U.S. patent number RE32,745 [Application Number 07/021,151] was granted by the patent office on 1988-09-06 for polymeric resins derived from 1-oxa-3-aza tetraline group-containing compounds and cycloaliphatic epoxides.
This patent grant is currently assigned to Gurit-Essex AG. Invention is credited to Herbert Schreiber.
United States Patent |
RE32,745 |
Schreiber |
September 6, 1988 |
Polymeric resins derived from 1-oxa-3-aza tetraline
group-containing compounds and cycloaliphatic epoxides
Abstract
A composition comprising a polymeric resin derived from (A) at
least one compound containing an average of more than one
1-oxa-3-aza-tetraline group per molecule with (B) at least one
cycloaliphatic epoxide containing at least two epoxide groups, at
least one of said epoxide groups being part of said ring, the mole
ratio of (b) to (a) .Iadd.epoxide groups to 1-oxa-3-aza-tetraline
groups .Iaddend.being in the range of about 0.2 to about 2.
Inventors: |
Schreiber; Herbert (Wollerau,
CH) |
Assignee: |
Gurit-Essex AG (Freienbach,
CH)
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Family
ID: |
6245447 |
Appl.
No.: |
07/021,151 |
Filed: |
March 3, 1987 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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Reissue of: |
774433 |
Sep 10, 1985 |
04607091 |
Aug 19, 1986 |
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Foreign Application Priority Data
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Sep 14, 1984 [DE] |
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3433851 |
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Current U.S.
Class: |
525/504; 528/97;
528/96 |
Current CPC
Class: |
C08G
59/24 (20130101); C07D 265/16 (20130101); B22C
1/226 (20130101); C08G 14/06 (20130101); C08G
59/5046 (20130101); B22C 1/20 (20130101) |
Current International
Class: |
B22C
1/16 (20060101); C08G 59/50 (20060101); B22C
1/20 (20060101); C07D 265/16 (20060101); B22C
1/22 (20060101); C08G 59/00 (20060101); C08G
59/24 (20060101); C08G 14/00 (20060101); C07D
265/00 (20060101); C08G 14/06 (20060101); C08G
059/24 (); C08G 059/50 () |
Field of
Search: |
;525/504,489
;528/96,97 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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574979 |
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Apr 1976 |
|
CH |
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579113 |
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Aug 1976 |
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CH |
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606169 |
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Oct 1978 |
|
CH |
|
Primary Examiner: Nielsen; Earl
Attorney, Agent or Firm: Tarolli, Sundheim & Covell
Claims
I claim:
1. A composition comprising a polymeric resin derived from
(A) at least one compound containing an average of more than one
1-oxa-3-aza-tetraline group per molecule .[.with.]. .Iadd.and/or
the prepolymers thereof with .Iaddend.
(B) at least one cycloaliphatic epoxide containing at least two
epoxide groups, at least one of said epoxide groups being part of
said ring, the .[.mole.]. ratio of .[.(B) to (A).]. .Iadd.epoxide
groups to 1-oxa-3-aza-tetraline groups .Iaddend.being in the range
of about 0.2 to about 2.
2. The composition of claim 1 wherein component (B) has at least
one epoxide group directly attached to said ring.
3. The composition according to claim 1, wherein said
1-oxa-3-aza-tetraline groups include an aromatic substituent at the
nitrogen atom.
4. The composition of claim 1 wherein component (A) is the reaction
product of at least one amine, at least one phenol, and
formaldehyde.
5. The composition of claim 4 wherein said phenol is selected from
the group consisting of phenol, m- and p-cresol, m- and
p-ethyl-phenol, m- and p-isopropylphenol, m- and p-methoxy-phenol,
m- and p-ethoxyphenol, m- and p-isopropyloxy-phenol, m- and
p-chlorophenol and B-naphthol.
6. The composition of claim 4 wherein said phenol is selected from
the group consisting of 4,4'-dihydroxydiphenylmethane,
3,3'-dihydroxy-diphenylmethane, 2,2-bis-(4-hydroxy-phenyl)-propane,
4,4'-dihydroxystilbene, hydroquinone, pyrocatechin and
resorcin.
7. The composition of claim 4 wherein said amine is selected from
the group consisting of aniline, o-, m- and p-phenylene diamine,
benzidine, 4,4'-diaminodiphenyl methane, and
2,2-bis-(aminophenyl)propane.
8. The composition of claim 1 wherein component (A) is
.Iadd.derived from .Iaddend.a Novolak resin.
9. The composition of claim 1 wherein component (B) has an
equivalent weight in the range of about 70 to about 250.
10. The composition of claim 1 wherein component (B) has an
equivalent weight in the range of about 120 to about 200.
