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Патент USA US2407480

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Patented Sept. 1-0, 1946
2,407,479
‘UNITED STATES PATENT, OFFICE
2,407,479
INTERPOLYMERIZATION PRODUCTS
Gaetano F. D’Alelio, Pitts?eld, Mass., assignor to
General Electric Company, a corporation 01'
New York
No Drawing. Application October 31, 1939,
Serial No. 302,167
1; Claims. (01. use-42)
1
.
This invention relates to the production of new
materials having valuable and characteristic
properties that make them especially suitable for
use in industry, for example in molding, laminat
2
to proceed to a. limited degree. One reason for
this is because the unreacted alcohol and acid
groups then unreasonably limit the solubility of
the partial ester in polymerizable monomers. An
ing, casting, coating and adhesive applications,
other reason is that the presence of such unre
and for other purposes. The invention is con
cerned more particularly with compositions of
matter comprising an interpolymer (copolymer)
or interpolymers of at least one polymerizable
esteri?cation product of at least one polyhydric
alcohol, at least one alpha unsaturated alpha beta
polycarboxylic acid and at least one esteri?able
monohydroxy organic compound with at least one
acted groups makes the ?nal copolymerization
product of such low resistance to the action of
water, weak alkalies, etc., that it is unsuited for
the usual commercial applications.
I have discovered that these di?iculties can be
obviated by producing the copolymer from an un
saturated alkyd resin which has been internally F
modi?ed by an esteri?able monohydroxy organic
other polymerizable compound containing the
grouping -—CH=C<, e. g., ethylene compounds
such as vinyl esters, acrylic esters, alkacrylic
esters, itaconic esters, allyl esters. etc. For pur
monobasic acid.
pose of brevity, the above-described esteri?ca
tion product is hereafter designated generally as
terrupt and shorten the chain of the ultimate
esteri?cation product. These modi?ed unsatu
a “modi?ed unsaturated alkyd resin.”
rated alkyd resins are more fluid and more solu
Speci?
cally the invention relates to the production of
synthetic, polymerized materials consisting of the
compound, speci?cally a monohydric alcohol or a
These mono-esteri?able com
pounds interesterify with the polyhydric alco
hol and the polycarboxylic acid, serving to in
ble in,
and compatible with, polymerizable
monomers than the unmodi?ed unsaturated
alkyd resins.- It was surprisingly found that
product of polymerization of a mixture of co
polymerizable materials consisting of (1) a poly
despite the shortening of the ester chain by
merizable monohydric alcohol polyester of an 25 modifying the unsaturated alkyd resin with a
alpha unsaturated alpha beta polycarboxylic acid
mono-esteri?able compound, the thus modi?ed
and (2) a polymerizable esteri?cation product se
unsaturated alkyd resin had substantially, the
lected from the class consisting of polymerizable
same copolymerizing capacity with polymerizable
esteri?cation products of a polyhydric alcohol, an
compounds containing a -—CH=C< grouping as
alpha unsaturated alpha beta polycarboxylic acid 30 the unmodi?ed unsaturated alkyd resins. This
anda monocarboxylic acid, polymerizable esteri
was quite unexpected and could not have been
?cation products of a monohydric alcohol, a poly
predicted from the known properties of unsatu
hydric alcohol and an alpha unsaturated alpha
rated alkyd resins.
beta polycarboxylic acid, and polymerizable ester
i?cation products of a monohydric alcohol, a poly
In carrying the present invention into e?'ect
a polymerizable esteri?cation product of a poly
hydric alcohol, an alpha unsaturated alpha beta
hydric alcohol, an alpha unsaturated alpha beta
polycarboxylic acid and a monocarboxylic acid.
polycarboxylic acid and a mono-esteri?able or
The unmodi?ed unsaturated alkyd resins, that
ganic compound is prepared in accordance with
is, unmodi?ed esteri?cation products of a poly
technique now well known to those skilled in
hydric alcohol with an alpha unsaturated alpha ~10 the alkyd resin art. Any polyhydric alcohol
beta polycarboxylic acid, do not lend themselves
containing at least two esteri?able aliphatic hy»v
readily to the production of copolymers with other
droxyl groups, or mixtures of such alcohols, may
polymerizable materials. Because of their ex
be used in preparing the modi?edunsaturated
tended linear structure and advanced resinous
alkyd resin. Examples of such polyhydric alco
nature, it is quite difficult to obtain homogeneous
hols are ethylene glycol, di-, tri- and tetra-eth
mixtures or solutions of such alkyd resins with
many polymerizable monomeric materials. It is
especially dif?cult and costly to obtain copoly
mers of uniform characteristics when the ratio of
unsaturated alkyd resin to the polymerizable
acid, or mixtures of such acids, may be reacted
with the polyhydric alcohol or alcohols to form
monomer is high, say 90 or 95 parts of unsat
urated alkyd resin to 5 or 10 parts of the poly
merizable monomer. Also, it is not feasible to
prepare an unsaturated alkyd resin of low molec
the polymerizable resin. Examples of such poly
carboxylic acids are maleic, monohalomaleic,'
fumaric, monohalofumaric, citraconic, mesa
conic, acetylene dicarboxylic, itaconic acid and
ylene glycols, propylene glycol, trimethylene gly
col, thiodiglycol, glycerine, pentaerythritol, etc.
