Note: Descriptions are shown in the official language in which they were submitted.
Mo-1670-G
LeA 16,592
~.O.~ Z~
HIGH MOLECULAR WEIGHT, INSOLUBLE CARBODIIMIDIZATION CATALYSTS
BACKGROUND OF THE INVENTION
Carbodiimides can be produced from isocyanates with
phospholine oxides as catalysts in a particularly simple reaction
even at room temperature based on the process disclosed in
German Patent 1,130,594. The commercially most important and
most effective catalysts, which carbodiimidize the aromatic
mono- and polyisocyanates very quickly, even at room temperature,
and can convert less reactive aliphatic or cycloaliphatic mono-
and polyisocyanates into carbodiimides at temperatures aboveapproximately 150C are those of the general formulae
R~/ 0~-- ~H
wherein
R and R', which may be the same or different, represent
aromatic or aliphatic hydrocarbon radicals with
1 to 14, and preferably 1 to 4 carbon atoms. R'
can also represent a hydrogen atom.
These catalysts have already been used commercially
for the preparation of polycarbodiimide foams ~elative to
compounds of the formula Ic, see Journal of Organic Chemistry
32, 4066 (1967)).
Experience has shown that it is not possible to
stop carbodiimide formation occurring in the homogeneous phase
with the above-mentioned slightly soluble catalysts in such a
way that storage stable, carbodiimide or polycarbodiimides
LeA 16,592
1094241
containing isocyanate groups are obtained. It is likewise not
possible to produce stable solutions of diisocyanato-
carbodiimides, ~ diisocyanato-bis-carbodiimides, ~
diisocyanato-tris-carbodiimides or the isocyanateuretone imines,
5 such as those corresponding to the formula:
(II) H3C ~ N C -- -- N ~ 3
o C N NCO
~,
- I NCO
CH3
in excess monomeric mono or polyisocyanates. Thus, the
carb~diimidization under the influence of the catalytically
hiqhly effective soluble phospholine oxides cannot be completely
stopped with deactivation agents such as phosphoroxychloride,
zinc chloride, dimethyl carbamic acid chloride, benzoyl chloride,
hydrochloric acid, boron trifluoride, alkylation agents and the
like, with the result that high molecular weight, insoluble,
low quality products are produced. As a result of progressive
(and even though in some cases, slow) formation of carbodiimide,
a high carbon dioxide pressure soon develops in cloud reaction
and/or storage vessels, which may result in serious and danger-
ous accidents.
DESCRIPTION OF THE INVENTION
Ithas now surprisingly been found that it is
possible to bond carbodiimidization catalysts without any sub-
stantial loss of their catalytic effect via covalent bonds on,
LeA 16,592-G - 2 -
1094241
in, or to a high molecular weight, organic matrix which is
capable of swelling, but, which is insoluble in polyisocyanates.
In this way high molecular weight, insoluble catalysts capable
of swelling are obtained, which can be removed at any time
from the reaction mixture. It is thus possible to convert
mono and preferably, polyisocyanates into storage stable
carbodiimides or polycarbodiimides or the uretone imines
thereof with functional NCO-groups. It is also possible to
produce storage stable mixtures of (poly) carbodiimides or their
uretone imines with polyisocyanates. One particularly surprising
finding is that it is even possible to carry out selective
carbodiimidization of certain mono- or polyisocyanates of an
isocyanate mixture.
The object of the present invention is therefore
to provide high molecular weight, carbodiimidization catalysts
which are insoluble in polyisocyanates, and which consist
of a high molecular weight matrix and a low molecular weight
carbodiimidization catalyst covalently bonded in, on, or to
this matrix. The preferred low molecular weight carbodiimi-
dization cataly~t are the saturated or unsaturated 5-membered
or saturated 4-membered cyclic phosphinic oxide.
The molecular weight of the matrix according to
the invention is generally above 2000. According to the
invention highly cross linked products are preferably used.
The present invention also relates to a process
for the production of such catalysts characterized in that
a high molecular weight matrix having functional groups or
monomers suitable for the construction of a high molecular
weight matrix are reacted with low molecular weight
carbodiimidization catalysts or precursors thereof, which
LeA 16,592 - 3 -
109424~
contain groups reactive towards the functional groups of the
matrix or the monomers.
For the production of the high molecular weight
carbodiimidization catalysts according to the invention,
basically any known low molecular weight carbodiimidization
catalysts or precursor thereof are suitable. These precursors
are generally converted into the catalytically effective form
when incorporated into the matrix. The known low molecular
weight carbodiimidization catalysts must where necessary for
incorporation into the high molecular weight matrix be modified
by functional groups, which can react with the matrix or the
monomers used for the preparation of the matrix.
The coupling between the low molecular weight
carbodiimidization catalysts and the high molecular weight matrix
can be effective via essentially any covalent bond such as
carbon-carbon bonds, ether, ester, urethane, amide, sulphide
groups and the like. The preferred couplings are ester groups
and, most preferred are aliphatic carbon-carbon bonds.
The preferred low molecular weight catalysts
according to the invention are cyclic phosphinic oxides of the
above-described type (formula Ia) and cyclic phosphinic oxides
derived therefrom. These materials may, in addition, exhibit
ring substituents with functional groups for uniting covalent
bonds, for use as low molecular weight carbodiimidization
catalysts for the production of the high molecular weight
carbodiimidization catalysts according to the invention.