11. The composition of claim 1 wherein component (B) is selected
from the group consisting of
2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane,
1 to 4 times methylated
2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane,
4-(1,2-epoxyethyl)-1,2-epoxycyclohexane,
.[.1,2,8,9-diepoxy-p-methane,
2,2-bis(3,4-epoxycyclohexyl)propane.].,
.Iadd.1,2,8,9-diepoxy-p-menthane,
2,2-bis(3,4-epoxycyclohexyl)propane
.Iaddend.bis-(2,3-epoxycyclopentyl)ether,
1,2,5,6-diepoxy-4,7-hexahydromethanoindane,
bis-(3,4-epoxy-cyclohexylmethyl)adipate,
bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate,
bis(3,4-epoxy-cyclohexylmethyl)terephthalate,
bis(3,4-epoxy-6-methyl-cyclohexylmethyl)-terephthalate,3,4-epoxy-cyclohexa
ne carboxylic acid-(3,4-epoxy-cyclohexylmethyl)ester,
3,4-epoxy-6-methylcyclohexanecarboxylic
acid-(3,4-epoxy-6-methylcyclohexylmethyl)ester,
1,2-bis-(5(1,2-epoxy)-4,7-hexahydromethanoindaneoxy)-ethane,
.[.1,1,1-tris((5-(1,2-epoxy)-4,7-hexahydromethynoindaneoxy)-methyl)-propan
e.].
.Iadd.1,1,1-tris((5-(1,2-epoxy)-4,7-hexahydromethanoindaneoxy)-methyl)prop
ane .Iaddend.and 4,5-epoxyhexahydrophthalic
acid-bis-(3,4-epoxycyclohexylmethyl)ester.
12. The composition of claim 1 wherein component (B) is selected
from the group consisting of
2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane,
1 to 4 times methylated
2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane,
bis(3,4-epoxy-cyclohexylmethyl)adipate,
bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate,
3,4-epoxy-cyclohexane-carboxylic
acid-(3,4-epoxy-cyclohexylmethyl)ester and
3,4-epoxy-6-methylcyclohexane carboxylic
acid-(3,4-epoxy-6-methylcyclohexylmethyl)ester.
13. The composition of claim 1 wherein component (B) is represented
by the formula
wherein:
X is a 3,4-epoxycyclohexyl group or a mono- or dimethyl substituted
3,4-epoxycyclohexyl group; and
Y is a group represented by the formula ##STR13## wherein n is a
number in the range of from zero to 2, or a group represented by
the formula ##STR14## or a group represented by the formulae
or
wherein:
X is as defined above, and Z is .[.derived from.]. .Iadd.the acid
radical of .Iaddend.an aliphatic, cycloaliphatic or aromatic
dicarboxylic acid group.
14. The composition of claim 1 wherein .[.the.]. .Iadd.said
.Iaddend.mole ratio .[.of (B) to (A).]. is in the range of from
about 0.8 to about 1.5.
15. The composition of claim 1 wherein components (A) and (B) are
reacted at a temperature in the range of about 50.degree. C. to
about 300.degree. C.
16. The composition of claim 1 wherein components (A) and (B) are
reacted at a temperature in the range of about 100.degree. C. to
about 250.degree. C.
17. The composition of claim 1 wherein components (A) and (B) are
reacted at a temperature in the range of about 140.degree. C. to
about 230.degree. C.
18. The composition of claim 1 wherein components (A) and (B) are
reacted in the presence of an effective amount of catalyst to
accelerate the reaction.
Description
TECHNICAL FIELD
This invention relates to polymeric resins derived from 1-oxa-3-aza
tetraline group-containing compounds and cycloaliphatic epoxides.
More particularly, this invention relates .Iadd.to
.Iaddend.polymeric resins derived from compounds containing an
average of more than 1-oxa-3-aza tetraline group, and
cycloaliphatic epoxides containing at least one aliphatic ring and
an average of at least two epoxide groups, at least one of said
epoxide groups being part of said ring.
BACKGROUND OF THE INVENTION
Compounds containing 1-oxa-3-aza-tetraline groups, and their
prepolymers, are known, for example, from Swiss Pat. Nos. 574,978,
579,113 and 606,169. They can be obtained, for example, from
phenols by reaction with formaldehyde and an amine, according to
the formula: ##STR1## wherein R is, for example, hydrogen, halogen,
alkyl or alkoxy, and R' is an aliphatic or aromatic group. In
contrary to other known condensation reactions of phenols, amines
and formaldehyde, in the reaction outlined above phenolic OH-groups
are consumed. It is thereby possible, according to the formula (a)
hereinabove, to determine the amount of the synthesized 1-oxa-3-aza
tetraline group from the analytic determination of the said
OH-groups in the rection mixture.
