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Патент USA US3036038

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3,030,028
Patented May 22, 1962
2
phenol. Assuming that at the time that the phenol is
3,03% 028
PHENOL-MELAMINE-FQ’RMALDEE RESIN
added, that all of the formaldehyde initially introduced
ware
has become reacted with the melamine, one may add
formaldehyde in a mol ratio between about 0.5 and about
2.0 per mol of phenol added. It is preferred that the
amount of formaldehyde added be about 0.9 mol per
No Drawing. Filed Oct. 20, 1958, Ser. No. 768,044
1 5 Claims. (Cl. 260-451)
mol of phenol.
Among the tertiary amines that may be used in the
AND PROCESS ()F PREPG SAME
_
Alex J. Malashevitz, Cincinnati, Ohio, assignor to Formica
Corporation, Cincinnati, Ohio, a corporation of Dela
practice of the process of the present invention are tri
This invention relates to a novel melamine resin and 10 methyl amine, triethyl amine, diethyl methyl amine, di
to the process of preparing the same. More particularly,
methyl ethyl “amine, and the like.
this invention relates to a melamine resin modi?ed with a
Among the phenols that may be used in the practice of
phenol and to the process of preparing‘the same.
the process of the present invention, in addition to phenol
One. of the objects of the present invention is to pro
per se, are ortho, meta, para-cresol, or the xylenols such
duce a melamine resin modi?ed with a phenol. A further 15 as 2,3-dimethyl phenol, 3,4-dimethyl phenol, 3,5-dimethyl
‘art;
object of the present invention 'is to produce a melamine
phenol, 2,6-dimethyl phenol, 2,4-dimethyl phenol, 2,5-di
resin modi?ed with a phenol, which resin will have utility
methyl phenol, or the dihydric phenols such as resorcinol,
in a plurality of ‘directions but particularly in the ?eld of
bis phenol-A (propylidene bis paraphenol) and the like.
impregnation of paper for use in making laminates. A
Quite obviously, these phenols may be used either singly
further object of the present invention is to produce a 20 or in combination with one another and in fact, it is, on
phenol modi?ed melamine resin for use in producing elec
_ certain occasions, desirable to use mixtures of phenols
trical grade laminates. These and other objects of the
such as mixed xylenols and the like.
present invention will be discussed in greater detail herein
The pH of the reaction system will be calibrated to the
below.
amount and type of alkaline material present such as the
In the practice of the process of the present invention,
triethyl amine, and the like.
melamine and formaldehyde are coreacted in the presence
of from about 0.2% to about 10% by weight, based on
In order that the present invention may be more com
over a fairly wide range, such as between about 1:1 and
detail contained therein should not be interpreted as a
limitation on the case except as is indicated in th
pletely understood, the following examples are set forth in
the weight of the melamine, of a tertiary amine having a
which all parts are parts by Weight unless otherwise indi
boiling point up to 100° C. The mol ratio of the mela
cated. These examples are set forth primarily for the
mine to formaldehyde is not critical and may be varied 30 purpose of illustration and any speci?c enumeration of
1:6, respectively. It is preferred, however, that the mol
ratio of melamine to formaldehyde be controlled within
appended claims.
_
I
the range of 1:1.5 and 122.5, respectively. The amount
Example 1
of tertiary amine is preferably between about 2% and 5% 35
Into ‘a suitable reaction vessel equipped with ther
by weight based on the total weight of the melamine.
mometer, stirrer and re?ux condenser, there is introduced
The reaction of the melamine and formaldehyde in the
630 parts of melamine, 810 parts of a 37% aqueous soluh
presence of the tertiary amine may be carried out at a
tion of formaldehyde ‘and 10 parts of triethyl amine. The
temperature between about 70° C. and the re?ux tem
perature. This part of the process is continued until the 40 charge is heated to re?ux and maintained at that tempera
ture until the Water tolerance is 1000% whereupon there
resin produced has a water tolerance between about 300%
is added 470 parts of phenol, 610 parts of a 37% aqueous
and 5000%. It is preferred that the water tolerance be
solution of'formaldehyde, and 30 parts of a 28% aqueous
between about 500% and 1000%. The term water toler
solution of ammonia. The charge is heated again to re
ance is one conventionally used in the art to indicate the
?ux
and re?uxed for about 15 minutes whereupon the
45
measure of dilutability which ‘a given resinsyru-p will
resinous material indicates signs of becoming hydrophobic
tolerate. When a sample of resin has a water tolerance
whereupon there is added 350 parts of ethyl valcohol and
of 500%, it is an indication that that sample of resin can
the charge cooled to room temperature.
