Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
(`) L~ L ,q~
HARDENABLE llR~THANE-EPOXY R~IN MIXTURE
The present invention pertains to h~rdenable, i.e.
curab].e, synthetic resin mixtures comprising (1) a glycidyl
compound having an average of more than one epoxy group per
moiecule and (2) the reaction product formed between
prepolymeric aryl esters of carbamic acid and di- or
poly-functional amino compounds having two or more active
hydrogen atoms per molecule.
Synthetic resins comprising epoxy resins cured
with polyamines are distinguished in practice bv a number of
desirable properties, such as qood adhesion to organic and
inorganic substrates, good solvent stability, and high
resistance to the action of chemicals. Because of their
high cro.sslinking density, amine cured epoxy resins, and
especially those comprising diphenylpropane and
epichlorohydrin, are hard and brittle, with ~lass transition
t.emperatures above 20C.
~ owever, these synthetic resins fall short o
meeting actual requirements in all field of use where impact
stren~th and shock resistance as well as ~lexibility are
required. This is true especially of the constru~tion
field, where shrinXage cracks in concrete, ~or example, must
be permanently filled.
To some extent, an internal increase in
flexibility can he obtained by reducinq the crosslinking
'`'`~
density, and an external increase in flexibility by the
addition of plasticizers.
External elasticizers such as tar, phthalate
esters, high-boiling alcohols, vinyl polymers and the like
are nonreactive and are not incorporated into the thermoset
plastic network. They merely result in an expansion throuyh
the filling out of space.
Internal elasticization can be secured by reducing
the functionality of the curing agent.
Although the long chain amino amides of low
functionality comprising dimerized fatty acids, which have
been in use for a long time and on a large scale, do offer a
satisfactory combination of properties as flexible curina
agents for epoxy resins, they cannot be used as desired in
some areas.
German patent application DE-AS 21 52 506
describes curable synthetic resin ~ixtures consisting of (a~
certain glycidyl ethers and ~b) certain phenyl esters of
carbamic acid formed from prepolymeric isocvanates and alkvl
phenol~s, and (c) polyamines or polyamino amides. However,
because of the high viscosities of their components,
mixtures of carbamic acid phenyl esters and epoxy resins
have a final viscosity that is too high for practical use.
The preparation of a mixture ready for use therefore
requires the addition of a diluent. Another problem is that
because of the widely differing equivalent weights of the
resin and curin~ agent com~onents, rel~tivelv large
proportions of resin (epoxy plus polyurethane~ must be mixed
with relatively small pr~portions of curing agent, so that
homo~enization is far from simple and requires great care,
al~o because of poor miscibility ~ue to the difference in
the viscosity of the resin and curing agent components.
According to German patent application DE-O~ 23 38
256, high molecular weight amine ter~inated polvether
urethane ureas are~prepared by the reaction of prepolymers
containing free isocvanate groups with amines in strongly
diluted solutions and are then curea with epoxy resins.
Although the use of solvents, and especially of aromatic
solvents, is d~leterious in practice and undesirable for
both health and technical reasons~ it is essential in this
process because gelling would otherwise occur. On the other
hand, the ~riscosity of the solventless reaction products
selectively obtained according to ~erman patent application
D~-OS 23 38 256 is far too high for actual use.
German patent application DE-AS 2 418 041
describes a process for the production of elast,ici2ed molded
parts and sheetlike articles in which certain epoxv
compounds are re~cted with amino compounds obtained by the
hydrolysis of certain prepolymeric ketimines or,enamines.
This process permits the production of durable thermoset
resin (clurorners) which are resistan-t to chemicals and have
improved properties. However, during the hydrolysis of -these
compounds, ketones or aldehydes are libera-ted and rnust be removed.
Moreover, s-till further improvement oE -the flexihility
of the cured products is desirable.
The object of -the present invention is to overcome
these drawbacks and to provide curable synthetic resin mixtures
which give coa-tings that have chemical resis-tance and good adhe-
sion, adhesives, shee-tlike articles, sealing and caulking com-
pounds, and molded ar-ticles possessing high impact strength and
shock resistance as well as improved flexibility.
