Cyanoacrylate Esters
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Abstract:
The invention comprises compounds of the formula <1048906><1048906><1048906><1048906><1048906><1048906><1048906>1048906>1048906>1048906>1048906>1048906>1048906>1048906>
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PATENT SPECIFICATION
NO DRAWINGS 1,048,906
Inventors: BENJAMIN DAVID HALPERN, JACK DICKSTEIN, and
ROSE-MARIE HOEGERLE
Date of Application and filing Complete Specification: july 23, I 964.
No. Z9684/64.
Complete Specification Published: Nov. 23, I966.
© Crown Copyright I966.
1.0-48,906
Index at acceptance :—C2 021320; 03 P(4A, 4014B, 4C17, 4C20C‘, 4D3B1, 4K8, 4P1D, 4P1E1,
4P1E5, 4P3, 4P5, 4T2A, 7A, 7C14B, 7C17, 7C20C, 7D2-‘A1, 7D21A2B, 7K8,
7P1D, 7P1E1, 7P1E5, 7P3, 7P5, 7T2A., 8A, 8C14B, 8C17, 8C20C, 8D2A,
8D2B2, 8D2B3, SD5, 8K4, 8K7, 8K8, 8K10, 8P1D, 8P1E1, 8P1E5, SP3,
SP5, 8T2A, 10A, 10C14B, ZLOC17, 10C20C, 10D1A, 10K8, 10P1D,
10P1E1, 10PlE5, 10P3, 1OP5, 10T2A) ; C3 R27K8D
Int. o1.:_0 07 c 121/30 // C 08 f, g
COMPLETE SPECIFICATION
Cyanoaerylate Esters
_We, THE BORDEN COMPANY, a corpora- ethylenic bond which makes possible poly-
tion organised under the laws of the State of merisation and cross-linking. 15
New Jersey, United States of America, of The present invention provides compounds
350, Madison Avenue, New York, State of of the formula
5 New York, United States of America, do CH2
hereby declare the invention, for which we
pray that a patent may be granted to us, and NC—C-—COOR
the method by which it is to be performed,
to be particularly described in and by the wherein R represents one of the radicals
10 following statement : —
This invention relates to cyanoacrylate CH2
esters. H 20
These esters have the special feature of an —CH2—CH2OOC—G—CN
CH2
ll
—-(CH2—CI-I._.—O—CH2—CH2)xOOC—C-—CN
or by weight thereof with 1 to 9 parts by weight
CH3 of vinyl chloride, vinyl acetate, methyl
acrylate, ethyl acrylate, methyl methacrylate,
—CH2—C—CH-_»—OOC—C—CN ethyl methacrylate, styrene and/or vinyl
I toluene. 30
CH3 The present invention, thereof, comprises
the new cyanoacrylates illustrated in the
wherein X is a number from 2 to 30, homo- following Table I and provides also adhesives
25 polymers thereof and copolymers of 10 parts made from these compounds.
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1,048,906
TABLE I
Compound Name
Ethylene glycol 2,2 '-
dicyanoacrylate
Dicyanoacrylates of
polyethylene glycol
Formula
CH. CH..
H H
NC—C—-COOCH2CH2OOC—C—CN
cH._.
ll
NC--C-COO(C2H,,—O—-C._.H.,)::c—
CH2
:1
OO C—C—CN
Neopentyl glycol
2,2-dicyanoacrylate
CH2 Ion, CH,
H {I
NC—C——COOCH2-C-CH20OC—C—CN
I
CH3
Here x is a number from 2 to 30.
The invention provides also adhesive com-
positions comprising a solution of one part
by weight of any of the materials set out
above in 2 to 10 parts by weight of a volatile,
chemically inert solvent.
These compounds are made as shown in
the following Examples. Except where
specifically stated to the contrary, all dryings
are carried out over anhydrous magnesium
sulphate at room temperature and all pro-
portions are expressed by weight.
EXAMPLE 1.
Ethylene Glycol Dicyanoacrylate.
Ethylene glycol dicyanoacetate was first made
as follows:
A mixture of 190 g. of cyanoacetic acid,
62 g. of ethylene glycol, 5 g. of p-toluene-
sulphonic acid and 440 g, of anhydrous
benzene were boiled under reflux with con-
Analysis, 7, calcd. for C,H,.N;.0,,: C, 4 .
4
Found.