be diluted with ?ve times its volume of water without
Example 2
displaying any milkiness, indicating the end point of
water tolerance has been reached. When a resin has a 50
Into a suitable reaction vessel equipped as before, there
water tolerance of 1000%, it means that the resin pro
is introduced 630 parts of melamine, 810 parts of a 37%
duced can be diluted with about ten times its volume of
aqueous solution of formaldehyde, 10 parts of triethyl
water without displaying any milkiness. The same is
amine and the charge is heated to re?ux and maintained at
true for resins having a water tolerance of about 300%
that temperature to a water tolerance of 1000%. There
up to about 5000% on a calibrated basis. When the 55 'upon, there is added 305 parts of a 37% aqueous solution
melamine and formaldehyde have been reacted in the
presence of the tertiary amine to a water tolerance Within
the stated ranges, a phenol is added ‘and reacted with the
of formaldehyde, 470 parts of phenol and 30 parts of a
28% aqeuous solution of ammonia. The charge is re
heated to re?ux and maintained at that temperature for
melamine-formaldehyde resin until the ultimate resin pro
about 15 minutes whereupon 350 parts of. ethyl alcohol
duced becomes hydrophobic. The amount of phenol to 60 are added and the charge cooled to room temperature.
be introduced into the reaction sphere can be varied over
a fairly wide range such as on a mol ratio basis from
about 1:9 to about 9:1, melamine to phenol, respectively.
It is preferred that the mol ratio of melamine to phenol
be controlled within the range of 6:4 and 4:6, respective
ly. If desired, one can add additional formaldehyde with
or subsequent to the addition of the phenol depending on
whether or not the initial charge of formaldehyde intro
duced to react with the melamine has been fully reacted
Example 3
Example 1 is repeated in every detail except that in
the place of the 30 parts of the 28% aqueous solution of
ammonia, there is used 10 parts of hexamethylene tetra
mine.
Example 4
Example 1 is repeated in every detail except that in the
place of the 10 parts of triethyl amine, there is substituted
or whether there is an excess of unreacted formaldehyde 70 20 parts of triethyl amine and no aqueous ammonia is
available for further reaction with either melamine or a
'added with the phenol. .
3,036,028
4
tolerance between about 300% and 5000% is attained,
adding a phenol and reacting until the resin produced be
Example 5
Example 3 is repeated in all details except that the
initial melamine-formaldehyde triethyl amine charged is
comes hydrophobic, wherein the mol ratio of melamine to
formaldehyde is between about 1:1 and 1:6, respectively,
heated to 80° C. instead of re?ux and is maintained at
that temperature until the water tolerance is 1000%. A
further differentiating feature resides in the fact that re
?uxing is maintained for
minutes and 500 parts of
followed by the addition
followed by a cooling to
and the mol ratio of melamine to said phenol is between
about 1:9 and 9:1, respectively.
2. A process comprising heat reacting melamine and
only 5 minutes instead of 15
formaldehyde in the presence of from about 0.2% to
water are vacuum-distilled off
10% by weight based on the weight of melamine of a
of 900 parts of ethyl alcohol
10 tertiary amine, having a boiling point up to 100° C., at a
room temperature.
temperature from about 70° C. to re?ux until a water
Example 6
tolerance between about 500% and 100096 is attained,
adding a phenol and reacting until the resin produced be
Into a suitable reaction vessel equipped as in Example
comes hydrophobic, wherein the mol ratio of melamine
of a 37% aqueous solution of formaldehyde, and 10 parts 15 to formaldehyde is between about 1:1 and 1:6, respec
tively, and the mol ratio of melamine to said phenol is
of triethyl amine. The charge is heated to re?ux and held
between about 1:9 and 9: 1, respectively.
at that temperature for a water tolerance of 1000% where
3. A process comprising heat reacting melamine and
upon there is added 610 parts of a 37% aqueous solution
formaldehyde
in the presence of from about 0.2% to 10%
of formaldehyde, 540 parts of cresylic acid (a commer
by
weight
based
on the weight of melamine of a tertiary
20
cially available product comprising predominantly mixed
amine, having a boiling point up to 100° C., at a tem
xylenols) and 10 parts of hexamethylene tetramine. The
perature from about 70° C. to re?ux until a water toler
charge is reheated to re?ux for about 15 minutes where
ance between about 300% and 5000% is attained, adding
uponthere is added 350 parts of ethyl alcohol and the
a phenol and reacting until the resin produced becomes
charge cooled to room temperature.