It is also known from the above-mentioned patents that these
compounds containing 1-oxa-3-aza-tetraline groups can be cured with
epoxide resins, including cycloaliphatic epoxide resins. The
products obtained up to now have been useful for various
applications, but their stability is limited. The Martens heat
stability of the hardest resins obtained up to now is only between
about 120.degree. C. and 135.degree. C., with peak values from
about 160.degree. C. to 170.degree. C.
For many applications, higher heat stabilities are necessary. For
example, electric insulating materials of high heat stability are a
constant requirement of the electric industry. Plastics reinforced
with glass, quartz, carbon fibers and the like would probably be
considered for many new areas of application if the heat resistance
of the polymeric resin could be increased.
SUMMARY OF THE INVENTION
The present invention contemplates the provision of polymeric
resins characterized by particularly outstanding heat stabilities
in combination with good mechanical properties. Broadly stated, the
present invention provides for a composition comprising a polymeric
resin derived from (A) at least one compound containing an average
of more than one 1-oxa-3-aza tetraline group per molecule with (B)
at least one cycloaliphatic epoxide containing at least one
aliphatic ring and an average of at least two epoxide groups, at
least one of said epoxide groups being part of said ring, the mole
ratio of (B) to (A) being in the range of about 0.2 to about 2.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The polymeric resins provided in accordance with the present
invention are derived from (A) compounds containing an average of
more than one-1-oxa-3-aza-tetraline group per molecule and/or
.[.per.]. .Iadd.the .Iaddend.pre-polymer of said compound and (B)
cycloaliphatic epoxides containing at least one aliphatic ring and
an average of at least two epoxide groups per molecule, at least
one of said epoxide groups being part of said aliphatic ring and
the remaining epoxide groups either being part of said ring or
being directly attached to said ring.
Throughout this specification and in the appended claims, the
terminology "part of a ring" with respect to the position of an
epoxide group on an aliphatic ring refers to the following
structure ##STR2## The terminology "directly attached to a ring"
refers to the following structure ##STR3##
Compounds with more than one 1-oxa-3-aza-tetraline group in the
molecule can be obtained from polyvalent phenols and/or amines,
according to one of the following reaction schemes (b) or (c), or
can be obtained by other methods known in the art.
In .[.contrary.]. .Iadd.contrast .Iaddend.to other known
condensation reactions of phenols, amines and formaldehyde, in the
reaction outlined above phenolic OH-groups are consumed. It is
thereby possible, according to the formula (a) hereinabove, to
determine the amount of the synthesized 1-oxa-3-aza tetraline
groups from the analytic determination of the said OH-groups in the
reaction mixture. ##STR4## is the nth part of a phenol with n
phenol OH groups;
A is the group resulting from ##STR5## after splitting off of OH
and H in ortho position;
R' is an aliphatic or, preferably, an aromatic group; and
n is a number greater than 1, preferably less than 6, more
preferably from about 1.5 to about 3. ##STR6## wherein:
B is the mth part of a m-valent aliphatic or, preferably, aromatic
group, which may also contain hetero atoms, especially oxygen, or
may be substituted by R;
R is hydrogen, halogen, alkyl or alkoxy with 1 to about 6 carbon
atoms, preferably in met.alpha.- or para-position of the phenol;
and
m is a number greater than 1, preferably less than about 6, more
preferably from about 1.5 to about 3.
The phenol nuclei may also be part of a condensed ring system.
Values of n or m that are not whole numbers mean that mixtures of
different functional phenols or amines with the average value n or
m are provided.
Suitable for use as 1-oxa-3-aza-tetraline group containing
compounds are .Iadd.also .Iaddend.the reaction products which are
prepared, for example, in accordance with the teachings of Swiss
Pat. No. 606,169 (which is incorporated herein by reference), from
phenols, amines and formaldehyde in non-stoichiometric proportions.
Mole ratios of the reactants that provide an average of more than
one 1-oxa-3-aza tetraline group per molecule must be used.
Prepolymers of 1-oxa-3-aza-tetraline group containing compounds are
also useful in accordance with the invention. Since some of the
1-oxa-3-aza-tetraline groups may react during polymerization, these
prepolymers may contain a fewer number of said
1-oxa-3-aza-tetraline groups than provided by the monomers used to
form such prepolymers. It is essential, however, that the
.[.resulting prepolymers.]. .Iadd.intermediate monomer reaction
products .Iaddend.contain more than one 1-oxa-3-aza-tetraline group
per molecule. This can be calculated by a skilled artisan from the
functionality and the ratios of starting materials.
A 1-oxa-3-aza-tetraline composition according to the invention or
the prepolymers thereof are obtained, for example, if per mole of
multifunctional phenol or amine more than two moles of formaldehyde
and more than one mole of monofunctional amine and phenol,
respectively, are brought into reaction, whereby the mole
proportions are within the limit defined by the disclosure of Swiss
Pat. No. 606,169.
