CA1065096A - Thermally resistant curable compositions - Google Patents
Thermally resistant curable compositionsInfo
- Publication number
- CA1065096A CA1065096A CA236,691A CA236691A CA1065096A CA 1065096 A CA1065096 A CA 1065096A CA 236691 A CA236691 A CA 236691A CA 1065096 A CA1065096 A CA 1065096A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- group
- carbon atoms
- hydrogen
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
Abstract
ABSTRACT OF THE DISCLOSURE
Adhesive and sealant compositions are described having improved strength properties at elevated temperatures and improved resistance to thermal degradation. The composition comprises a mixture of an acrylate or methacrylate monomers polymerizable by free-radical initiation or anaerobic composition and an additive selected from:
Adhesive and sealant compositions are described having improved strength properties at elevated temperatures and improved resistance to thermal degradation. The composition comprises a mixture of an acrylate or methacrylate monomers polymerizable by free-radical initiation or anaerobic composition and an additive selected from:
Description
~065096 BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to certain adhesive and sealant compositions having improved strength prop~rties at elevated temperatures and improved resistance to thermal degradation.
; Prior Art Adhesive and sealant compositions based on acrylate - and methacrylate monomers polymerizable by free-radical initiation are known in the art. Likewise, anaerobic com- -positions are known in the art (see, for example U.S. patents
Field of the Invention This invention relates to certain adhesive and sealant compositions having improved strength prop~rties at elevated temperatures and improved resistance to thermal degradation.
; Prior Art Adhesive and sealant compositions based on acrylate - and methacrylate monomers polymerizable by free-radical initiation are known in the art. Likewise, anaerobic com- -positions are known in the art (see, for example U.S. patents
2,895,950, 3,043,820, and 3,218,305). Anaerobic compositions ` are characterized by their ability to remain liquid in the ~
presence of air, but cure to a strong adhesive bond when air -is excluded, as by assembling a mated nut and bolt to which the composition has been applied.
` While serving many useful purposes, both standard acrylate compositions as well as anaerobic-type acrylate compositions have been limited in applicability due to degrad-ation of adhesive strength at elevated temperatures, e.g., 250F or more.
SUMMARY OF THE INVENTION
According to the present invention there is provided an adhesive and sealant composition having significantly improved strength at elevated temperatures and improved re-; sistance to thermal degradation. This composition comprises a mixture of ta) a monomçr selected from the group consisting ofethoxylated bisphenol A diacrylate, ethoxylated bisphenol A
dimethacrylate, and an acrylate ester corresponding to the - 1 - ~ , 106S~96 : formula 2)mtC ¦ C_o3~C-c=
R' R'' R R' p .~, .
wherein R represents a radical selected from the group con- ~ .
sisting of hydrogen, lower alkyl of 1-4 carbon atoms, inclusive, hydroxy alkyl of 1-4 carbon atoms inclusive, and : .
O
-cH2-o-c-c=cH2 R' .
~ R' is a radical selected from the group consisting of hydrogen, :~
halogen, and lower alkyl of 1-4 carbon atoms; R" is a radical -:` selected from the group consisting of hydrogen, - OH and :.~
; ,, :
` 10 -O-C-C=CH2 :
: m is an integer equal to at least 1, e.g., from 1 to 8 or higher, for instance, from 1 to about 4 inclusive; n is an ` integer equal to at least 1, for example, 1 to 20 or more; `
` and p is 0 or 1;
(b) about 1 to about 50 percent by weight of the ; total composition of an additive selected from the group ~ consisting of :
.. 2 ~065~9~
o o o ¢ > N--R ¢ ~N--R'--N < ?
-. O :
\ N-R o o ~ > N-R'-N <
O O
wherein R and R' are selected from the group consisting of alkyl, cycloalkyl, aralkyl, alkaryl.
The invention further relates to a process for seal-ing or adhering surfaces comprising applying a composition of this invention to surfaces ~o be sealed or.adhered,placing the ~- surfaces in abutting relationship and allowing the composition .
to cure.
DETAILED DESCRIPTION OF THE INVENTION
. . .
One class of monomers suited for use in this in-vention comprises acrylate esters having the following general formula:
, '.
' ., ~
.: . - . . .. . . .
: . , , . . ,. , ~ :, \ \
~()65096 ...