25 hydrophobic, wherein the mol ratio of melamine to
Example 7
formaldehyde is between about 1:1.5 and 122.5, respec
tively, and the mol ratio of melamine to said phenol is
Into a suitable reaction vessel equipped as before, there
between about 1:9 and 9:1, respectively.
is introduced 630 parts of melamine, 810 parts of a 37%
4. A process comprising heat reacting melamine and
aqueous solution of formaldehyde and 10 parts of triethyl '
amine. The charge is heated to re?ux and maintained at 30 formaldehyde in the presence of from about 0.2% to 10%
by weight based on the weight of melamine of a tertiary
that temperature until a water tolerance of 1000% is
amine, having a boiling point up to 100° C., at a tem
reached. There is then added 610 parts of a 37% aqueous
1, there is introduced 630 parts of melamine, 810 parts
solution of formaldehyde, 540 parts of meta/paracresol
and 10 parts of hexamethylene tetramine. The charge is
re?uxed for 15 minutes and upon the addition of 350 parts
of ethyl alcohol, the mixture is cooled to room tempera
perature from about 70° C. to re?ux until a water toler
ance between about 300% and 5000% is attained, adding
a phenol and reacting until the resin produced becomes
hydrophobic, wherein the mol ratio of melamine to form
aldehyde is between about 1:1 and 1:6, respectively,
ture.
>
and the mol ratio of melamine to said phenol is between
Example 8v
about 6:4 and 4:6, respectively.
Example 4 is repeated in every detail except that in the .
5. A process comprising heat reacting melamine and
place of the 20 parts of triethyl amine, there is used 40 formaldehyde in the presence of from about 2% to 5%
only 10 parts of triethyl amine. The re?uxing is for 30
by weight based on the weight of melamine of a tertiary
minutes instead of for 15 minutes and there, is added 360
amine, having a boiling point, up to 100° C., at a [tem
parts of ethyl alcohol instead of 350 parts of ethyl alcohol.
perature from about 70° C. to re?ux until a water toler
Example 9
45 ance between about 300% and 5000% is attained, adding
Into a suitable reaction vessel equipped as’ in Example
1, there is introduced 630 parts of melamine, 1215 parts
of a 37% aqueous solution of formaldehyde and 10 parts
of triethyl amine. The charge is heated to re?ux and
maintained at that temperature to a water tolerance of
1000%. There is then added 610 parts of a 37% aqueous
solution of formaldehyde, 470 parts of phenol and 10
parts of triethyl amine. The charge is then reheated to
re?ux and maintained at that temperature for 15 minutes
whereupon 350 parts of ethyl alcohol are added and the
a phenol and reacting until the resin produced becomes
hydrophobic, wherein the mol ratio of melamine to form
aldehyde is between about 1:1 and 1:6, respectively, and
the mol ratio of melamine to said phenol is between about
1:9 and 9:1, respectively.
6. A process comprising heat reacting melamine and
formaldehyde in the presence of from about 0.2% to 10%
by weight based on the weight of melamine of a tertiary
amine, having a boiling point up to 100° C., at a tem
perature from about 70° C. to re?ux until a water toler
ance between about 500% and 1000% is attained, adding
a phenol and reacting until the resin produced becomes
Example 10
hydrophobic, wherein the mol ratio of melamine to form
aldehyde is between about 1:l.5 and 122.5, respectively,
Into a suitable reaction vessel equipped as in Example
1, there is introduced 315 parts of melamine, 405 parts 60 and the mol ratio of melamine to said phenol is between
about 1:9 and 9:1, respectively.
of a137% aqueous solution of formaldehyde and 10 parts
7. A process comprising heat reacting melamine and
of triethyl amine. The charge is heated to re?ux and
formaldehyde in the presence of from about 0.2% to 10%
maintained at that temperature until a water tolerance of
by weight based on the weight of melamine of a tertiary
1.000%. is attained. There is then added 610 parts of a
37% aqueous solution ‘of formaldehyde, 470 parts of 65 amine, having a boiling point up to 100° C., at a tem
total charge is cooled to room temperature.
'
phenol and 10 par-ts of hexamethylene tetramine. The
charge is re?uxed again for 15 minutes whereupon 450
parts of ethyl alcohol are added and the charge cooled to
perature from about 70° C. to re?ux until a water toler
ance between about 500% and 1000% is attained, adding
a phenol and reacting until the resin produced becomes
‘hydrophobic, wherein the mol ratio of melamine to form
room temperature.
