Note: Descriptions are shown in the official language in which they were submitted.
~ 335389
K-17198/=
Epoxy Resins Modified with Block Polymers
The present invention relates to mixtures of epoxy resins and special
diene/lactone block polymers, to curable mixtures of this type addition-
ally containing hardeners for epoxy resins, to adducts of said block
polymers with epoxy resins, to the crosslinked products obtained from
said curable mixtures, and to the use of the multicomponent mixtures as
adhesives, especially as structural adhesives.
Epoxy resins are distinguished by numerous good properties. Cured
products, however, have insufficient flexibility and impact strength for
certain applications and their adhesion to oily steel is inadequate.
Although the known flexibilising modifiers do in general effect an
enhancement of the flexibility of the cured products, the peel strength
is largely unsatisfactory. In addition, the incorporation of such
modifiers reduces the lap shear strength and the glass transition
temperature.
The use of polycaprolactone and butadiene copolymer flexibilisers is
known per se. For example, US patent specification 3 678 131 discloses
adhesive compositions of enhanced toughness which contain, as epoxy resin
component, a reaction product of a polyepoxide with a smaller amount of a
carboxyl group containing polymer, for example a butadiene/acrylonitrile
copolymer, and with 2,2-bis(4-hydroxyphenyl)sulfone.
Modified epoxy resin compositions which contain, as flexibiliser, a
butadiene/acrylonitrile copolymer or a butadiene/methacrylonitrile
copolymer containing COOH, OH or SH end groups are disclosed in US patent
specification 3,947,522. The properties of the compositions, which are
used for the preparation of adhesives, are enhanced by vulcanising the
butadiene copolymer with an organic peroxide or with sulfur.
- 2 - ~ 3 3 ~ 3 ~ 9
Epoxy resins modified with polycaprolactone or with polypropylene oxideare described in the Journal of Polymer Science, Polymer Chemistry
Edition, Vol. 12, pp. 689-705 (1974). The mixtures are cured with
anhydride hardeners. The use of modifiers with a suitable molecular
weight gives two-phase crosslinked systems which display a superior
balance of heat distortion temperature and impact strength.
The modification of epoxy resins with reactive polybutadienes is
described in Polym. Mater. Sci. Eng., Vol. 49, pp. 383-387 (1983). The
miscibility of the epoxy resin with the polybutadiene is increased either
by pre-reacting the terminal carboxyl groups of the polybutadiene with
the epoxy groups of the resin or by attaching a polyester block to the
polybutadiene. The polyester block is formed in situ by reacting the
terminal hydroxyl or carboxyl groups of the polybutadiene with phenyl
glycidyl ether as diol component and hexahydrophthalic anhydride as acid
component. Such end-capped polybutadienes are used as flexibilising
modifiers with epoxy resin based on bisphenol A, and the mixture is cured
with hexahydrophthalic anhydride or with diethylenetriamine.
Mixtures of epoxy resins and phenol-capped polyurethanes are disclosed in
GB patent specification 1,399,257. The polyurethanes are obtained by
reacting prepolymeric diisocyanates with unsubstituted or substituted
monophenols. The products no longer contain any free phenolic hydroxyl
groups. They are combined with epoxy resins and polyamine hardeners to
give curable coating compositions which display particular elasticity.
Prior art products based on epoxy resins and butadiene homopolymers or
copolymers normally do not contain large amounts of the flexibilising
modifier, as compositions containing a large amount of modifier cannot be
cured or can only be insufficiently cured, or their viscosities are too
high. Polybutadiene oligomers with epoxy reactive groups are not compat-
ible with the epoxy resin.
1 335389
It has now been found that it is possible to cure
mixtures of epoxy resins and large amounts of special
diene/lactone block polymers and thus to prepare highly flexible
products. The diene/lactone block polymers as defined herein are
readily dispersible without the addition of further dispersing
auxiliaries.
Accordingly, the present invention relates to
compositions comprising
(A) an epoxy resin, and
(B) a block polymer containing
at least one block IBl) of a 1,3-diene-homopolymer or
-copolymer which contains, in addition to the diene
component, 0.1 to 50 mol-% of a vinylaromatic compound,
acrylonitrile, methacrylonitrile or of an acrylic acid
or methacrylic acid derivative and
at least two blocks (B2) of a lactone homopolymer or
copolymer which contains, in addition to the lactone
component, up to 10% by weight of an alkylene oxide or
a diol as co-component, and, if required,
(C) a compound of formula I
1 1 2
R X - C -Y - R ~ )m ( )
wherein m is 1 or 2, n is 2 to 6, Rl is the n-valent radical
of an elastomeric prepolymer, which is soluble or dispersible
in epoxy resins, after removal of the terminal isocyanate,
1 335389
-3a-
amino or hydroxyl groups, X and Y each are independently of
the other -0- or -NR3-, with the proviso that at least one of
these groups is -NR3-, R is an m+1-valent radical of a poly-
phenol or aminophenol after removal of the phenolic hydroxyl
groups or of the amino group, and R is hydrogen, C1-C6alkyl
or phenyl, and, if required,
(D) a hardener for epoxy resins, and, if required,
(E) an accelerator.
In principle, any of the epoxy resins customarily
employed in epoxy resin technology may be used as component (A).
Examples of epoxy resins are:
I) polyglycidyl and poly-(~-methylglycidyl) esters
which can be obtained by reacting a compound containing at least
two carboxyl groups in the molecule with epichlorohydrin or ~-
methylepichlorohydrin. The reaction is conveniently carried out
in the presence of a base.
An aliphatic polycarboxylic acid may be used as the
compound containing at least two carboxyl groups in the molecule.
Examples of such polycarboxylic acids are oxalic acid, succinic
acid, glutaric acid, adipic acid, pimelic acid, suberic acid,
azelaic acid and dimerised or trimerised linoleic acid.
It is also possible, however, to use cycloaliphatic
polycarboxylic acids, for example tetrahydrophthalic acid, 4-
methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-
methylhexahydrophthalic acid.
1 335389
-3b-
Examples of further aromatic polycarboxylic acids which
may be used are phthalic acid, isophthalic acid and terephthalic
acid.
4 1 335339
II) Polyglycidyl or poly-(~-methylglycidyl) ethers which can be obtained
by reaction of a compound containing at least two free alcoholic hydroxyl
groups and/or phenolic hydroxyl groups with a suitably substituted
epichlorohydrin under alkaline conditions, or in the presence of an acid
catalyst, and subsequent treatment with alkali.
Ethers of this type are derived, for example, from acylic alcohols suchas ethylene glycol, diethylene glycol and higher poly(oxyethylene)
glycols, 1,2-propanediol or poly(oxypropylene) glycols, 1,3-propanediol,
1,4-butanediol, poly(oxytetramethylene) glycols, 1,5-pentanediol,
1,6-hexanediol, 2,4,6-hexanetriol, glycerol, 1,1,1-trimethylolpropane,
pentaerythritol, sorbitol and polyepichlorohydrins.
They are also derived, for example, from cycloaliphatic alcohols such as
1,4-cyclohexanedimethanol, bis(4-hydroxycyclohexyl)-methane or 2,2-bis(4-
hydroxycyclohexyl)-propane, or they contain aromatic nuclei such as
N,N-bis(2-hydroxyethyl)aniline or p,p'-bis(2-hydroxyethylamino)diphenyl-
methane.
The epoxide compounds may also be derived from mononuclear phenols, forexample resorcinol or hydroquinone, or they are based on polynuclear
phenols, for example bis(4-hydroxyphenyl)methane, 4,4'-dihydroxybiphenyl,
bis(4-hydroxyphenyl)sulfone, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane,
2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)-
propane, as well as novolaks which can be obtained by condensing
aldehydes such as formaldehyde, acetaldehyde, chloral or furfuraldehyde,
with phenols such as phenol, or with phenols which are substituted in the
nucleus by chlorine atoms or C1-Cgalkyl groups, for example 4-chloro-
phenol, 2-methylphenol or 4-tert-butylphenol, or by condensation with
bisphenols, as described above.
III) Poly(N-glycidyl) compounds which may be obtained by dehydrochlor-
inating the reaction products of epichlorohydrin with amines which
contain at least two amino hydrogen atoms. These amines are, for example,
aniline, n-butylamine, bis(4-aminophenyl)methane m-xylenediamine or
bis(4-methyl-aminophenyl)methane.
_ - 5 ~ 1 3 3 5 3 8 9
The poly-(N-glycidyl) compounds also comprise, however, triglycidyl
isocyanurate, N,N'-diglycidyl derivatives of cycloalkyleneureas such as
ethyleneurea or 1,3-propyleneurea, and diglycidyl derivatives of
hydantoins such as 5,5-dimethylhydantoin.
IV) Poly(S-glycidyl) compounds, for example di-S-glycidyl derivatives
derived from dithiols, for example ethane-1,2-dith~l or bis(4-mercapto-
methylphenyl) ether.
V) Cycloaliphatic epoxy resins, for example bis(2,3-epoxycyclo-
pentyl) ether, 2,3-epoxycyclopentyl glycidyl ether, 1,2-bis(2,3-epoxy-
cyclopentyloxy)ethane or 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclo-
hexanecarboxylate.
