United States Patent Office 3,178,379

Patented Apr. 13, 1965

2
wherein R is an alkyl, alkenyl, cyclohexyl or phenyl radical
3,178,379 of from about 1 to 16 carbon atoms. Esters in which
METHOD FOR PREPARNG CYANCACRYLATE R is an alkyl group, preferably a methyl, ethyl, n-propyl,
MONOMER ADHESEVE COMPOSITIONS iso-propyl, or amyl group, are particularly effective as
Thomas H. Wicker, Jr., and Newton H. Shearer, Jr., adhesives.
Kingsport, Tenn., assignors to Eastman Kodak Com A number of polymers are useful as viscosity regul
pany, Rochester, N.Y., a corporation of New Jersey lators or modifiers for the cyanoacrylates to provide
No Drawing. Filed June 14, 1961, Ser. No. 116,950 viscous adhesive formulations. In general they are stable
6 Claims. (C. 260-7)
This invention relates to an improved method for the polymeric substances that form with the cyanoacrylate
O either a true or a colloidal solution of substantially
preparation of adhesive formulations. More particularly, higher viscosity than the cyanoacrylate monomer and
it relates to the preparation of adhesive compositions con that do not adversely affect the adhesive characteristics
taining esters of ox-cyanoacrylic acid. of the cyanoacrylate when formulated therewith in minor
Several patents of ourselves and our co-workers have amounts. Suitable polymers include, for example, poly
disclosed adhesive compositions containing monomeric meric alkylcyanoacrylates, polyacrylates, poly(alkylacry
o-cyanoacrylates. These esters have been discovered to lates), cellulose nitrate, cellulose acetate, cellulose propio
be outstanding high-strength adhesives for bonding all nate, cellulose butyrate, and other similar cellulose or
kinds of materials, such as glass, metals, plastics, rubber, ganic acid esters or other polymeric materials which are
wood, cement, paper, cloth, etc., to themselves or to soluble in the polymer.
each other. The mechanism by which these cyanoacry
lates function as adhesives is not completely understood; in Ina the method of the invention the polymer is dissolved
selected volatile organic solvent for blending with
but it is thought that the adhesive properties are attribut the ox-cyanoacrylate. The solvent must be a Substance
able to the rapidity with which thin films of the mono that will not cause polymerization of the cyanoacrylate
meric ox-cyanoacrylates polymerize in the absence of heat, monomer. It must also be sufficiently volatile to be
light or polymerization catalyst. When two surfaces are readily distillable from the adhesive composition. Pref
placed together with a thin film of a monomeric c erably the solvent should have a boiling point no higher
cyanoacrylate between them, the monomer rapidly po than about 80° C. at atmospheric pressure. Examples of
lymerizes and forms a highly tenacious bond. suitable solvents include chloroform, dichloromethane,
The patent to Coover and Shearer, U.S. 2,794,788, dis benzene, acetone, ethyl bromide, ethylene dichloride,
closes that in using an e-cyanoacrylate adhesive for bond- : ethyl acetate, methyl propionate, etc.
ing porous materials the low viscosity of the O-cyano The concentration of polymer in the volatile solvent
acrylate monomer may result in excessive penetration of can be within a considerable range. In general, it is pre
the porous material and that the viscosity of the adhesive ferred to form a solution containing from about 5 to 30
can be increased to an optimum level by dissolving minor weight percent of the polymer, but somewhat higher or
proportions of polymeric alkylcyanoacrylates in the mon lower concentrations can be used.
omer. Such compositions have been formed simply by The amount of polymer solution to be used relative to
mixing the monomeric cyanoacrylate with the desired the monomer will be an amount sufficient to form a final
polymeric viscosity regulator and with other ingredients adhesive composition containing the desired concentration
normally used in such adhesives, such as a polymerization of the polymeric thickener or viscosity regulator. The
inhibitor, and thereafter agitating the mixture to achieve 4 polymer is normally a minor component of the final com
solution. While such compositions have rendered good position. In general, up to about 25 weight percent of
results we have now discovered that the properties of the polymer based on the final adhesive composition can be
adhesive composition can be markedly improved by fol employed to regulate the viscosity of the cyanoacrylate
lowing a novel method of incorporating the polymeric monomer without adversely affecting the adhesive charac
viscosity modifier with the cyanoacrylate monomer. teristics of the composition. Concentrations of about 1.