A further preferred type of low molecular weight
catalysts for the production of the high molecular weight
carbodiimidization catalysts according to the invention are the
Le~ 16,592-G - 4 -
1(~9~
cyclic phosphinic oxides of the general formula (Ib). These
contain at the ring or at the phosphorus atom, alkyl, aryl or
aralkyl substituents with functional groups, by which covalent
bonds can be coupled to the polymeric matrix.
5Compounds of this type are, for example, those
of the general formula
R4 (IIIa) R4 R3 R4 H
U ~RlR2R3 ~R RSJ ~U (IIIb)
OH H OH
R4 ~f R3
H ~ 2 ( I I IC )
in which
Rl represents halogen, an alkoxy group, aryloxy group
with up to 14 carbon atoms or an amino group,
which can be substituted with alkyl, alkenyl, aryl
or aralkyl radicals with up to 14 carbon atoms,
or an alkyl, alkenyl, aryl or aralkyl radical
which may have an amino or hydroxyl group, with
up to 14, and preferably 1 to 4 carbon atoms and
R2; R3; R ; R5 represents hydrogen, halogen, a
carboxyl group, Cl - C14, preferably Cl - C4,
alkyl or alkoxy carbonyl radicals, phosphonic acid
ester - or Cl - C4 - alkoxy - or alkyl mercapto
radicals, which may contain further functional
groups such as olefinic carbon to carbon double
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1(~94241
bonds, amino or hydroxyl groups.
Typical representatives of such compounds include:
H H HR6
2 V X ~ (CH2-CH - O) HX = O; S. (IV)
/~ O~CH2-CH-O)bH R - H and/or CH3
O CH3
H R6
H2 1 1 I~H (V) H I ~ I H (VI)
H ~ O-CH2-CH=CH2 or 2 ~ 2
O CH3 CH2-CH=CH2
OH H
H ~ f OH OH
l (VII) H
H2 - ~--H2 H ~=¦~H
H/~H
- O// CH3
H H O
H ~ 3 H ~ CH2 C~
H ~ H H ~ H OC2H5
O CH3
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Low molecular weight catalysts of this type can be
produced in the following way:
Compounds of the type (IV) are produced by reaction
of a compound of the formula
H
H2 ~ "_,~ O-H (X = O; S.)
H2 ~ ~ H - O-H
O CH3
with ethylene oxide or propylene oxide. The reaction takes
place at 0 to 180C, preferably 50 to 150C, and can be carried
out at both normal pressure and at increased pressure, and may
also be carried out in an inert solvent.
Low molecular weight carbodiimidization catalysts .~- -
alkyl substituted at the phospholane ring of the type (IV) can
be obtained in a similar manner (see also German Offenlegungs-
schrift 2,504,400).
Compounds of the type (V) can be obtained by reacting
15 compounds of the general formula
R7 ~ R8
H2 ~ ~ R
in which
R represents an alkyl or an aryl radical with up to
14 carbon atoms and
R7,R8,R9 which may be the same or different represent a
Cl to C4 alkyl radical or hydrogen with
a compound of the general formula
LeA 16,592-G - 7 -
~94~41
R10 - O - H
in which
R10 represents an alkyl, aryl or aralkyl radical
with 1 to 14 preferably 1 to 4 carbon atoms,
which may also contain other functional groups
such as olefinic carbon to carbon double bonds,
in the presence of alkaline catalyst.
Compounds of the type (VI) are produced by a
reaction of the general compound
R2 R3 [Izvestiya Akademi
¦ / NaukSSSR, Seriya
~ 1--, Khimischeskaya, No. 8
H l R4 pp. 1847-1848
2 ~ ~ ~ (further literature
~ \ therein)]
in which
X represents a halogen atom (e.g. chlorine, bromine
or iodine) and
R2 R3 R4 which may be the same or different represent a
Clto C4 alkyl radical or hydrogen,
with an organometallic compound e.g. a Grignard compound of
which the organic radical may contain the desired functional
group such as olefinic carbon to carbon double bonds. Solvents
generally used for this reaction include hydrocarbons and
ether (T~F).
Compounds of the type (VII) are produced by the
hydrolysis of 3,4-epoxyphospholane-1-oxides. (B. A. Arbusov,
A. P. Rakow, A. O. Vizel, Izv. Akad. Nauk SSSR, 196~9. 2230 -
2234).
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1(~94Z~l
In the high molecular weight catalysts according to
the invention based on t:he compounds of formula I to III, the
phosphorus content is in general between 0.05 and 23% by
weight, and preferably between 0.3 and 8% by weight.
"Precursors" of the low molecular weight carbodi-
imidization catalysts according to the invention include com-
pounds of the type
~¦ ¦ ,' (see US Patent No.
(VIII) R3 ~ ¦ ~1 3,723,520)
~1 .
in which
0 Rl, R2 and R3 represent hydrogen or Cl - C 14' preferably
Cl - C4, alkyl radicals and
X represents halogen.
Such compounds can, for example, be incorporated
into a high molecular weight matrix as illustrated in the
following diagram with the formation of the catalytically
effective cyclic phosphinic oxide grouping:
macromolecule ~
OH o
-HX >
Heat ~ ,~
(Alkyl iodide as ~.
catalyst) ~
LeA 16,592-G - 9 -
24~.