According to -the present invention there is provided
the method of hardening a glycidyl compound having more than one
epoxy group per molecule, which method comprises admixing wi-th
said glycidyl compound an approximately s-toichiometric amount of
an amino hardener which is a polyether urethane urea amine pre-
pared by the reaction of: (1) a prepolymer having a blocked iso-
cyanate groups, prepared by reacting a phenol or alkylphenol wi-th
the reaction product of a polyether polyol or polythioether polyol
with an excess of a polyisocyanate, with (2) a polyfunc-tional
amino compound having (a) at least two reactive amino hydrogen
atollls per molecule or (b) at least one reactive arnino hydrogen
atom and at least one azornethine group per molecule, the amine
then being liberated from the reaction product formed between (1)
arld 2(b) by hydrolysis of the azome-thine group.
t~
The polyfunctional amine compouna used according
to (A)(2) is prepared by the reaction of a polyfunckional
masked aliphatic or cycloaliphatic isocyanate, preferably an
isocyanate of an optionally substituted aliphatic or
cycloaliphatic hydrocarbon, with an excess of at least one
polyfunctional amino compound having two or more active
amino hydrogen atoms per molecule, and/or with an amino
compound having at least one reactive amino hydrogen atom
and at least one azomethine group per molecule.
The compounds containing polyfunctional masked
isocyanate groups which are used in this reaction may be
products containing linear or branched reaction products
containing hydroxyl or sulfhydryl groups and obtained by
prior art processes by the reaction of polyalkylene
polyether polyols and/or polyalkylene thioether polyols with
polyisocyanates (including diisocyanates)in an NCO/OH(SH)
~ --I ,
- ~ )
ratio of from 1.5 to 2.5, followed by reaction of the
terminal NCO group with the masking agents col~monly used in
this field.
Suitable linear or branched polyols having an
average molecular weight ranging from 150 to 10,000,
preferably from 40Q to 5000, and more preferably of about
2000, are polyalkylene polyether polyols such as are
ob~ained by the copolymerization, bulk copolymerization, or
anionic polymerization of alkylene oxides, and in particular
of ethylene oxide and propylene oxide, with di- or
polyfunctional alcohols such as 1,2-ethanediol,
1,3-propanediol, 1,4-butanediol, and particularly alcohols
with higher functionality, such as l,l,l-trimethylolethane,
l,l,l-trimethylolpropane, glycerol, and 1,2,6-hexanetriol~
or with amines such as ethylene diamine and
1,6-hexamethylene diamine as starting components, or they
may be made by cationic polymerization and copolymerization
of cyclic ethers such as tetrahydrofuran, ethylene oxide,
and propylene oxide with acidic catalysts, or by
polycondensation of polycondensable glycols such as
1,6-hexanediol in the presense of acidic etherification
catalysts.
Suitable polyalkylene thioether polyols are
primarily the polycondensation products of thiodiglycol with
itself and with diols and/or polyols, for example,
1,6-hexanediol, triethylene glycol,
2,~-dimethyl-1,3-propanediol and l,l,l-trimethylolpropane,
--6--
~) )
~l2~
in the presence of acidic etherification catalysts such as
phosphoxic acid and phosphorous acid.
A suitable polyacetal is the polycondensation
product of formaldehyde and diols and/or polyols, for
example diethylene glycol, triethylene glycol,
1,4-butanediol, 1,6-hexanediol, thiodiglycol, and
l,l,l-trimethylolpropane, with acidic catalysts such as
phosphoric acid and para-toluene sulfonic acid.
Further suitable polyol components are the
addition pxoducts of compounds containing reactive multiple
bonds and polyhydroxyl and sulfhydryl components such as
polyisobutylenediol and polyisoprenediol as well as the
corresponding compounds containing terminal SH groups. (See
U.S. Patent 3,984,370).
These hydroxyl or sulfhydryl components are
conventionally reacted with a polyfunctional isocyanate in
an NCO/OH ratio ranging from 1.5 to 2.5, and preferably from
1.8 to 2.2, to give the corresponding prepolymeric compounds
having terminal N~O groups.
Suitable aliphatic and cycloaliphatic
polyisocyanates include 1,6-hexamethylene diisocyanate,
isophorone diisocyanate, xylylene diisocyanate,
2,4,4,(2,2,4)-trimethyl-1,6-diisocyanathohexane,
l-methyl-2,4(2,6~-diisocyanatocyclohexane,
methylenebis(4-cyclohexylisocyanate), and the isocyanate
prepared by conventional methods from dimeric fatty diamine.
~2~3~6
The terminal NCO groups of the polyfunctional
prepolymeric compounds are then reacted with the maskiny
agents commonly used in this field in at least
stoichiometric amounts at temperatures ranging from 50 to
120C, optionally by the use of catalysts.