In accordance with the present invention the polymeric to 5 weight percent polymer generally are preferred.
viscosity modifier for the cyanoacrylate adhesive is first The blending operation is preferably carried out by
dissolved in a volatile organic solvent which is compatible stirring the polymer solution with the cyanoacrylate
with the cyanoacrylate monomer. The solution of the monomer at normal temperature and pressure. However,
polymer is then blended with the monomer. Thereafter 50 it may be desired to warm the mixture to achieve good
the volatile organic solvent is stripped from the mixture solubility or to increase pressure to prevent premature
under vacuum. The adhesive composition prepared in vaporization of the volatile solvent. In any event, the
this manner has unexpected advantages over compositions combination of temperature and pressure during the blend
containing the same principal ingredients but prepared by ing step must be such that the solvent, the polymer, and
the previous method without the use of a volatile solvent. the c-cyanoacrylate monomer remain in the liquid phase
Advantages of the new method are that the product un and in solution.
expectedly has superior clarity, superior bulk stability and Following the blending step, the pressure is reduced on
superior activity in the rapid formation of a strong ad the solution to a level below about 10 mm. Hg to achieve
hesive bond. Still another advantage is obtained when vaporization of the volatile solvent. Advantageously, a
preparing an adhesive formulation from a cyanoacrylate 60 dry inert gas such as nitrogen is bubbled through the liq
monomer which, for storage purposes, has a high content uid to aid in the vacuum stripping of the solvent. The
of a volatile polymerization inhibitor such as Sulfur di solution can also be warmed to facilitate vaporization of
oxide. The vacuum-stripping step of our new method the solvent. Thus, in general, the conditions of pressure
aids in removing the volatile inhibitor from the monomer and temperature during the vacuum-stripping stage are
and reducing its concentration to a desired lower level. 65 such that the solvent substantially entirely vaporizes and
The method of the invention can be practiced with any distils from the liquid mixture while the polymer and
of the cyanoacrylate adhesives. The cyanoacrylates cyanoacrylate monomer remain substantially entirely in
having adhesive properties are compounds of the general the liquid phase and in solution.
formula: Although our invention provides an improved method
CHieC-C-OR 70 of incorporating a polymeric viscosity modifier in the
CN O cyanoacrylate monomer, it should be understood that the
method is applicable to preparation of cyanoacrylate ad
 fy
3,178,379
s 4.
hesive compositions containing additional ingredients. Example 5
Such other ingredients can include, for example, plas A solution of 3.0 g of poly(methyl 2-methacrylate)
ticizer esters in amounts of 1 to 20 weight percent, as dis was prepared in 100 grams of dichloromethane and placed
closed in U.S. 2,784, 127, polymerization inhibitors such in a flask fitted with reflux condenser and water separating
as sulfur dioxide and hydroquinone in amounts of 0.001 tube. The mixture was refluxed until no additional water
to 0.05 weight percent, as disclosed in U.S. 2,765,332, was removed and was then used to prepare a stable, ac
etc. As already mentioned our method aids in reducing tive, viscous adhesive formulation as described in Ex
the content of volatile stabilizer in the monomer that ample 1.