..
¦/ R \ R O
H2C=C-C-O tt R" J R - C-C=CH2 P n wherein R represents a radical selected from the group consisting of hydrogen, lower alkyl of 1-4 carbon atoms, inclusive, hydroxy alkyl of 1-4 carbon atoms inclusive, and .' o ..
2 , 2 R' is a radical selected from the group consisting of hydrogen, halogen, and lower alkyl of 1-4 carbon atoms; R" is a radical -~
selected from the group consisting of hydrogen, - OH and " O
.~ , .. .
-O-C-C=CH
R
m is an integer equal to at least 1, e.g., from 1 to 8 or higher, for instance, from 1 to 4 inclusive; n is an integer equal to at least 1, for example, 1 to 20 or more; and p is one of the . following: O,l.
~: The polymerizable polyacrylate esters utilized in accordance with the invention and corresponding to the above general formula are exemplified by, but not restricted to, the following materials: diethylene glycol dimethacrylate, tri-ethylene glycol dimethacrylate, tetraethylene glycol dimeth- ~ :
acrylate, dipropylene glycol dimethacrylate, di-(pentamethylene ~ 20 glycol) dimethacrylate, tetraethylene diglycerol diacrylate, .. :
- 4 - ;
,, .
.. ... , , . ~ :
, . :
..
' ' ' : ' . , - : . ' ' , ' : .. . - . ~ : .
1065~9~
diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylene dimethacrylate, neopentyl glycol diacrylate and tri-methylol propane triacrylate. Of t~ese, the preferred monomers are triethylene glycol dimethacrylate and polyethylene glycol dimethacrylate.
The most preferred class of monomers for use in this invention, however, is ethoxylated bisphenol A dimeth-acrylate, which has the following structural formula:
(C33)2-CL ~-o-c32-C32--C-c-c~2 The ocher critical component of the composition is an additive which conforms to any of the following structures:
.' '"
, O O O
J~- R¢'~ N--R '--N ~ 3 : o . o o . .
.. o o o - ¢~>N-R OE~ ~N--R' -N )3 O O
The nature of R and R' iS not critical for purposes of this invention and may be any organic radical which does not contain any group which will adversely affect the composition - for purposes disclosed herein. Most commonly, R and R' are selected from the group consisting of alkyl, cycloalkyl, aralkyl, alkaryl, any of which may be exceptionally large radicals, e.g., containing up to about 200 carbon atoms or more; preferably they - will contain from 6 to about 100 carbon atoms, most preferably, . .
. ~ .
- . ~ .. . : . . .
6 to about 50 carbon atoms.
It has been found that resistance to thermal oxi-dative degradation is improved if R or R' are aromatic; however, this is not required for the general improvement of this in-vention to be realized. It will, of course, be understood that both R and R' can consist of relatively complicated moieties, provided only that they do not contain functionality which interferes with the performance of the additive for its intended purposes. The useful concentration range for this additive is 10 about 1 to about 50, preferably about 5 to about 35, percent by ~; weight of the total composition.
~ In general, these compositions are readily curable by ; application of moderate heat.
` The compositions may also be rendered anaerobic and curable at room temperature by inclusion of a peroxy initiator of free-radical polymerization, which is a preferred embodiment of this invention. A number of such initiators are well known . ~ . .
in-the anaeEobic art, e.g.j hydroperoxides, such as cumene hydro-peroxide, paramenthane hydroperoxide, tertiary butyl hydroper-.
- 20 oxide, and peresters which hydrolyze to peroxides such as - tertiary butyl perbenzoate, and the like. The amount of such peroxy compounds may vary from about 0.1 to about 10, preferably - about 1 to about 5, percent by weight of the total composition.
, Accelerators of anaerobic polymerization may also be -advantageously included. Such accelerators include a variety of secondary and tertiary organic amines as well as sulfimides (e.g., benzoic sulfimide) which are also known in the art. These - may be used at a concentration range of about 0.1 to about 5, preferably about 1 to about 2, percent by weight of the total composition.
:
' .. . . . . . .. . . . . .
.. ~ , . . .
.. . . .
Other agents such as thickeners, plasticizers, etc., are also known in the art and may advantageously ~e incorporated where functionally desirable, provided only that they do not interfere with the functioning of the additive for its intended purpose. This, of course, can be determined by simple experimentation.