It is also possible, however, to use epoxy resins in which the 1,2-epoxy
groups are attached to various heteroatoms or functional groups. These
compounds comprise, for example, the N,N,O-triglycidyl derivative of
4-aminophenol, the glycidyl ether/glycidyl ester of salicylic acid,
N-glycidyl-N'-(2-glycidyloxypropyl)-5,5-dimethylhydantoin or 2-glycidyl-
oxy-1,3-bis(5,5-dimethyl-1-glycidylhydantoin-3-yl)propane.
It is preferred to use epoxy resins having an epoxy content of 2 to
10 equivalents/kg and which are glycidyl ethers, glycidyl esters or
N-glycidyl derivatives of aromatic, heterocyclic, cycloaliphatic or
aliphatic compounds.
Particularly preferred epoxy resins are polyglycidyl ethers of bis-
phenols, for example 2,2-bis(4-hydroxyphenyl)propane or bis(4-hydroxy-
phenyl)methane, of novolaks obtained by reacting formaldehyde with a
phenol, or of the aliphatic diols mentioned above, especially 1,4-butane-
diol.
The most preferred epoxy resins are polyglycidyl ethers based on bis-
phenol A.
- 6 ~ 1 335389
The block polymer (B) of the compositions of this invention contains atleast one block (B1) of a 1,3-diene homopolymer or copolymer and at least
two blocks (B2) of a lactone homopolymer or copolymer. The block polymer
may be of the type B2-Bl-B2, Bl(B2) or -~Bl-B2~-. If the blocks Bl
or B2 are copolymers, they are preferably random polymers.
Examples of 1,3-dienes for the preparation of the block (Bl) are
butadiene, isoprene and chloroprene. Copolymers based on butadiene are
preferred.
In addition to the diene component, the block Bl may contain 0.1 to
50 mol%, preferably 0.1 to 30 mol%, based on the entire block, of one or
more ethylenically unsaturated co-components, especially of a vinyl-
aromatic compound, acrylonitrile, methacrylonitrile or of an acrylic acid
or methacrylic acid derivative.
Examples of suitable ethylenically unsaturated comonomers for the
preparation of the block (B1) are acrylic acid, methacrylic acid, esters
of acrylic or methacrylic acid, for example the methyl, ethyl or glycidyl
esters, amides of acrylic or methacrylic acid, fumaric acid, itaconic
acid, maleic acid or the esters or hemiesters thereof, for example the
monomethyl or dimethyl esters, or maleic acid, or itaconic anhydride;
vinyl esters, for example vinyl acetate, styrene, substituted styrenes
such as styrenes which are chlorinated or brominated in the nucleus, or
vinyl toluene, ethylene, propylene, or preferably acrylonitrile or
methacrylonitrile.
Preferred co-components of the block (Bl) are styrene, acrylates,
methacrylates or, preferably, acrylonitrile. The block (Bl) of the block
polymer is preferably a butadiene/acrylonitrile copolymer or, most
preferably, a butadiene homopolymer.
The length of the block (Bl) is preferably equivalent to a molecular
weight M of 500 to 10 000, more particularly from 1000 to 5000. If the
co-component, or one of the co-components, of the block (Bl) contains
groups which are reactive with epoxy resins of cyclic lactones, for
- _ 7 _ 1 3 3 5 3 8 9
example the carboxyl groups of acrylic acid or methacrylic acid, then the
block (B1) preferably contains not more than 10 mol% of said co-
component.
Block polymers of the type B2-Bl-B2 re obtained by polymerising cyclic
lactones on to end groups of the block (Bl) which are reactive with
ryGlic lactones. Block polymers of the type Bl(B2) are obtained by
polymerising cyclic lactones on to functional groups of comonomer units
of the block Bl, which functional groups are reactive with cyclic
lactones.
The block polymer (B) preferably contains not less then 20 % by weight,most preferably 25 to 55 % by weight, of the 1,3-diene, based on the
total weight of the blocks (Bl) and (B2).
The blocks (B2) of the block polymer are preferably obtained by homo- or
copolymerisation of lactones of formula
~ ~ ~ O or /C= ~ ~ ~ =O
wherein the substituents R are independently of one another hydrogen,
alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl, with the proviso that
the total number of carbon atoms of the sustituents R is not greater than
12, and wherein a is 1, 3, 4 or 5.
Alkyl groups R are straight-chain or branched radicals and are, for
example, methyl, ethyl n-propyl, isopropyl, n-butyl, isobutyl, tert-
butyl, n-pentyl, n-hexyl, 2-ethylbutyl, n-heptyl, n-octyl, 2-ethylhexyl,
n-nonyl, n-decyl, n-undecyl or n-dodecyl. Preferably R is C1-C6alkyl,
especially straight-chain C1-C6alkyl and, most preferably, is methyl.
R as cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl,
cyclooctyl or cyclododecyl. The preferred meanings are cyclohexyl and
cyclopentyl.
~ -- 8
1 335389
R as alkenyl is, for example, vinyl, allyl, l-propenyl, l-butenyl,
l-pentenyl or l-hexenyl, preferably vinyl or l-propenyl and, most
preferably, allyl.
Cycloalkenyl is, for example, cyclohexenyl or cyclopentenyl. The
preferred aryl radical is phenyl. R is preferably hydrogen.
Examples of suitable lactones are ~-propiolactone, ~-valerolactone,
E-caprolactone and lactones of the following acids: 2-methyl-3-hydroxy-
propionic acid, 3-hydroxynonanoic acid or 3-hydroxypelargonic acid,
2-dodecyl-3-hydroxypropionic acid, 2-cyclopentyl-3-hydroxypropionic acid,
3-phenyl-3-hydroxypropionic acid, 2-naphthyl-3-hydroxypropionic acid,
2-n-butyl-3-cyclohexyl-3-hydroxypropionic acid, 2-phenyl-3-hydroxytri-
decanoic acid, 2-(2-methylcyclopentyl)-3-hydroxypropionic acid, 2-methyl-
phenyl-3-hydroxypropionic acid, 3-benzyl-3-hydroxypropionic acid,
2,2-dimethyl-3-hydroxypropionic acid, 2-methyl-5-hydroxyvaleric acid,
3-cyclohexyl-5-hydroxyvaleric acid, 4-phenyl-5-hydroxyvaleric acid,
2-heptyl-4-cyclopentyl-5-hydroxyvaleric acid, 2-methyl-3-phenyl-5-
hydroxyvaleric acid, 3-(2-cyclohexylethyl)-5-hydroxyvaleric acid,
4-benzyl-5-hydroxyvaleric acid, 3-ethyl-5-isopropyl-6-hydroxycaproic
acid, 2-cyclopentyl-4-hexyl-6-hydroxycaproic acid, 3-phenyl-6-hydroxy-
caproic acid, 3-(3,5-diethylcyclohexyl)-5-ethyl-6-hydroxycaproic acid,
4-phenylpropyl-6-hydroxycaproic acid, 2-benzyl-5-isobutyl-6-hydroxy-
caproic acid, 2,2,4-trimethyl-3-hydroxy-4-pentenoic acid, 7-phenyl-6-
hydroxy-6-octenoic acid, 2,2-bis(l-cyclohexyl)-5-hydroxy-5-heptenoic
acid, 2,2-dipropenyl-5-hydroxy-5-heptenoic acid, 2,2-dimethyl-4-propenyl-
3-hydroxy-3,5-heptadienoic acid and the like. Mixtures of two or more of
the above lactones may also be used.
The lactone-containing block (B2) may also contain smaller amounts,
preferably up to 10 % by weight, of co-components. Examples of suitable
co-components are alkylene oxides such as ethylene oxide or propylene
oxide, or diols such as hexanediol.
It is especially preferred to use E-caprolactone as lactone component of
the block (B2).
1 335389
g
Block polymers containing 1,3-diene homopolymer or copolymer blocks andlactone homopolymer or copolymer blocks are known and can be prepared in
known manner.
The blocks (B1) can be prepared, for example, by radical or anionic
polymerisation of ethylenically unsaturated compounds using known
catalysts. The blocks (B1) contain functional groups such as COOH, OH,
SH, NHz, /NH or -¢-M groups, where M is an alkali metal such as Li,
which may react further with the lactone monomer to give the block
polymer. The functional groups can be introduced by using a suitable
functional initiator or by incorporating comonomers which contain
functional groups into the polymer chain.
Suitable diene-containing polymers containing functional end groups as
well as methods of preparing them are described, for example, in Rubber
Chemistry and Technology, Vol. 42, pp. 71-109 (1969).
The diene-containing block (Bl) may also consist of microparticles
having a diameter of ca. 0.1-50 ~m, preferably of 0.1-20 ~m, which are
prepared, for example, by emulsion polymerisation of dienes with
comonomers which contain OH or COOH groups, or by polymerisation of such
mixtures of monomers in a lactone such as ~-caprolactone. Suitable
methods of preparing emulsion polymers are described, for example, in
W.R. Sorensen, T.W. Campbell, Preparative Methods of Polymer Chemistry,
Interscience Publishers, John Wiley & Sons, New York 1968, page 313.
Many such suitable diene-containing functional polymers are commercially
available, for example HYCAR~ CTB, CTBN or ATBN polymers sold by
Goodrich.
