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Патент USA US2403791

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Patented July 9, 17946
I
‘ T‘ ‘
2,403,791 *
_ UNITED 1 STATES PATENT
OFFICEj '
2,403,791
INTERPOLYMERS OF A I. METHYLENE
MALONIC ESTER AND AN UNSATU
RATED ALKYD RESIN . r
‘ ' Gaetano F. D’Alelio, Pitts?eld, Mass., assignor to
General Electric Company, a corporation of
New York
‘No Drawing. Original application November 16,
1939, Serial No. 304,783, now - Patent No.
' 2,330,033, dated September 21, 1943. Divided
and this application April 30, 1943, Serial No.
485,178
17 Claims. (01, 260-42)
1
' 2
This application is a division of my copending
V or aromatic hydrocarbon radical such as methyl,
ethyl, propyl, isopropyl, butyl, amyl, hexyl, octyl,
allyl, methallyl, crotyl, phenyl, cyclohexyl, meth
application Serial No. 304,783, ?led November‘
16, 1939 now Patent No. 2,330,033, issued Septem
ber 21, 1943, and assigned to the same assignee
asthe present invention.
.
'
'
v
‘
This invention relates to the production of
vorganic plastic masses having‘valuable and char
acteristic properties that make them especially
oxyethyl, etc.
7
~
By the above method I have been able to ob
“ tain not only methylene dimethyl and methylene
diethyl malonates, but also other esters of meth
ylene malonic acid.
These esters are useful not
only in themselves but I have found that they
ing, laminating, casting, coating and adhesive ap 10; are particularly adapted for the production of
new and useful copolymers.
plications, and for other purposes. The invention
Illustrative examples of some of the methylene
is concerned more particularly with compositions
malonic esters that may be prepared and used in
of‘ matter comprising an .interpolymer (copoly
practicing the present invention are methylene
mer) ‘of ingredients comprising a methylene
malonic ester and another polymerizable organic 15: dimethyl malonate, methylene diethyl malonate,
suitable ‘for use in industry, for example in mold
methylene dipropyl malonate, methylene di-iso
compound,'speci?cally 'a, polymerizable unsatu
.propyl malonate, methylene dibutyl malonate,
rated alkyd resin obtained by reaction of ingredi
methylene di-(secondary amyl) malonate, meth
ents comprising a vpolyhydric alcohol and an
ylene di-(secondary butyl carbinyl) malonate,
alpha unsaturated alpha beta polycarboxylic acid.
The invention claimed in my parent applica 20. methylene di-(diethyl carbinyl) malonate, etc.
_ Other examples will be apparent from the illus
tion Serial No. 304,783 is based on my discovery
trative examplesof radicals that R in the above
that improved yields of methylene malonic esters,
formulas may represent.
_
_
more particularly yields of the order of 30 per
V Illustrative examples of some of the malonic
cent and higher, can'be obtained by reacting
(condensing) a malonic ester with formaldehyde 25 esters, many of Which are new, which I have pre
pared and which may be reacted with formalde
in thefratio. of vone mol of the former to at least’
hyde as above brie?y described to obtain sub
one’, mol of the latter and under alkaline condi
stantial yields of the corresponding methylene
tions to form a methylol derivative, acidifying
the mass, dehydrating the acidi?ed mass to obtain 30,
malonicesters are:
a composition comprising a. methylene malonic
Malonic ester
ester, and separating themethylene malonic es
ter, as by distillation, from the said composition.
The general reaction may be written graphically
as'follows:_
.
'
000R
OH:
I
»
—->
19s:
98.5-99 at 4 mm. pressure.
93-95 at 12 mm. pressure.
I
COOR
0H
+CH2O
HOH2C—-C
coon '
'
-
—H—6
100,03
160-166 at 6 mm. pressure.
123-137 at 4 mm. pressure.
2
40
000a
-
~~
0:
900R
-HOHzG
-
OH-
\
+2CHa0—-—-—>.
/
Home‘
000R
45
n a e.
—H20
60;
000B.
011.:0
' ‘
142-149 at 3.5 mm. pressure.
129-135 at 4 mm. pressure.
119-123 at 4 mm. pressure;
145-149 at 4.5 mm. pressure.