Any alpha unsaturated alpha beta polycarboxylic
ular weight merely by allowing the esteri?cation 65 its homologues as, for instance, alpha methyl ita
2,407,470
3
conic acid. alpha ethyl itaconic acid, alpha alpha
dimethyl itaconic acid, etc. Part of these un
saturated polycarboxylic acids, that is. up to
' about 75 mol per cent, may be replaced by non
carboxylic acids, unsaturated alcohol esters of
saturated monocarboxylic acids, etc.
More specific examples of compounds contain
ing a —CH=C< grouping are the unsaturated
alcohol esters, e. g., the allyl, methallyi, crotyl,
ethylenic polycarboxylic acids, e. g., the satu
rated aliphatic polycarboxylic acids such as suc
propargyl, l-chloraliyl, 2-chlorallyl, cinnamyi,
cinic, adipic, glutaric, pimelic, sebacic, azelaic,
suberic, tricarballylic, tartaric, citric, etc., cyclic
polycarboxylic acids, more specifically the satu
1-phenyl-2-propyn-1-yl, 3-methyl-4-nonyn-3-yl,
4-methyl-5-decyn-4-yl, 4-methyl-5-undecyn-4
3-methyl allyl, vinyl, methvinyl, Z-phenyl allyl,
etc, esters of saturated and unsaturated, ali
rated cycloaliphatic polycarboxylic acids such as 10 yl,
phatic and aromatic, monobasic and polybasic
the cyclopropane dicarboxylic acids, the cyclo
acids such, for instance, as acetic, propionic,
hexane dicarboxylic acids, the alkyl cycloalkane
butyric,
valerlc, caproic, acrylic, alkacrylic (e. g.,
polycarboxyllc acids, etc., and the aromatic poly
methacrylic, ethacrylic, etc.), crotonic, oxalic,
carboxylic acids, e. g., phthalic, benzoyl phthalic,
terephthalic, benzophenone - 2,4’ dicarboxylic 15 malonic, succinic, glutaric, adipic, pimelic, su
beric, azelaic, sebacic, maleic, fumaric, citraconic,
acids, etc. Anhydrides of the polycarboxylic
mesaconic, itaconic and its homologues (e. g.,
acids, if available, also may be used. The term
alpha methyl itaconic, alpha ethyl itaconic, al
“polycarboxylic acid” as used generally herein
pha alpha dimethyl itaconic, etc.), acetylene
and in the appended claims therefore is intended
dicarboxylic, benzoic, toluic, phenyl acetic,
20
to include within its meaning the anhydrldes of
phthalic, terephthalic, benzoyl phthalic, benzo
the acids.
phenone-2,4' dicarboxylic, cinnamic, etc.; the
Various mono-esteri?able compounds may be
saturated alcohol esters, e. g., the methyl, ethyl,
incorporated into the unsaturated alkyd resin in
propyl, butyl, isobutyl, ethylene glycol, glycerol,
order to modify the same. Thus, in producing
etc., esters of the unsaturated aliphatic
the copolymers of this invention I may use an 25 monobasic and polybasic acids, illustrative ex
unsaturated alkyd resin which has been modi?ed
by incorporating therein a saturated or unsatu- _
amples of which appear above; vinyl cyclic com
pounds, e. g.- styrene, vinyl naphthalene, vinyl
rated, normal or isomeric monohydric alcohol, or
cyclohexane, methylene-tetrahydronaphthalene,
mixtures thereof, a saturated or unsaturated
vinyl furane, divinyl benzene, etc.; unsaturated
monocarboxylic acid, or mixtures thereof, or both 30 ethers, e. g., ethyl vinyl ether, diallyl ether, allyl
such esterifiable monohydroxy organic com
pounds. Examples of monohydric alcohols
ethyl ether, divinyl ether, vinyl allyl ether, meth
which may be used as modi?ers of the alkyd resin
methyl vinyl ketone, methyl methvinyl ketone,
ethyl methvinyl ketone, divinyl ketone, methyl
allyl ketone, etc.; methylene malonic esters;
are propyl, isopropyl, butyl, isobutyl, amyl, iso~
amyl, hexyl, octyl, decyl, dodecyl to octadecyl,
inclusive, allyl, methallyi, 1-chlorallyl, 2-chlor
allyl, crotyl, cinnamyl alcohols, S-hydroxy bu
allyl propyl~ ether, etc.; unsaturatedketones, e. g.,
' 2-chlorobutadiene; etc.