‘
I claim:
‘
p
70 aldehyde is between about 1:1 and 1:6, respectively, and
the mol ratio of melamine to said phenol is between about
1. A process comprising heat reacting melamine and
6:4 and 4:6, respectively.
formaldehyde in the presence of from about 0.2% to
8. A process comprising heat reacting melamine and
10% by weight based on the weight of melamine of a
formaldehyde in the presence of from about 2% to 5%
tertiaryamine, having a boiling point up to 100° C., at a
temperature from about 70° C. to re?ux until a water 75 by Weight based on the weight of melamine of a tertiary
am‘
3,036,028
5
6
amine, having a boiling point up to 100° C., at a tem
formaldehyde in the presence of vfrom about 0.2% to 10%
by weight based on the weight of melamine of a tertiary
amine, having a boiling point up to 100° C., at a tem
perature from about 70° C. to re?ux until a water toler
ance between about 500% and 1000% is attained, adding
a phenol and reacting until the resin produced becomes
hydrophobic, wherein the mol ratio of melamine to form
perature from about 70° C. to re?ux until 1a water toler
ance between about 300% and 5000% is attained, adding
a cresol and reacting until the resin produced becomes
hydrophobic, wherein the mol ratio of melamine to {form
aldehyde is between about 1:1 and 1:6, respectively, and
the mol ratio of melamine to said cresol is between about
aldehyde is between about 1:.1 and 1:6, respectively, and
v.
the mol ratio of melamine to said phenol is between about
1:9 and 9:1, respectively.
9. A process comprising heat reacting melamine and
formaldehyde in the presence of from about 0.2% to 10% 10 1:9 and 9:1, respectively.
13. A process comprising heat reacting melamine and
by weight based on the weight of melamine of a tertiary
formaldehyde in the presence of from about 0.2% to 10%
amine, having a boiling point up to 100° C., at a tem
by weight based on the weight of melamine of a tertiary
perature from about 7 0° C. to re?ux until ‘a water toler
amine, having a boiling point up to 100° C., at a tem
ance between about 500% and 1000% is attained, adding
a phenol and reacting until the resin produced becomes 15 perature from about 7 0° C. to re?ux until a water toler
hydrophobic, wherein the mol ratio of melamine to form
ance between about 500% and 1000% is attained, adding
a cresol and reacting until the resin produced becomes
aldehyde is between about 1:1.5 and 1:25, respectively,
hydrophobic, wherein the mol ratio of melamine to ‘form
and the mol ratio of melamine to said phenol is between
about 6:4 and 4:6, respectively.
aldehyde is between about 1:1.5 and 1:25, respectively,
10. A process comprising heat reacting melamine and 20 and the mol ratio of melamine to said cresol is between
formaldehyde in the presence of from about 2% to 5%
about 6:4 and 4:6, respectively.
by weight based on the weight of melamine of a tertiary
14. A process comprising heat reacting melamine and
amine, having a boiling point up to 100° C., at a tem
formaldehyde in the presence of ‘from about 2% to 5%
perature from about 70° C. to re?ux until a water toler
by weight based ‘on the weight of melamine of a tertiary
ance between about 500% and 1000% is attained, adding 25 amine, having a boiling point up to 100° C., at a tem
a phenol and reacting until ‘the resin produced becomes
perature from about 70° C. to re?ux until a water toler
hydrophobic, wherein the mol ratio of melamine to form
ance between about 500% and 1000% is attained, adding
aldehyde is between about 1:1.5 ‘and 1:25, respectively,
a cresol and reacting until the resin produced becomes.
and the mol ratio of melamine to said phenol is between
hydrophobic, wherein the mol ratio of melamine to form
30 aldehyde is between about 121.5 and 1:2.5, respectively,
about 1:9 and 9:1, respectively.
11. A process comprising heat reacting melamine and
and the mol ratio of melamine to said cresol is between
formaldehyde in the presence of ‘from about 2% to 5%
about 6:4 and 4:6, respectively.
by weight based on the weight of melamine of a tertiary
15. The resinous reaction product produced according
amine, having a boiling point up to 100° C., at a tem
perature from about 70° C. to re?ux until a water toler
ance between about 500% and 1000% is attained, adding
a phenol and reacting until the resin produced becomes
hydrophobic, wherein the mol ratio of melamine to ‘form
aldehyde is between about 1:15 and 1:2.5, respectively,
to the process of claim 1.
35
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,826,559
Updegraft, et al _______ __ Mar. 11, 1958
614,037
Great Britain __________ __ Dec. 8, 1948
and the mol ratio of melamine to said phenol is between
about 6:4 and 4:6, respectively.
12. A process comprising heat reacting melamine and
FOREIGN PATENTS
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