Ethoxy ethyl malonate _ _ _ _ _ _ _
_ __
165-170 at 4.5 mm. pressure.
Butoxy ethyl malonate. _ _ _
Methoxy ethyl malouate _________ __ 129.5-130 at 2 mm. pressure.
Metltioxy diethylene glycyl malo 190-205 at 1.5 mm. pressure.
Ethoxy diethylene glycyl malonate. 180-187 at 2.0 mm. pressure.
Butoxy diethyleue glycyl malonate. 200-222 at 1.5 mm. pressure.
'.—>
000R
160-195 at 4.5 mm. pressure.
Diethyl carbinyl malonate _______ __
3+
C‘
/, \
Alpha-ethyl hexyl malonate
Methyl propyl carbinyl malonat
coonv
\
188-193 at 4.5 mm. pressure.
118-122 at 10 mm. pressure.
Secondary butyl carbinyl malonate
or, with a molecular excess of formaldehyde,
cooa'
Oetyl malonate __________ __
Allyl malonate ___________ __
Isobutyl carbinyl malonate ______ ._ 143-146 at 4 mm. pressure.
CHFC
'
Boiling point at °G.
The methylene malonic esters have boiling
points only slightly higherthan the correspond
ing malonic esters, and di?er therefrom only
+ 01120,
soon
in‘ thé above equations n represents “an aliphatic,
within about a 10-degree range.
In producing the organic plastic masses of this
invention heat, light, orrheat and light may be
2,403,791
3
4
used to e?fect polymerization, although under
such conditions the rate of polymerization is
relatively. slow. Hence, to accelerate. the poly-.
heated at 90° C. for 17 hours, it was exceptionally
hard.
Parts
merization, I prefer to use a catalyst, accom
panied by heat, light, or heat and light.
'
Example?
Methylene di-(secondary butyl carbinyl)
Ex
20
malonate; _____________________________ __
Diethylene glycol maleate prepared as de
ozone, hydrogen peroxide, sulfuric acid, aluminum
scribed under'Example 1, _______________ __
80
chloride, boron ?uoride, superoxides such’ as ali
phatic acyl peroxides, e. g., acetyl peroxide,_
Benzoyl peroxide _______________________ __
1
stearyl peroxide, etc., peroxides of the aromatic 10 were'heated- for 2: hours at 90° C. to give a soft
acid series, e. g., benzoyl peroxide;_etc. Benzoyl=
gel, which; became a hard copolymer after 17
peroxide is the preferred catalyst because of its'
hours.
ease of handling, its relative freedom from ex
Example 6
plosive hazards and its ready solubility in; the.‘
Parts
monomeric or partially polymerized: methylene.’ ‘ Methylene ('diethylcarbinyl) malonate_____ 20
malonic esters. The rate of’ polymerization is a‘
Diethylene, glycol maleate prepared as de
function of the temperaturerandimay be carried
scribed under Example l._________________ 80
amples of catalysts that may be used are oxygen,
out at from room temperature (20°-309 C.) to
Benzoyl. peroxide _______________________ __
1
temperatures materially above 100° C., for ex
ample about 130° C.
20 were heated for 1 hour and 5 minutes at 90° C‘. to
giveasoft gel: When-.heated?or; lf'l'hdurs at:90°
‘In-order that those-sleilledin the'art betteremay~
C; a. hard copolymer Wasformedr
understand how‘ the ‘present invention may vbe
Illustrative examples.» of . other-polyhydric: alco-.
carried into > effect, the following’ illustrative ex
hol. esters eof alpha unsaturated. alpha. beta poly’...
25 carboxylic acids that may. he-copolymerizediwith.
amples are given. All parts are by weight.
methylene malonic esters to: provide: new: and
Example 1‘ .
.
useful organic; plastic". masses . are: ethylene. glycol:
Parts:
Methylene dibutyl malonate _____________ __
20;.
maleataztriethylenaglycol maleate, glyceryl mar-1.
Poly-hydric alcohol. ester of.‘ an-alpha unsatu
rated’ alpha. beta ‘polycarboxylic. acid ~1____.
