CA1172792A - Addition polymerizable isocyanate-polyamine anaerobic adhesives - Google Patents
Addition polymerizable isocyanate-polyamine anaerobic adhesivesInfo
- Publication number
- CA1172792A CA1172792A CA000392075A CA392075A CA1172792A CA 1172792 A CA1172792 A CA 1172792A CA 000392075 A CA000392075 A CA 000392075A CA 392075 A CA392075 A CA 392075A CA 1172792 A CA1172792 A CA 1172792A
- Authority
- CA
- Canada
- Prior art keywords
- adhesive
- polyamine
- isocyanate
- bond site
- polymerization initiator
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
This invention is directed to an anaerobic adhesive and to a method of bonding substrates at a bond site. The anaerobic adhesive comprises the reac-tion product of an addition polymerizable ethylenically unsaturated isocyanate and a polyamine, wherein the reaction between the polyamine and the isocyanate has been carried out in the absence of a catalyst; and a polymerization initiator. The method of bonding substrates at a bond site comprises placing the adhe-sives of this invention at the bond site so as to form a bond.
This invention is directed to an anaerobic adhesive and to a method of bonding substrates at a bond site. The anaerobic adhesive comprises the reac-tion product of an addition polymerizable ethylenically unsaturated isocyanate and a polyamine, wherein the reaction between the polyamine and the isocyanate has been carried out in the absence of a catalyst; and a polymerization initiator. The method of bonding substrates at a bond site comprises placing the adhe-sives of this invention at the bond site so as to form a bond.
Description
~1 ~
' i7279~
ADDITION POLYMERIZABLE ISOCYANATE-POLYAMINE
~ ANAEROBIC ADHESIVES
;~ The instant invention relates to novel formu- lations useful as anaerobic adhesives.
~, Anaerobic adhesives are well known and have - been in commercial use for several years. Most anae-robic adhesives are compositions containing a monomer, ; or combination of monomers, which will polymerize under ` certain conditions but not und~r other conditions.
`` Those conditions generally favoring polymerization include the absence of oxygen cmd, i~ a redox initiator is used, the presence of metal ions. Oxygen will act as a polymerization inhibitor, and metal ions will act '`! ~ as polymerization promoters.
':,' . :
~ Consequently, these adhesives find optimal :
.~ use in situations where they are pressed tight between `~ 15 two metal surfaces, such as between the threads of a bolt and nut. The close fit effectively removes oxygen, and the metal surface provides metal ions. This com-bination of conditions causes the adhesive to polymerize, and a strong bond results.
.
,~,;
~, , ~
29,323-F -1-: `
., ,, .. , . , ,, .~ .
!
;' .
! 172792 Practical formula~ions often also contain initiators, accelerators, stabilizers, thickeners, plasticizers, diluents, chela-ting agents and~or adhe-sion promoters.
This invention is directed to an anaerobic adhesive comprising:
(a) The reaction product of:
(1) an addition polymerizable ethylenically unsaturated isocyanate and
' i7279~
ADDITION POLYMERIZABLE ISOCYANATE-POLYAMINE
~ ANAEROBIC ADHESIVES
;~ The instant invention relates to novel formu- lations useful as anaerobic adhesives.
~, Anaerobic adhesives are well known and have - been in commercial use for several years. Most anae-robic adhesives are compositions containing a monomer, ; or combination of monomers, which will polymerize under ` certain conditions but not und~r other conditions.
`` Those conditions generally favoring polymerization include the absence of oxygen cmd, i~ a redox initiator is used, the presence of metal ions. Oxygen will act as a polymerization inhibitor, and metal ions will act '`! ~ as polymerization promoters.
':,' . :
~ Consequently, these adhesives find optimal :
.~ use in situations where they are pressed tight between `~ 15 two metal surfaces, such as between the threads of a bolt and nut. The close fit effectively removes oxygen, and the metal surface provides metal ions. This com-bination of conditions causes the adhesive to polymerize, and a strong bond results.
.
,~,;
~, , ~
29,323-F -1-: `
., ,, .. , . , ,, .~ .
!
;' .
! 172792 Practical formula~ions often also contain initiators, accelerators, stabilizers, thickeners, plasticizers, diluents, chela-ting agents and~or adhe-sion promoters.