might be excessive for the intended uses of the adhesive From the above examples it can be seen that our new
compositions. 0. method of incorporating a polymeric viscosity regulator in
The ultimate adhesive composition based on a cyano an adhesive composition of the cyanoacrylate type pro
acrylate monomer must be essentially free of water to vides unexpected advantages in the properties of the result
avoid polymerization of the monomer in storage. The ing product. Thus the product of Example 1 was haze
use of a solvent for incorporating the polymer in the ad free, stable and active. On the other hand, the product of
hesive composition in accordance with the invention offers 5 Example 4, after a 1-hour vacuum distillation to remove
the advantage that one can start with a polymer or a excess sulfur dioxide, still had low activity. An additional
solvent that contains water and dry the polymer solution vacuum distillation period of 45 minutes was required
azeotropically before mixing the solution with the dry to form an adhesive of satisfactory activity. However,
cyanoacrylate monomer. The azeotropic drying is ac this adhesive was not so stable as one formed by the new
complished by refluxing the polymer solution in distilla 20 method and polymerized on standing for one week.
tion apparatus provided with a water separator in the re The invention has been described in considerable detail
flux line. This eliminates the need for separate drying of with particular reference to certain preferred embodiments
the polymer and the solvent. thereof, but it will be understood that variations and modi
The following examples offer a comparison of one en fications can be effected within the spirit and scope of the
bodiment of the method of the invention with another 25 invention as described hereinabove, and as defined in the
method for preparing cyanoacrylate adhesive composi appended claims.
tions: We claim:
Example I 1. In the formulation of an essentially water-free adhe
A 500-ml, three-neck flask was equipped with a mag sive composition based on an ox-cyanoacrylate monomer of
30 the formula
netic stirrer, a nitrogen capillary tube for the introduction
of nitrogen below the surface of the liquid, and an outlet CII-C-C-OR
to a vacuum system. Into the flask was charged 45.5
parts methyl 2-cyanoacrylate containing 100 p.p.m. Sul
fur dioxide, 1.5 parts dimethyl sebacate, and 20 parts of a wherein R is a radical of about 1 to 16 carbon atoms from
15% solution of a polymethyl methacrylate in dichloro the group consisting of alkyl, alkenyl, cyclohexyl and
methane. Vacuum was applied to the system, slowly at phenyl, and containing a minor amount of a viscosity regu
first, and the dichloromethane and excess Sulfur dioxide lating polymer, the improvement which comprises forming
were removed at a final pressure of 5-6.5 mm. After one a solution of said polymer in a volatile organic solvent,
hour, a product was obtained which was haze-free, stable 40 blending the solution with the cyanoacrylate monomer
and active. under conditions of temperature and pressure at which
Example 2 the solvent, the polymer and the cyanoacrylate monomer
Example 1 was repeated with the exception that chloro are in the liquid phase, subjecting the resulting mixture
form was used as the solvent for the polymer. The fin to distillation conditions of temperature and pressure
ished adhesive product was free of haze or insoluble mat adapted to vaporize the volatile solvent but not the poly
ter, gave 10 second, glass-glass bonds and was stable for mer and the cyanoacrylate, removing the vaporized solvent
a period of time in excess of one year. from the mixture and recovering an adhesive composition
comprising said ox-cyanoacrylate and a minor amount of
Example 3 said polymer.
Example 1 was repeated with the exception that ben 50 2. In the formulation of an essentially water-free ad
hesive composition based on an alkyl ox-cyanoacrylate mon
zene was used as a solvent for the polymer. The result omer of the formula
ing adhesive product was haze-free, active and stable.