A further method of production using precursors the Arbusov-
reaction:
Arbusov-
~ reaction
CH2X + RO-
CH2-P~ l + RX
O \~
Further "precursors" of carbodiimidization catalysts
are in addition, for example, compounds of the type R-PX2
(X = halogen), in which the radical - PX2 is bonded to an
alkyl, aryl or aralkyl radical, which in its turn may already
be part of a high molecular weight polymer. An example of
this type is provided by the reaction products of PX3 with
polystyrene.
Compounds R-PX2 can easily be converted into cyclic
phosphinic oxides by reaction with dienes and subsequent
hydrolysis:
(X) IrlL ~ H20 _~
lS \ p / ¦ 0~ R
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Suitable polymers for use as the high molecular
weight matrix for the catalyst according to the invention
contain functional groups for a covalent bond coupling to the
low molecular weight carbodiimidization catalyst. On the
other hand it is, of course, also possible in the production
of the catalysts according to the invention to start from
monomers which, during polymerization to a high molecular
weight product, incorporate the low molecular weight
carbodiimidization catalysts having the suitable functional
groups.
A preferred matrix for the catalyst according to the
invention are unsaturated polyester resins. In this variation
of the process according to the invention, dicarboxylic acids
and diols are first condensed by known methods, with at least
one of the components being unsaturated, to form an unsaturated
polyester. Approximately 10 to 70% by weight based on the
polyester, of a phospholine oxide are then added, which may
contain a substituent with an additional olefinic double bond,
and the mixture is heated together with reaction in~tiators.
Instead of the free dicarboxylic acid, according
to the invention, the corresponding dicarboxylic acid anhydrides
or corresponding carboxylic acid esters of low alcohols or
mixtures thereof can be used for the production of the poly-
esters. The carboxylic acids can be of the aliphatic, cyclo-
aliphatic, aromatic and/or heterocyclic type and may be sub-
stituted, for example, by halogen atoms. Examples which can
be mentioned include malonic acid, succinic acid, adipic
acid, suberic acid, azelaic acid, fatty acid, phthalic acid,
isophthalic acid, trimellitic acid, phthalic acid anhydride,
tetrahydrophthalic acid anhydride, hexahydrophthalic acid
LeA 16,592-G - 11 -
~(~94Z41
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, which may be mixed
with monomeric fatty acids, ~rephthalic acid dimethyl ester
and terephthalic acid-bis-glycol ester and any mixtures
thereof. Diols to be considered include for example ethyl-
eneglycol, propyleneglycol-(1,2) and -11,3)butyleneglycol-
(1,4) and (2,3), hexanediol-11,6), octianediol-(1,8), neo-
pentylglycol, cyclohexanedimethanol (1,4-bis-hydroxymethyl-
cyclohexane), 2-methyl-1,3-propanediol, the isomeric butene-
diols, diethylene-glycol, triethyleneglycol, tetraethylene-
glycol, polyethyleneglycol, dipropyleneglycol, polypropylene-
glycols, dibutyleneglycol and polybutyleneglycols.
Preferred acid components are malonic acid and
esters thereof, maleic acid anhydride, maleic acid and its
esters, fumaric acid and its esters and muconic acid and its
esters.
Preferred diols are ethane diol, propane diol, and
the polycondensates thereof (preferably up to a molecular
weight of 400), butene diols, butane diols and mixtures of these
diols.
Reaction initiators which are considered for the
reaction of the polyesters with phospholine, phospholane or
phosphetane oxide containing double bonds, include radical
forming agents which are active in the temperature range of
from 50 to 300C. Particularly useful are organic peroxides,
aliphatic azo compounds and high energy radiation. Examples
include dialkyl peroxides such as di-tert.-butylperoxide,
diacylperoxides such as dibenzoylperoxide, p-chloro-benzoyl-
LeA 16,592-G - 12 -
1C~94Z~l
peroxide, 2,4-dichlorobenzoylperoxide, succinylperoxide, non-
anoylperoxide~ lauroylperoxide, peroxyesters such as tert.-
butyl-peroctoate,tert.-butyl-periosbutyrate, tert.-butyl-
peracetate, tert.-butylperbenzoate, tert.-butylperivalate
and peroxyketals and percarbonates, azoisobutyric acid nitrile,
azo-bis-isobutanol-di-acetate and ultra violet radiation,
X-rays or gamma rays.
Catalysts based on polyesters according to the
invention can also be produced by replacing a part of the
diol component in the known preparation of polyesters by
phospholine oxides or phospholane oxides of the above described
type (formulae I, III, IV and VII) substituted with dihydroxy
alkyl groups.
Of course the low molecular weight carbodiimidization
catalysts can also be incorporated in a similar manner into
other polycondensation or polyaddition resins via suitable
functional groups (e.g. -OH, -NH2 or -COOH), e.g. in polyamides,
polyurethane~ or epoxide resins.
It is also possible to produce high molecular
weight cataly~ts according to the invention by incorporating
low molecular weight carbodiimidization catalysts in, preferably,
cross-linked polystyrene. Thus, for example, one of the
compounds of the formula I, III or VIII can be copolymerized
with styrene and, optionally, from about 1 to 10~ by weight
of divinyl benzene, by means of the above mentioned reaction
initiators.
A further method of producticn is to metallize a
halogenated polystyrene (see Houben-Weyl XIV/2, 764 (1963)),
preferably by means of tert.-butyl-lithium, and then to react
it with a halogen-substituted phospholine or phospholane oxide,
LeA 16,592-G - 13 -
i(~94241
and preferably with a l-chloro-phospholine oxide.