In accordance with the invention, preferred
masking agents are phenols and alkylphenols, wherein the
by alkyl substituent has from 1 to 18 carbon atoms, for
example, butylphenols, tetramethylbutylphenols, amylphenols,
hexylphenols, heptylphe~ols, and especially 4-butylphenol
mixtures of 4-nonylphenol isomers.
Suitable polyfunctional amino compounds to be
used in the further reaction are diprimary, disecondary, and
primary/secondary aliphatic, cycloali.phatic, heterocyclic,
and araliphatic amines as well as their condensation
products with carboxylic acids (polyaminoamides)~ These
amines, which may be substituted and which have at least two
active amino hydrogen atoms per molecule, are reacted in a
ratio of amino group to masked NCO group ranging from 1.5 to
2.5, and preferably from 1.8 to 2.2, at temperatures ranging
from 40 to 100C, and preferably from 60 to 80~C, with the
component containing the aryl carbamate ester groups to give
the corresponding prepolymeric amino compounds alone or in
admixture.
--8--
- . / J
~2~
It is also possihle to use the amine component in
larger amounts and to remove the excess on completion of the
reaction, by distillation for example. ~he phenol component
liberated during the reaction can remain in the reaction
mixture.
In accordance with the invention, one or more of
the following compounds are used as amino compounds:
(~ ) Amines of the formula
R - NH - Rl - NH - R (I),
wherein R is linear or branched alkyl having from 1 to 4
carbon atoms, or hydrogen, and Rl is linear or branched
aliphatic, cycloaliphatic, or araliphatic hydrocarbon, which
may be substituted, having from 2 to 20 carbon atoms, and in
particular 1,2-diaminopropane, or Rl is the alkyl portion of
a dimeric fatty diamine which may be interrupted by hetero
atoms, and in particular oxygen atoms;
(~ ) an amine of the formula
R2-(~3-NH ) -R3-R lII),
wherein R is -N=C~R4)(R ), R3 is -CH2-CH2- and/or
-CH2-C}~2-CH2- ~
R4 and R' are the same or different and arè -CH3, -CH2-CH3,
or -C(CH3)3, and m is 1 or ~;
~ ~ - ~
( ~3 an aminP o~ the formula
HN X - R5 (IIIl~
~ .
wherein R5 is H, or wherein R5 is -(C~k - R2 and k is 2 or
3, or wherein
~5 is (-CH2)h - ~ ~ (CH2)k -R6~
~nd R is -NHR or-R , h is 0, 1, 2, or 3, and X is C
or N; and/or
(~) condensation products of these amines with
carboxylic acids wherein, when an amine of formula ~II) is
used with m being 1 and~or an amine of formula (III) is used
with R6 being R2, the ratio of amino groups to carhamate
aryl ester groups is 1:1, and wherein, when an amine of
formulas (I) or (II) is used with m being 2, or an amine is
used of formula (III) with R~ being -NHR, the ratio of amino
groups to carbamate aryl ester groups ranges from 1.8:1 to
2:1, and wherein the amino group is liberated by hydrolysis
from the compounds containing the group R2.