Preferred organic com
pounds which are used in carrying the present
tene-l, etc. The use of methyl and ethyl alco
invention into e?ect are compounds having at
hols is not precluded, but in general these alco
least one CH2=C< grouping, e. g., acrylic esters
hols are less suitable because of their lower boil 40 such as ethyl acrylate, alkacrylic esters such as
ing points. As monobasic acids may be used, for
ethyl methacrylate, etc. For certain applica
example, the unsubstituted saturated or unsatu
tions, as for instance in the production of so
rated, normal or isomeric acids containing only
called “solventless varnishes," I prefer to co
one esteri?able group such as acetic, propionic,
polymerize the modi?ed unsaturated alkyd resin
butyric to stearic, inclusive, benzoic, acrylic, 45 with a monohydric alcohol ester of an alpha
methacrylic, cinnamic, etc., acids of drying,
unsaturated alpha beta polycarboxylic acid, e. g.,
semi-drying and non-drying oils, e. g., the acids
diethyl itaconalte, diallyl maleate, diallyl ita
of tung oil, linseed oil, rape seed oil, soya bean
conate,
etc.
oil, castor oil, etc. The mono-esteri?able com
To achieve copolymerization of,the modified
pound may be introduced into the esteri?cation 50
product before, during or after the esteri?cation
of the polyhydric alcohol with the polycarboxylic
acid under conditions that interesteri?cation of
the mono-esteri?able compound with the incom
pletely esteri?ed polyhydric
unsaturated alkyd resin with the monomeric or
partially polymerized organic compound contain
ing a -CH=C< grouping, a solution of the said
resin in the said organic compound first prefer
ably is effected, The organic compound employed
alcohol-polycar 55 advantageously
may act as a carrier for a small
boxylic acid reaction product is obtained. That
is, the mono-esteri?able compound must be in
troduced into the reaction mass before all of the
acid groups of the polybasic acid or all of the
amount of a polymerization. catalyst. Examples
of polymerization catalysts which may be used
are ozone, ozonides, inorganic super-oxides such
as barium peroxide, sodium peroxide, etc., all
alcohol groups of the polyhydric alcohol have 60 phatic acyl peroxides, e. g., acetyl peroxide, lauryl
been esteri?ed.
peroxide, stearyl peroxide, etc., peroxides of the
In carrying the present invention into effect
aromatic acid series, ‘e. g., ‘benzoyl peroxide,
organic compounds containing the polymerizable
various per-compounds such as perborates, per
grouping -CH=C<, or mixtures thereof, are in
65 sulfates, perchlorates, etc., aluminum salts such
terpolymerized with one or more modified un
saturated alkyd resins, such as above described,
to produce new and valuable compositions. Il
lustrative examples of compounds containing
as the halides, e. g., aluminum chloride, organic
and inorganic acids such as methacrylic, hydro
?uoric, etc., metal compounds of the unsaturated
acids as, for instance, cobalt and manganese
such a grouping are esters containing ethylenic
or acetylenic unsaturation in either the alcohol 70 resinates, linoleates, maleates, etc. \Benzoyl per
oxide is the preferred catalyst. Any suitable
radical or the acid radical, or in both, e. g., satu
amount of catalyst may be used, but in general
rated and unsaturated alcohol esters of unsatu
the catalyst concentration will be within the
rated monocarboxylic and polycarboxylic acids,
range of 0.1 to 2.0 per cent by weight of the
unsaturated alcohol esters of non-ethylenic
(e. g., aromatic and saturated aliphatic) poly 75 whole.
2,407,479
5
.
When rapidity of interpolymerization between
.
6
copolymer: of modi?ed unsaturated alkyd resins
the components is of secondary importance, co
with -CH=C< compounds-Continued
polymerization may be e?ected merely under the
in?uence of heat, light, or heat and light and in
>
‘
cnmmua of
the absence of an accelerator of polymerization. 5 Resin Parts —CH=C<eompound
Parts copolymer after 24
hours at 70° 0.
The rate of copolymerizationand the properties
of the ?nal product vary with the time, temper
D._._. 90 Diallyl itaoonate._... 10 Very viscous.
ature and, if a catalyst is used, also with the
B___-. 90 Diallyl itaconate..-.. 10 Staff; clear, elastic, gel
catalyst concentration. Copolymerization may
e.
1r_____
9o \ Dlaliyl itaoonate.-...
10 Hard, clear.
be eifected at .from room temperature (20° to
90 Diallyl ltaconate...__ 10 Hard, clear.
30° C.) to temperatures above 100° C., for ex
ample about 130° C., but ordinarily I use temper
90 Diallyl itaeouate._-..
o0 Diallyl
itaeonate
atures within the range of 60° to 120° C. in cans
ing the mixed components to interpolymerize.
