 
component (A) and to use the organic polyisocyanate, the modified 
polyisocyanate (a) or a mixture of said polyisocyanates and, if used, the 
blowing agent (d) as component (B). 
The starting components are mixed at from 15 to 100.degree. C., preferably 
at from 25.degree. to 55.degree. C., and introduced into the open or 
closed mold at atmospheric pressure or superatmospheric pressure. The 
mixing can be effected mechanically using a stirrer or a stirring screw or 
carried out under high pressure by the countercurrent injection method. 
The mold temperature is expediently from 20.degree. to 120.degree. C., 
preferably from 30.degree. to 80.degree. C., in particular from 45.degree. 
to 65.degree. C. If the moldings are to be produced in a closed mold, the 
degree of compaction is in the range from 1.2 to 8.3, preferably from 2 to 
7, in particular from 2.4 to 4.5. 
The amount of reaction mixture introduced into the mold is advantageously 
such that the moldings obtained have an overall density of from 0.1 to 
0.98 g/cm.sup.3, preferably from 0.3 to 0.7 g/cm.sup.3. The addition of 
fillers allows densities of up to 1.2 g/cm.sup.3 or more to be achieved. 
The cellular PU elastomer prepared or the moldings produced from the 
cellular PU elastomer, by the process according to the invention are used, 
for example, in the automotive industry, for example as buffer or spring 
elements and as shock absorbers, and as cycle or motorcycle saddles. They 
are furthermore suitable as fenders and as shoe cores or soles. 
EXAMPLES 
The OH number and the mean molecular weight Mn (number average) were 
determined as follows: 
The mean molecular weight Mn (number average) was calculated from the OH 
number (Mn=112,200/OH number). The OH number was determined by 
potentiometric titration by the phthalic anhydride method.

EXAMPLE 1 
Preparation of the Polyether Carbonate Diols 
1750 g (7.54 mol) of polyoxytetramethylenediol having Mn=232 and 778 g 
(6.59 mol) of diethyl carbonate were heated to the boil with 12.5 g (0.5% 
by weight) of tetraisopropyl orthotitanate, and the ethanol formed during 
this reaction was continuously separated from unreacted diethyl carbonate 
by distillation on a column (packing level: 25 cm, packing: 5 mm stainless 
steel meshes) at atmospheric pressure at a reflux ratio of 4:1. The 
reaction was carried out at 180.degree. C. The low-boiling components were 
removed under reduced pressure at 0.3 mbar (30 Pa). 
Yield: 1920 g 
Mn=1970 
OH number=57. 
EXAMPLE 2 
Preparation of a Cellular PU Elastomer by the Semi-Prepolymer Process 
Component A 
1000 g (0.508 mol) of polyether carbonate diol, prepared as described in 
Example 1, were mixed at 40.degree. C. with 
110 g (1.774 mol) of ethylene glycol 
5 g of triethylenediamine (diazabicyclooctane), 
1.7 g of silicone-based stabilizer (DC 193 from Dow Corning) and 
40 g of trichlorotrifluoroethane. 
The water content was adjusted to 0.3% by weight, based on the total 
weight, by adding water. 
Component B 
Urethane-containing polyisocyanate mixture having an NCO content of 19% by 
weight and prepared by reacting 1000 g (4 mol) of 4,4'-diphenylmethane 
diisocyante with 600 g (0.3 mol) of polyoxytetramethylene glycol having a 
mean molecular weight of 2000 for 1.5 hours at 80.degree. C. and 
subsequently cooling the reaction mixture to 40.degree. C. 
In order to produce the molding, 
100 parts by weight of component A and 
97 parts by weight of component B 
were mixed vigorously with stirring at 40.degree. C. 375 g of the reaction 
mixture were introduced into a plate-shaped metallic mold having the 
internal dimensions 250.times.100.times.300 mm at a controlled temperature 
of 60.degree. C., the mold was closed, and the reaction mixture was 
allowed to expand and cure. 
After 10 minutes, the cellular PU elastomer having a density of 500 
g/liter, was demolded. 
COMATIVE EXAMPLE I 
The procedure was similar to that of Example 1, but polyether carbonate 
diol was replaced by 1000 g of a polyoxytetramethylene glycol having a 
mean molecular weight of 2000. 
The mechanical properties measured on the moldings are given in the table 
below. 
EXAMPLE 3 
Preparation of a Cellular PU Elastomer by the Prepolymer Process 
700 g (0.355 mol) of polyether carbonate diol, prepared as described in 
Example 1, and 
240 g (1.143 mol) of 1,5-naphthylene diisocyanate 
were mixed at 130.degree. C. with stirring and reacted for 30 minutes. The 
reaction mixture was then allowed to cool slowly to 90.degree. C., giving 
an NCO-containing prepolymer having an NCO content of 6.5 % by weight. 
2.6 parts by weight of a fatty acid ester (50% strength by weight aqueous 
emulsifier, additive SM from Bayer AG), 
1.0 parts by weight of triethylenediamine and 
3.4 parts by weight of polyether carbonate diol, prepared as described in 
Example 1, 
were added at 90.degree. C. with vigorous stirring to 100 parts by weight 
of this NCO-containing prepolymer, and 375 g of the reaction mixture were 
introduced into the mold described in Example 2, at a controlled 
temperature of 50.degree. C., the mold was closed, and the reaction 
mixture was allowed to expand and cure for 20 minutes. 
The mechanical properties mentioned below were measured on the moldings 
obtained. 
COMATIVE EXAMPLE II 
The procedure was similar to that of Example 3, but the polyether carbonate 
diol was replaced by 1000 g of a polyoxytetramethylene glycol having a 
mean molecular weight of 2000. 
TABLE 
______________________________________ 
Mechanical properties of the cellular PU 
elastomers prepared 
Example 
2 3 
Comparative Example 
I II 
______________________________________ 
Density (DIN 53420) 
500 500 500 500 
[g/liter] 
Tensile strength 
4.3 5.2 3.0 4.0 
(DIN 53 571) [N/mm.sup.2 ] 
Elongation at break 
590 460 480 260 
(DIN 53 571) [%] 
Tear propagation strength 
12.9 12.4 14.3 12.8 
(DIN 53 515) [N/mm] 
Compressive set at 70.degree. C. 
14.0 12.4 6.2 6.5 
(DIN 53 572) [%] 
______________________________________