Examples of polyamines suitable for use in
accordance with the invention are:
Ethylene diamine, diethyl.ene triamine,
1,2-diamino-propane, 1,3-diaminopropane, 1,3-diaminobutane,
1,4-diaminobutane, 3-(n-isopropylamino)propylamine,
hexapropyleneheptamine, l-cyclohexylamino-3-aminopropane,
1,4-diaminocyclohexane, 1,3-diaminocyclohexane,
--10--
~z~
2,~-diaminocyclohexane, 1,3-di(aminocyclohexyl)propane, N,N'-
diethyl-1,3-diaminopropane, N,N'-diethyl-1,4-diaminOCyclOheX
ane, N-aminoethylpiperazine, N-aminopropylpiperazine, N-
aminobutylpiperazine, 1,3-dipiperazinylpropane, 1,3-
dipiperidylpropane, 3-(2-aminoe-thyl)-aminopropylamine, N,N'-
bis-(3-aminopropyl)-ethylenediamine, a commercially available
primary aliphatic polyoxypropylene diami.ne or triamine,
phenlyenediamine, 4,4'-diaminodiphenylmethane, and other
diamines such as 1,7-diamino-4-oxaheptane, 1,7-diamino-3,5-
dioxaheptane, 1,10-diamino-4,7-dioxadecane, 1,10-diamino-4,7-
dioxa-~-methyldecane, l,ll-diamino-6-oxaundecane, 1,11-
diamino-4,8-dioxaundecance, 1,11-diamino-4,8-dioxa-5-methyl-
undecane, l,ll-diamino-4,8-dioxa-5,6-dimethyl-7-propionyl-
undecane, l-12-diamino-4,9-dioxadodecane, 1,13-diamino-4,10-
dioxatridecane, 1,13-diamino-4,7,10-trioxa 5,8-dimethyltride-
cane, 1,14-diamino-4,11-dioxatetradecane, 1,14-diamino-4,7,10-
trioxate-tradecane, l,l6-diamino-4,7,10,13-tetrahexadecane,
1,20-diamino-4,17-dioxaeicosane, and especially hexa-
methylenediamine, 2,2,~(2,4,4)-trimethyl-hexamethylenediamine
and 3,3'dimethyl-4,4'-diaminodicyclohexylmethane, and particu-
larly isophoronediamine (l-amino-3-aminomethyl-3,5,5-
trimethyl-cyclohexane), N-aminoethylpiperazine, 1,2-
diaminopropane, methylpentamethylenediamine, xylylenediamine,
or mixtures of these amines.
The polyaminoamides also used in accordance with the
invention are condensation products o~ dicarboxylic acids such
as succinic acid, glutaric acid, adipic acid, pimelic acid,
suberic acid, azelaic acid, sebacic acid, nonamethylenedicar-
boxylic acid, decamethylenedicarboxylic acid, and -the dicar-
boxylic acids obtained b~ carbonylation of unsaturated fattyacids and excess amines, such as the compo~nds recited above.
Polyaminoamides, and polyaminoamides containing imi-
- 1 1 -
dazoline groups and based on monocarboxylic acids such as
acetic acid, propionic acid, butyric acid, valeric acid,
caproic acid, caprylic acid, myristic acid, palmitic acid,
oleic acid, linoleic acid, linolenic acid and the naturally
occurring animal and vege-table fatty acids or thelr es-ters and
the polyamines recited above, but especially polyalkylene
polyamines such as diethylenetriamine, triethylene-tetramine,
and tetraethylenepentamine, may also be used, either alone or
in mixture.
iO The amines which are preferred in accordance with
the invention are polyaminoamides and polyaminoamides contain-
ing imidazoline groups comprising dimerized fatty acids and
excess polyalkylene polyamines, which are used in
,7
- 12 -
the prior art as curing agents in the field of ~poxy resins,
or their mixtures with the amines recited above.
Along with the hardening or curing agents recited
above, which in accordance with the invention are preferred,
the amine curing agents for epoxy resins commonly employed
in this field may be used for modification.
The epoxy resins or glycidyl compounds ~B) which
are also used in accordance with the invention are curable
with these curing agents or with mixtures thereof when
either hot or cold. They contain an average of more than
one epoxy group in the molecule and are preferable glycidyl
ethers of polyhydric alcohols, for example of glycerol or of
neopentylglycol; of hydrogenated diphenylolpropane; or of
polyhydric phenols for example of resorcinol; of
diphenylolpropane; or of phenol-formaldehyde condensation
products. The glycidyl esters of polyhydric carboxylic
acids such as hexahydrophthalic acid or dimerized fatty
acids may also be used. The epoxy values of these compounds
are approximately between 0.2 and 0.7; preferably between
about 0.4 and 0.7.
The use of liquid epoxy resins comprising
epichlorohydrin and diphenylpropane having a molecular
weight from 340 to 450 is particularly preferred.
Optionally, monofunctional epoxy compounds may be
used to reduce the visco6ity of the mixtures and thus to
improve their processability. Examples of these are
-13-
~2~ 6
aliphatic and aromatic glycidyl ethers such as butylglycidyl
ether and phenylglycidyl ether, or glycidyl esters such as
glycidyl acrylate, or epoxides such as styrene oxide.
In the formulation of a reaction mass for coating,
adhesive or castin~ applications, the usual mineral and
organic fillers, pigments, plasticizers, accelerators, other
solvents commonly employed in the epoxy-resin ~ield, and
still other additives may be used.
The curable r.nixtures in accoraance with the
invention are ~uitable for coatings, adhesives, sheetlike
articles, caulking and sealing compounds, and molded
articles in all fields of application where good a~hesion,
chemical resistance, high impact strength and shock
resistance as well as improved flexibility and elasticitv
are required, as in the filling ~f cracks and joints in the
construction field, for example.