In order that those skilled in the art better 15
B.____
may understand how the present invention may
be carried into effect, the following examples are
given by way of illustration. All parts are by
D____.
weight. Reference is ?rst made to the com
ponents, and proportions thereof, used in the 20 B___..
preparation of the modi?ed unsaturated alkyd
I~‘_____
resins. These resins (identified by letter desig
F..__.
nations) were copolymerized with —CH=C<
10 Soft, clear, gel-like.
5 Firm, clear, gel-like.
vinyacetate.
90 Mietthallyl
methacrya e.
90 Glyteol
dimethacrye.
90 Glygil dimethacry-
10 Hard, clear.
10 Hard, clear.
10 Hard, clear.
00 0:31:01
dimethacrye.
10 Hard, translucent.
90
90
9o
90
90
Glytcol
dimethacrye.
Glygol dimethacrya e.
Glycol
dimethacrye.
M‘eihallyl
methacry-.
.a e.
Glygol dimethacry-
10
10
10
10
10
Flrm,translucent gel.
Hard, clear.
Hard, clear.
Hard, clear.
Very ?rm,gel-like.
compounds in varying amounts, using 1% by
H___._
weight of the mixed components of benzoyl per~ 25
oxide as an accelerator oi‘ polymerization. A brief
description of the properties of the copolymer
after 24 hours’ interpolymerization at 70° C. is
_A_____
10
Diallyl oxalate ..... __
B_____
90
Diallyl oxalate _____ __
10
Hard,
C_____
90
Diallyl oxalate ..... -.
10
Fill?lti, translucent gel
a e.
D
90
E
90
Modified unsaturated alkyd resins
Composition
rts)
parts) and soya bean acids (15.2 parts)
.
maleic
.
Very ?rm, gel-like.
Diallyl oxalate . _
.
10
_
.
10
10
Gel-like. ?rm, clear.
Firm, clear. rubbery.
Dlally maleate_ _
.
10
Hard, clear.
Diallyl maieate.-
.
90
Hard, clear.
Diethyl itaconate..._
90 Diallyl itaconate.__..
l0 Veil-g soft, clear, gel
e.
l0 Vulairky soft, clear, gel
90
10
Diallyl itaconate___-.
Diethyl itaconate__._
10
10
Soft. clear, gel-like.
e.
Hard, clear.
Hard, clear.
l0 Elli-£1, translucent gel
1 e.
l0 Self?é translucent gel
1 e.
80
Diallyl itaconate_._._
20
Hard, clear, resilient.
M ..__
80
Diethyl itaconate__._
20
Soft, clear, resilient.
N __.__
90
Diailyl itaconate__-..
10
Hard, clear.
N_____
0_____
90
90
Diethyl itacoi'late_.-_
Diallyl itaccnate_.___
10
10
Slightly soft. clear.
Hard, translucent.
10
10
10
10
Soft, clear, gel-like.
Soft, clear, gel-like.
Very ?rm, slightly
translucent.
Soft, clear, gel-like.
O__...
90 Diethyl itaconate_...
Diethyl itaconate._..
Diallyl itaconate___-.
Diallyl itaconate_._._
Diethyl itaconate.
anhydride (21.93
pa rts)
_
ery.
Diethyl itaconate.
10
Diallyl itaconate.
10 Veil; ?rm, clear, gel
Clear, viscous.
Diallyl maleate- _
Diallyl maleate. _
l0
10
Firm, clear. gel-like.
Clear, gel-like, soft.
K
Diethylene. glycol (35.4 parts), maleic anhydride (27.95 65 L_____
parts) and linseed oil acids (7.7 parts)
Ethylene glycol (18 parts), maleic anhydride (27.93 parts)
. M____
90
Diallyl maleate. .
_
10
Firm, clear.
90
Diallylmaleate ____ ..
10
Fllrréi, translucent gel
80
Diallyl maleate .... -.
20 vFirm, clear. resilient.
N___..
90
Diallyl maleate- __
l0
and octyl alcohol (3 .9 parts)
_
Ethylene glycol (35.4 parts), maleic anhydride (29.4 parts; ,
1 e.
0___._
octyl alcohol (13 parts) and acetic anhydride (11.8 parts
90
Diallyl maleate.-.
_
10
Soft, clear, gel-like.
90
Diallyl maleate ____ _-
10
VerLy firm, clear, gel
10
10
10
10
Firm, clear, gel-like.
Firm, clear. gel-like.
Firm, clear, gel-like.
Firm, clear, gel-like.
1’9.
90
90 Ethyl aervlate
90 Vinyl acetate.
90 Methyl methacr
Characteristics of
copolymer after 24
hours at 70° C.
10
Clear, tough. insoluble
and infusable.
B..-__
90 Diethyl itaconate_...
10 Hard, clear, gel-like.
C_..__
90
10
D..."
H.._-.
A...“
B___..
B..."