Similarly to the above described method of
preparation for compounds of the formula (V) it is also possible
to add phospholine oxides preferably l-methyl-l-phospha-2-or-3-
cyclopentene-l-oxide, to a matrix with anionic groups (e.g.
alcoholate groups to polyvinyl alcohol).
Catalysts according to the invention can also be
produced via polymers functionalized with -PX2-groups (X = Cl,
Br) e.g. copolymers of styrene and divinyl benzene (se~ for
example Houben-Weyl XIV/l, p. 821 (1961)).
The catalytically active phospholine ring is
formed by addition of 1,3-dienes e.g. 1,3-butadiene isoprene
or 2,3-dimethyl-1,3-butadiene (see formula diagram X) at the
phosphorus atom.
In a similar manner, of course, compounds of the
formula I, III, or VIII which may contain further substituents
with olefinic carbon to carbon double bonds or compounds of
the type R-PX2 (X = Cl, Br) in which R represents an alkenyl
radical, can also be copolymerized with other olefinic un-
saturated monomers (e.g. ethylene, propylene, butene, butadiene,
vinylchloride, vinylacetate, N-vinylpyrrolidone, etc.) and,
in this way, be incorporated in a high molecular weight matrix.
Catalysts according to the invention, can also be
obtained by heating a phospholine halide of the formula (VIII)
(which can optionally also be saturated) with high molecular
weight polyhydroxyl compounds, e.g. polyvinyl alcohols,
optionally in the presence of bases, and with catalytic
quantities of alkyl halides. In this process according to
formula diagram IX the catalytically acting phospholine oxide
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1~4Z41
is produced at the matrix with the coupling of an additional
carbon-phosphorus bond (U. S. Patent No . 3,723,520; Houben-
Weyl XII/l, p. 150 (1963)).
By using the catalysts according to the invention
basically any aliphatic, cycloaliphatic, araliphatic, aromatic
and heterocyclic polyisocyanate can be carbodiimidized.
Suitable isocyanates are described for example by W. Siefken
in Justus Liebigs Annalen der Chemie, 562, pages 72 to 136, and
include ethylene diisocyanate; 1,4-tetramethylenediisocyanate;
1,6-hexamethylenediisocyanate; 1,12-dodecanediisocyanate;
cyclobutane-l, 3-diisocyanate; cyclohexane 1,3- and 1,4-di-
isocyanate and any mixtures of these isomers; l-isocyanato-
3,3,5-tri-methyl-5-isocyanatomethyl-cyclohexane (German
Auslegeschrift No. 1,202,785, U. S. Patent No. 3,401,190);
2,4- and 2,6-hexahydrotoluylenediisocyanate and any mixtures
of these isomers; hexahydro-1,3- and/or-1,4-phenylene
diisocyanate; perhydro-2,4'- and/or -4,4'-diphenylmethane
diisocyanate; 1,3- and 1,4-phenylenediisocyanate; 2,4- and 2,6-
toluylenediisocyanate and any mixtures of these isomerst
diphenylmethane 2,4'- and/or -4,4'-diisocyanate; naphthylene-
1,5-diisocyanate; triphenylmethane-4,4',4"-triisocyanate;
polyphenyl-polymethylenepolyisocyanates as obtained by aniline
formaldehyde condensation and sub~equent phosgenation and for
example described in Pritish Patents No. 874,430 and 848,671;
m- and p-isocyanatophenyl-sulphonyl isocyanates according to
U. S. Patent 3,454,606; perchlorinated aryl polyisocyanates,
as described in German Auslegeschrift No. 1,157,601 (U. S.
Patent No. 3,227,138); polyisocyanates having carbodiimide
groups as described in German Patent No. 1,092,007 (U. S. Patent
No. 3,152,162); diisocyanates as described in U. S. Patent
No. 3,492,330; polyisocyanates having allophanate groups, as
LeA 16,592-G -15-
Z41
for example described in British Patent No. 994,890; Belgian
Patent No. 761,626 and Published Dutch Patent Application
No. 7,102,524; polyisocyanates having isocyanurate groups,
as for example described in U. S. Patent No. 3,001,973;
German Patents No. 1,022,789, 1,222,067 and 1,027,394 and
German Offenlegungsschriften No. 1,929,034 and 2,004,048.
Polyisocyanates having urethane groups as for example described
in Belgian Patent No. 752,261 and U. S. Patent No. 3,394,164;
polyisocyanates having acylated urea groups according to
German Patent 1,230,778; polyisocyanates having biuret groups,
as for example described in German Patent No. 1,101,394, U. S.
Patents No. 3,124,605 and 3,201,372 and British Patent No.
889,050; polyisocyanates produced by telomerization reactions,
for example as described in U. S. Patent No. 3,654,106; poly-
isocyanates having ester groups, as for example described in
British Patents No. 965,474 and 1,072,956; U. S. Patent No.
3,567,763 and German Patent No. 1,231,688; reaction products
of the above mentioned isocyanates with acetals according to
German Patent No. 1,072,385 and polyisocyanates containing
polymeric fatty acid radicals according to U. S. Patent
3,455,883.