80 -
301 fumarate; . triethylene .- glycol; fumarata. propylene:
Benzoyl peroxide _______________________ __
1
leate',..ethyl'ene._ glycoli fumarate, .diethylene. glycol:
glycol._,fumarate,. glycol;itaconate,v diethylene- gly_-.
col. itaconate, ,triethylene; glycol; itaoonate, tetrasl
ethylene glycol itaconate; glyceryl: itaconate. or:
1_NQTE;—-This. polyhydric alcohol ester. was. prepared. by.
effectingv reaction between equal molar parts of maleic
anhydride- and‘ diethylene, glycol;
modifications of; these . esters. produced? by. incor».
The reactants were
mixedin, asuitable apparatusv and: thetemperature raised
porating. thereinv nonethylenic: Polybasic: acids.
to 200° C, over- a- period of one hour. Heating was. con
ti'nued'for sixphoursat 200° to 210° 0., at the end’ of’
Which‘iperiod of,'time therapies-obtained‘- a. v-iscouSi Pour-i
ableresinhaving an acid number of about 27.
such as the; saturated; aliphatic; acids;. e... g.,v
Ina-Ionic; succinia- glutaric, adinici pimelia. 8111-:
beria, sebacic... etc.,, the aromaticmolybasic; acids,
such. as. phthalic;_ din, tetrar and; hexaehydrcr
The» methylene dibutyl malonate was eopoly-.
merized-with- the above-described polyhydric- ale 40; phthalic, naphthalinedicarboxylic, eto.~,,or mix
tures of such acids,”
.
coholi ester at>90i C., yielding a soft gel at the'end
The; interpolymers- . obtained; by, copolymerizing;
of; 40~minutes and a hard copolymerwithin- two‘
methylene malonic. esters- with. other polymer-v
hours. This copolymer was exceptionally‘ hard
izable bodies havegawide; range of, properties.
andLabrasion-resistant after heating for a total
of: 17 hours. at. 90° C.
40:
'
Their, hardness and solubilities maybe-varied over.
a . considerable, range.v from. ?uid, compositions, of .
Example; 2.
Parts;
Methylene di-isopropyl malonate-_________ __
20'
eventhose ofi'a. hydrocarbonnaturer By suitable.
Diethylene glycol. maleate prepared as- de-»
scribed under Example 1. _______ _____,______
Benzoyl peroxide» _______________________ __
varied; intrinsic viscosity or soft, ?exible ,bodiesto
hard; rigid masses. that. can,“ be swelled ‘or dissolved in many volatileand' non-volatile solvents,
8O
1.
were treated at 90° C‘. for 1 hour and_50 minutes.
selection, of the, starting,_ monomeric or partly
polymerized" material's. interpolymers can be ob
tained‘ in an insoiubl‘e," infusible statepracti'cally
resistantto the destructive-effect‘ of -‘ other chem
to give-1 a soft, gel-like copolymer. Continued; ISISv ical bodies such as acids, bases, solvents and‘ the
heating for.v 1.7. hours at. 90° C.,gave aha-rd 0.0-‘
like.
polymer.
Themethylene malonicesterslnay. beconverted;
Example 3
into the: form of interpolymers in molds wither
without the application of pressure, in the pres
Parts
Methylene. di- (secondary amyl).. malonatedu 20 60 ence or absence of a material which is a solvent
Diethylene glycol maleate prepared‘ as. de.
for the. monomer but not for the polymer, or one
scribed, under Example 1._____________,_,___ so.
which is‘a solvent for both monomer and polymer,
Benzoyl', peroxide __________________ __._____
1
were‘heated‘ together at 90° C. for 17 hours to
givev a hard‘ copolymer.
Example 4v
1
7
Parts
Methylene dihexyl malonate_,___,____r,_____
20
Diethylene glycol‘ maleate prepared asv de- '
scribed under Example.I~_____;_________1__ 80'
Benzoyl' peroxide _____________ ___..__._._W__,_,_,
1
were heated at 90° C. for 4.0.minutesto give-a soft
or one which is not a solvent for either the
monomer _or_ polymer so that spongy or granulatedv
polymeric modi?cations are obtained;
The solid‘, thermoplastic copolymers of ‘this in
vention. with or without modifying; agents, may.‘
be used‘ in. injection, compression or transfer
molding processes to make numerous articles for
industrial, technical and novelty uses and for
other applications.