90 Diethyl itaconate.._.
90 Diethyl itaconate____
10 Diallyl itaeonate...__
90 Diallyl itaconate_.___
90 Diallyl
itaeonate
10 Clear, very viscous.
10 Very firm, gel-like.
90 Hard, ear.
10 Hard, clear. gel-like.
5 Hard, clear.
O..---
90 Diallyl itaeonate .... ..
10
Diethyl itaoonate. . ..
-
methyl methacrylate.
Very
firm,
gel-like,
translucent.
90
Styrene _______ ._
90
Ethyl acrylate ..... ._
0.
10
Firm, clear, gel-lkie.
l0
Firm, clear. gel-like.
10 Firm, clear, gel-like.
90
90
Vinyl acetate ...... ..
Styrene ............ ..
l0
10
Firm, clear, gel-like.
Firm, clear. gel-like.
90
Ethyl acryiate _____ ..
10
Hard, clear.
K..."
90
Methylmethacrylate.
10
Hard, clear.
K.____
K_____
90
Vinyl acetate ...... _.
Styrene ............ __
10
10
Hard, clear.
Hard, clear.
L_____
Ethyl acrylate ..... ..
10
70 L_____
90 Methylmethacrylate.
10 Filrgl, translucent gel
L_____
90
Vinyl acetate ...... _.
10
L_____
90
Styrene..- .......... _.
10
80
Vinyl acetate ...... ..
J
translucent gel
1 e.
1 e.
translucent gel
e.
‘
Filri'krn, translucent. gel
..
90 Methylmethacrylate.
'
Diallyl oxalate ..... ..
Hard, translucent.
90
Q
with -CH=C'< compounds
90
10
Slightly soft, clear.
P_____
C'opolymers of modi?ed unsaturated alkyd resins
Resin Parts ~CH=C<eompound Parts
Diallyl maleate-..
M____
75 M‘_.._
.
80 Methyl methacrylate
>
10 Solft, translucent rub
e.
90
90
Ethylene glycol (17.7 parts) , maleic anhydnde (26.46 parts)
A...“
Very viscous, clear.
M__..
Ethylene glycol (18 parts), muleic anhydride (29.4 parts‘,
octyl alcohol (2.6 partsl and stearic acid (5.16 parts).
and acetic anhydride (7.08 parts).
Very viscous, clear.
Very viscous, clear.
Diallyl oxalate. _
Dgallyl oxalate. .
90 Diallyl itaconate__.-.
90 Diethyl itaconate_..-
L_____
10
10
10
l0 Soliitk. clear, elastic, gel
e.
10 Hard, clear.
10
rm, ear.
10 Firm, clear, gel-like.
90
s .
Diethyleno
glycol (30.6 plat?) ,
parts) and decyl alcohol
Diallyl oxalate _____ __
Diallyl phahalate. . . .
Diallyl succinate. - _..
Diethyl itaconate._ ._
phthalic anhydride (8.9 parts) and‘liusced oil acids (10.1
parts .
Ethylene glycol (17.4 parts). maleic anhydride (28.8 parts)
and stearic acid (3.4 parts)
‘
Diethylene glycol (20.4 parts), maleic anhydride (16.6
ear.
Diallyl maleate._ __
Diallyl maleate..
Diallyl maleate__
Diallyl itaconate.
Ethylene glycol (66 parts), itaconic acid (130 parts) and
acetic anhydride ( 12 parts).
Diethylenc glycol (19.6 parts), ltaconic acid (26 parts) and
stearic acid (2.25 parts)
. Glycerine (12.2 parts), itaconic acid (19.5 parts) and linseed
oil acids (14.2 parts)
Glycerine (65 parts ), itaconic acid (16.5 parts) and linseed
oil fatty acids (140
Soft, translucent.
e.
given.
Glycerine (12.2 partsgaitaconic acid (11.2 parts), phthalio '
anhydride (5.4 parts) and soya bean acids (13.9 parts).
Ethylene glycol (6 parts), itaconic acid (14.3 parts) and
octadecyl alcohol (5.4 parts).
Ethylene glycol (10.6 parts), itaconic acid (14.4 parts) and I
decyl alcohol (3.7 part
E thylene glycol (15 parts), itaconic acid (31 parts) and tung
oil acids (65 parts .
Diethylene glycol (31.8 parts), maleic anhydride (27.9
parts) and tung oil acids (7.6 parts).
Ethylene glycol (12 parts), maleic anhydride (11.76 parts),
90
translucent gel
e.
20
Hard, clear.
20 Hard, clear.
2,407,479
7
as herelnbefore mentioned.
Incertain cases, instead 01 copolymerizing a
single -CH=C< compound with a single modi
with - H=C< compounds-Continued
‘
Characteristics oi
Resin Parts -—CH=C<compound Parts
fied unsaturated alkyd resin, I may copolymerize
copolymer after24
>
8
for instance accelerators of polymerizationesuch
Cop‘olu'mers of modi?ed unsaturated alkyd resins
hours at 70° G.
a plurality of the said compounds with a single
modified unsaturated alkyd resin or with a. plu
Bib lacrylate _____ ..