The additives of this invention tend to improve at least three properties of the cured composition, the extent and nature of the improvement appearing to depend on the specific monomer involved. These improvements comprise greater re-sistance to degradation of an adhesive bond caused by oxidative ~ effects incurred at elevated temperatures, greater strength of ; the bond or seal at elevated temperatures, and often also an improvement of the cure strength obtained under room temperature curing conditions. The precise nature of the improvement mechanism is not well understood. Without wishing to be bound by any particular theory, it appears that the additives of this invention tend to copolymerize with the monomers, thereby tend-ing to terminate the molecular "unzipping" effect which appears to characterize thermal degradation. The improvement of hot strength is believed due to the increase in glass transition temperature brought about by such copolymerization.
The following examples illustrate but in no way limit the invention. Percentages are by weight based on the total composition.
~::
Anaerobic compositions were prepared by mixing into bisphenol A dimethacrylate the following materials:
i ..
5% bisphenol A fumarate (suspending agent)
presence of air, but cure to a strong adhesive bond when air -is excluded, as by assembling a mated nut and bolt to which the composition has been applied.
` While serving many useful purposes, both standard acrylate compositions as well as anaerobic-type acrylate compositions have been limited in applicability due to degrad-ation of adhesive strength at elevated temperatures, e.g., 250F or more.
SUMMARY OF THE INVENTION
According to the present invention there is provided an adhesive and sealant composition having significantly improved strength at elevated temperatures and improved re-; sistance to thermal degradation. This composition comprises a mixture of ta) a monomçr selected from the group consisting ofethoxylated bisphenol A diacrylate, ethoxylated bisphenol A
dimethacrylate, and an acrylate ester corresponding to the - 1 - ~ , 106S~96 : formula 2)mtC ¦ C_o3~C-c=
R' R'' R R' p .~, .
wherein R represents a radical selected from the group con- ~ .
sisting of hydrogen, lower alkyl of 1-4 carbon atoms, inclusive, hydroxy alkyl of 1-4 carbon atoms inclusive, and : .
O
-cH2-o-c-c=cH2 R' .
~ R' is a radical selected from the group consisting of hydrogen, :~
halogen, and lower alkyl of 1-4 carbon atoms; R" is a radical -:` selected from the group consisting of hydrogen, - OH and :.~
; ,, :
` 10 -O-C-C=CH2 :
: m is an integer equal to at least 1, e.g., from 1 to 8 or higher, for instance, from 1 to about 4 inclusive; n is an ` integer equal to at least 1, for example, 1 to 20 or more; `
` and p is 0 or 1;
(b) about 1 to about 50 percent by weight of the ; total composition of an additive selected from the group ~ consisting of :
.. 2 ~065~9~
o o o ¢ > N--R ¢ ~N--R'--N < ?
-. O :
\ N-R o o ~ > N-R'-N <
O O
wherein R and R' are selected from the group consisting of alkyl, cycloalkyl, aralkyl, alkaryl.
The invention further relates to a process for seal-ing or adhering surfaces comprising applying a composition of this invention to surfaces ~o be sealed or.adhered,placing the ~- surfaces in abutting relationship and allowing the composition .
to cure.
DETAILED DESCRIPTION OF THE INVENTION
. . .
One class of monomers suited for use in this in-vention comprises acrylate esters having the following general formula:
, '.
' ., ~
.: . - . . .. . . .
: . , , . . ,. , ~ :, \ \
~()65096 ...
..
¦/ R \ R O
H2C=C-C-O tt R" J R - C-C=CH2 P n wherein R represents a radical selected from the group consisting of hydrogen, lower alkyl of 1-4 carbon atoms, inclusive, hydroxy alkyl of 1-4 carbon atoms inclusive, and .' o ..
2 , 2 R' is a radical selected from the group consisting of hydrogen, halogen, and lower alkyl of 1-4 carbon atoms; R" is a radical -~
selected from the group consisting of hydrogen, - OH and " O
.~ , .. .
-O-C-C=CH
R
m is an integer equal to at least 1, e.g., from 1 to 8 or higher, for instance, from 1 to 4 inclusive; n is an integer equal to at least 1, for example, 1 to 20 or more; and p is one of the . following: O,l.