The reaction of the diene-containing polymers containing COOH, OH, SH,
NH2 or /NH functional groups with a suitable lactone is preferably
carried out in a temperature range from ca. 100-250C, more particularly
at ca. 180C, for ca. 1 to 10 hours in the presence of a reaction
catalyst such as dibutyltin oxide, dibutyltin laurate or titanium
tetraisopropylate. The amount of catalyst is preferably 0.01 to 5 ~0 by
weight, most preferably 0.1 to 0.5 % by weight, based on the weight of
lo - 1 3 3 5 3 8 9
the lactone. The reaction of the diene-containing polymer which contains
-¢-M groups such as -¢-Li groups with lactones is preferably
carried out in the temperature range from ca. -30 to +150C, most
preferably from ca. O to 120C.
Specific methods of preparing the diene/lactone block polymers using
oxirane compounds or polyaziridinyl compounds are described by
L.H. Hsien et al. in US patent specification 3,585,257, in J. Appl.
Polym. Sci. 22, 1119-1127 (1978), and in US patent specifica-
tion 3,880,955. For example, an alkali metal containing diene polymer is
reacted first with an oxirane such as ethylene oxide, and the resultant
product is then reacted with a lactone such as ~-caprolactone to the
corresponding block polymer. In the aforementioned US patent 3,585,257,
individual cycloaliphatic diepoxides and individual glycerol tris(epoxy-
alkanoates) are also cited as suitable oxirane compounds and used in
Examples IX and X. Depending on their composition, the diene/lactone
block polymers referred to above have rubber-like, leather-like or
thermoplastic properties and display good mechanical properties and ozone
resistance.
According to the teaching of German Offenlegungsschrift 3,000,290,
similar block polymers are used together with aromatic polycarbonates as
impact strength modifiers in thermoplastic polyester compositions. The
block polymer is a homopolymer or copolymer of conjugated dienes and/or
vinyl aromatic compounds, which block polymer is end-blocked with a
rubber-like polyester, for example a styrene/butadiene copolymer which is
end-blocked with E-caprolactone.
The block length of the polylactone-containing block (B2) of the eligible
block polymers of this invention is preferably equivalent to a molecular
weight M of 200 to 10 000, most preferably of 500 to 3000.
The average functionality of the block polymers (B) is not less than 2,preferably from 2 to 6 and, most preferably, from 2 to 3.
1 335389
-- 11 --
The block polymers (B) may also contain glycidyl groups. One possible
method of preparing such glycidylated block polymers comprises reacting
the block polymers (B) with a glycidyl group containing epoxy resin. In
this process, the glycidyl groups of the resin react with the reactive
functional groups, for example with carboxyl groups, of the block
polymer. If desired, the reaction can also take place in the presence of
an advanceme~t agent for epoxy resins, for example of a bisphenol. The
reaction suitably takes place in the presence of a catalyst such as
triphenylphosphine, a tertiary amine, a quaternary ammonium or phospho-
nium salt or chromium acetylacetonate, at elevated temperature, for
example at 140C, for ca. 4 to 5 hours. In this reaction it is preferred
to use ca. 0.1-5 % by weight, more particularly ca. 1-2 % by weight, of
the catalyst, based on the amount of epoxy resin and, if used, the
advancement agent.
Another possible method of preparing the glycidylated block polymers
comprises reacting the 1,3-diene-containing blocks with a glycidyl group
containing epoxy resin in the absence of presence of an advancement
agent, for example a bisphenol, and subsequently reacting the adduct
obtained with a lactone, for example ~-caprolactone. In this method of
preparation, the epoxy groups of the resin react with reactive functional
groups, for example carboxyl groups, of the 1,3-diene polymer, and then
the secondary hydroxyl groups formed by the addition of the carboxyl
groups to the glycidyl groups react with the lactone to give the
glycidylated diene/lactone block polymer. The reaction conditions and any
catalysts used for the formation of the epoxy resin adducts and for the
polymerisation of the lactone conform to the conditions already referred
to for carrying out these reactions. The reaction of the epoxy resin
adducts with cyclic lactones may also be carried out in situ during the
curing if cyclic lactones with transesterification catalysts, for example
dibutyltin oxide, are added.
The above described glycidylated adducts are novel and also constitute an
object of this invention.
~~ - 12 - 1 335389
Accordingly, the invention relates to glycidylated adducts obtainable by
reacting a block polymer (B) which contains at least one block (B1)
based on a 1,3-diene homopolymer or copolymer and at least two
blocks (B2) of a lactone homopolymer or copolymer with a glycidyl group
containing epoxy resin.
The invention further relates to glycidylated reaction products
obtainable by reacting a lactone with an adduct of a 1,3-diene homo-
polymer or copolymer with a glycidyl group containing epoxy resin.
In addition to components (A) and (B), the composition of this invention
may further comprise (C) a compound of formula I
Rl X--C--Y--R2--~OH) (I),
-n
wherein m is 1 or 2, n is 2 to 6, R1 is the n-valent radical of an
elastomeric prepolymer, which is soluble or dispersible in epoxy resins,
after removal of the terminal isocyanate, amino or hydroxyl groups, X
and Y are each independently of the other -O- or -NR3-, with the proviso
that at least one of these groups is -NR3-, R2 is an m + l-valent radical
of a polyphenol or aminophenol after removal of the phenolic hydroxyl
groups or of the amino group, and R3 is hydrogen, C1-C6alkyl or phenyl.
Component (C) is a selected polyurethane or a selected polyurea derivedfrom a specific prepolymer. The term "elastomeric prepolymer radical R1"
will be understood as meaning within the context of this description the
radical of a prepolymer which, after capping the n-isocyanate, n-amino or
n-hydroxyl end groups of said radical, results in a compound of formula I
which, in conjunction with the epoxy resin (A) and the block polymer (B)
produces, after curing, an elastomer phase or a mixture of elastomer
phases. These elastomer phases may be homogeneous or heterogeneous
combinations of components (A), (B) and (C). The elastomer phase or
phases usually have a glass transition temperature below 0C.
The expression "prepolymer which is soluble or dispersible in epoxy
resins" will be understood as meaning within the context of this
description the radical of a prepolymer which, after capping the n iso-
- - 13 - 1 335389
cyanate, n amino or n hydroxyl end groups of said radical, results in a
compound of formula I which is soluble or dispersible in an epoxy
resin (A) or in a combination of an epoxy resin (A) and a block
polymer (B), without the addition of further auxiliaries, such as
emulsifiers. Hence a homogeneous phase forms, or at least no macroscopic
phase separation of one of components (A), (B) or (C) or of a mixture of
said components takes place.
The solubility or dispersibility of (C) in the combination of (A) and (B)
is effected primarily by the choice of suitable prepolymer radicals R1.
Examples of suitable radicals are cited hereinafter in the description of
the preparation of component (C).
The compound of formula I is preferably a water-insoluble compound, by
which is meant in the context of this description a compound whose
solubility in water is less than 5 % by weight, preferably less than
0.5 % by weight, and which, when stored in water, absorbs only a small
amount of water, preferably less than 5 % by weight, most preferably less
than 0.5 % by weight, or which, in the course thereof, exhibits only
slight swelling.
The prepolymers on which R1 is based usually have molecular weights
(number average) of 150 to 10 000, preferably 1 800 to 3 000.
The average functionality of these prepolymers is at least two, prefera-
bly 2 to 3 and, most preferably, 2 to 2.5.
The term "elastomeric polyurethane" or "elastomeric polyurea" is known
per se to those skilled in the art (cf. C. Hepburn: "Polyurethane
Elastomers", Applied Science Publishers, London 1982).
In general, elastomeric polyurethanes or polyureas contain rigid and
flexible components (hard and soft segments).
Component (C) may be a liquid or thermoplastic phenol-terminated poly-
urethane or polyurea of formula I. Compounds having a softening point
below 80C, preferably below 40C, are preferred.
_ - 14 ~ 1 3 3 5 3 & 9
Component (C) may also be used as an adduct of a phenol-terminated
polyurethane or polyurea of formula I with an epoxy resin. Adducts of
this type can be prepared in the manner described above.
For highly flexible systems, adducts of such polyurethanes or polyureascontaining glyc-idyl ethers of aliphatic diols, such as 1,4-butanediol or
1,6-hexanediol, are preferred.
Suitable components (C) can be linear or are branched types. The degreeof crosslinking is chosen such that the polymer does not form a macro-
scopic gel. This condition will generally be met if component (C) is
soluble or at least dispersible in a polar organic solvent or in an epoxy
resin.
The compounds of formula I in which X is -NR3- and Y is -NR3- or,
preferably, -O-, may be prepared by various routes, depending on the
nature of the prepolymer on which R1 is based.
Prepolymer isocyanates can be prepared by reacting compounds of
formula IIIa with polyphenols or aminophenols of formula IVa (process a)
Rl ~NCO ) ( I I I a), H--Y--R2 ~0H ) ( IVa);
polyureas of formula I, wherein X is -NR3- and Y is -NR3-, may also be
prepared by reacting prepolymeric amines of formula IIIb with urethanes
of formula IVb (process b)
R1-~NR3H) (IIIb), R11-O- 8 NR3-R2 ~OH) (IVb).