Hard, quite resilient.
y
Hard, uite resilient.
Hard, c ear.
St
Soit,clear. .
Soft, clear.
ene .... ..
Et lacryl
Met yl methacrylate.
Hard, translucent.
Hard, clear. '
St
Translucent, rubbery.
ne ............ ._
mil”: acrylate ..... ..
Firm, clear, gel~like.
Methyl methacrylate.
Firm, clear, gel-like.
Vinyl acetate ...... _.
Styrene ...... ..
Firm, clear, gel-like.
Firm, clear, gel-like.
Ethyl acrylate.
Vinyl acetate ______ -_
C .'._..
Methyl methacrylate.
Hard.
r ._--.
St
Hard.
Et ii acrylate _____ ._
Vinyl acetate ....... ._
Styrene ____________ __
1--....
10 per cent of a -CH=C< compound. it will be
understood, of course, that the invention is not
limited to these particular proportions of com
ponents. The incorporation of a small amount,
'
Firm, clear, gel-like.
Firm, clear, gel-like.
20 e. g., 3 or 4 per cent, of certain —CI-I=C< com
pounds, for example diallyl itaconate and other
unsaturated monohydric alcohol esters of alpha
Soit, clear, gel-like.
Boi't, clear, gel-like.
Methallyl methacry,
late.
Glycol dimethacry
Firm, clear, gel-like.
Firm, translucent gel
like.
Firm, clear, gel-like.
Firm, clear, gel-like.
H Mb->Ar1~HIa
late.
Mei'ihailyl
methacry
a e.
Glycol dimethacry
late.
Methallyl methacry
Glycol dimethacry
late.
Methallyl methacry
late.
Glycol dimothacry
unsaturated alpha beta polycarboxylic acids, into
a modi?ed unsaturated alkyd resin has a bene
?cial effect upon such alkyd resins, yielding prod
ucts of improved properties as compared with a
modi?ed unsaturated alkyd resin which has been
Hard, clear.
polymerized in the absence of such a —CH=C<
Hard, clear.
compound. However, somewhat better results
Fill-m,e. translucent gel 30 usually are obtained when the —CH=C< com
pound constitutes, say, 6 or 8 per cent by weight
of the mixed starting components. In most cases
the mixed components are so proportioned that
the —~CH=C< compound constitutes from 10 to
Hard, slightly trans 35 90 per cent by weight of the whole, but the use
of higher amounts is not precluded. Thus, in the
lucent.
Firm, translucent gel
like.
‘
Somewhat turbid,
slightly resilient.
Somewhat turbid,
slightly resilient.
late.
88‘8888888 8 8 8
merizing from, by weight, 10 to 90 per cent of
15 modified unsaturated alkyd resin with from 90 to
Firm, clear, gel-like.
ene ............ ._
Met yl methacrylate.
Although in the foregoing examples I have
shown the production of interpolymers by copoly
Firm, clear, gel-like.
q ____,
2
R.____
service application.
Soft, cloudy.
Hard, translucent.
Ethyl acrylate. - Vinyl acetate. _
?._____
rality of such resins. In this way it is possible
to obtain a composition comprising a mixture of
10 interpolymers best adapted to meet a. particular
Methallyl methacry
late.
Glycol. dimethacry
late.
Glycol dimethacry
late.‘
Slightly soft, clear.
Slightly soft translu
Metthallyl
methacry
e.
production of organic plastic vmasses or coating
compositions for certain particular applications,
the
--CH=C< compound may constitute, say, 96
Hard, translucent.
40 or 97%, or more, by weight of the whole, depend
Firm, gel-like translu
ing, for example, upon the particular starting
cent.
components employed and the particular prop
Firm‘; gel-like translu
Methallyl mcthacry
late.
Glycol dimethacry
late.
Glycol dimethacry
. late.
Methallyl methacry
cen .
cen .
Mletthallyl
methacrya e.
10
Gllycol dimethacryate.
Methallyl methacryGllycol dimethacry-
Diallyl succin e.
90
The interpolymerization products 01' this in
10 Very ?rm, translucent.
10 ltrlibber‘y, gel-like trans
10 Bolt, opaque, gel-like.
.
ate.
erties desired in the copolymer.
Very ?rm, translucent.
ucen
vention have a wide rangeof properties.
_
10
Very soft, clear gel-like.
_
10 Very soit, clear gel-like.
l0 Firm, clear, gel-like.
50 tion (temperature, time, pressure, presence or
10
Soft, clear, gel-like.
Diallyl oxalate _____ __
l0
Firm, clear.
Diallyl succinate- . _ __
10
Firm, clear.
Diallyl oxalate ...... ._
l0
Firm, translucent gel
absence of catalyst, kind of catalyst used, if any,
as well as the catalyst concentration, etc.) and
the extent of the interpolymerization, they vary
from soft, ?exible, soluble bodies to hard, rigid
0.