The reactants for forming the 1oxa-3-aza-tetraline group containing
compounds of the invention are phenols or phenol derivatives,
amines and formaldehyde. Examples of phenols that can be used
include monovalent phenols, such as phenol and m- and p-cresol, m-
and p-ethyl-phenol, m- and p-isopropylphenol, m- and
p-methoxy-phenol, m- and p-ethoxy-phenol, m-and
p-isopropyloxy-phenol, m- and p-chloro-phenol and B-naphthol.
Meta-substituted phenols are preferred, since they do not include
any blocked reactive positions. Ortho-substituted phenols are less
appropriate. Bivalent phenols that are useful include
4,4'-dihydroxy-diphenylmethane, 3,3'-dihydroxydiphenylmethane,
2,2-bis-(4-hydroxyphenyl)-propane, 4,4'-dihydroxy-stilbene,
hydroquinone, pyrocatechin and resorcin. Novolak resins.Iadd.,
eventually .Iaddend.mixed with a phenol.Iadd., .Iaddend.can also be
used.
Examples of amines that are useful include aniline, o-, m- and
p-phenylene diamine, benzidine, 4,4'-diaminodiphenyl methane and
2,2-bis-(aminophenyl)propane.
The epoxides are preferably bivalent or polyvalent cycloaliphatic
epoxides containing at least one epoxide group in a ring, and the
remaining epoxide groups also in a ring or directly attached to a
ring. Preferred epoxides are epoxide resins represented by the
formula
wherein:
X is a 3,4-epoxycyclohexyl group or a mono- or dimethyl substituted
3,4-epoxycyclohexyl group; and
Y is a group of the formula ##STR7## wherein n is a number in the
range of from zero to 2, or a group of the formula ##STR8## or a
group of the formulae
or
wherein:
X is as defined above, and Z is .[.derived from.]. .Iadd.the acid
radical of .Iaddend.an aliphatic, cycloaliphatic or aromatic
dicarboxylic acid, such as, for example, adipic acid, terephthalic
acid or 4,5-epoxy-hexahydrophthalic acid.
Particularly preferred epoxides are epoxide resins having
equivalent weights in the range of from about 70 to about 250,
preferably from about 120 to about 200.
Examples of epoxides that can be used include
2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane,
1 to 4 times methylated
2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy) cyclohexane-m-dioxane,
4-(1,2-epoxyethyl)-1,2-epoxycyclohexane,
1,2,8,9-diepoxy-p-.[.methane.]. .Iadd.menthane.Iaddend.,
2,2-bis(3,4-epoxycyclohexyl)propane, bis-(2,3-epoxycyclopentyl)
ether, 1,2,5,6-diepoxy-4,7-hexahydromethanoindane,
bis-(3,4-epoxy-cyclohexylmethyl) adipate,
bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate,
bis-(3,4-epoxy-cyclohexylmethyl)terephthalate,
bis-(3,4-epoxy-6-methyl-cyclohexylmethyl)-terephthalate,3,4-epoxy-cyclohex
ane carboxylic acid-(3,4-epoxy-cyclohexylmethyl) ester,
3,4-epoxy-6-methylcyclohexanecarboxylic
acid-(3,4-epoxy-6-methylcyclohexylmethyl)ester,
1,2-bis-(5(1,2-epoxy)-4,7-hexahydromethanoindane oxy)-ethane
.[.1,1,1-tris((5-(1,2-epoxy)-4,7-hexahydromethynoindane
oxy)-methyl)-propane.].
.Iadd.1,1,1-tris((5-(1,2-epoxy-4,7-hexahydromethanoindane
oxy)-methyl)-propane .Iaddend.and 4,5-epoxyhexahydrophthalic
acid-bis-(3,4-epoxycyclohexylmethyl)ester. Particularly preferred
epoxide resins include 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)
cyclohexane-m-dioxane, 1 to 4 times methylated 2-(3,4-epoxy)
cyclohexyl-5,5-spiro (3,4-epoxy)cyclohexane-m-dioxane,
bis(3,4-epoxy-cyclohexylmethyl)adipate,
bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate,
3,4-epoxy-cyclohexane-carboxylic acid-(3,4-epoxy-cyclohexylmethyl)
ester and 3,4-epoxy-6-methylcyclohexane carboxylic
acid-(3,4-epoxy-6-methylcyclohexylmethyl) ester.