It is also possible to use the distillation
residues having isocyanate groups which occur in commercial
isocyanate production, optionally dissolved in one or more
of the above mentioned polyisocyanates. In addition it is
possible to use any mixtures of the above mentioned poly-
isocyanates. Aromatic polyisocyanates preferred according to
the invention are 2,4-toluylene diisocyanate, 2,6-toluylene
diisocyanate and any mix*ures of these isomers, m-phenylene-
diisocyanate, p-phenylenediisocyanate and approximately 10 to
LeA 16,592-G - 16 -
1~94Z4~
40~ by weight solutions of biuretization, allophanatization,
urethanization, trimerization and dimerization products of
these polyisocyanates in monomeric polyisocyanates, and in
particular in monomeric toluylene diisocyanate.
Of the aliphatic, cycloaliphatic,araliphatic
polyisocyanates, tetramethylenediisocyanate; pentamethylene-
diisocyanate; hexamethylenediisocyanate; dicyclohexylmethane-
diisocyanate; l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-
cyclohexane; lysinesterdiisocyanates; m- and p-xylylene-
diisocyanate and mixtures thereof are preferred, as are the
solutions of their biuretization and dimerization products in
the corresponding monomeric polyisocyanates.
Naturally, monoisocyanates can also be carbodiimidized.
Suitable monoisocyanates are for example methyl isocyanate;
ethyl isocyanate; propyl isocyanate; isopropyl isocyanate;
diisopropylphenyl isocyanate; n-butyl isocyanate; n-hexyl
isocyanate; ~-chlorohexyl isocyanate; phenyl isocyanate;
tolyl isocyanate; p-chlorophenyl isocyanate; 2,4-dicloro-
phenyl isocyanate and trifluoromethylphenyl isocyanate.
The carbodiimidization of these mono and poly-
isocyanates or their mixtures is carried out so that the
isocyanates which may be dissolved in inert solvents such as
toluene; xylene; chlorobenzene; o-dichlorobenzene; decalin;
dimethylformamide; dimethylacetamide; butylacetate; carbon
tetrachloride; trichloroethylene and tetramethylurea, are
brought into contact with, preferably 0.2 to 10% particularly
preferably 1 to 4% by weight of the matrix charged with
catalyst molecules based on the isocyanates at a temperature
of between approximately 50and 200C, preferably 80 to 185C
and optionally under pressure. This reaction is carried out
LeA 16,592-G - 17 -
1~94Z41
in the simplest manner so that the catalyst is introduced into
the liquid or dissolved isocyanates under agitation and, after
reaching the desired degree of carbodiimidization is removed
by decanting or filtration. The degree of reaction can be
easily followed by measuring the volume of the carbon dioxide
generated during the carbodiimidization reaction. The catalysts
according to the invention can generally be reused more than 10
to 20 times without affecting their effectiveness. Of course
it is also possible to conduct the carbodiimidization contin-
uously in a column, provided that a suitable arrangement ismade for the unhindered escape of the carbon dioxide formed in
the reaction.
Naturally, the carbodiimidized mono and/or poly-
isocyanates produced according to the invention can subsequently,
if desired only partially be mixed with further polyisocyanates.
In this way, storage stable mixtures of high and/or low mole-
cular weight polyisocyanates can be produced with high and/or
low molecular weight carbodiimides or uretone imines which
may have isocyanate groups.
Since the carbodiimidization catalysts according to
the invention can be completely removed after the reaction in
contrast with the hitherto known catalysts, in principle,
mixtures with any carbodiimide group content can be produced.
However, according to the invention preference is given to
mixtures which contain approximately 3 to 70% by weight,
especially preferably 10 to 60% by weight, of carbodiimides,
polycarbodiimides or uretone imines. As is well known in
the art, uretone imines are addition compounds of a carbodi-
imide and an isocyanate. The following polyisocyanate/
carbodiimide-mixtures are of particular commercial importance:
LeA 16,592-G - 18 -
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a) A mixture of lO0 parts by weight of 4,4'-
diisocyanato-diphenylmethane and/or l,S-
naphthylene diisocyanate and 5 to 30 parts by
weight of an equilibrium mixture of the
diisocyanatocarbodiimides of the toluylene
diisocyanate and the corresponding
triisocyanatouretone imines.
b) Mixtures of 100 parts by weight of 4,4'-
diisocyanato-diphenylmethane and/or 1,5-
naphthylene diisocyanate and 10 to 30 parts
by weight of an equilibrium mixture of
carbodiimides of phenyl isocyanate, hexamethy-
lenediisocyanate, tetramethylene-diisocyanate,
cyclohexylisocyanate or tolylisocyanate and
lS the uretone imines thereof.
c) Mixtures of 100 parts by weight of toluylene
diisocyanate and 5 to 30 parts by weight of
an equilibrium mixture of carbodiimidized
phenyl isocyanate or tolyl isocyanate and
the uretone imines thereof.
d) A mixture of lO0 parts by weight of modified
toluylene diisocyanate, containing lO to 40%
by weight of biuret allophanate, urethane or
isocyanurate polyisocyanates based on toluylene
diisocyanate and lO to 20 parts by weight of
an equilibrium mixture of toluylenediisocyanato
carbodiimide and the corresponding triisocyanato
uretone imine.