~: The polymerizable polyacrylate esters utilized in accordance with the invention and corresponding to the above general formula are exemplified by, but not restricted to, the following materials: diethylene glycol dimethacrylate, tri-ethylene glycol dimethacrylate, tetraethylene glycol dimeth- ~ :
acrylate, dipropylene glycol dimethacrylate, di-(pentamethylene ~ 20 glycol) dimethacrylate, tetraethylene diglycerol diacrylate, .. :
- 4 - ;
,, .
.. ... , , . ~ :
, . :
..
' ' ' : ' . , - : . ' ' , ' : .. . - . ~ : .
1065~9~
diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylene dimethacrylate, neopentyl glycol diacrylate and tri-methylol propane triacrylate. Of t~ese, the preferred monomers are triethylene glycol dimethacrylate and polyethylene glycol dimethacrylate.
The most preferred class of monomers for use in this invention, however, is ethoxylated bisphenol A dimeth-acrylate, which has the following structural formula:
(C33)2-CL ~-o-c32-C32--C-c-c~2 The ocher critical component of the composition is an additive which conforms to any of the following structures:
.' '"
, O O O
J~- R¢'~ N--R '--N ~ 3 : o . o o . .
.. o o o - ¢~>N-R OE~ ~N--R' -N )3 O O
The nature of R and R' iS not critical for purposes of this invention and may be any organic radical which does not contain any group which will adversely affect the composition - for purposes disclosed herein. Most commonly, R and R' are selected from the group consisting of alkyl, cycloalkyl, aralkyl, alkaryl, any of which may be exceptionally large radicals, e.g., containing up to about 200 carbon atoms or more; preferably they - will contain from 6 to about 100 carbon atoms, most preferably, . .
. ~ .
- . ~ .. . : . . .
6 to about 50 carbon atoms.
It has been found that resistance to thermal oxi-dative degradation is improved if R or R' are aromatic; however, this is not required for the general improvement of this in-vention to be realized. It will, of course, be understood that both R and R' can consist of relatively complicated moieties, provided only that they do not contain functionality which interferes with the performance of the additive for its intended purposes. The useful concentration range for this additive is 10 about 1 to about 50, preferably about 5 to about 35, percent by ~; weight of the total composition.
~ In general, these compositions are readily curable by ; application of moderate heat.
` The compositions may also be rendered anaerobic and curable at room temperature by inclusion of a peroxy initiator of free-radical polymerization, which is a preferred embodiment of this invention. A number of such initiators are well known . ~ . .
in-the anaeEobic art, e.g.j hydroperoxides, such as cumene hydro-peroxide, paramenthane hydroperoxide, tertiary butyl hydroper-.
- 20 oxide, and peresters which hydrolyze to peroxides such as - tertiary butyl perbenzoate, and the like. The amount of such peroxy compounds may vary from about 0.1 to about 10, preferably - about 1 to about 5, percent by weight of the total composition.
, Accelerators of anaerobic polymerization may also be -advantageously included. Such accelerators include a variety of secondary and tertiary organic amines as well as sulfimides (e.g., benzoic sulfimide) which are also known in the art. These - may be used at a concentration range of about 0.1 to about 5, preferably about 1 to about 2, percent by weight of the total composition.
:
' .. . . . . . .. . . . . .
.. ~ , . . .
.. . . .
Other agents such as thickeners, plasticizers, etc., are also known in the art and may advantageously ~e incorporated where functionally desirable, provided only that they do not interfere with the functioning of the additive for its intended purpose. This, of course, can be determined by simple experimentation.
The additives of this invention tend to improve at least three properties of the cured composition, the extent and nature of the improvement appearing to depend on the specific monomer involved. These improvements comprise greater re-sistance to degradation of an adhesive bond caused by oxidative ~ effects incurred at elevated temperatures, greater strength of ; the bond or seal at elevated temperatures, and often also an improvement of the cure strength obtained under room temperature curing conditions. The precise nature of the improvement mechanism is not well understood. Without wishing to be bound by any particular theory, it appears that the additives of this invention tend to copolymerize with the monomers, thereby tend-ing to terminate the molecular "unzipping" effect which appears to characterize thermal degradation. The improvement of hot strength is believed due to the increase in glass transition temperature brought about by such copolymerization.