As, modifying agents various ?llers may be
used, for example wood ?our, alpha flock, sand,
asbestos, mica, paper, cloth, cellulose derivatives
gel that became hard within two hours; When 76 such as- cellulose» itself; cellulose others; natural‘
' 2,403,791.
5
6
and" synthetic?lamentsor ?bers, etc., in con
tinuous, shredded or comminuted form.g,,‘r:'ig
tionalso'include, compositions ‘of matter com
such as dibutyl phthalate, esters of monobasic
and polybasic acids, etc., may be incorporated
, loniciesterv of an alcohol having at least three
prisingan vinterpolymer of (1») a methylene ma
lonic ester,‘ more particularly a methylene ma
ments, dyes, opaci?ers,yplastici_zing substances
carbon atoms, e. g.,v methylene dipropyl malonate,v
methylene, dibutyl malonate, etc., and (2) at
into the copolymers of this invention toimodify
the same._ Natural andrysynthetic resins, gums,
least one. polyhydric alcohol ester of analpha
unsaturated alpha beta polycarboxylic acid, e.: g.,
oils, waxes, polyhalogenated aromatic derivar
a, polyhydric alcohol ester of’ maleic,, fumaric or
ti'ves, etc., likewise may be added _.as modifying
agents.
,
{r
"
,
i
»
ln-a solvent, ;or withouta solvent utilizing a
10 itaconic
What I
acid.
claim
-; as , new'and
v
I
desire
. tosecureby
Letters Patent of the United States is:
1. A polymerizable composition comprising (1)
may be used in adhesive and laminating applica
a methylene malonic ester, (2) a polymerizable
tions to bond/paper, wood, mica ?akes, glass
sheets, rubber sheets, etc., ?brous materials such 15 unsaturated alkyd resin, and (3) a catalyst for
accelerating the copolymerization of thelmate
as silk, asbestos, glass ?bers, synthetic ?bers in
rials of (1) and (2).
?lament, thread or fabric (woven or felted)
.2. A composition comprising an interpolymer
form, etc., cellulose derivatives in sheet, com
of ingredients including a methylene malonic
minuted or ?ber form, etc. In the form of liquid
coating compositions such as lacquers, enamels, 20 ester and an unsaturated alkyd resin, said ma
terials being copolymerizable.
varnishes, etc., they ?nd application in surface
3. A composition containing an interpolymer of
protective coatings, such as for walls, desks, wire,
ingredients includingv (1) a methylene dialkyl
concrete, porcelains, etc. In a flowable condition
malonate and (2') an unsaturated alkydresin ob
without the use of solvents they may be used as
tained by reaction of ingredients comprisingv a
impregnants for many porous bodies, such as
polyhydric alcohol and an alpha unsaturated
cork, pottery, felts, or fabricated bodies with in
alpha beta polycarboxylic acid, said materials of
terstices, such as the windings of electrical coils,
(1) and (2) being copolymerizable.
netted ?ber, interwoven ?brous materials, etc.
melt process, the fusible or soluble compositions
} 4. A composition comprising an interpolymer
From the foregoing description it will be seen
that the present invention provides a method of
producing new. synthetic compositions which
comprises polymerizing a polymerizable compo--,
sition comprising (1) a methylene malonic ester,
more particularly an ester corresponding to the
general formula
of ingredients including (1) a methylene malonic
ester and (2)’ an unsaturated alkyd resin ob
tained by reaction of ingredients comprising a
dihydric alcohol and an alpha unsaturated alpha
betadicarboxylic acid, said materials of (1) and
35
(2) being copolymerizable.
000R
5. A composition comprising an interpolymer
of ingredients including (1) a methylene malonic
coon
hol; said materials of (1) and (2) being copoly
ester and (2') a maleic ester of a polyhydric alco
where R represents an aliphatic or aromatic hy
drocarbon radical, (2) a polymerizable unsatur
ated alkyd resin, and (3) a catalyst for acceler
ating the copolymerization of the materials oi!