This invention is directed to an anaerobic adhesive comprising:
(a) The reaction product of:
(1) an addition polymerizable ethylenically unsaturated isocyanate and
(2) a polyamine, wherein the reaction between the polyamine and the isocyanate has been carried out in the absence of an added catalyst; and (b) a polymerization initiator.
., This invention is also directed to a method of bonding substrates at a bond site comprising placing the above described adhesive at the bond site so as to form a bond.
Suitable isocyanates include any readily addition polymerizable ethylenically unsaturated mono-isocyanate. Examples include vinyl isocyanate and vinylbenzene isocyanate. Preferred are isocyanato acrylates of the formula:
Rlo " . ~, `. "~ H2C-C-C-O-R2-N=C=O
wherein R1 is a hydrogen or a carbon chain of from 1 to :
:
29,323-~ -2-.
i _3_ ll 72~92 5 carbon atoms and R2 is a carbon chain of rom 1 to 7 caxbon atoms. More preferred is 2-isocyanatoethyl acrylate. Most preferred is 2-isocyanatoethyl meth~
acrylate (IEM).
The products of polyamines and isocyanates - have an unusually long shelf life. Unlike other poly-active hydrogen compounds, polyamines react readily with isocyanate moieties, without the ne~d for added catalyst. It is believed that this lack of catalyst in the amine/isocyanate reaction contributes to the long shelf life of these adhesives.
In this conte~t, "polyamine" is intended to mean any polyac~ive hydrogen compound wherein an average greater than one of the active hydrogen moieties is provided by amine groups. A polyamine may generally be illustrated by the formula:
wherein R3 and R4 are each a hydrogen or an organic group and R5 is an organic group. Aminated polyglycols are examples of suitable polyamines. Other examples include ethylenediamine, 1,4-butylenediamine, 1,2- and 1,3-diaminopropane, 1,7-diaminohexane, diaminobenzene and diaminotoluene. Interestingly, experiments with ~` Jeffamine~ polyamines showed that polyamines with higher molecular weight produced adducts with lower viscosity.
~ Trademark ';
, 29,323-F -3-~`
., - ;
In formulating an adhesive according to the ; invention, the isocyanate and polyamine should be reacted in a ratio such that the reactant is capable of being addition polymerized to a substantially solid material. Since suitable polyamines specifically include those compounds having 3 or more active hydrogen moieties per molecule, in defining reaction ratios it is important to specify ~hether equivalent ratios or molecular ratios are being used. It is generally desirable, from a toxicological standpoint, to have a slight excess of active hydrogen moiety. From an adhesive standpoint, it is desirable to have at leas~ 1 molecule of isocyanate for each molecule of polyamine.
An excess of isocyanate is not unduly harmful to the adhesive properties. Preferably, there should be about one equivalent of isocyanate for each equivalent of polyamine.
To be useful as an anaerobic adhesive, the ; isocyanate-polyamine reac~ion product requires a free radical generating means capable of initiating addition polymerization of the reaction product. Any free radical generating means such as a peroxygen compound, an azo compound, a W source and/or a heat source which ~ is suitably employed in the addition polymerization of ;~ 25 ethylenically unsaturated monomers is suitably employed in the practice of this invention. Examples of such free radical generating means and conditions of use are set forth in U.S. Patent No. 3,043,820. Preferred free radical generating means are chemical initiatars, especially the peroxygen compounds such as hydrogen peroxide and the entire class of organic peroxides and ., hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxidP. Such initiators or other free radical 29,323-F -4-:' .1 7~7g2 ~5-generating means are employed in a curing amount, thatis, an amount sufficient to cause the desired polymeri-zation of the reaction product. In ~he case of the hydroperoxides, such are preferably employed in amounts as low as 0.01 weight percent based on the weight of the reaction product, more preferably from 1 to 10 weight percent.
Although not re~uired, it is often preferable to employ an accelerator in combination with the initi-ator. Accelerators are compounds which are believed toassist in the breakdown of the initiator and increase the rate of initiator breakdown. Typical accelerators include tertiary amines such as N,N'-dimethylaniline;
N,N'-dimethyl-p-toluidene; triethylamine; and imides such as benzoic sulfimide. Such accelerators may be used in quantities of 0.01 to 15 percent by weight, based on the weight of initiator, with 0.1 to 7 percent being preferred.