90
Diallyl succinate___-_
10
80
Diallyl oxalate ..... _-
20
Firm, resilient, clear.
80
Diallyl succinate-.__-
20
Hard, clear.
Firm, translucent gel
90
Diallyl oxalate. __
__
l0
Slightly so! t, clear.
90
90
Diallyl succinate_--._
Diallyl oxalate _____ .-
10
l0
Slightly soit, clear. _
'l‘rganséucent,
fairly
e.
ar
90
Diallyl succinate._.-.
10
90
Diallyl oxalate _____ -.
10
90
90
Diallyl oxalate._
Diallylsuccinate.
Diallyl succina
10
90
90
90
Diallyl succinate.
Diallyl oxalate.
De
pending, for example, upon the particular modi
?ed unsaturated alkyd resin and the particular
--CH=C< compound employed, the particular
proportions thereof, the conditions of polymerize
.
10
10
.
Translucent, hard.
Soft, clear, gel-like.
Bolt, clear, gel-like.
Hard, clear.
Hard, clear.
l0 Firm, clear, gel-like.
10 Firm, clear, gel-like.
It will be understood, of course, that my inven
tion is not limited to the production of copolymers
of the particular modi?ed unsaturated alkyd
resins with the particular -CH=C< organic
55 masses of varying resistance to solvents. In in
termediate stages of copolymerization some form
fluid compositions of varying intrinsic viscosities
and may be so used. For coating or impregnating
applications where the presence of a small
60 amount of solvent in the cured composition is
not objectionable, the mixed polymerizable ma
terials may be diluted with volatile or non-vola
tile solvents to viscosities best adapted to meet
the particular service application, and then may
65 be copolymerized after application of the solu
compounds set forth in the above examples and '
' tion to the particular article to be coated or im
pregnated. By suitable selection of the start
ing materials and the conditions of interpoly
merization, interpolymcrs can be obtained in an
that modi?ed unsaturated alkyd resins and 70. insoluble, infusible state practically resistant to
the destructive e?ect of other chemical bodies
-CH=C< compounds other than those above
such as acids, bases, solvents and the like.
given by way of illustration may be employed in
These new compositions may be used alone
producing the new interpolymerization products
or
with ?llers, dyes, pigments, opaci?ers, lubri
of this invention. Also, polymerization catalysts
other than benzoyl peroxide may be employed, 75 cants, plasticizers, or other modifying agents in,
9
2,407,479
for example, casting, molding and laminating
90 per cent of a polymerizable esteri?cation prod
uct of a monohydric alcohol, a polyhydric alcohol
and an alpha unsaturated alpha beta polycar
boxylic acid.
6. As a new product, a synthetic resin consist
ing of an interpolymer of diallyl maleate and a
applications, as adhesives, impregnants and sur
face coating materials. In coating, impregnat
ing and similar applications the mixed compo
nents, without added solvent, may be applied to
the object to be treated and polymerized as here;
inbe'iore described, with or without the appli
polymerizable esteri?cation product of a mono
cation of pressure, to form the copolymer in situ.
hydric alcohol, a polyhydric alcohol and an al
They may be used as impregnants for many por
pha unsaturated alpha beta polycarboxylic acid.
ous bodies, such as cork, pottery, felts, or fabri 10
7. A hard, clear synthetic resin obtained by
cated bodies with interstices, such as the wind
polymerization of a mixture composed of, by
ings of electrical coils, netted ?bers, interwoven
weight,labout 10 per cent of diallyl maleate and
?brous materials, etc. They also may be used
about 90 per cent of a polymerizable esteri?ca
for protectively coating impervious articles such
as metals, e. g., iron or copper wire, or for coat
tion product of ethylene glycol, itaconic acid and
15 acetic anhydride.
ing or coating and impregnating articles such ‘
8. A hard, clear synthetic resin obtained by
as paper, wood, cloth, glass ?bers in felted, woven
polymerization of a mixture composed of, by
or other form, concrete, linoleum, synthetic
weight, about 10 per cent of diallyl maleate and
boards, etc. They also may be employed in the
about 90 per cent of a polymerizable esteri?ca
production of wire enamels and winding tapes. 20 tion product ofv ethylene glycol, itaconic acid and
The mixed components or partial interpolymers
octadecyl alcohol.
thereof, with or without modifying agents, may
9. A composition comprising the product of
be cast and molded under heat or under heat
polymerization of a polymerizable mixture in
and pressure. They also may be molded by in
cluding (1) a polymerizable unsaturated alkyd
jection, extrusion or compression molding tech 25 resin obtained by reaction of ingredients com
nique whereby they are heat- and pressure-hard
prising a polyhydric alcohol, a monocarboxylic
ened to yield numerous molded articles of manu
acid and itaconic acid and (2) a polyallyl ester
facture for industrial, household and novelty
of an alpha unsaturated alpha beta polycarbox
, uses.
ylic acid, said ester being compatible with the
‘What I claim as new and desire to secure by 80 resin of (1).