Compounds of formula I, wherein X is -NR3- and Y is -NR3- or -O-, and
which have ortho-phenols or peri-phenols or ortho-aminophenols or
peri-aminophenols as end groups, can also be prepared by reacting
compounds of formula IIIb with cyclic carbonates or urethanes of
formula IVc (process c)
~ - 15 - l 3 3 5 3 8 9
Rl-~NR3H) (IIIb), O=C ~ 12 (IVc)
In the formulae IIIa, IIIb, IVa, IVb and IVc above, the substituents R1,
R2, R3 and Y and also the indices m and n are as defined previously, R
is a radical which acts as a leaving group, for example alkyl or aryl,
preferably C1-C6alkyl or phenyl, a~d R12 is a divalent, carbocyclic-
aromatic radical which has one of the meanings given for R2 and at which
each of the groups -O- and -Y- are in the ortho- or peri-position
relative to one another.
The compounds of formula I, wherein X is -O- and Y is -NR3-, may be
obtained by methods analogous to those described in European patent
application 247,467.
For example, an elastomeric and hydroxyl-terminated prepolymer of
formula V, which is soluble or dispersible in epoxy resins, is reacted
with an amount equivalent to the OH content of the prepolymer, of a
carbamate of the formula IVb as defined above
R1-~OH) (V), Rl1-O-C-NR3-R2-~OH) (IVb).
n m
In these formulae, the substituents R1, R2, R3 and R11 and also the
indices m and n are as defined above.
In another embodiment, the prepolymer of formula V may be reacted firstwith an amount of phosgene equivalent to the OH content, and the
resultant chlorocarbonyloxy derivative can then be reacted with a phenol
or aminophenol of formula IVa.
The radical R2 is normally derived from phenols or aminophenols con-
taining a mononuclear or polynuclear, carbocyclic-aromatic radical.
Phenol or aminophenol radicals containing several carbocyclic-aromatic
radicals can be condensed or, preferably, attached through bridge
members.
1 335389
- 16 -
Examples of phenols or aminophenols which contain condensed radicals are
dihydroxynaphthalenes or dihydroxyanthracenes or aminonaphthols.
Preferred radicals R2 are derived from bisphenols of formula VI
HO OH
(VI),
(~R4) (Rs)
P q
wherein Z is a direct C-C bond or a bridge member selected from the group
consisting of -CR6R7-, -O-, -S-, -SOz-, -CO-, -COO-, -CONR8- and
-SiR9R10-, R4 and Rs are each independently of the other C1-C2calkyl~
Cz-C6alkenyl, Cz-C6alkynyl or halogen, p and q are each independently of
the other O, 1 or 2, R6, R7 and R3 are each independently of the other
hydrogen, -CF3 or C1-C6alkyl, or R6 and R7, together with the carbon atom
to which they are attached, form a cycloaliphatic radical having
5-12 ring carbon atoms, and R9 and R1~ are C1-C6alkyl.
Particularly preferred radicals R2 are derived from bisphenols of
formula VI, wherein the hydroxyl groups are in the 4,4'-position,
epsecially the derivatives in which p and q are 1 and R4 and Rs are
allyl.
Other particularly preferred radicals R2 are derived from bisphenols offormula VI, wherein Z is selected from the group consisting of -CHz-,
-C(CF3)2-, -O-, -SO2-, a direct C-C bond and, especially, -C(CH3)z-, p
and q are each O or 1 and R4 and Rs are C~-C6alkyl, Cz-C6alkenyl,
particularly allyl, or Cz-C6alkynyl, preferably propargyl.
Further preferred radicals R2 are derived from mononuclear aminophenols,
for example 2-, 3- or 4-aminophenol, or from mononuclear polyphenols, for
example resorcinol, hydroquinone or pyrogallol.
Patricularly preferred radicals R2 are derived from bisphenols. Examples
of bisphenols are 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)ether,
bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)methane, 2,2-bis(4-
- 17 - l 3 3 5 3 8 9
hydroxyphenyl)propane and the corresponding 3,3'-dimethyl, 3,3'-dinonyl,
3,3'-diallyl, 3,3'-dichloro, 3,3'-dibromo and 3,3',5,5'-tetrabromo
derivatives of these compounds.
R4 or Rs as C1-Czoalkyl are linear or branched radicals. Examples of
these radicals are: methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-
butyl, tert-butyl, n-pentyl, n-hexyl, 2-ethylbutyl, n-heptyl, n-octyl,
2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl,
n-hexadecyl, n-octadecyl or n-eicosyl. R4 and Rs are preferably C1-C6-
alkyl, more particularly linear C1-C6alkyl and, most preferably, methyl.
Radicals defined as C1-C6alkyl are preferably linear radicals, i.e.
methyl, ethyl, n-propyl, n-butyl, n-pentyl or n-hexyl, most preferably
methyl.
R4 and Rs as C2-C6alkenyl are typically vinyl, allyl, 1-propenyl, 1-
butenyl, 1-pentenyl or 1-hexenyl. Vinyl, 1-propenyl and allyl are
preferred, and allyl is most preferred.
R4 and Rs as C2-C6alkynyl are typically ethynyl, propargyl, 1-butynyl,
1-pentynyl or 1-hexynyl. Propargyl is preferred.
R4 and Rs as halogen may be fluoro, chloro, bromo or iodo. Chloro or
bromo is preferred, and bromo is most preferred.
Compounds of formula VI containing alkyl or alkenyl substituents are
preferably used if the composition of this invention is to have high
adhesion to oily steel.
Halogen-containing compounds of the formula VI generally increase the
flame resistance.
A cycloaliphatic radical CRsR7 is, for example, a cyclopentylidene,
cyclohexylidene, cycloheptylidene, cyclooctylidene or cyclododecylidene
radical. Cyclohexylidene and cyclododecylidene are preferred.
R3 is preferably hydrogen.
- 18 - 1 335389
The isocyanate of the formula IIIa is either a prepolymer al) which is
derived from the addition of a polyisocyanate, preferably a diisocyanate
or triisocyanate and, most preferably, a diisocyanate, to a prepolymer
polyhydroxyl or polysulfhydryl component or to a mixture of such pre-
polymer components, if appropriate in combination with chain extenders
(short-chain polyhydroxyl, polysulfhydryl or polyamine compounds) or a
prepolymer polyisocyanate a2) which is derived from a prepolymer poly-
amine of the formula IIIb, especially from a prepolymer polyetheramine.
Prepolymer components for the preparation of al) may be condensation oraddition polymers on to which in some cases 1-olefins may be grafted,
which 1-olefins also contain polar groups, for example nitrile, ester or
amide groups, in addition to non-polar groups. Examples of such polymers
are polyesters, polyethers, polythioethers, polyacetals, polyamides,
polyester-amides, polyurethanes, polyureas, alkyd resins, polycarbonates
or polysiloxanes, provided these compounds are hydroxyl-terminated or
sulfhydryl-terminated, result in compounds of formula I which are soluble
or dispersible in epoxy resins, and impart elastomeric properties to
these resins in accordance with the above definition.
Polyethers or segmented prepolymers containing polyether segments, suchas polyether amides, polyether urethanes and polyether ureas, are
preferred.
These compounds are known to those skilled in the art in the field of
polyurethane chemistry as components for the preparation of poly-
urethanes. They can be linear or branched; linear types are preferred.
Preferred components for prepolymers al) are hydroxyl-terminated pre-
polymers having average molecular weights (number average) of 150-10 000,
most preferably 500-3 000.
In addition to the hydroxyl-terminated or sulhydryl-terminated pre-
polymers, chain extenders may also be used for the preparation of the
prepolymer polyisocyanates al).
1 335389
-- 19 --
Such monomers are preferably difunctional or trifunctional.
If trifunctional or polyfunctional hydroxyl-terminated or sulfhydryl-
terminated prepolymers or trifunctional or polyfunctional chain extenders
are used for the preparation of component al), these components should be
chosen such that an adduct al) which is soluble or at least swellable in
organic solvents is formed.
When using polyfunctional components, the degree of crosslinking can beregulated in a manner known per se by the nature and ratios of said
components. It is also possible to vary the elastomer properties in a
manner known per se by means of the degree of crosslinking.
Thus when using difunctional prepolymers or trifunctional or poly-
functional chain extenders, normally only a small proportion of the
polyfunctional component will be used. But if a combination of di-
functional and trifunctional or polyfunctional prepolymers is used, then
usually a larger amount of the polyfunctional chain extender can be
present without excessive crosslinking taking place. The degree of
crosslinking will also depend on the functionality of the polyisocyanate.
Thus if trifunctional or polyfunctional, hydroxyl-terminated or sulf-
hydryl-terminated components are present, diisocyanates will normally be
used; but if difunctional, hydroxyl-terminated or sulfhydryl-terminated
components are used, then polyfunctional isocyanates will also be used.
Examples of prepolymer components for the preparation of polyiso-
cyantes al) are hydroxyl-terminated polyethers, in particular polyethers
which lead to water-insoluble compounds of the formula I.