The following examples illustrate but in no way limit the invention. Percentages are by weight based on the total composition.
~::
Anaerobic compositions were prepared by mixing into bisphenol A dimethacrylate the following materials:
i ..
5% bisphenol A fumarate (suspending agent)
3~ cumene hydroperoxide 1.5~ benzoic sulfimide 1~ diethyl paratoluidene 0.5~ dimethyl orthotoluidene 25~ additive of this invention as shown in the Table 1.
These compositions were applied to steel pins and collars, which were then assembled and allowed to cure for 24 hours at room temperature until bond strength had fully developed. The samples were then aged at 450F for the periods shown in Table 1. They were then allowed to cool to room temperature and the pins were pressed from the collars using an Instron tester.
Table 1 reports the results in pounds per square inch of shear strength and shows the desirable improvement in thermal aging strength retention.
Weeks at 450F 1 2 4 8 11 15 26 N-phenylmaleimi-de 3900 3350 2000 1200 -- -- 0 m-phenylene di-maleimide 4300 5000 5000 5000 ~000 -- 0 "Kerimide 601"* 4500 4600 4700 4300 4300 2200 700 Control-no additive 3500 1100 0 *Sold by Rhodia Corp., New York, N. Y. A reaction product of a bismaleimide with a diamine.
EXAMPLE ll Formulations were prepared similar to those of Example 1 except that only Keramid 601[Trade Mark] was employed as the additive and the monomer was polyethylene glycol dimeth-acrylate, having a molecular weight of about 330. The formula-tions in Table 11 were used to adhere 1/4-20 steel nuts and bolts together. The samples were aged at 400F for the times shown, but were tested at room temperature, as before. Table 11 shows "break/prevail" strength in foot-pounds. "Break"
strength is the torque required to cause the first movement between nut and bolt. "Prevail" strength is the torque re-quired to unwind the nut 180 beyond the break point.
"
~, .
~0~;5096 Time at 400F One Day One Week Two Weeks 10% additive142/400 93/340 ` 33/145 30% additive172/390 178/465 165/445 Control-no additive 48/330 7/18 0J2 A sample corresponding to the 30% additive level in Table 11 was tested after two weeks' aging at 400F. The test : was performed at 400 with the following break/prevail results:
180/235.
Example 11 again illustrates the improved resistance to thermal degradation and Example 111 illustrates the improved strength at high temperature which characterize the formulations of this invention. :
''' ~
', ~- ,.
:: - 9 -., . ~ . .
These compositions were applied to steel pins and collars, which were then assembled and allowed to cure for 24 hours at room temperature until bond strength had fully developed. The samples were then aged at 450F for the periods shown in Table 1. They were then allowed to cool to room temperature and the pins were pressed from the collars using an Instron tester.
Table 1 reports the results in pounds per square inch of shear strength and shows the desirable improvement in thermal aging strength retention.
Weeks at 450F 1 2 4 8 11 15 26 N-phenylmaleimi-de 3900 3350 2000 1200 -- -- 0 m-phenylene di-maleimide 4300 5000 5000 5000 ~000 -- 0 "Kerimide 601"* 4500 4600 4700 4300 4300 2200 700 Control-no additive 3500 1100 0 *Sold by Rhodia Corp., New York, N. Y. A reaction product of a bismaleimide with a diamine.
EXAMPLE ll Formulations were prepared similar to those of Example 1 except that only Keramid 601[Trade Mark] was employed as the additive and the monomer was polyethylene glycol dimeth-acrylate, having a molecular weight of about 330. The formula-tions in Table 11 were used to adhere 1/4-20 steel nuts and bolts together. The samples were aged at 400F for the times shown, but were tested at room temperature, as before. Table 11 shows "break/prevail" strength in foot-pounds. "Break"
strength is the torque required to cause the first movement between nut and bolt. "Prevail" strength is the torque re-quired to unwind the nut 180 beyond the break point.
"
~, .
~0~;5096 Time at 400F One Day One Week Two Weeks 10% additive142/400 93/340 ` 33/145 30% additive172/390 178/465 165/445 Control-no additive 48/330 7/18 0J2 A sample corresponding to the 30% additive level in Table 11 was tested after two weeks' aging at 400F. The test : was performed at 400 with the following break/prevail results:
180/235.