LeA 16,592-G - 19 -
~(~'3~Z4~
e) A mixture of 100 parts by weight of a
biuret polyisocyanate of hexamethylene
diisocyanates (preferably reaction products
from 1 mol water and approximately 2 to 3
mol hexamethylene diisocyanate) and 10 to 30
parts by weight of an equilibrium mixture of
the carbodiimide of hexamethylene diisocyanate
and the corresponding uretone imine poly-
isocyanates.
f) Mixtures of 100 parts by weight of an a,~ -
diisocyanato prepolymer (obtained from 1 mol
a,~ - dihydroxypolyesters or polyethers of the
type known in the art and 1.4 to 2.5, preferably
1.6 to 2 mol toluylene diisocyanate, diisocyanato-
lS diphenylmethane or hexamethylene diisocyanate)
and 5 to 30 parts by weight of an equilibrium
mixture of carbodiimides, or carbodiimide
diisocyanates and the corresponding uretone
imine polyisocyanates of phenyl isocyanate,
tolyl isocyanate, tetramethylene diisocyanate,
hexamethylene diisocyanate or toluylene
diisocyanate.
The carbodiimides which may have isocyanate groups
which are produced with the catalysts according to the invention
and the solutions thereof in carbodiimide group freepoly-
isocyanate are valuable starting products for the diisocyanate-
polyaddition process and can be used for the production of
greatly varying hard to elastic, optionally cellular, plastics
for the production of lacquers, coverings, coatings, films and
LeA 16,592-G - 20 -
1(~94;~1
moldings. Polyurethanes produced in this way contain, in
the polymer molecule, permanently incorporated carbodiimide
groups and uretone imine groups (= masked carbodiimide groups),
which at the same time constitute anti-ageing agents against
the hydrolysis of ester bonds and, in addition, reduce the
inflammability of the plastics material.
The production of polyurethane takes place in a
known manner by the react:Lon of the polyisocyanatemixtures
with high and, optionally, also low molecular weight compounds,
having at least two hydrogen atoms capable of reacting with
isocyanates.
The following Examples illustrate the present
invention.
Unless otherwise specified, all figures are to be
understood as parts or percentages by weight.
LeA 16,592 - 21 -
1(~94Z41
EXAMPLE 1
a) 70 parts by weight of a polyester having an acid
number of approximately 8 (produced from 406 parts by weight
maleic acid anhydride and 438 parts by weight diethylene
glycol) are heated slowly with 30 parts by weight l-methyl-l-
phospha-2 and 3-cyclopentene-1-oxide (l-methyl-phospholine
oxide) in the presence of 1.5 grams benzoyl peroxide under
agitation to 150C. At 110C a solid, crumbly product is
produced. After extraction of residual monomers, first with
toluene and then with chloroform, the polymer contains 1.25
by weight of phosphorus.
b) Example la is repeated, but with the addition of
3.5 parts by weight styrene to the reaction mixture. A rather
harder product is obtained, having a phosphorus content of
0.5% by weight.
25 parts by weight of the catalyst of Example
la and 40 parts by weight of toluene are added to 34.8 parts
by weight of an isomer mixture of 2,4- and 2,6-toluylene -
diisocyanate (80 : 20) and heated to 110C. After 1 hour,
3.6 liters of carbon dioxide had been generated and the
isocyanate content of the solution of the isocyanate mi~ture had
fallen to 8.6% by weight.
EXAMPLE 2
a) 35 parts by weight of an unsaturated polyester
[from 1 mol maleic acid anhydride and 1 mol tetraethylene glycol
(acid number 9)] are mixed well with 15 parts by weight 1-
methyl-l-phospha-3-cyclopentene-1-oxide and 0.7 parts by weight
benzoyl peroxide and slowly heated under agitation to 150C.
LeA 16,592-G - 22 -
1~94Z41
The crumbly product produced after washing with toluene and
chloroform has a phosphorus content of 0.75% by weight.
b) If Example 2a is repeated but instead of l-methyl-
1-phospha-3-cyclopentene-1-oxide, 1-methyl-1-phospha-2-cyclo-
pentene-l-oxide is used then the phosphorus content of the
reaction product is 0.2% by weight.
EXAMPLE 3
14 parts by weight of the unsaturated polyester of
Example 2 are mixed with 6 parts by weight 1-allyl-1-phospha-2-
and 3-cyclopentene-1-oxide and 0.3 parts by weight benzoyl
peroxide and slowly heated under agitation to 150C. A
crumbly product is produced which, after extraction with
toluene and chloroform, has a phosphorus content of 2.7% by
weight.
On heating 5 parts by weight of the catalysts with
150 parts by weight of a mixture of 2,4- and 2,6- toluylene-
diisocyanate (80:20) to 90C, 3 liters carbon dioxide are
generated under carbodiimidization within one hour.
EXAMPLE 4
9.8 parts by weight maleic acid anhydride and 5.2
parts by weight diethylene glycol are heated under nitrogen to
175C with 25.6 parts by weight of a diester of an isomer
mixture of l-methyl-2- or -3-phosphonic acid phospholane
oxide and polypropylene glycol (molecular weight 511) and the
water produced during the esterification reaction is distilled
off. The gel-like product is mixed with 0.6 parts by weight
benzoyl peroxide and heated to 150C. Soluble constituents
are extracted from the crumbly product produced with toluene
eA 16,592-Ca - 23 -
424~
and chloroform.
If 1 part by wei~ht of the catalyst is heated to
110C with 34.8 parts by weight of a mixture of 2,4- and 2,6-
toluylene diisocyanate (80 : 20), 2 liters of carbon dioxide
are produced within 10 minutes.