These polyethers comprise, for example, the polyalkylene ether polyols
which are obtained by anionic polymerisation, copolymerisation or block
copolymerisation of alkylene oxides such as ethylene oxide, propylene
oxide or butylene oxide, with difunctional or polyfunctional alcohols
such as 1,4-butanediol, l,l,l-trimethylolethane, l,l,l-trimethylol-
propane, 1,2,6-hexanetriol, glycerol, pentaerythritol or sorbitol, or
with amines such as methylamine, ethylenediamine or 1,6-hexylenediamine,
as initiator components, or by cationic polymerisation or copolymerisa-
tion of cyclic ethers such as tetrahydrofuran, ethylene oxide or
~ ~ - 20 - l 3353~9
propylene oxide, using acid catalysts such as BF3.etherate or by poly-
condensation of glycols which are able to undergo polycondensation with
the elimination of water, for example 1,6-hexanediol, in the presence of
acid etherification catalysts such as p-toluenesulfonic acid. It is also
possible to use oxalkylation products of phosphoric acid or phosphorous
acid with ethylene oxide, propylene oxide, butylene oxide or styrene
oxide.
Other preferred hydroxyl-terminated polyethers are those on to which
1-olefins, such as acrylonitrile, styrene or acrylic acid esters, have
been grafted. In this case the proportion by weight of the graft
component is generally 10-50 ~/0, particularly 10-30 %, relative to the
amount of polyether employed.
Other examples of prepolymer components for the preparation of polyiso-
cyanates al) are hydroxyl-terminated polyester-polyols derived from
dicarboxylic and/or polycarboxylic acids and diols and/or polyols,
preferably from dicarboxylic acid and diols.
Examples of such polycondensates are the hydroxyl-terminated polyesters
which can be obtained by polycondensation of adipic acid, sebacic acid,
azelaic acid, dimeric and timeric fatty acids, phthalic acid, isophthalic
acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid
and endomethylenetetrahydrophthalic acid with propylene glycol, 1,4-
butanediol, 1,6-hexanediol, diethylene, triethylene and tetraethylene
glycol, dipropylene, tripropylene and tetrapropylene glycol, dibutylene,
tributylene and tetrabutylene glycol, 2,2-dimethylpropane-1,3-diol,
1,1,1-trimethylolpropane, 1,1,1-trimethylolethane and 1,2,6-hexanetriol.
Other suitable prepolymer components for the preparation of polyiso-
cyanates al) are hydroxyl-terminated polybutadienes, which are reacted
especially with hydroxyl-terminated polyethers to form component al).
Further examples of suitable prepolymer components for the prepartion of
polyisocyanates al) are polymerisation products of lactones, for example
E-caprolactones; or polyalkylene thioether polyols, for example the
~ - 21 - 1 335389
polycondensation products of thiodiglycol with itself and with diols
and/or polyols, for example 1,6-hexanediol, triethylene glycol, 2,2-di-
methyl-1,3-propanediol or 1,1,1-trimethylolpropane.
The preferred prepolymer components for the preparation of polyiso-
cyanates al) are hydroxyl-terminated polyethers or polyesters.
Yet further preferred prepolymer components for the preparation of
polyisocyanates al) are mixtures of hydroxyl-terminated polybutadiene and
hydroxyl-terminated polyalkylene glycol or hydroxyl-terminated poly-
alkylene glycols on to which 1-olefins have been grafted, in particular
styrene or acrylic acid derivatives such as acrylic acid esters or
acrylonitrile.
~specially preferred prepolymer components for the preparation of
polyisocyanates al) are hydroxyl-terminated polyethers, in particular
dihydroxyl-terminated polyalkylene glycols.
Chain extenders for the preparation of the prepolymer polyisocyanate al)
are known per se. Examples of these chain extenders are the diols and
polyols mentioned above for the preparation of the hydroxyl-terminated
polyethers, in particular the diols and triols such as 1,4-butanediol,
1,1,1-trimethylolpropane or hydroquinone 2-hydroxyethyl ether, or
diamines such as diaminoethane, 1,6-diaminohexane, piperazine, 2,5-di-
methylpiperazine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane,
4,4'-diaminocyclohexylmethane, 1,4-diaminocyclohexane and 1,2-propylene-
diamine, or hydrazine, amino acid hydrazides, hydrazides of semi-
carbazidocarboxylic acids, bishydrazides and bissemicarbazides.
The preferred chain extenders are short-chain diols or triols.
The prepolymer polyisocyanate a2) can be obtained in a manner known perse from amino-terminated prepolymers of formula IIIb, preferably from
amino-terminated polyethers, by reaction with phosgene or with polyiso-
cyanates, preferably diisocyanates or triisocyanates and, most prefera-
bly, diisocyanates. In addition to containing the amino groups, the
amino-terminated prepolymers generally do not contain any further
- - 22 ~ 1 335389
radicals having active hydrogen atoms. Prepolymers having terminal amino
groups are derived in general from the hydroxyl-terminated condensation
or addition polymers described above as components for al), particularly
from polyethers.
They can be obtained by reacting said condensation or addition polymerscontaining secondary hydroxyl groups with ammonia,:~r by reacting said
condensation or addition polymers containing primary hydroxyl groups, for
example polybutylene glycol, with acrylonitrile, and subsequently
hydrogenating these products.
Prepolymeric amino-terminated poly-THF can also be obtained by the method
of S. Smith et al. in Macromol. Sci. Chem., A7(7), 1399-1413 (1973), by
terminating a difunctional, still active cationic THF polymer with
potassium cyanate.
The polyisocyanates used for the preparation of components al) or a2) are
normally aliphatic, cycloaliphatic, aromatic or araliphatic diiso-
cyanates, triisocyanates or tetraisocyanates, or precursors which can be
converted into such isocyanates.
Preferred polyisocyanates are the aliphatic, cycloaliphatic or
araliphatic diisocyanates or triisocyanates, the aliphatic or cyclo-
aliphatic diisocyanates being especially preferred.
The preferred aliphatic diisocyanates are usually linear or branched
~,~-diisoscyanates. The alkylene chains may be interrupted by oxygen or
sulfur atoms and may or may not contain ethylenically unsaturated bonds.
~,~-Diisocyanates having linear, saturated Cz-C2~alkylene radicals are
preferred.
Examples of such radicals are ethylene, trimethylene, tetramethylene,
pentamethylene, hexamethylene, heptamethylene, octamethylene, deca-
methylene, dodecamethylene, tetradecamethylene, hexadecamethylene,
octadecamethylene and eicosamethylene.
_ - 23 ~ 1 335389
Examples of preferred aliphatic ~ diisocyante radicals which are
interrupted by hetero atoms are -(CH2-CH2-O)o CH2-CHz-,
-(CH(CH3)-CHz-O) - CH(CH3)-CH2-, -(CH2-CHz-CH2-CH2-O)o CHz-CH2-CH2-CH2-
and -(CH2-CH2-S) - CHz-CH2-, wherein o is 1 to 20.
The preferred cycloaliphatic diisocyantes are usually derivatives whichare derived from substituted or unsubsti~uted cyclopentanes, cyclohexanes
or cycloheptanes. Two such rings may also be attached to one another
through a bridge member.
Examples of such radicals are 1,3-cyclohexylene, 1,4-cyclohexylene or
dodecahydrodiphenylmethane-4,4'-diyl.
It is also possible to use diisocyanates or triisocyanates derived fromdimeric or trimeric fatty acids. These compounds can be obtained in a
manner known per se from the fatty acids by rearrangement to give the
corresponding diisocyanates or triisocyanates (Hoffmann, Curtius or
Lossen rearrangements).
Examples of preferred aromatic diisocyanates correspond to the examplesof divalent phenol radicals cited above, in which the -OH groups are
replaced by -NCO groups.
Examples of araliphatic diisocyanate radicals are 1,2-xylylene and
1,4-xylylene.
Specific examples of suitable polyisocyanates are 2,4-diisocyanatotoluene
and technical mixtures thereof with 2,6-diisocyanatotoluene, 2,6-diiso-
cyanatotoluene, 1,5-diisocyanatonaphthalene, 4,4'-diisocyanatodiphenyl-
methane and technical mixtures of various diisocyanatodiphenylmethanes
(for example the 4,4'- and 2,4'-isomers), urethanised 4,4'diisocyanatodi-
phenylmethane, carbodiimidised 4,4'-diisocyanatodiphenylmethane, the
uretdione of 2,4-diisocyanatotoluene, triisocyanatotriphenylmethane, the
adduct formed from diisocyanatotoluene and trimethylolpropane, the trimer
formed from diisocyanatotoluene, diisocyanato-m-xylylene, N,N'-bis-(4-
methyl-3-isocyanatophenyl)urea, mixed trimerisation products of diiso-
cyanatotoluene and 1,6-diisocyanatohexamethylene, 1,6-diisocyanatohexane,
~ - 24 - ~ 335389
3,5,5-trimethyl-1-isocyano-3-isocyanatomethylcyclohexane (isophorene
diisocyanate), N,N',N"'-tris-(6-isocyanatohexyl)biuret, 2,2,4-tri-
methyl-1,6-diisocyanatohexane, 1-methyl-2,4-diisocyanatocyclohexane,
dimeryl, diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, trimeric
isophorone diisocyanate, trimeric hexane diisocyanate and methyl
2,6-diisocyanatohexanoate.
The preparation of component al) or a2) is effected in a manner known per
se by reacting the hydroxyl-terminated, sulfhydryl-terminated or amino-
terminated elastomeric prepolymer component with a polyisocyanate or
with a mixture of these components The reactions may be carried out in
the presence or absence of a chain extender.