1 mole of the ethylene glycol dicyanoacetate
so made was then mixed with 2 moles of
formaldehyde and condensed, in benzene solu-
tion in contact with 0.2 mole of zinc acetate
dihydrate as condensing agent and boiled for
1 hour. The water formed in the condensa-
tion was distilled ofl and collected in a water
trap.
The benzene was removed by boiling under
atmospheric pressure. The residue remaining
was then washed with three separate portions
of dioxane and thus separated from impuri-
ties preferentially soluble in the dioxane.
tinuous stirring for 10 hours. During this
period, the theoretical amount of water was
formed, distilled away and collected in a
water trap. As the dicyanoacetate ester
formed, the benzene separated. The benzene
was removed by distillation under reduced
pressure and replaced by 1,000 g. of
methylene dichloride. The resulting solution
was washed with saturated aqueous potassium
bicarbonate solution and then with water.
The washed liquid that remained was dried
and filtered and the volatile material was
distilled off. The oily residue that remained
was first dried under 12 mm. pressure and
subsequently for 4 hrs. under 0.5 mm. pres-
sure, yielding 170 g. of colourless crystals of
ethylene glycol dicyanoacetate of m.p. 37°——
40° C. Recrystallisation from methanol gave
thin needles of m.p. 41°—45° C_ and b.p.
210° C. at 2 mm.
.0
The residue so washed was dried as above.
The residue was ethylene glycol 2,2’-dicyano-
acrylate.
For use as an adhesive, the ethylene glycol
dicyanoacrylate is dissolved in a solvent
therefor, e.g., a volatile ketone such as
acetone, methyl ethyl ketone or mixtures
thereof, as in the proportion of 1 to 10 parts
of the ketone for 1 part of the cyanoacrylate.
EXAMPLE 2.
Polyethylene glycol dicyanoacrylate.
The composition and procedure of Ex-
ample 1 were followed except that the
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1,048,906
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ethylene glycol there used was replaced, first,
by an equimolecular proportion of diethylene
glycol, so that the intermediate compound
first formed was diethylene glycol dicyano-
acetate. This was then condensed with form-
aldehyde and processed as described in Ex-
ample 1.
In a modification of this Example, the di-
ethylene glycol was replaced by an equimolar
weight of another polyethylene glycol, as for
example by glycol 400 and glycol 1000, used
separately and in turn. The products are
alpha-acrylates of the polyglycols, and have
cross-linking properties because of their di-
functional nature.
cesses of Examples 1 and 2, of using dilferent
inhibitors of polymerisation of ethylenic
bonds added during the formation of the di-
cyanoacrylate esters and of different
atmospheres under which the mixture was
maintained during the condensation. It shows
also the amount of water separated from the
trap during the condensation, as a percentage
of the theoretical maximum for a perfect
yield of condensed product, the reaction time
in hours, and the physical nature of the
finished glycol 2,2’-dicyanoacrylate which
undergoes, to some extent, polymerisation of
the carbon-to-carbon double bonds. In this
table the zinc acetate, when used, was the di-
hydrate. In two instances the zinc acetate was
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EXAMPLE 3. used in combination with acetic acid (ACOH)
Condensing Agents. as shown. The abbreviations “DEG” and
The following Table II shows the effect “EG” represent diethylene glycol and
of using various condensing agents in the pro— ethylene glycol, respectively.
TABLE II
Atmosphere Water Reaction Nature
Glycol Condensing During Sep. % Time, of End
used Agent Inhibitor Condensation of theory Hours Product
DEG — t—butyl N2 67 5 Rubbery mass
catechol
,, Zn(0Ac)2—Ac0H — air 87 0.75 Highly viscous
oil
,, Piperidine S02 S02 24 2.0 Hard, White
Solid
precipitate
,, Piperidine — air 48 2.0 Polymeric gel
acetate
EG Zn(OAc) 2 — air 72 0 .75 Orange red gel
,, Zn(OAc)2—AcOH — air 25 1.30 Hard, rubbery
,, Piperidine —- air 0.5 0.10 Hard, white
acetate polymeric
:_:.
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50
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These esters of the glycols are adhesives.
They are suitable for application to glass,
paper or aluminium foil, for example in a
solution of 20 parts of the esters for 100 of
a volatile ketone solvent.
EXAMPLE 4.
Neopentyl glycol 2,2’—dicyanoacrylate.