The mole ratio of .[.epoxides.]. .Iadd.epoxide groups .Iaddend.to
1-oxa-3-aza-tetraline .[.group containing compounds.]. .Iadd.groups
.Iaddend.that are useful in accordance with the invention are
preferably in the range of from about 0.2 to about 2, more
preferably from about 0.8 to about 1.5
For purposes of calculating equivalent ratios, the number of
equivalents of a 1-oxa-3-aza-tetraline group containing compound is
based on the amount of primary amine brought into reaction;
independently of whether it actually forms part of a
1-oxa-3-aza-tetraline group. It is assumed that for each mole of
formaldehyde that is reacted, one mole of water will be split off.
Thus, for example, in Example 6 below, the theoretical equivalent
weight of the 1oxa-3-aza-tetraline group containing compound is
based on the following calculation
______________________________________ 1 gram equivalent Novolak
(equiv. weight = 100) = 100 g +0.8 mole .[.analine.]..Iadd.aniline
= 74.4 g +1.5 mole formaldehyde = 45 g -1.5 mole water = -27 g =
192.4 g ______________________________________
The N-equivalent weight is equal to 192.4 divided by 0.8 which
equals 240.5.
If, in the production of the 1-oxa-3-aza-tetraline group containing
compounds, no other nitrogen compounds other than the primary
amines are added, the equivalent weight may also be calculated from
the nitrogen content using known techniques. Compounds with more
than one 1-oxa-3-aza-tetraline group per molecule have N-equivalent
weights that are less than the average molecular weight.
The reaction between the 1-oxa-3-aza-tetraline group containing
compound and epoxide, which is in effect a curing reaction, is
preferably conducted at a temperature in the range of about
50.degree. C. to about 300+ C., more preferably about 100.degree.
C. to about 250.degree. C., more preferably about 140.degree. C. to
about 230.degree. C.
For various applications, it is advantageous to initially carry out
the curing in at least two steps to produce as an intermediate
product a solid or highly viscous, but still soluble or meltable,
prepolymer. Alternatively, the prepolymer can be formed during the
production of the 1-oxa-3-aza-tetraline group containing compound
.[.prior to reaction.]..Iadd., or it can be formed prior to, during
or after the reaction .Iaddend.with the epoxide. The final curing
step is then preferably carried out at a temperature in the range
of about 140.degree. C. to about 230.degree. C.
The final curing step can be improved by addition of a catalyst to
accelerate the reaction. In particular, the curing time can be
shortened in this way. Examples of catalysts that can be used
include, for example, acids, Friedel-Crafts catalysts, amines,
phosphines or quaternizing agents for tertiary amines, and
especially alkyl, aralkyl and aryl halides or sulfates, such as,
for example, benzyl chloride, chlorobenzol, iodobenzol, iodoform,
bromoform, methyl iodide or methyl sulfate.
Prior to or during the curing reaction to produce the polymeric
resins of the invention, additives such as fillers, colorants,
reinforcing fibers, plasticizers and the like can be added to the
reaction mixture. These additives can be provied at levels of up
to, for example, about 50% by weight of reaction mixture.[.,
preferably from about 10% to about 20% by weight of the mixture.]..
The polymeric resins of the invention can also be combined with
other plastics, resins or polymerizable monomers or prepolymers
such as, for example, aldehyde condensation resins (e.g., phenol
formaldehyde resins.Iadd.) .Iaddend.and other epoxide resins.[.)
prior to or during curing.]. .Iadd.as well as curing agents of
these resins.Iaddend.. The amount of the above mentioned additives
which may be mixed with resin according to the invention or which
are soluble therein should not exceed 50% of the mixture and
preferably should be in the region of 10 to 20%.
The polymeric resins of the present invention can be used for many
purposes such as, for example, casting, laminating, impregnating,
coating, gluing, painting, binding or insulating, or in embedding,
pressing, injection molding, extruding, sand mold binding, foam and
ablative materials.
The polymeric resins of the invention are especially suitable for
use in applications wherein relatively high heat stabilities are
required. Thus, these resins are useful in electric coils, for
example; their use permitting the use of higher voltages or the
reduction of wire diameters. These resins are also useful in
electric motors and in miniaturized electric devices and
construction elements.
The polymeric resins of the invention are especially suitable for
use in plastics reinforced with glass, quartz, carbon or aramide
fibers, and the like. With the increase in heat stability resulting
from the use of the polymeric resins of the invention, these
reinforced plastics can be used for applications not previously
suited for plastics such as, for example, in the replacement of
metals or ceramic materials in heat-stressed construction
applications. In these applications, the high bending resistance
and impact strength of the resins of the invention are particularly
advantageous.
In order to illustrate the preparation of the 1-oxa-3-aza-tetraline
group containing compounds that are useful in the preparation of
the polymeric resins of the invention, the following Examples 1-6
are provided. In the following examples as well as throughout the
specification and claims, all parts and percentages are by weight
and all temperatures are in degrees centigrade unless otherwise
indicated.