A better understandin~ of the present invention
and of its many advantages will be had from the fol.lowing
examples, giv~n by way of illustration~
A. PREPARATION OF P~I.YETHER llRET~ANF.
CARBAMIC ACID ARYL ESTERS
Exampl _
Preparation of a ~ifunctional polyether havin~ terminal
carbamate (4-nonylphenyl ester~ groups
-14-
` (?
1000 g of a linear polypropylene glycol of OH
number 56.1 iMW=2000) were mixed with 222.3 g of
isophoronediisocyanate. After the addition of 1.2 g of
dibutyltin dilaurate, the ~ixture was heated to 75~C with
vigorous stirring and held at tha~ temperature for 2.5
hours.
The reaction product had an isocyanate CnnteJIt of
3.4~.
0.3 g of zinc acetylacetonate and 215.7 ~ of a
technical 4-nonylphenol mixture with branched nonyl radicals
were added to the isocyanate prepolymer, cooled to 20 to
25 C. The mixture was then heated in two hours to 50 C
with stirring. ~he product then contained practically no
isocyanate and had about 2.87% blocked NCO groups.
Example 2
P aration of a trifunctional olyether havinq terminal
rep p
carbamate 14-nonylphenyl ester) groups
1000 g o a branched trifunctional polypropylene
glycol of OH number 35.6 (~=4700~ were mixed with 141 g of
isophoronediisocyanate. After the addition of 1.2 g of
dibutyltin dilaurate, the procedure of Example 1 was
followed and a reaction product having an isocyanate content
of 2.2% was obtaine~.
~~ 0.3 g zinc acetylacetonate and 131.1,g of a
technical 4-nonylphenol mixture with branched nonyl radicals
-15-
were added to the isocyanate prepolymer, cooled to 20 -to 25C.
The further procedure was as in Example 1, a product containing
1.95% blocked NCO groups and practically no isocyanate thus being
obtained.
EXAMPLE 3
Preparation of a carbamate (p-tert. butylphenol) ester - Example
1 was repeated with the difference that 147.1 g of p-tert.-butyl-
phenol were used as -the capping agent. The product then con-
tained practically no isocyanate and had abou-t 3% blocked NCO
groups.
EXAMPLE 4
Preparation of a prepolymer with a difunc-tional poly-
ether and TMDI - A prepolymer was formed between a difunctional
polyether and 2,4,4 -(2,2,4)-trimethylhexamethylenediisocyanate
('~`M~L) by reacting 1,000 g of a linear polypropylene glycol hav-
ing an O~ number o~ 56.1 with 210 g of TMDI as ln Example Atl).
The reaction product has an isocyanate content of 3.47 percent.
Following Example A(l), the corresponding carbamic acid
ester was prepared with 215.7 g of 4-nonylphenol. The product
shows practically no unreacted isocyana-te and has about 2.9 per-
O~llt oE bLocked NCO groups.
- 16 -
.,
~2~ 6
Example 5
Preparation of a prepolymer of polytetrahydrofuran and IPDI
250 g of polytetrahydrofuran having a molecular
weight of about 2,000 and an OH number of 55.5 were reacted
according to Example A~ 1) with 5~.35 g of isophorone diiso-
cyanate IPDI. The reaction product has an isocyanate number
of 38.8.
300 g of this reaction product were reacted for 2
hours at 50C. with 45.6 g of a technical 4-nonylphenol isomer
mixture. Thereafter, the product contained practically no
free isocyanate and contains about 2.52 percent of blocked NCO
groups.
Example 6
Preparation of a prepolymer of a linear polyglycol and IPD
1,000 g of a linear polyglycol, prepared by the
copolymerization of propylene glycol with propylene oxide and
ethylene oxide and having a molecular weight of about 2,000
and a OH number of 55, were reacted with 22.3 g of isophorone
diisocyanate. After the addition of 1.2 g of dibutyltin
dllaurate, the mixture was warmed to 75C with vigorous stir-
rln~ and maintained at this temperature for 2.5 hours. The
reaction has an isocyanate content of 3.4 percent.
0.3 g of zinc acetylacetonate and 215.7 g of a tech-
nical 4-nonylphenol isomer mixture having branched nonyl
groups were added to the isocyanate prepolymer after cooling
the latter to 20-25C. Subsequently, the mixture was stirred
for 2 hours at 50C. The product thereaf-ter contained practi-
cally no isocyanate and contained about 2.87 percent of
blocked NCO groups.
