Patented Sept. 20.

1949 ' 2,482,508 1"

. UNITED srAras PATENT OFFICE 2,482,508

MODIFIED METHYLOL MELsMmc aasms
Mass. assignor to
Stuart 11. Rider, Spring?eld, St. Louis, Mo., a \
Monsanto Chemical Company,
" corporation of Delaware
at niawinr. Application August 21, 1946,
Serial No. 692,137
8 Claims. (Cl- 260-673)
softened and regained its normal hardness after
This invention relates to modi?ed methylol drying for 15 minutes. ,
melamine ether resins. More particularly it re The ortho- silicates which may be used to pro
lates to methylol melamine ether resins modi?ed duce the resins of this invention are the alkyl .
with ortho esters of silicon. derivatives of ortho silicic acid. The alkyl sub
An object of this invention is to provide modi stituents may be identical or‘ two or more dif
?ed methylol melamine ether resins. ferent alkyl substituents may be present. Ex
A further object is to modify methylol mela amples of the ortho silicates are tetramethyl,
mine ether resins with ortho esters of silicon. tetraethyl, tetrabutyl, tetraisobutyl, tetraamyl,
vThese and other objects are attained by re 10 tetrahexyl, dimethyl diethyl, diethyl dibutyl, etc.
acting an ether of a methylol melamine with orthosilicates. ,
an ortho ester. of silicon under anhydrous condi The methylol melamine ethers which may be
used are the alkyl ethers of any of the methylol
tions.
The following examples are given to illustrate meiamines from mono to hexamethylol mela
this invention and are not intended to limit the mines or mixtures of the same. Thus the methyl,
scope thereof. ~Where parts are mentioned they 15 ethyl, propyl, isopropyl, butyl, isobutyl, amyl,
are parts by weight. hexyl, octyl ethers of mono, di dri, vtetra,
Example I penta or hexamethylol, melamines' may be
- used. Care must be taken to eliminate all water
300 parts (about .‘15 mol) of an anhydrous including water I of crystallization from the
methyl ether of hexamethylol melamine were 20 methylol melamine ethers prior to the reaction
mixed with 200 parts (about 1 mol) of tetraethyl with the ortho silicates.
ortho silicate in a suitable vessel provided with The ratio of methylol melamine ether to alkyl
a re?ux condenser. A calcium chloride tube was ortho silicate may be varied over a wide range
placed in the top of the condenser to exclude e. g. 1 mol of methylol melamine ether may be
moisture during the reaction. The mixture was 25 reacted with from about 0.2 to 3 or more mols
heated at 150° C. for 21/2 hours. Excess silicate of alkyl ortho silicate. An excess of the alkyl
ester was removed by distillation to yield a rub ortho silicate may be used and the excess re
bery water-white resin, insoluble in water and moved by distillation after completion of the re
soluble in xylol. 30 action. ‘ ,