EXAMPLE 1
.Iadd.To .Iaddend.210 grams of 30% formaldehyde (2.1 moles),
.Iadd.contained in a stirred vessel equipped with reflux cooling
and heated to a temperature of 80.degree. C., .Iaddend.94 grams of
phenol (1 mole) and 99 grams of 4,4'-diaminodiphenyl methane (0.5
mole) are added .[.to a stirred vessel equipped with reflux cooling
and heated to a temperature of 80.degree. C., for.]. .Iadd.within
.Iaddend.15 minutes. The mixture is allowed to settle. The top
aqueous layer is separated, and the remaining water is distilled
off in a vacuum at 100.degree. C. The resulting resin-like
1-oxa-3-aza tetraline group containing compound has an N-equivalent
weight of 217.
EXAMPLE 2
4.1 moles formaldehyde, 2 moles aniline, 1 mole of phenol and 0.5
mole bisphenol A (2,2-bis(4-hydroxyphenyl)-propane) are reacted
using the procedures in Example 1. The resulting product has an
N-equivalent weight of 221.
EXAMPLE 3
Formaldehyde, phenol and 1,4-diaminobenzol in mole ratio 2:1:0.5
are reacted using the procedures in Example 1. The resulting
product has an N-equivalent weight of 172.
EXAMPLE 4
37.6 kilograms (400 moles) of phenol, 15 kilograms (200 moles) of
40% formaldehyde and 2 kilograms of 10% sulfuric acid are heated to
40.degree. C. in a stirred vessel. The mixture exotherms to
96.degree. C. The mixture is maintained at 96.degree. C. with
stirring for 30 minutes. The mixture is cooled to room temperature
and allowed to settle. The aqueous layer is removed. The remaining
product is a phenol-Novolak mixture with an average number of
nuclei of 2, a water content of 15% and a phenol content of 22%.
The equivalent weight of phenol is 117.7.
EXAMPLE 5
157.5 grams (2.1 mole) of 40% formaldehyde containing 5 millimoles
of potassium hydroxide, 117.7 grams of the product of Example 4
containing 1 mole phenol hydroxyl groups, and 93 grams (1 mole) of
aniline are mixed together for 7 minutes at 95.degree. C. with
stirring, then heated under reflux conditions for 30 minutes. The
mixture is cooled to room temperature, allowed to settle and the
aqueous layer is removed. The resulting product is distilled under
a vacuum and at a temperature of 123.degree. C. to remove remaining
water. The product has an N-equivalent weight of 217.
EXAMPLE 6
A resin containing an average of 1.6 1-oxa-3-aza-tetraline groups
per molecule is produced from 1.5 moles of formaldehyde, 1 gram
equivalent of the product of Example 4, and 0.8 mole of aniline
using the procedures of Example 5. The resulting product has an
N-equivalent weight of 240.5.
The following Examples 7-25 are provided to illustrate the
preparation of the polymeric resins of the invention. In these
examples, some of the epoxide resins identified in Table 1 are
used. The remaining epoxide resins in Table 1 are also useful in
making the polymeric resins of the invention.
TABLE 1 ______________________________________ Sym- bol Epoxide
Resin ______________________________________ A
4-(1,2-epoxyethyl)-1,2-epoxycyclohexane B
1,2,8,9-diepoxy-p-menthane C 2,2-bis-(3,4-epoxycyclohexyl)-propane
D Bis-(2,3-epoxycyclopentyl)ether(liquid form) E
Bis-(2,3-epoxycyclopentyl)ether(isomer crys- talline form) F
1,2,5,6-diepoxy-4,7-hexahydromethanoindane G
1,1,1-tris((5-(1,2-epoxy)-4,7-hexahydromethano- indane
oxy)methyl)-propane H
1,2-bis(5(1,2-epoxy)4,7-hexahydromethanoindane oxy)-ethane I
3,4-epoxycyclohexane carboxylic acid-(3,4-
epoxycyclohexylmethyl)ester K 3,4-epoxy-6-methylcyclohexane
carboxylic acid- (3,4-epoxy-6-methylcyclohexylmethyl)ester L
2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)- cyclohexane-m-dioxane
M 2-(3,4-epoxy-4-methylcyclohexyl-5,5-spiro(3,4-
epoxy)cyclohexane-m-dioxane N
.[.2-(3,4-epoxy-4-methylcyclohexyl)-5,5-spiro(3,4- epoxy)-4-methyl
cyclohexane-m-dioxane O
2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)-4-
methylcyclohexane-m-dioxane.]. .Iadd.2-(3,4-epoxy)cyclohexyl-5,5-
spiro(3,4-epoxy)-4-methylcyclohexane- m-dioxane
2-(3,4-epoxy-4-methylcyclohexyl)- 5,5-spiro(3,4-epoxy)-4-methyl
cyclohexane-m-dioxane.Iaddend. P
2-(3,4-epoxy)-4,6-dimethylcyclohexyl-5,5-spiro-
(3,4-epoxy)-4-methylcyclohexane-m-dioxane Q
2-(3,4-epoxy)-4,6-dimethylcyclohexyl-5,5-spiro-
(3,4-epoxy)-4,6-dimethylcyclohexane-m-dioxane R
Bis-(3,4-epoxy-6-methylcyclohexylmethyl)adipate S
Bis-3,4-epoxycyclohexylmethyl)adipate T
Bis(3,4-epoxy-cyclohexylmethyl)-terephthalate U
Bis-(3,4-epoxy-6-methylcyclohexylmethyl)-tere- phthalate V
4,5-epoxy-hexahydrophthalic acid-bis-(3,4-
epoxy-cyclohexylmethyl)ester ##STR9## G ##STR10## H ##STR11## L
##STR12## ______________________________________
EXAMPLE 7
100 parts of the product of Example 1 are mixed at 140.degree. C.