EXAMPLE 5
9.8 parts by weight maleic acid anhydride are con-
densed for 3 hours at 175C under an atmosphere of nitrogen
with 9 parts by weight diethylene glycol and 3.7 parts by
weight of a product obtained by heating 1 mol l-methyl phos-
pholane-2 and 3-phosphonic acid-dimethylester with 2 mol di-
ethanol amine. The water produced is continuously distilled
off and, subsequently, the condensate is treated with toluene
and chloroform, to extract residual soluble components. The
product thus obtained has a phosphorus content of 0.6% by weight.
1 part by weight of this product is heated with 84
parts by weight hexamethylene diisocyanate to 190C and 2 liters
of carbon dioxide are generated within 5 hours.
10 parts by weight of the product are heated with
174 parts by weight of a mixture of 2,4- and 2,6-toluylene
diisocyanate to 70C. Within 30 minutes, 10 liters of carbon
dioxide are developed as a result of the incipient carbodi-
imidization of the isocyanate.
EXAMPLE 6
7.1 parts by weight of a 2% by weight solution of
poly-p-iodine styrene in toluene are added dropwise at 0C
to 150 ml (0.22 mol) of an n-butyl lithium solution in toluene.
LeA 16,592-G - 24 -
m~4z~l
Subsequently 35.5 parts by weight 1-chloro-3-methyl-1-phospha-2
and 3-cyclopentene-1-oxide are added rapidly at 20C. After
1 hour of agitation, the reaction mixture is mixed with 5 ml
water concentrated, digested with a little water and then
dried in a desiccator using phosphorus pentoxide.
Toluylene diisocyanate can be carbodiimidized at
60C by means of the highly effective catalysts produced.
EXAMPLE 7
15 parts by weight poly-p-iodine styrene, cross-
linked with 2~ divinyl benzene, are soaked in 100 ml toluene and200 ml of a 1.5 normal solution of n-butyl lithium are
added dropwise in n-hexane. The metallized solid product is
removed by suction under nitrogen and reacted at room temperature
with 9.7 parts by weight 3-chloro-1-methyl-1-phospha-2 and
3-cyclopentene-1-oxide, produced from chloroprene and dichloro-
methyl phosphine. The product is filtered and treated with
toluene and chloroform.
Using the catalyst, toluylene diisocyanate can be
carbodiimidized at 100C.
EXAMPLE 8
50 parts by weight polystyrene are mixed with
268 parts by weight phosphorus trichloride and the mixture is
reacted for 5 days at 200C (see also U. S. Patent No. 2,844,
546). The excess phosphorus trichloride is then distilled off,
the residue is absorbed 3 times with perchloroethylene and,
in each case, the solvent is distilled off.
LeA 16,592-G - 25 -
1~94Z41
190 parts by weight isoprene and 0.6 parts by
weight ionol are added to the solid product thus purified
under nitrogen and the mixture is left to stand for 10 days
at room temperature. The solid product is washed with per-
chloroethylene, hydrolyzed in 1 liter ice water, removed by
suction and dried using phosphorus pentoxide.
34.8 parts by weight of an isomer mixture of 2,4-
and 2,6-toluylene diisocyanate (80 : 20) are carbodiimidized
using 3 parts by weight of the catalyst at 140C. 1 liter
of carbon dioxide is produced within 1 hour.
EXAMPLE 9
A mixture of
3 parts by weight polystyrene,
6 parts by weight styrene,
1 part by weight l-allyl-phospholinoxide (l-allyl-
l-phospha-2 and 3-cyclopentene l-oxide)[produced from equivalent
parts of l-chloro-phospholinoxide (l-chloro-l-phospha-2 and
3-cyclo-pentene-1 - oxide) and allylmagnesium iodide in tetra-
hydrofuran]
0.6 parts by weight divinyl benzene and
0.008 parts by weight dibenzoylperoxide is poured
into a cylinder tube under nitrogen. After 30 days at 32C
the solid product is scraped and released of residual soluble
constituents with toluene and chloroform. The phosphorus
content of the product is 0.3% by weight.
Under the effect of the catalyst, toluylene
diisocyanate converts into the carbodiimide at 75C.
EXAMPLE 10
LeA 16,592-~ - 26 -
.,
10~4Z4~
9 parts by weight styrene and 0.1 parts by weight
divinyl benzene are mixed with 1 part by weight l-methyl-l-
phospha-2 and 3-cyclopentene-1-oxide and polymerized with
0.3 parts by weight benzoyl peroxide as the initiator at 110C.
After washing with toluene and chloroform, the product has
a phosphorus content of 1~ by weight.
EXAMPLE 11
6.8 parts by weight 1-chloro-1-phospha-2 and
3-cyclopentene dissolved in 20 parts by weight dichlorobenzene
are added to 2 parts by weight of a polyvinyl alcohol
(molecular weight approximately 15000) at room temperature
(U.S. Patent No. 3,723,520), 4 parts by weight pyridine are
added dropwise, 0.1 parts by weight ethyl iodide are added
and the mixture is heated to 110C. The solid product produced
is removed by suction, washed with water and then with ether
and dried by means of phosphorus pentoxide.
The product is a good carbodiimidization catalyst
for 2,4- and 2,6-toluylene diisocyanate at a temperature of
150C. 3 liters of carbon dioxide are evolved at 170C from
70 parts by weight of a mixture of 2,4- and 2,6- toluylene
diisocyanate (80 : 20) and 2 parts by weight of catalyst
within 10 minutes.