The preparation of the component al) or a2) is carried out without a
solvent or in solvents which are inert to isocyanates.
Examples of inert solvents are esters such as ethyl acetate, butyl
acetate, methyl glycol acetate and ethyl glycol acetate; ketones such as
methyl ethyl ketone or methyl isobutyl ketone; aromatic compounds such as
toluene or xylene, or halogenated hydrocarbons such as trichloroethane or
dichloromethane.
If a certain additional chain extending reaction via urethane or urea
groups is tolerated or is even desired, then the prepolymers containing
hydroxyl, sulfhydryl or amino groups and the monomers which may be
present are reacted with the diisocyanate or polyisocyanate in an NCO/OH,
NCO/SH or NCO/NHz ratio of 1.5-2.5, preferably 1.8-2.2, first at 0-25C
and with cooling, and subsequently for several hours by heating to
preferably 50-120C.
If a chain extending reaction is not desired, then normally a sub-
stantially larger excess of diisocyanate or polyisocyanate, for example
an NCO/OH, NCO/SH or NCO/NHz ratio of 3-5, and no chain extender, will be
used, and the procedure is otherwise as described for low NCO/OH, NCO/SH
or NCO/NHz ratios. After the reaction, any excess diisocyanate or
polyisocyanate is removed, for example by thin film distillation or by
solvent extraction.
~ - 25 - 1 335389
The reaction of the hydroxyl-terminated, sulfhydryl-terminated or
amino-terminated prepolymers with polyisocyanates is carried out in the
presence of catalysts which are known per se.
Examples of these catalysts are diazabicyclooctane, dibutyltin dilaurate
or tin(II) octoate. These catalysts are added in the customary amounts,
for example in amounts of 0.001-2 % by weight, based on the amount of
polyisocyanate.
The reaction of components al) or a2) (polyisocyanate IIIa) with the
phenol or aminophenol IVa is carried out in similar manner to the
above-described reaction of the hydroxyl-terminated, sulfhydryl-
terminated or amino-terminated component with the polyisocyanate.
The amount of polyphenol or aminophenol IVa used in this reaction is
preferably such that the free NCO groups are substantially consumed by
the reaction and that mainly one -OH or -NHz group reacts per polyphenol
or aminophenol.
This condition will generally be met if about 2 or 3 mol of OH groups of
the bisphenol or trisphenol or about 1 mol of NHz groups of the amino-
phenol are supplied per 1 mol of free isocyanate groups.
In the case of the polyphenols IVa, the OH:NCO ratio is generally 1.5:1.0
to 3.0:1.0, preferably 1.8:1.0 to 2.5:1Ø
In the case of the aminophenols IVa, the NHz:NCO ratio is generally
0.8:1.0 to 1.2:1.0, preferably 0.8:1.0 to 1.0:1Ø
It is, of course, also possible to use excess amounts of component IVa,in which case chain lengthening can take place via the phenol; however,
the end product should not contain more than 50 % by weight, preferably
less than 10 % by weight, of unreacted component IVa, based on the total
mixture.
~ - 26 - 1 3 3 ~ 3 8 9
In the case of the aminophenols IVa, a stoichiometric amount is generally
desirable.
It is also possible to employ mixtures of phenol and/or aminophenol IVafor capping the polyisocyanate IIIa. These mixtures can also contain
small proportions of monophenols. In this process variant, the proportion
of monophenol is chosen such that the reaction ~roduct consists mainly of
compounds of formula I which contain free phenolic OH groups.
The amino-terminated prepolymers IIIb in process b) or c) will normallybe the prepolymer polyamines which have already been described in
process a) and which were used in that process for the preparation of the
prepolymer polyisocyanate components IIIa. Preferred compounds IIIb are
amino-terminated polethers as defined above.
The urethanes IVb are derived from aminophenols HR3N-R2-(oH) , wherein
R2, R3 and m are as defined above. Urethanes IVb are prepared by capping
these aminophenols with Rl1-O-CO-Cl in a manner known per se. In this
formula, Rll is as defined previously. The reaction of components IIIb
and IVb (process b) is generally carried out by adding the two components
in stoichiometric proportion or using a small excess of component IVb and
by heating the mixture such that virtually all the free amino groups of
IIIb are capped.
The reaction is preferably carried out in an inert solvent. Examples ofthese solvents have been listed above.
The cyclic carbonates or urethanes IVc are derived from ortho- or
peri-bisphenols or ortho- or peri-aminophenols of formula HO-Rl2-OH or
HR3N-Rl2-oH, respectively. In these formulae R3 and Rl2 are as previously
defined. The compounds IVc can be obtained therefrom by reaction with
phosgene. The reaction of components IIIb and IVc (process c) is
generally carried out by adding the two components in stoichiometric
proportion or using a small excess of component IVc. In other respects
the reaction is carried out as described in process a).
-- - 27 - 1 335389
The molecular weight M of the polyurethanes or polyureas (C) is
usually within the range from 500 to 50 000, preferably within the range
from 500 to 10 000 and, most preferably, within the range from 500 to
3 000.
The viscosity of these compounds is normally less than 150 000 mPa-s,
preferably less than 100 000 mPa-s (measured at 80C in an ~pprecht
viscosimeter).
The structures of the phenol-terminated polyurethanes or polyureas of
formula I which are derived from the reaction according to process a), b)
or c) differ, depending on the functionality of the prepolymer radical
Rl .
In process a) this functionality is determined, for example, by the
functionality of the hydroxyl-terminated, sulfhydryl-terminated or
amino-terminated prepolymers, by the chain extenders which may be used,
by the functionality of the isocyanate used for the preparation of IIIa,
and by the ratios of the individual reactants. Preferred components (C)
are compounds of formula I in which X is -NH- and Y is -NH- and, most
preferably, -O-.
Components (C) which are also preferred are compounds of formula I which
are substantially free from isocyanate groups and contain at least two
free phenolic hydroxyl groups and can be obtained by reacting
a) a prepolymer polyisocyanate which is
al) an adduct of a polyisocyanate with a prepolymer polyhydroxy or
polysulfhydryl compound or with a mixture of such compounds, without or
in conjunction with a chain extender, or
a2) is derived from a prepolymer polyether-amine, with
b) at least one phenol containing two or three phenolic hydroxyl groups
or an aminophenol containing one or two phenolic hydroxyl groups.
~specially preferred compounds of formula I are derived from prepolymer
polyisocyanates a) which have an average isocyanate functionality of
2 to 3.
- - 28 - 1 3 3 5 3 8 9
Compounds of formula I which are particularly preferred are those in
which component al) is an adduct of a polyisocyanate with a hydroxyl-
terminated prepolymer having an average molecular weight M of 150 to
10 000. The most preferred compounds of formula I are those in which the
component for the preparation of component al) is a hydroxyl-terminated
polyether or polyester.
This component for the preparation of component al) is preferably used in
conjunction with chain extenders.
Especially preferred compounds of formula I are those in which the
polyisocyanate for the preparation of component al) is an aliphatic,
cycloaliphatic, aromatic or araliphatic diisocyanate or triisocyanate.
In a preferred embodiment of the invention, the preparation of compo-
nent al) is carried out using a hydroxyl-terminated polyether or poly-
ester, in the absence of a chain extender and using an amount of polyiso-
cyanate equivalent to the OH content or an excess thereof, to give, after
capping with the polyphenol or aminophenol, polyurethanes of formula VII
[~(HO--~--R2-X-C-NH ~ Rl3-NH-8-o ~ R14 (VII),
wherein R2, m and n are as defined above, r is an integer from 1 to 3, X
is -O- or -NH-, Rl3 is the r + l-valent radical of an aliphatic, cyclo-
aliphatic, aromatic or araliphatic polyisocyanate after removal of the
isocyanate groups, and Rl4 is an n-valent, hydroxyl-terminated polyester
or polyether radical after removal of the terminal OH groups, with the
proviso that the index m and the radicals R2 and Rl3 may be different
within a given molecule.
Compositions containing compounds of the formula VII as component (C) are
preferred.
The index m is preferably 1. The index n is preferably 2 or 3, most
preferably 2. The index r is preferably 1. Preferred components (C) are
compounds of formula VII in which m is 1, n is 2 or 3, r is 1, X is -O-,
Rl3 is derived from an aliphatic, cycloaliphatic or aromatic diisocyanate
-
- 29 - 1 3 3 5 3 8 9
and R1 4 is a divalent or trivalent radical of a hydroxyl-terminated
polyester or polyether having a molecular weight M of 150 to 10 000
after removal of the terminal hydroxyl groups.
Especially preferred components (C) are compounds of formula VII, wherein
m is 1, n is 2 or 3, r is 1, X is -0-, R13 is derived from an aliphatic
or cycloal;phatic diisocyanate and R1 4 is a divalent or trivalent radical
of a polyalkylene ether polyol having a molecular weight M of 150 to
3 000 after removal of the terminal hydroxyl groups.
The particularly preferred components (C) of this last-defined type
comprise those in which n is 2 and R14 is a structural unit of
formula VIII
-(C H2s-0-)X CsH2s (VIII)
in which s is 3 or 4, x is an integer from 5 to 40 and the units
-C -H2 ~~ may differ within a given structural unit of formula VIII,
within the scope of the given definitions.