with 100 parts of epoxide resin I and poured under vacuum into a
mold for a plate 10 millimeters thick. The mixture is cured for one
hour at 180.degree. C., then for one hour at 200.degree. C. and
then for two hours at 220.degree. C. Test bodies prepared from the
plate show no decomposition at 250.degree. C. These bodies have a
bending resistance of 115 .[.MPs.]. .Iadd.MPas.Iaddend., an E
modulus of 4800 .[.MPs.]. .Iadd.MPas.Iaddend., an electrical
resistance over 10.sup.15 ohms and a loss factor of less than
10.sup.-2. The glass transition temperature is 230.degree. C. The
term "glass transition" temperature is used herein to refer to the
temperature at which the polymer changes from a brittle, vitreous
state to a plastic state.
EXAMPLES 8-23
Cast resin plates were prepared from the resin mixtures given in
Table 2 using the method described in Example 7. The epoxide resins
used are listed in Table 1. The properties of the cured resins are
listed in Table 2.
TABLE 2
__________________________________________________________________________
Example No. 8 9 10 11 12 13 14 15
__________________________________________________________________________
1-Oxa-3-aza-tetra- 5 5 5 5 5 5 5 5 line compound from Example No.
N--equavalent weight 217 217 217 217 217 217 217 217 (1) Wt. of
1-oxa-3-aza- 100 100 100 100 100 100 100 100 tetraline compound, g
Epoxide resin K S L L L L L L Epoxide equivalent 140 (3) 183 (3)
162 (2) weight Wt. of epoxide, g 100 100 100 20 40 66 75 150
Equivalent ratio (6) 1.55 1.18 1.36 0.27 0.54 0.9 1.0 2.0 Curing
cycle (7) 180.degree. C..fwdarw. .fwdarw. .fwdarw. .fwdarw.
.fwdarw. .fwdarw. .fwdarw. (7) 200.degree. C..fwdarw. .fwdarw.
.fwdarw. .fwdarw. .fwdarw. .fwdarw. .fwdarw. (7) 220.degree.
C..fwdarw. .fwdarw. .fwdarw. .fwdarw. .fwdarw. .fwdarw. .fwdarw.
Recuring (10) 250.degree. C. Behavior at 220.degree. C. (4) (4) (4)
(4) (4) (4) (4) (4) (4) 250.degree. C. (4) (4) (4) (4) (4) (4) (4)
(4) (5) Bending 25.degree. C. 115 100-110 resistance 220.degree. C.
65 at, MPs 250.degree. C. 50 Glass transition .sup. 220.degree.
.sup. 190.degree. 250.degree. 280.degree. .sup. 210.degree. .sup.
250.degree. >260.degree. >260.degree. >260.degree.
temperature, C..degree.
__________________________________________________________________________
Example No. 16 17 18 19 20 21 22 23
__________________________________________________________________________
1-Oxa-3-aza-tetra- 5 5 2 3 6 5 5 5 line compound from Example No.
N-equavalent weight 217 217 231 172 240 217 217 217 (1) Wt. of
1-oxa-3-aza- 100 100 100 100 100 100 100 100 tetraline compound, g
Epoxide resin I O R I L R .multidot. L K .multidot. A A Epoxide
equivalent 126 (3) 147 (3) 197 (3) 160 (3) -- -- 70 (3) weight Wt.
of epoxide, g 100 100 100 100 50 50 .multidot. 50 80 .multidot. 20
26 Equivalent ratio (6) 1.7 1.5 1.2 1.36 0.75 -- -- 0.8 Curing
cycle .fwdarw. .fwdarw. .fwdarw. .fwdarw. .fwdarw. .fwdarw. (8)
140.degree. C. (8) 140.degree. C. .fwdarw. .fwdarw. .fwdarw.