Example 7
Preparation of a prepolymer of polypropyle,ne ~lycol and XDI
1,000 g of a linear polypropylena glycol having a OH
~.
- 17 -
lZ~ 36
number of 56.1 were reacted with 188 g of xylylene diiso-
cyanate (XDI) as in Example A(l). The reaction product has an
isocyanate content of 3.53 percent.
By reaction with 215.7 g of 4-nonylphenol, the cor-
responding carbamic acid ester was prepared. The product
shows practically no isocyanate and contains about 2.98 per-
cent of blocked NCO groups.
B. PREPARATION OF POLYETHER URETHANE UREA AMINES
Example 1
25.3 g of 1,2-diaminopropane were heated to 70C and
250 g of the product obtained under A, Example 1, were added
through a dropping funnel over a period of 6 hours, the tem-
perature being maintained at 70C. Excess 1,2-diaminopropane
was then drawn off at 70C under a vacuum of 0.1 mm Hg. The
reaction product had an amino group content corresponding to
35 mg KOH/g (theoretically 36.5).
- 18 -
Example 2
59.~ g of 1,2-diaminopropane were mixed with 1175
g of the product obtained under A, Example 1, and the
mixture wa~ heated to 80C with vigorous stirring and held
at that temperature for 3.5 hour~.
The reaction product had an amino group content
corresponding to 34.7 mg KOH/g.
Example 3
26.9 g of trimethylhexamethylenediamine ~T~D) were
reacted with 250 g of the product obtained under A, Example
1, as in Example 2~ The reaction product had an amino group
content corresponding to 38 mg KOH/g.
Example 4
23.2 g of m xylylenediamine (XDA) were reacted
with 250 g of the product obtained under A, Example 1, as in
Example 2. The reaction product had an amino group con~ent
corresponding to 39 mg KOH/g.
Example 5
29 g of isophoronediamine (IPD) were reacted with
250 g of the product obtained under A, Example 1, as in
Exa~ple 2. The reaction product had an amino group content
~orresponding to 39 mg KOH/g.
F.xample h
33.7 g of p,p'-diaminodiphenylmeth~ne (~SDA) were
mixed with 250 g of the product obtained under A, Example 1,
--19--
and the mixture was heated to 100 C with vigorous stirring
and held at that temperature for lÇ hours. The reaction
product had an amino group corresponding to 37 mg KOH/g.
Example 7
23.4 9 of 1,2-diaminopropane were reacted with 340
g of the product obtained under A, Example 2, as in Example
1. The reaction product had an amino group content
corresponding to 22 mg KOH/g.
Example 8
7.19 g of piperazine were reacted with 180 g of
the product obtained undex A, Example ~, as in Example 2.
The reaction product had an amino group content
corresponding to 26 mg KOH/g.
Example 9
30 y of 1,2-diaminopropane were reacted according
to Example B(l) with 250 g of the product prepared above
according to A(4).
The reaction product has a content of amino groups
corresponding to 37.0 mg KOH/g Itheory = 37.3).
Example 10
35 g of 1,2-diaminopropane were reacted according
to B(l) with 250 g of the product prepared under A(7~.
The reaction product has a content of amino groups
corresponding to 38.0 mg of KOI~/g (theory = 37.~).
-20-
~2~
Example 11
3~5.6 g of the product prepared according to A(5)
were reacted with 30.6 g of 1,2-diaminopropane according to
Example B(1).
The reaction product has a content of amino groups
corresponding with 26.9 mg KOH/g.
Example 12
293.4 g of the product prepared according to A(l)
were reacted with 80 g of an aminoamide containing imidazoline
groups, comprising fatty acid and triethylenetetramine and
having an amine number of 420.
The reaction product has a content of amino groups
corresponding with 58 mg of XOH/g.
C. PREPARATION OF ELASTICIZED EPOXY-RESIN MASSES
Example 1
85 parts by weight of an epoxy resin based on
bisphenol A and epichlorohydrin and having an epoxy value of
0.53 and a viscosity of about Pa.s at 25C were diluted with
15 parts by weight of a glycidyl ether based on C12 to C14
f~tty alcohols and epichlorohydrin and having an epoxy value
of about 0.35 and a viscosity of about mPa.s at 25C. The
latter is a reagent and also functions as a diluent viscosity
regulator.