Letters Patent of the United is:
10. A composition comprising the product of
l. A synthetic, polymerized material consist
polymerization of a polymerizable mixture in
ing of the product of polymerization of a mixture
cluding (1) a polymerizable unsaturated alkyd
of copolymerizable materials consisting of a poly
resin obtained by reaction of ingredients com:
merizable monohydric alcohol polyester of an 35 prising a monohydric alcohol, a polyhydric alcm
alpha unsaturated alpha beta polycarboxylic acid
hol and an alpha unsaturated alpha beta poly
and a polymerizable esteri?cation product of a
carboxylic acid and (2) a polyallyl ester of an al
monohydric alcohol, a polyhydric alcohol and a
pha unsaturated alpha beta polycarboxylic acid,
plurality of polycarboxylic acids at least one of
said ester being compatible with the resin of (1).
which is an alpha unsaturated alpha beta poly 40
11. A composition comprising the product of
carboxylic acid.
polymerization of a polymerizable mixture in
2. A synthetic, polymerized material consisting
cluding (l) a polymerizable unsaturated alkyd
of the product of polymerization of a mixture
resin obtained by reaction of ingredients com
of copolymerizable materials consisting of a poly
prising a monohydric alcohol, a‘ polyhydric al
merizable monohydric alcohol polyester of an 45 cohol and itaconic acid and (2) a polyallyl ester
alpha unsaturated alpha beta polycarboxylic acid
of an alpha unsaturated alpha beta polycarbox
and a polymerizable esteri?cation product of a
ylic acid, said ester being compatible with the
monohydric alcohol, a polyhydric alcohol and
resin of (1).
an alpha unsaturated alpha beta polycarboxylic
12. A composition comprising the product of
acid.
50 polymerization of a‘ polymerizable mixture in
3. A synthetic, polymerized composition con
cluding (1) diallyl itaconate and (2) a polymer
sisting of an interpolymer obtained by polymeri
izable unsaturated alkyd resin obtained by reac
zation of a mixture of copolymerizable materials
tion of ingredients comprising a monohydric al
consisting of a polymerizable monohydric alcohol
cohol, a polyhydric alcohol and an alpha unsat
polyester of an alpha unsaturated alpha beta 55 urated alpha beta polycarboxylic acid, said resin
polycarboxylic acid and a polymerizable esteri?
being compatible with the diallyl itaconate of
cation product of a monohydric alcohol, a polyhy
( l.
dric alcohol, a monocarboxylic acid and an alpha
' 13. A composition comprising the product of
unsaturated alpha beta polycarboxylic acid.
polymerization of a polymerizable mixture in
4. A synthetic, resinous composition consisting
cluding (1) a polymerizable unsaturated alkyd
of the product of polymerization of a mixture 60 resin obtained by reaction of ingredients com
of copolymerizable materials consisting of, by
prising a monohydric alcohol, a polyhydric alco
weight, from 10 to 90 per cent of a polyallyl ester
hol and a plurality of polycarboxylic acids at
of an alpha unsaturated alpha beta polycarbox
least one of which is an alpha unsaturated alpha
ylic acid and from 90 to 10 per cent of a poly
beta polycarboxylic acid and (2) a polymerizable
65
merizable esteri?cation product of a polyhydric
monohydric alcohol polyester of an alpha un
alcohol, a monohydric alcohol and an alpha un
saturated alpha beta polycarboxylic acid, said
saturated alpha beta polycarboxylic acid.
ester being compatible with the resin of (1) .
5. A synthetic, resinous composition obtained
14. A composition as in claim 13 wherein the
by polymerization of a mixture of copolymeri
polyester of (2) is a polyallyl ester of an alpha
70
zable materials consisting of, by weight, about 10
unsaturated alpha beta polycarboxylic acid.
per cent of a polyallyl ester of an alpha unsatu
rated alpha beta polycarboxylic acid and about
GAETANO F. D'ALEIJO.
11
l
112
Certi?cate of Correction
Patent No. 2,407,479.
‘
September 10, 1946.
GAETANO F. D’ALELIO
It is hereby certi?ed that errorsv appear in the printed speci?cation of the above
numbered patent requiring correction as follows: Column 5, line 73, in the table,
fourth column thereof, following “methyl methacrylate” insert 5; column 6, line 13,
same table, third column thereof, for “viny acetate” read vinyl acetate; same line,
fourth column, under “Parts” insert 5; line 32, same table, third column thereof, for
“Dially” read D'i'allyl; same'table, line 63, ?fth column thereof, for “gel-lkie” read
gel-like; and that the said Letters Patent should be read with these corrections therein
that the same may conform to the record of the case in the Patent O?ice.
Signed and sealed this 13th day of May, A. D. 1947.
[m]
LESLIE FRAZER,
First Assistant Oommissz'oner of Patents.
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