EXAMPLE 12
160 grams malonic acid diethyl ester are heated under
reflux with 106 grams diethylene glycol and 1 ml 10% sulphuric
acid in 100 ml toluene for 24 hours and, subsequently, the
toluene is slowly distilled off. 240 g of this product are
mixed with 240 g of an unsaturated polyester of equivalent
quantities of maleic acid anhydride and diethylene glycol
LeA 16,592-G - 27 -
4Z41
(acid number 8), 206 g 1-methyl-1-phospha-2 and 3-cyclopentene
-l-oxide and 10 g benzoyl peroxide are added and heated to 150C.
The crumbly product produced, after extraction with toluene
and chloroform, has a phosphorus content of 1~.
If 1 g of the catalyst is heated to 85C with
34.8 g of a mixture of 2,4- and 2,6-toluylene diisocyanate
(80 : 20), 4 liters of carbon dioxide are evolved within 3
hours.
EXAMPLE 13
350 g of an unsaturated polyester having an acid
number 9, (produced from equivalent quantities of maleic acid
anhydride and tetraethylene glycol) are mixed with 150 g
l-methyl-2 and 3-allyloxy-1-phospha-cyclopentene-1-oxide,
subsequently heated slowly to 150C with 7.5 g benzoyl peroxide
under agitation and then agitated for 1/2 hour. The crumbly
product produced is extracted with toluene and with chloroform.
EXAMPLE 14
133 g o-tolyl isocyanate are heated with 5 g of a
solid insoluble catalyst according to Example la under
agitation to 180C. After the evolution within 1.5 hours of
12.3 liters of carbon dioxide, the catalyst is removed by
suction and the filtrate distilled. 95.3 g di-o-tolyl-carbodi-
imide of Kp. 135 - 137C/0.1 Torr (87% of theoretical yield)
are produced.
EXAMPLE 15
133 g o-tolylisocyanate are heated under agitation
to 140C with 5 g of a solid insoluble catalyst according to
Example 2a. After the evolution within 2 hours of 12.1 liters
LeA 16,592-G - 28 -
~.~94Z41
carbon dioxide, the catalyst is removed by suction and the
filtrate distilled. 103.5 g di-o-tolylcarbodiimide of Kp 130
to 132C/0.1 Torr (94% of theoretical yield) are obtained.
EXAMPLE 16
203 g 2,6-diisopropyl-phenylisocyanate are heated
under agitation to 200C with 5 g of a catalyst according
to Example la. After the evolution within 12 hours of 8.9
liters carbon dioxide, the catalyst is removed by suction and
the filtrate (177 g) distil]ed. 132 g bis-(2,6-diisopropyl-
phenyl)-carbodiimide of Kp 165 - 168C/0.1 Torr (71% of
theoretical yield) are obtained.
EXAMPLE 17
1500 g of a mixture of 2,4- and 2,6 -toluylene
diisocyanate (80/20) are heated to 100C with 50 g of catalyst
according to Example 2a. After the evolution of 38 liters
carbon dioxide the product is filtered. It has a viscosity
n 24 = 14 cP and an isocyanate content of 39%.
EXAMPLE 18
300 g diphenyl methane-4,4'-diisocyanate are
heated at 80 to 100C with a catalyst according to Example la.
After 3 liters carbon dioxide have been developed, a product
which is liquid at room temperature is obtained, having an
isocyanate content of 29% and a viscosity n24 = 46 cP.
EXAMPLE 19
168 g 1,6-hexamethylenediisocyanate are heated to
150C with 5 g of a catalyst according to Example la. After
the formation of 14 liters carbon dioxide, the product is
LeA 16,592-G - 29 -
~O9~Z4~
filtered and formed into thin layers. Then it has a viscosity
~24 = 580 cP and an isocyanate content of 23%.
When applied to a glass plate, the product forms a
scratch - resistant elastic film as a result of the reaction
with atmospheric molsture.
EXAMPLE 20
A mixture of 111 parts by weight l-isocyanato-
3,3,5-trimethyl~5-isocyanatomethyl-cyclohexane and 84 parts by
weight l,6-hexamethylene diisocyanate is heated to 160C and
mixed with 5 g of a catalyst according to Example la. After
the development of 7.3 liters carbon dioxide, the product
(viscosity n24 = 170 cP) is filtered and formed into thin
layers at 80C/0.12 Torr, with monomeric isocyanate being
drawn off. The product formed into thin layers has, in
addition to carbodiimides a high content of isocyanato-
~retoneimines. (n24 = 916 cP; isocyanate content = 23.9).
EXAMPLE 21
S00 g (2 mol) diphenylmethane-4,4'-diisocyanate
are heated to 140C with 20 g of the catalyst of Example la.
After 20 liters carbon dioxide have been released, the
isocyanatocarbodiimide containing uretone imine groups is
released from the catalyst by filtration.
The product is stirred in proportions of 10, 30 and
50~ (a; b; c;) into molten diphenylmethane-4,4'-diisocyanate,
producing storage stable products which are liquid at room
temperature.
a) isocyanate content = 31 % n 24 = 22 cP
LeA 16,592-G - 30 -
109~Z4~1
b) isocyanate content = 28% n 24 = 140 cP
c) isocyanate content = 25.2% ~24 = 1300 cP
LeA 16,592-G - 31 -