The following example illustrates the preparation of CH---or
a viscous adhesive formulation without the aid of a vola &N O
tile solvent. 55
Example 4 wherein R is an alkyl radical of about 1 to 16 carbon
atoms, and containing a minor amount of a viscosity regu
In a clean, dry bottle as placed 45.5 parts of methyl 2 lating polymer, the improvement which comprises forming
cyanoacrylate containing 100 p.p.m. sulfur dioxide, 1.5 a solution of a volatile organic solvent having a boiling
parts dimethyl sebacate and 3.0 parts of polymethyl 60 point at atmospheric pressure no higher than 80° C. and
methacrylate. The bottle was placed on a set of rolls and a polymer that forms a mixture with the cyanoacrylate
the mixture was rotated for three hours. At the end of this monomer of higher viscosity than said monomer, the con
time, solution was complete and the mixture was trans centration of polymer in said solution with said organic
ferred to a flask equipped as described above. Vacuum Solvent being in the range of 5 to 30 weight percent, blend
was applied to the fiask and the excess sulfur dioxide was ing the Solution with the alkyl ce-cyanoacrylate monomer
removed at a final pressure of less than 1 mm. for one in proportions adapted to form an ultimate adhesive com
hour. At the end of the one-hour period, the material position containing about 1 to 25 weight percent polymer
would not give a glass-glass bond within 30 seconds. based on the cyanoacrylate monomer, said blending being
After an additional pumping period of 45 minutes, a sam carried out under conditions of temperature and pressure
ple was obtained which gave a ten second, glass-glass 70 at which the polymer, the solvent and the cyanoacrylate
bond (the sample was not stable and polymerized on monomer are in the liquid phase, thereafter, in a vacuum
standing for a period of one week). stripping stage, Subjecting the resulting mixture to con
The following example illustrates the drying of poly ditions of temperature and pressure, including a pressure
(methyl 2-cyanoacrylate) prior to the mixing with mono below 10 mm. Hg, at which substantially all of said sol
mer and removal of solvent. vent vaporizes from the mixture and substantially all of
 3,178,879
5 6
said polymer and cyanoacrylate monomer remain in the roform, dichloromethane, benzene, acetone, ethyl bromide,
liquid phase. ethylene dichloride, ethyl acetate and methyl propionate,
3. The method according to claim 2 in which an inert. the concentration of polymer in said solution being in the
gas is passed through the liquid mixture during the vac range of 5 to 30 weight percent, blending the solution with
uum-stripping stage. the methyl ox-cyanoacrylate monomer in proportions
4. The method according to claim 2 in which said adapted to form an ultimate adhesive composition con
cyanoacrylate monomer prior to blending with the poly taining about 1 to 5 percent polymer based on the cyano
mer solution contains an amount of volatile polymeriza acrylate monomer, said blending being carried out under
tion inhibitor in a concentration excessively high for the conditions of temperature and pressure at which the poly
ultimate adhesive composition and in which the concen O mer, the solvent and the cyanoacrylate monomer are in
tion of said volatile polymerization inhibitor is reduced to the liquid phase, thereafter, in a vacuum-stripping stage,
a desired level during the vacuum-stripping stage. maintaining the resulting mixture at a pressure below
(5. The method according to claim 2 in which said poly about 6.5 mm. Hg and at about room temperature while
mer initially contains water and in which said water is passing an inert stripping gas through the mixture, whereby
substantially entirely removed from the polymer before the 5 to vaporize substantially all of said solvent from the mix
latter is incorporated with the cyanoacrylate monomer by ture, and recovering a methyl ox-cyanoacrylate adhesive
azeotropic distillation of the solution of polymer and or composition containing said polymer.
ganic solvent prior to blending of the solution with the
cyanoacrylate monomer. References Cited by the Examiner
6. In the formulation of an essentially water-free ad 20 UNITED STATES PATENTS
hesive composition based on methyl ox-cyanoacrylate and 2,613,156 10/52 McGaffin et al.-------- 260-34.2
containing a minor amount of a viscosity regulating poly 2,765,332 10/56 Coover et al. ---------- 260-17
mer, the improvement which comprises forming a solution
of a polymer selected from the group consisting of poly 2,794,788, 6/57 Coover et al.------------ 260-17
meric alkyl cyanoacrylates, poly(alkylacrylates), cellulose JOSEPH L. SCHOFER, Primary Examiner.
nitrate and cellulose organic acid esters and a volatile
organic solvent selected from the group consisting of chlo LEON J. BERCOVITZ, Examiner.