(1) and (2).
merizable.v
alcohol, said materials of (1) and (2) being co
The new synthetic compositions of this inven 45
tion may be described as being compositions com
prising the product of polymerization of a poly
ated alkyd resin obtained by reaction of ingred
ients comprising a polyhydric alcohol, e. g., a
dihydric alcohol, and an alpha unsaturated alpha
beta polycarboxylic acid, e. g., an alpha unsatur
ated alpha beta dicarboxylic acid, the materials
of (1) and (2) being copolymerizable. Speci?c
embodiments of the invention include composi
tions comprising the product of polymerization of
a polymerizable mixture 01‘ copolymerizable ma
terials including (1) a methylene malonic ester,
e. g., a methylene dialkyl malonate suchIfor in
stance, as methylene dimethyl malonate, methy
lene diethyl malonate, methylene dipropyl ma
'
ester-and (2) a fumaric ester of a polyhydric
I.
merizable mixture including (1) a methylene ma
lonic ester, e. g., a methylene dialkyl malonate, a
methylene diaryl malonate, and (2) an unsatur
ated alkyd resin, more particularly an unsatur
V
6. A composition comprising an interpolymer of
ingredients including (1) a methylene malonic
polymerizable.
‘
,7. A composition comprising an interpolymer
of ingredients including (1) a methylene malonic
ester and-(2) an itaconic ester of a polyhydric
alcohol, said materials of, (1) and (2) vbeing
60
copolymerizable.
'
I
*
a
8.‘ A composition containing an interpolymer
of copolymerizable materials including a maleic
diester of a dihydric alcohol and a methylene
dialkyl malonate.
9. A composition containing an interpolymer
of copolymerizable materials including a fumaric
diester of a dihydric alcohol and a methylene
dialkyl malonate.
10. A composition containing an interpolymer
" of vcopolymerizable materials including an ita
to xconic diester of a dihydric alcohol and a methyl
ene dialkyl malonate.
11'. A composition of matter comprising an in
terpolymer of ingredients including (1) a meth"
lonate, etc., and (2)‘a maleic, fumaric or itaconic 65 ylene malonic ester and (2) a maleic diester of
a glycol, said materials of (l) and (2) being
ester of a polyhydric alcohol, more particularly
copolymerizable.
a maleic, fumaric or itaconic diesteryof a dihy
12. A composition of matter comprising an in
dric alcohol. Also included within the scope of
terpolymer of methylene dimethyl malonate and
the present invention are compositions compris
ing the product obtained by copolymerization of V70 an unsaturated alkyd resin copolym'erizablethere
ingredients comprising a glycol maleate, fumar
1 13. A composition of matter comprising an in
ate or itaconate, e. g., diethylene glycol maleate,
terpolymer of methylene diethyl malonate and
while the said ingredients are admixed with a
an unsaturated alkyd resin copolymerizable
small amount of a polymerization catalyst, ‘e. g.,,
‘an organic peroxide. The products of the inven 76 therewith.
‘
'
with.
-
I
v
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mos-7:91
~ 14.-v A" composition of matter compri'sing'an 1n
8.
16. As a1 new'product, an‘ interpol'ymeruof di
ter-polyme'r‘ofiingredients‘including (1) a-methyl
ethylene = glycol? maleate ‘ andlv'ar methylene 'dialk'yl
ene malonic ester of’ an alcohol having at least
malonat'e‘ copolymeri’zable therewith;
three carbon atoms andi (2) a polyhydric alcohol
- 1'1.a The method, of‘ producing! new synthetic
ester‘ of'anr alpha unsaturated'alphar beta‘ poly; 5 compositions which comprises polymerizing- a
polymerizable= composition’ comprising (1)’ a
methylene'malonic' ester, (2) apolymerizable un
15‘.
composition comprising an interpolymer
saturated alkyd‘ resin, and (3) a catalyst for
of ingredients comprising a" glycolrmalealt'eiand
accelerating‘ thefcopolymeriza'tion- of the mate
a methylene dialkyl malonate copolymerizable 1'0 rials of (1) and (2).
carboxylic-acid, said materialsvof (1) and- (2)
being copolymerizable. ‘
therewith. H
I’
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GAETANO'»
D’ALELIO'.
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