Example 11 again illustrates the improved resistance to thermal degradation and Example 111 illustrates the improved strength at high temperature which characterize the formulations of this invention. :
''' ~
', ~- ,.
:: - 9 -., . ~ . .
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A curable composition having improved thermal properties comprising a mixture of (a) a monomer selected from the group consisting of ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A
dimethacrylate, and an acrylic ester corresponding to the formula wherein R represents a radical selected from the group con-sisting of hydrogen, lower alkyl of 1-4 carbon atoms, inclusive, hydroxy alkyl of 1-4 carbon atoms inclusive and R' is a radical selected from the group consisting of hydrogen, halogen, and lower alkyl of 1-4 carbon atoms; R" is a radical selected from the group consisting of hydrogen, -OH and m is an integer equal to at least 1; n is an integer equal to at least 1; and p is 0 or 1;
(b) about 1 to about 50 percent by weight of the total composition of an additive selected from the group consisting of wherein R and R' are selected from the group consisting of alkyl, cycloalkyl, aralkyl, alkaryl.
dimethacrylate, and an acrylic ester corresponding to the formula wherein R represents a radical selected from the group con-sisting of hydrogen, lower alkyl of 1-4 carbon atoms, inclusive, hydroxy alkyl of 1-4 carbon atoms inclusive and R' is a radical selected from the group consisting of hydrogen, halogen, and lower alkyl of 1-4 carbon atoms; R" is a radical selected from the group consisting of hydrogen, -OH and m is an integer equal to at least 1; n is an integer equal to at least 1; and p is 0 or 1;
(b) about 1 to about 50 percent by weight of the total composition of an additive selected from the group consisting of wherein R and R' are selected from the group consisting of alkyl, cycloalkyl, aralkyl, alkaryl.
2. The composition of Claim 1 wherein the monomer is ethoxylated bisphenol A.
3. The composition of Claim 1 wherein the monomer is polyethylene glycol dimethacrylate.
4. The composition of Claim 1 wherein the additive is
5. A curable anaerobic adhesive sealant composition comprising a mixture of (a) a monomer selected from the group consisting of ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A
dimethacrylate, and an acrylate ester corresponding to the formula wherein R represents a radical selected from the group consisting of hydrogen, lower alkyl of 1-4 carbon atoms, inclusive, hydroxy alkyl of 1-4 carbon atoms inclusive, and R' is a radical selected from the group consisting of hydrogen, halogen and lower alkyl of 1-4 carbon atoms; R" is a radical selected from the group consisting of hydrogen, -OH, and m is an integer equal to at least 1; n is an integer equal to at least 1; and p is 0 or 1;
(b) about 1 to about 50 percent by weight of the total composition of an additive selected from the group consisting of wherein R and R' are selected from the group consisting of alkyl, cycloalkyl, aralkyl, alkaryl; and (c) about 0.1 to about 10 percent by weight of the total composition of a peroxy initiator of free-radical polymerization, said composition being curable at room temperature upon substantial exclusion of oxygen.
dimethacrylate, and an acrylate ester corresponding to the formula wherein R represents a radical selected from the group consisting of hydrogen, lower alkyl of 1-4 carbon atoms, inclusive, hydroxy alkyl of 1-4 carbon atoms inclusive, and R' is a radical selected from the group consisting of hydrogen, halogen and lower alkyl of 1-4 carbon atoms; R" is a radical selected from the group consisting of hydrogen, -OH, and m is an integer equal to at least 1; n is an integer equal to at least 1; and p is 0 or 1;
(b) about 1 to about 50 percent by weight of the total composition of an additive selected from the group consisting of wherein R and R' are selected from the group consisting of alkyl, cycloalkyl, aralkyl, alkaryl; and (c) about 0.1 to about 10 percent by weight of the total composition of a peroxy initiator of free-radical polymerization, said composition being curable at room temperature upon substantial exclusion of oxygen.
6. The composition of Claim 5 wherein the monomer is ethoxylated bisphenol A dimethacrylate.
7. The composition of Claim 5 wherein the monomer is polyethylene glycol dimethacrylate.
8. The composition of Claim 5 wherein the additive is
9. The composition of Claim 5 wherein the initiator is cumene hydroperoxide.
10. A process for providing between close-fitting, abutting surfaces, a seal having improved thermal properties comprising applying the composition of Claim 1 to either of such surfaces, placing the surfaces in abutting relationship and allowing the composition to cure by application of moderate heat.