Example II The temperature of the reactionv may be varied

from about 100 to about 200° C. with a. resultant
650 parts (about 1 mol) of an anhydrous butyl decrease in the reaction time from about 4 hours
ether of hexamethylol melamine were mixed with at 100° C. to about 1 hour at 200° C. No catalyst
200 parts (about 1 mol) of tetraethyl ortho sili
cate in a suitable container fitted with a re?ux35 need be used to accelerate the reaction.
The resins of this invention are soft, rubbery,
condenser and a calcium chloride moisture trap. and generally water-white. They are softened
The mixture was heated at 180° C. for 2 hours. slightly by water and are soluble in hydrocarbon
Excess silicate ester was removed by distillation solvents especially those of the aromatic series.
to produce a soft rubbery water-white resin solu The resins may be partially cured without cata
ble in aromatic hydrocarbons such as benzene, lysts at ,from about 120° C. to about 300° C. to
xylol, etc. ' r. produce hard, glossy ?exible ?lms. They are
Example III still soluble in aromatic hydrocarbons and will
soften slightly when immersed in water but re
400 parts (about 1 mol) of an anhydrous methyl 45 cover their original hardness on removal of the
ether of hexamethylol melamine were mixed with water.
180 parts (1 mol) of dimethyl diethyl ortho The resins may be further cured to an insolu
silicate in a suitable container provided with a ble. infusible, water-inert stage by incorporating
re?ux condenser and a calcium chloride moisture an acid catalyst therein and heating at about 100
trap. The mixture was reacted at 130° C. for 50 to about 200° C. The fully cured resins are ex
4 hours. Excess silicate ester was then removed tremely hard. .
by distillation to produce a soft rubbery water An unusual feature of- the uncured resins of
white resin soluble in aromatic hydrocarbons. ' this invention is their
low viscosity coefficient.
The reaction conditions must be anhydrous For example, at the end of the reaction producing
to produce the resins of this invention since the 55 the resins, the resins are so sti? and viscous that
ortho silicates readily hydrolyze in the presence they will ride up and cling to the stirring device
of even very small amounts of water. After the even though the temperature is about 150° 0.;
reaction is completed, water has only a slight yet at room temperature, ca. 30° C., they are still
softening e?ect on the resin and does not cause soft rubbery materials.
hydrolysis. For example a partially cured ?lm 60 The uncured resins are compatible with alkyd
immersed in water for 18 hours was. only slightly
' resins increasing the hardness oi ?lms cast there
from.
4
5. The process as in claim 4 wherein the alkyl
The uncured resins may be used in ‘coating ether of methylol melamine is the methyl ether
compositions as modi?ers for alkyd resins. They of hexamethylol melamine. . ‘
may also be used for impregnating paper, glass 6. The process as in claim’ 4 wherein the alkyl
and textile webs for use in laminates. They are ether of methylol melamine is the butyl ether of
valuable as adhesives particularly in the’ making hexamethylol melamine.
of abrasives. 7. The process which comprises reacting 1 mol
The uncured resins may be modi?ed by the in of the methyl ether of hexamethylol melamine
corporation of conventional additives such as 10 with from 0.2 to 3 mols of tetraethyl orthosilicate
?llers, pigments, dyes, etc. under substantially anhydrous conditions at tem
It is obvious that many variations may be made peratures of from 100 to 200° C.
in the products and processes of this invention 8. The process which comprises reacting 1 mol
without departing from the spirit and scope of the methyl ether of hexamethylol melamine
thereof as de?ned in the appended claims. with from 0.2 to 3 mols of dimethyl diethyl ortho
What is claimed is: silicate under substantially anhydrous conditions
1. The resinous heat reaction product under at temperatures from 100 to 200° C.
substantially anhydrous conditions of 1 mo] 01' STUART H. RIDER.
an alkyl ether of methylol melamine with from
0.2 to 3 mols of an alkyl ortho silicate. REFERENCES CITED
2. The resinous heat reaction product under 20 The following references are 01' record in the
substantially anhydrous conditions of 1 mol of file of this patent:
the methyl ether of hexamethylol melamine with
from 0.2 to 3 mols of tetraethyl orthosilicate. UNITED STATES PATENTS
3. The resinous heat reaction product under Number Name Date
substantially anhydrous conditions or 1 mol of 25 2,187,566 Bruson __________ _.. Jan. 16, 1940
the methyl ether of hexamethylol melamine with 2,313,678 Simons __________ __. Mar. 9, 1943
from 0.2 to 3 mols of dimethyl diethyl orthosili 2,320,817 D'Alelio _____.______ June 1, 1943
cate.
4. The process which comprises reacting 1 mol . ‘ FOREIGN PATENTS

of an alkyl ether of a methylol melamine with 30 Number Country Date

698,389 Germany ________ __ Nov. 8, 1940
OTHER REFERENCES
O?icial Digest, November 1945, pages 424-441.