Examples of structural units of formula VIII are:
-(CHz-CH(CH3)-O) -CH2CH(CH3)-, -(CH2-CH2-CH2-CH20)x-CHzCH2CH2-CHz- and
copolymers containing these structural units.
Preferred components (C) of this invention also comprise compounds which
are obtainable by reacting
al) an adduct of a substantially equivalent amount of a diisocyanate with
a mixture of a dihydroxyl-terminated or trihydroxyl-terminated polyether
or polyester and less than 1 mol ~0, based on the hydroxyl-terminated
prepolymer, of a diol or triol, preferably of a short-chain diol or
triol, and
b) an amount of a bisphenol or trisphenol which is substantially equiva-
lent to the NC0 content.
In another preferred embodiment of the invention, the preparation of
component a2) is carried out using an amino-terminated polyalkylene
ether, reacting said ether, in the absence of a chain extender, with an
amount of diisocyanate which is equivalent to the NH2 content or with an
- _ 30 - 1 335389
excess thereof, or with phosgene, and capping the resultant polyiso-
cyanate with a polyphenol or aminophenol IIIa, to give a compound of
formula IX
(Ho-~-R3-Y-~-C-NH-R1s ~ ~-NH R1 6 (IX),
m -n
wherein R3, Y, m and n are as defined above, t is 0 or 1, R~ is the
divalent radical of an aliphatic, cycloaliphatic, aromatic or araliphatic
diisocyanate after removal of the isocyanate groups, and R16 is the
n-valent radical of an amino-terminated polyalkylene ether after removal
of the terminal NH2 groups.
Compositions containing compounds of formula IX as component (C) are
preferred.
Particularly preferred compositions contain, as component (C), compounds
of formula IX, wherein m is 1, n is 2 or 3, Y is -0-, R1s is derived from
an aliphatic, cycloaliphatic or aromatic diisocyanate and R1 6 is a
divalent or trivalent radical of an amino-terminated polyalkylene ether
having a molecular weight M of 150 to 10 000 after removal of the
terminal amino groups.
More especially preferred compositions contain, as component (C),
compounds of formula IX in which m is 1, n is 2, t is 0, Y is -0- and R16
is derived from a divalent, amino-terminated polyalkylene ether having a
molecular weight M of 150 to 6 000.
Most especially preferred compositions contain, as component (C),
compounds of formula IX in which m and t are 1, n is 2, R1s is the
divalent radical of an aliphatic or cycloaliphatic diisocyanate after
removal of the isocyanate groups, and R1 6 is derived from a divalent,
amino-terminated polyalkylene ether having a molecular weight M of 150
to 6 000.
The especially preferred components (C) of these two last-defined types
comprise those in which R1s is a structural unit of formulae X, XI, XII
or XIII
~ - 31 - 1 335389
-8H-CHz ( O-CHz-CIH-~- (X), Z1 [ ( CIH-CH2-O-~-CH2-ICH ~ (XI),
CH3 Y CH3 y
in which y is 2 to 70, Z1 is a group -NH-CO-NH or _o-R17-o-, z2 is a
group _o-~l 8 _o_, Rl 7 iS a radical of an aliphatic diol after the removal
of the two OH groups, and R18 is a radical of an aliphatic triol after
removal of the three OH groups.
The preparation of the compositions of the invention is effected in
conventional manner by mixing the components withe aid of known mixing
units (stirrers, rolls).
The compositions of the invention can be cured to crosslinked productsusing customary hardeners for epoxy resins. The invention accordingly
relates also to compositions which, in addition to containing the above
described components (A), (B) and (C), also contains a hardener (D) for
epoxy resins and an optional accelerator (E).
Typical examples of hardeners (D) are aliphatic, cycloaliphatic, aromatic
and heterocyclic amines such as bis(4-aminophenyl)methane, aniline/
formaldehyde resin, bis(4-aminophenyl)sulfone, propane-1,3-diamine, hexa-
methylenediamine, diethylenetriamine, triethylenetetramine, 2,2,4-tri-
methylhexane-1,6-diamine, m-xylylenediamine, bis(4-aminocyclohexyl)-
methane, 2,2-bis(4-aminocyclohexyl)propane and 3-aminomethyl-3,5,5-tri-
methylcyclohexylamine (isophoronediamine); polyaminoamides such as those
obtained from aliphatic polyamines and dimerised or trimerised fatty
acids; polyphenols such as resorcinol, hydroquinone, 2,2-bis(4-hydroxy-
phenyl)propane and phenol/aldehyde resins; polythiols such as the
polythiols commercially available as "Thiokols~"; polycarboxylic acids
and anhydrides thereof, for example phthalic anhydride, tetrahydro-
phthalic anhydride, hexahydrophthalic anhydride, hexachloroendomethylene-
tetrahydrophthalic anhydride, pyromellitic anhydride, 3,3',4,4'-benzo-
phenonetetracarboxylic dianhydride, the acids of the aforementioned
anhydrides as well as isophthalic acid and terephthalic acid. Suitable
hardeners are also carboxyl-terminated polyesters, especially if the
- 32 - 1335389
curable mixtures of this invention are used as powder coating composi-
tions for surface protection. It is also possible to use catalytic
hardeners, for example tin salts of alkanoic acids, e.g. tin octanoate,
Friedels-Craft catalysts such as boron trifluoride and boron trichloride
and their complexes and chelates which are obtained by reacting boron
trifluoride with e.g. 1,3-diketones; and substituted cyanamides such as
dicyandiamide.
Examples of accelerators (E) are tertiary amines and salts or quaternary
ammonium compounds thereof, such as benzyldimethylamine, 2,4,6-tris(di-
methylaminomethyl)phenol, 1-methylimdiazole, 2-ethyl-4-methylimidazole,
4-aminopyridine, tripentylammonium phenolate or tetramethylammonium
chloride; or alkali metal alcoholates such as sodium alcoholates of
2,4-dihdroxy-3-hydroxymethylpentane; or substituted ureas such as
N-(4-chlorophenyl)-N',N'-dimethylurea or N-(3-chloro-4-methylphenyl)-
N',N'-dimethylurea (chlortoluron).
Surprisingly, it is possible to cure a composition containing a high
proportion of component (B) and optionally (C), for example more than
50 % by weight, based on the amounts of (A), (B) and (C).
Curing of the compositions of the invention can be effected at room
temperature or at higher temperatures.
In general the curing temperatures for hot curing are in the range from80 to 250C, preferably from 100 to 180C. If desired, curing can also be
carried out in two steps, for example by discontinuing the curing
procedure or, if a hardener for higher temperatures is used, partially
curing the curable composition at low temperature. The products so
obtained are still fusible and soluble precondensates (B-stage resins)
and are suitable, for example, for the preparation of moulding compounds,
sintered powders or prepregs.
Components (B) and especially also (C) of the compositions of this
invention effect a significant increase in the peel strength, and the
cured products exhibit a diminished tendency to crack propagation and
have high peel strength without loss of lap shear strength.
1 335389
Depending on the resin formulation, it is possible to prepare with these
modifiers elastic products of high peel strength and with low glass
transition temperature or high-strength products with high glass transi-
tion temperature and of high peel strength. The high-strength products
display high resistance to crack formation, and crack propagation is
markedly diminished even when the nroducts are subjected to very severe
shock impact.
The properties of the cured final product can be varied in accordance
with the proportion of components (A), (B) and optionally (C).
The following percentages relate in each case to the total weight of
components (A), (B) and optionally (C).
.
If it is desired to obtain products having high strength, high glass
transition temperature, high peel strength, high impact strength and high
resistance to crack propagation (crack resistance), then the proportion
of components (B) and optionally (C) should normally not exceed 60 % by
weight. Systems of this type are normally heterogeneous. The lower limit
will depend on the desired properties, for example peel strength. The
proportion of components (B) and optionally (C) should normally be more
than 5 % by weight, preferably more than 10 % by weight.
If, on the other hand, it is desired to obtain products of the highest
possible flexibility, then the proportion of components (B) and
optionally (C) should be not less than 40 % by weight, preferably more
than 60 % by weight.
The weight ratio of (B) to (C) may vary within wide limits. The preferred
range of (B) to (C) is 50:1 to 1:50, more particularly 20:1 to 1:10 and,
most preferably, 5:1 to 1:5.
The proportion of the epoxy resin (A) to the total amount of (A), (B) and
(C) may also vary within wide limits. For cured products of increased
flexibility, small amounts of (A), for example 10 to 30 % by weight, will
normally be used, which component (A) may also be in the form of an
- _ 34 _ 1 335389
adduct with (B), whereas for cured products of high strength, substantial
amounts of (A), for example 50 to 95 ~0 by weight, preferably 60 - 80 ~0 by
weight, will normally be used.
If desired, reactive diluents, for example styrene oxide, butyl glycidyl
ether, 2,2,4-trimethylpentyl glycidyl ether, phenyl glycidyl ether,
cresyl glycidyl ether or glycidyl esters of synthetic, highly branched, ..
mainly tertiary, aliphatic monocarboxylic acids, can be added to the
curable mixtures to reduce their viscosity further.