A mixture of 52 g. of neopentyl glycol, 94
g. of cyanoacetic acid, 2 g. of p-toluene-
sulphonic acid and 265 g. of benzene were
heated under reflux for 17 hours, during
which the theoretical amount of water was
distilled off azeotropically. The remaining
mixture had only one phase. It was washed
with aqueous potassium carbonate solution,
dried, and filtered. On distilling ofi the
solvent, a colourless oily residue was obtained
which did not crystallise after several hours
of further drying under 0.5 mm. pressure at
room temperature. 113 g. of neopentyl glycol
dicyanoacetate were isolated.
The infrared absorption spectrum showed
that there was no cyanoacetic acid remaining
in the product.
11.9 g. of this neopentyl glycol dicyano-
acetate was added gradually to 3.5 g. of para-
formaldehyde in 44 g. of benzene, contain-
ing 3 drops of piperidine, at 75° C. A colour-
less precipitate separated immediately. After
boiling for 6.5 hr., 1.9 g. of water (100% of
theory) had separated in the water trap. The
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4 1,048,906
residue of the reaction mixture was filtered,
washed several times with benzene and dried,
yielding 13.0 g. of neopentyl glycol 2,2’-di-
cyanoacrylate with a decomposition range of
240°,—295° C. and of only very slight solu-
bility in chloroform, benzene, acetone,
methyl ethyl ketone and ethyl acetate.
Infrared absorption spectrum: 22[50 cm“‘
(C=N); 1620, 940, 865 cm"1
The neopentyl 2,2’-dicyanoacrylate is un-
usually resistant to decomposition by heat.
EXAMPLE 5.
Cross—Linking,
The cyanoacrylate esters described herein
undergo cross-linking more rapidly at elevated
temperatures, for example, 80 to 150° C. to
accelerate the rate of cross-linking or to lower
the temperature used, an initiator, such as
any of the percompounds commonly used to
initiate polymerisation of ethylenic double
bonds, e.g., sodium or potassium per-
sulphate, benzoyl peroxide and azobisiso-
butyronitrile, may be incorporated, advan-
tageously from 0.5% to 1% of the percom—
pound based on the dry weight of the di-
- cyanoacrylate.
In a modification of this Example, the
cyanoacrylate esters that are the final products
' of each of the Examples 2, 3 and 5 are co-
polymerised with an comonomer containing
an ethylemc double bond, e.g., vinyl chloride,
vinyl acetate, methyl or ethyl acrylate or
methacrylate, styrene, or vinyl toluene, in the
proportion of 1 to 9 parts by weight of the
combined cyanoacrylate and the comonomer,
and with 10°/,, of any of the initiators set out
above, on the total weight, at 100° C.
To make an adhesive, the final product of
any of the Examples 1 to 5 is dissolved in any
anhydrous and chemically inert solvent
therefor, of which N,N-dimethylformamide is
an example. Proportions of the solvent that
are suitable are 2 to 10 parts by weight for
1 part by weight of the final product.
The adhesives made as described herein are
applied to the surface to be bonded and main-
tained at a such a temperature as will give
setting of the adhesive at the desired rate.
For most purposes either no warming or only
moderate warming is required.
WHAT WE CLAIM IS:—
1. Compounds of the formula
tea
I
NC—C—COOR
wherein R represents one of the radicals
CI-I2
ll
—CH2—CH2OOC—C—-CN
CH.
H
or
CH3
I H
—CHg—C-—CH2—O0C—C—CN
I
CH3
CH2
wherein x is a number from 2 to 30, homo-
polymers thereof and copolymers of 10 parts
by weight thereof with 1 to 9 parts by weight
of vinyl chloride, vinyl acetate, methyl
acrylate, ethyl acrylate, methyl methacrylate,
ethyl methacrylate, styrene and/or vinyl
toluene.
2. Ethylene glycol 2,2’-dicyanoacrylate.
-3. Polyethylene glycol 2,2’-dicyanoacrylate
containing 2 to 30 polyethylene glycol units
per molecule.
4. Neopentyl glycol 2,2’-dicyanoacrylate.
5. Compounds as claimed in claim 1 sub-
stantially as described with reference to any
of the Examples.
6. An adhesive composition comprising 1
part by weight of a compound or compounds
as claimed in any of the preceding claims in
Z to 10 parts by weight of a volatile,
chemically inert solvent.
ELKINGTON & FIFE,
Chartered Patent Agents,
High Holbom House, 52-54, High Holbom,
London, W.C.1,
Agents for the Applicants.
Leamington Spa: Printed for Her Majesty's Stationery Office, by the Courier Press
(Leamington) Ltd.—1966. Published by The Patent Ofi'ice, 25 Southampton Buildings,
London, W.C.2, from which copies may be obtained.
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