- 21
~ ! `
420 parts by weight of a polyether urethane urea
amine according to B, Example 1, as w~ll as 28 parts by
weight of 2,4,6-tris-(dimethylaminomethyl)phenol (DMP) and
1.6 parts by weight of 4 nonylphenol lNP) were added. The
DMP functions as an accelerator. The NP is both a viscosity
regulator and an accelerator.
This epoxy resin mass was cast into plates 4 mm
thick and allowed to cure at 23C. The increase in hardness
was determined (Shore hardness in conformity with DIN 53505)
and, after 7 days' curing at 23~C, also the tensile
strength, the elongation ~DIN 53455), and the crack
propagation resistance ~DIN 53505).
The fully cured mass was clear/transparent and
nearly nontacky on the surface.
The following resins were prepared and tests
thereon were conducted as described in Example 1. The
m~surements presented in the following Table are average
values from three tests.
Example 2
100 parts by weight of the epoxy mixture of
Example 1 were mixed with 372 parts by weight of the amine
of B, Example 3, and with 16 parts by weight of DMP and 29
parts by weight of NP.
t
-22-
~%~
Example 3
100 parts by weight of the epoxy resin mixture of
Example 1 were mixed with 359 parts by weight of the amine
of B, Example 4, and with 24 parts of DMP and 28 parts of
NP.
Example 4
30 parts by weight of an epoxy resin based on
bisphenol A and bisphenol F in a weiyht ratio of 70:30 and
epichlorohydrin of an epoxy value of 0.54 and a viscosity of
7 mPa.S at 25C were diluted with 20 parts by weight of
dibutylphthalate (as a so-called "plasticizer") and then
mixed with 300 parts by weight of the amine of Example B6,
as well as with 20 parts of DMP and 32 parts of NP.
Example 5
85 parts by weight of the epoxy resin of Example 1
were diluted with 15 parts of the glycidyl ether formed from
neopentyl glycol and epichlorohydrin, said ether having an
epoxy value of 0.68 and a viscosity of 20 mPa.s at 25C~
This was then mixed with 356 parts by weight of the amine of
B, Example 5, and with 24 parts of DMP and 29 parts of NP.
Example _
100 parts by weight of the epoxy resin mixture of
Example 1 were cured with 539 parts o the amine of B,
Example 7, and with 43 parts of DMP and 63 parts of NP.
-23-
Example 7
lO0 parts by weight of the epoxy resin mixtur~ of
Example 5 were reacted with 1062 parts by weight of the
amine of B, Example 8, and with 71 parts of DMP and 90 part-
of NP.
Example 8
lO0 parts by weight of the epoxy resin of Example
C(l) were combined with 272 parts by weight of the amine
from Example B(l~, 4.7 parts by weight of isophorone
diamine, 18.3 parts by weight of DMP, and 11.4 parts by
weight of NP. After dilution with 44 parts by weight of
methylene chloride/i-propanol, (l/l), the mixture was
homogenously combined with 110 parts by weight of calcite
filler having an average particle size of approximately 20
microns.
Example 9
100 parts b~ weight of the epoxy resin mixture of
Example C(l) were mixed with 155 parts by weight of the
amine from Example B(l~, 30.5 parts by weight of NP, and 7
parts by weight of DMP~ 58 parts by weight of an aminoamide
imidazoline curing agent comprising a dimerized tall oil
fatty acid and diethylene triamine ~having an amine number
about 280, an amine equivalent weight of about 170, and a
viscosity of 25C of about 28~9 mPa.s) were added thereto.
-24-
The mixture was diluted with 49 parts by weigh-t o:E
methylene chloride/i-propanol (1/1) and then filled with 90
parts by weight o~ calcite (around 20 microns average par-ticle
size) and 10 parts by weight oE tl-tanium dioxide-ru-tile.
Example 10
100 parts be weight of a plgmented synthetic resin
mass as in Example C 8) were combined with 1 part by weight of
pyrogenic silicic acid subsequent to thixotrpping.
Comparative Example
100 parts by weight of the epoxy mixture of Example
1 were mixed with 400 parts by weight of an aryl carbamate
ester according to A, Example 1. A mixture of 20 parts by
weight of 1,2-diaminopropane, 28 parts of DMP and 1.6 parts NP
was added to this as a curing-agent component.
The fully cured material had a milky opacity and was
very tacky on the surface.
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