The amount of hardener (B) or of accelerator (E) will depend on the type
of hardener and will be chosen by the skilled person in a manner known
per se. The preferred hardener is dicyandiamide. In this case, it is pre-
ferred to use 0.1 - 0.5 mol of hardener per mol of epoxy groups.
As further conventional modifiers the compositions of this invention may
contain plasticisers, extenders, fillers and reinforcing agents, for
example coal-tar, bitumen, textile fibres, glass fibres, asbestos fibres,
boron fibres, carbon fibres, mineral silicates, mica, powdered quartz,
alumina trihydrate, bentonites, kaolin, silica aerogel or metal powders,
for example aluminium powder or iron powder, and also pigments and dyes,
such as carbon black, oxide colourants, titanium dioxide, flame re-
tardants, thixotropic agents, flow control agents such as silicones,
waxes or stearates (some of which can also be used as mould release
agents), couplers, antioxidants and light stabilisers.
The cured products are distinguished by the advantageous properties
described at the outset.
The invention therefore also relates to the crosslinked products
obtainable by curing compositions which contain (A), (B), (D) and
optionally (C) and (E).
The compositions of this invention can be used, for example, as
adhesives, adhesive films, patches, matrix resins, lacquers or sealing
compounds or, quite generally, for the preparation of cured products.
They can be used in a formulation adapted to suit each particular end
~ 335389
use, in an unfilled or filled state, as paints, coating compositions,
lacquers, compression moulding materials, dipping resins, casting resins,
impregnating resins, laminating resins, matrix resins and adhesives.
The invention also relates to the use of the compositions of this
invention for the preparation of adhesives, adhesive films, patches,
matrix resins, casting resins, coating compositions or sealing compounds.
As the compositions of this invention also have good adhesion to non-
degreased objects, the present invention further relates to the use of
the compositions for enhancing the compatability of adhesives with oil.
The invention is illustrated by the following Examples.
Examples
A. Preparation of the components
Phenol-terminated polyurethane lA
354 g of anhydrous polypropylene glycol (M = 2 OOO), 1.8 g of tri-
methylolpropane and 0.1 ml of dibutyltin dilaurate are added at 100C and
under nitrogen to 54.4 g of hexamethylene diisocyanate. After stirring
the mixture at 100C for two hours and the isocyanate content has fallen
below 4 %, this prepolymer is run at 80C into 135 g of anhydrous
3,3'-diallylbisphenol A, and the mixture is stirred for 2.5 hours at 80C
and for 30 minutes at 100C until free isocyanate is no longer detect-
able. The following analytical data are obtained for the viscous resin:
viscosity ~40 = 128 600 mPa-s;
phenol content: 2.5 equivalents/kg;
molecular weight (GPC): M = 1260, M /M = 11.4.
Prepolymer for Example 1
A mixture of 33.3 g of carboxyl-terminated polybutadiene (Hycar~ CTB
2000 x 162, ex Goodrich), 66.6 g of dry ~-caprolactone and 0.3 g of
dibutyltin oxide is heated, under nitrogen, for 2 hours to 220C. The
mixture is then cooled to 140C and 150 g of bisphenol A diglycidyl ether
- 36 - 1 3 3 5 3 ~ 9
(epoxy value: 5.4 Val/kg) and 2.5 g of triphenylphosphine are added. The
batch is stirred for 2 hours at 140C, to give a viscous resin for which
the following analytical data are obtained:
viscosity (according to Epprecht): 1560 mPa-s (80C)
epoxy content: 2.9 Val/kg.
Prepolymers for Examples 2-9
Carboxyl-terminated butadiene/acrylonitrile copolymer (Hycar~ CTBN
1300 x 8 and 1300 x 13, ex Goodrich) and dry E-caprolactone are heated,
under nitrogen, for 3 hours at the temperature indicated in Table 1 in
the presence of 0.5 % of dibutyltin oxide. The properties of the com-
pounds obtained are listed in Table 1. These carboxyl-terminated
segmented polyesters are then reacted with an epoxy resin based on
bisphenol A (epoxy value: 5.4 Val/kg) in the weight ratio of 1:1 by
heating for 2 hours at 140C in the presence of 1 ~0 triphenylphosphine.
The properties of the epoxy adducts so obtained are listed in Table 1.
3~ 1 335389
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1 335389
- - 38 -
Prepolymers for Examples 10-12
a) Preparation of butydiene/acrylonitrile copolymer epoxy resin adducts
With stirring, 500 g of carboxyl-terminated butadiene/acrylonitrile
copolymer (26 % acrylonitrile, 2.4 % carboxyl content, Hycar~ CTBN
1300 x 13, ex Goodrich) are reacted with 1000 g of bisphenol A diglycidyl
ether (epoxy value: 5.4 Val/kg) for 3 hours at 140C in the presence of
2 g of triphenylphosphine. The resultant viscous resin has a viscosity
(according to Epprecht) of 115 20 mPa-s (40C) and an epoxy value of
3.4 Val/kg.
b) Reaction of the epoxy resin adduct with E-caprolactone
To 300 g of the adduct obtained in a) are added E-caprolactone in the
amounts indicated in Table 2 and 2 g of dibutyltin oxide. The capro-
lactone is grafted on to the adduct by heating for 4 hours to 190C. The
analytical date are indicated in Table II.
Table II: Prepolymers for Examples 10-12
Example E-CaprolactoneViscosity (40C)Epoxy content
(g) (mPa-s) (Val/kg)
100 34560 2.3
11 200 115200 1.7
12 300 125440 1.5
Prepolymer for Example 13
a) Preparation of the butadiene/acrylonitrile copolymer epoxy resin
adduct
In a ground glass flask equipped with stirrer, nitrogen inlet and reflux
condenser, 730 g of bisphenol A diglycidyl ether (epoxy content:
5.4 Val/kg), 200 g of carboxylated-terminated acrylonitrile/butadiene
copolymer (26 % acrylonitrile content, acid value 32 mg KOH/g,
Hycar~ CTBN 1300 x 13, ex Goodrich), 64 g of bisphenol A and 5 g of
1 335389
-- 39 --
triphenylphosphine are heated for 3 hours at 1 30C until a viscous resin
with an epoxy content of 3.3 Val/kg and having a viscosity according to
Epprecht of 130 000 mPas (40C) forms.
b) Reaction of the epoxy resin adduct with E-caprolactone
In this Example, ~-caprolactone is added as reactive diluent to the
mixture, and the butadiene/acrylonitrile caprolactone block copolymer is
formed in situ during the curing of the epoxy resin adduct. This is
brought about by further adding dibutyltin oxide as catalyst to the
curable mixtures (q.v. Table III).
B. Preparation and testing of the adhesive compositions
The components listed in Table III are mixed on a three-roll mill and
used for bonding to degreased aluminium or steel. The test specimens with
an overlap of 1.25 cm2 are cured for 1 hour at 180C.
The lap shear strength according to DIN 53 285 is determined using 1.5 mm
thick steel and aluminium pieces which have been washed free of oil with
methylene chloride.
The T-peel strength according to DIN 53 282 is determined using oil-free
steel specimens having a thickness of 0.6 mm.
Table III: Adhesive compositions and test results
2 3 4 5 6 7 8 9 10 11 12 13
Example A B A B A B A B A B A B
diglycidyl ether of
bisphenol A 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35
(epoxy content
5.4 Val/kg) (g)
butanediol di-
glycidyl ether 2 52.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5
(epoxy content
9.2 Val/kg) (g)
phenol-terminated 15 - 15 15 - 15 - 15 - 15 15 - 15 15 15 15 15
polyurethane lA (g)
prepolymer (g) 32 15 32 15 15 32 15 32 15 32 15 15 32 15 15 15 15 15 15
~-caprolactone (g) - - - - - - - - - - - - - - - - _ _ 7.5
dibutyltin oxide (g) - - - - - - - - - - - - - - - - - - 0.1 ~
dicyanidiamide (g)4.9 4.9 4.9 4.9 4.9 4.9 4.9 4.9 4.9 4.9 4.9 4.9 4.9 4.9 4.9 4.9 4.9 4.9 4.9 W
chlortolurone (g)0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 C3
wollastonite P1 )(g) 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15
PY g 2) 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5
silica (g)
Table III: Adhesive compositions and test results (continuation)
2 3 4 5 6 7 8 9 10 11 12 13
Example A B A B A B A B A B A B
lap shear strength 14.822.7 20 5 27 6 29 225 0 29.7 19.0 25.2 27.9 28.8 31.7 28.5 30.3 31.1 33.0 27.0 23.8 28.2
on Al (N/mm2)
lap shear strength 20.923 8 13 1 23 5 21 924 6 23.0 16.1 21.4 21.0 25.3 25.0 24.6 23.7 25.1 26.7 24.1 21.0 27.1
on steel (N/mm2)
T-peel strength n.d. 7.32.67.4 6.4 2.6 8.1 2.4 7.2 2.6 8.5 7.6 2.4 8.1 5.6 6.4 5.1 5.6 6.9
) (N/mm2 )
fracture n.d. 80n.d.n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 70 70 70 70 ~~
(cohesion fracture
in %)
) Sold by Interpace (Willsboro, N.Y.)
) Aerosil~9 380, ex Fa. Degussa ~
3) W
n.d. = not determined ~