.fwdarw. .fwdarw. .fwdarw. (9) 200.degree. C. (9) 160.degree. C.
.fwdarw. .fwdarw. .fwdarw. .fwdarw. .fwdarw. .fwdarw. (9)
200.degree. C. Recuring Behavior at 220.degree. C. (4) (4) (4) (4)
(4) (4) (4) (4) 250.degree. C. (4) (4) (4) (4) (4) (4) (4) (5)
Bending 25.degree. C. 115 resistance 220.degree. C. at, MPs
250.degree. C. Glass transition .sup. 230.degree. .sup. 220.degree.
.sup. 200.degree. .sup. 240.degree. .sup. 180.degree. .sup.
220.degree. .sup. 220.degree. .sup. 170.degree. temperature,
C..degree.
__________________________________________________________________________
(1) Calculated from production. (2) Analytically determined. (3)
Calculated from theoretical formula. (4) Unchanged (5) Cracks and
bubbles observed. (6) Ratio of equivalents of 1oxa-3-aga-tetraline
to epoxide. (7) 1 hour at (8) 24 hours at (9) 2 hours at (10) 3
hours at
EXAMPLE 24
75 grams epoxide resin L are mixed, under vacuum at 120.degree. C.
with 100 grams of the 1-oxa-3-aza-tetraline compound according to
Example .Iadd.5 .Iaddend.and 200 grams quartz meal, and poured into
a mold. The cast piece is cured for 1 hour at 200.degree. C., then
for 1 hour at 220.degree. C. The resulting product has a bending
resistance of 60 MPs and shows no deformation at 250.degree. C.
EXAMPLE 25
A glass cloth with a glycidyl-propyl silane finish and a .[.surface
area.]. .Iadd.weight .Iaddend.of 120 grams per square meter is
impregnated with a 60% solution of the resin mixture of Example 21,
and dried in a two-step hot air channel at 100.degree.-140.degree.
C. Eight layers of the Prepreg are pressed between layers of copper
foil for one hour at 180.degree. C. to form a plate. The laminate
shows no delamination in the solder bath test at 260.degree. C. The
electrical resistance is over 10.sup.15 ohm --cm, the loss factor
under 0.01. The bending resistance amounts to 500 MPs.
EXAMPLES 26-28
Examples 26-28 are provided for purposes of comparison. Cast resin
plates were prepared from resin mixtures provided in Table 3. In
Examples 26 and 27, cycloaliphatic epoxide resins other than the
type required by the present invention were used. In Example 28,
the monofunctional 1-oxa-3-aza-tetraline compound disclosed in
Example 1 of Swiss Pat. No. 579,113 was used. The results of these
examples indicate that polymers with less heat stability or lower
glass transition tempertures were achieved when compared to the
polymeric resins of the invention.
TABLE 3
__________________________________________________________________________
Example No. 26 27 28
__________________________________________________________________________
1-Oxa-3-aza-tetraline 5 5 N--Phenyl-1-oxa-3-ara- compound from
Example tetraline No. N--equivalent (1) Wt. of 1-oxa-3-aza- 100 100
100 tetraline compound, g. Epoxide resin Tetrahydrophthalic
Hexahydrophthalic 1 acid diglycidylester acid diglycidylester
Epoxide equivalent 140 (1) Wt. of epoxide, g. 100 100 40 Equivalent
ratio (6) 0.60 Curing cycle 2 hrs. at 180.degree. C. 2 hrs. at
180.degree. C. 2 hrs. at 160.degree. C. .sup. 1 hr. at 200.degree.
C. .sup. 1 hr. at 200.degree. C. .sup. 1 hr. at 200.degree. C.
Behavior at 220.degree. C. (5) (5) (4) Glass transition temp-
110.degree. C. erature, .degree.C.
__________________________________________________________________________
(1) Calculated from production. (2) Analytically determined. (3)
Calculated from theoretical formula. (4) Unchanged (5) Cracks and
bubbles observed. (6) Ratio of equivalents of 1oxa-3-aza-tetraline
to epoxide.
The polymeric resins of the invention obtained in the above
examples show, in comparison with the structurally closest
previously known resins, of which the properties are well known, a
generally far higher heat resistance, along with very good
mechanical properties, especially with high bending and impact
resistance. The comparison tests (Examples 26-28) confirm this
observation.
While the invention has been explained in relation to its preferred
embodiments, it is to be understood that various modifications
thereof will become apparent to those skilled in the art upon
reading this specification. Therefore, it is to be understood that
the invention disclosed herein is intended to cover such
modifications as fall within the scope of the appended claims.
* * * * *