11. A process for providing between close-fitting, abutting surfaces, a seal having improved thermal properties comprising applying the composition of Claim 5 to either of such surfaces, placing the surfaces in abutting relationship and allowing the composition to cure.
12. The composition of Claim 5 which additionally contains about 0.1 to about 5 percent by weight of the total composition of an accelerator of anaerobic polymerization.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US51360974A | 1974-10-10 | 1974-10-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1065096A true CA1065096A (en) | 1979-10-23 |
Family
ID=24043964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA236,691A Expired CA1065096A (en) | 1974-10-10 | 1975-09-30 | Thermally resistant curable compositions |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5913555B2 (en) |
| AU (1) | AU8547775A (en) |
| CA (1) | CA1065096A (en) |
| DE (1) | DE2545555A1 (en) |
| FR (1) | FR2287476A1 (en) |
| GB (1) | GB1528626A (en) |
| IT (1) | IT1047814B (en) |
| SE (1) | SE416478B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX150395A (en) * | 1978-05-22 | 1984-04-30 | Felt Products Mfg Co | IMPROVED ANAEROBICALLY CURABLE SHUTTER COMPOSITION |
| JPS57202312A (en) * | 1981-06-09 | 1982-12-11 | Ube Ind Ltd | N-substituted maleimide copolymer |
| JPS61291667A (en) * | 1985-06-19 | 1986-12-22 | Nippon Shokubai Kagaku Kogyo Co Ltd | Anaerobic adhesive composition |
| JPS61293277A (en) * | 1985-06-21 | 1986-12-24 | Nippon Shokubai Kagaku Kogyo Co Ltd | Anaerobic adhesive composition |
| JPS6210179A (en) * | 1985-07-09 | 1987-01-19 | Nippon Shokubai Kagaku Kogyo Co Ltd | Anaerobic adhesive composition |
| FR2605636B1 (en) * | 1986-10-24 | 1989-02-24 | Rhone Poulenc Chimie | DIAMINE-FREE IMIDE GROUP POLYMERS AND PROCESSES FOR THEIR PREPARATION |
| JPS63251255A (en) * | 1987-04-08 | 1988-10-18 | Tdk Corp | Thermal head |
| DE4406858A1 (en) * | 1994-03-02 | 1995-09-07 | Thera Ges Fuer Patente | Prepolymers and free-radically polymerizable preparations made therefrom and processes for their preparation |
| JP3995490B2 (en) | 2002-02-05 | 2007-10-24 | ミネベア株式会社 | Pivot assembly and manufacturing method thereof |
| DE102014102311A1 (en) | 2014-02-21 | 2015-08-27 | Ebm-Papst St. Georgen Gmbh & Co. Kg | Fan with a paddle wheel |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3041322A (en) * | 1959-07-20 | 1962-06-26 | Vernon K Krieble | Anaerobic curing compositions containing acrylic acid diesters |
-
1975
- 1975-09-30 CA CA236,691A patent/CA1065096A/en not_active Expired
- 1975-10-07 AU AU85477/75A patent/AU8547775A/en not_active Expired
- 1975-10-08 SE SE7511286A patent/SE416478B/en unknown
- 1975-10-09 FR FR7530917A patent/FR2287476A1/en active Granted
- 1975-10-10 DE DE19752545555 patent/DE2545555A1/en not_active Ceased
- 1975-10-10 IT IT51732/75A patent/IT1047814B/en active
- 1975-10-10 GB GB41608/75A patent/GB1528626A/en not_active Expired
- 1975-10-11 JP JP50122835A patent/JPS5913555B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| SE7511286L (en) | 1976-04-12 |
| AU8547775A (en) | 1977-04-21 |
| JPS51125185A (en) | 1976-11-01 |
| SE416478B (en) | 1981-01-05 |
| JPS5913555B2 (en) | 1984-03-30 |
| IT1047814B (en) | 1980-10-20 |
| GB1528626A (en) | 1978-10-18 |
| FR2287476A1 (en) | 1976-05-07 |
| DE2545555A1 (en) | 1976-04-22 |
| FR2287476B1 (en) | 1981-08-07 |
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