Metal ions are particularly effective and ~0 useful accelerators. While metal ions may be specifi-cally added to the composition, a trace amount will possibly be present as an impurity. In any event, if the a &esive is applied to a metal substrate, the substrate will provide the metal ion source. The application of the adhesive to a metal is particularly advantageous in that it delays the breakdown of the initiator until the adhesive is actually being used.
Exa~ples of effective metal ions include Cu , Fe Cr++ and V++. The metal ions need be present only in catalytic (trace) amounts.
29,323-F -5-Because the aforementioned initiators or combination of initiator and accelerators promote polymerization quite well, it is generally required to employ an inhihitor to prevent premature polymerization.
~xamples of such inhibitors are antioxidants including phenols such as 2,6-di-tert-butyl-4-methylphenol (Ionol~), quinones such as benzoquinone, hydroquinones and other compounds that are known to inhibit addition polymeriza tion of ethylenically unsaturated monomers.
An effective amount of an inhibitor must be added to a useful adhesive formulation. An "effective amount" of an inhibitor is an amount which will prevent premature polymerization of the formulation. Excess inhibitor will cause long cure times. Preferably, the inhibitor is a quinone or a hydroquinone which is preferably employed in an amount in the range from 5 to 10,000 ppm based on the formulation weight, more prefer-ably from 50 to 1,000 ppm~
While a ree-radical initiatox is, in practi-cal terms, a requirement, the other components of theinitiator system are optional. ',ome applications will need none or only some of the other ingredients, but others will require all of them.
The adhesive of the instant invention is 2~ utilizable in a num~er of applications. Uses include adhesives and metal impregnation. Specific applica-tions include locking threaded assemblies, sealing threaded, porous and flanged assemblies, strengthening Trademark 29,323-F -6 ~ 1 72792 cylindrical assemblies and structural bonding. Sub-strates to be bonded include metals, plastics, ceramics and glass. Potential medical applications include tooth and bone cementing sealants.
In applications such as locking the threads of steel bolts and nuts, the oxygen which is present in the adhesive is quickly consumed by the initiator, and the physical barrier of the threads prevents the infu-sion of new oxygen. In other applications or in parti-cular formulations, however, it may be desirable to specifically remove the oxygen from the system. Such removal may be by mechanical means such as a vacuum pump or by chemical means such as an oxygen consuming agent.
Further details of the invention will become apparent in the following examples. In the examples, all percentages are by weight, unless otherwise speci-fied.
PREPARATION OF IEM ADDUCT
IEM-Ethylenediamine Adduct Ethylenediamene (60.0 g, 2 equivalents active hydrogen) and Ionol~ antioxidant (O.15 g) were combined in a reaction vessel. The mixture was at room tempera-ture and IEM (194 g, 1.9 moles) was added over a 1-hour period. The temperature rose to 125C. The final product was a solid which will not melt at 125C.
Trademark 29,323-F -7-~ 1 72~92 Example 1 Shelf Stability of IEM-Poly~ine Adduct Formulation Jeffamine~ D400 polyamine, available from Jefferson Chemical Co., (120.24 g, dried over a molecu-lar sieve3 was blended with 0.11 g Ionol~ inhibitor.
The amine was added dropwise to the IEM at a rate such that the temperature of the reaction mixture did not exceed 50C. An infrared spectograph showed that the reaction was complete. The product was a translucent amber viscous liquid. Accelerated aging tests showed the product to have excellent shelf stability.
The procedure was repeated except that the temperature was not allowed to exceed 30C. The results were slmllar.
The first reaction product was formulated with 2.0 percent cumene hydroperoxide and 500 ppm Ionol~. When placed in an 82C bath, the formulation gelled in 20 minutes.
Comparative Run A
Shelf Stability of IEM-Po~yol Adhesive Formulation IEM (145.2 g) was reacted with tetraethylene glycol (90.0 g) in the presence of 0.235 g zinc octoate and a total of 00227 g Ionol~ and 0.225 g Da~co~ (tri-ethylenediamine). A~ in Example 1, the product was formulated with 2.0 percent cumene hydroperoxide and 500 ppm Ionol~. This formulation gelled in less than 3 minutes when placed in an 82C bath.
~ Trademark -; 29,323-F -8-
., This invention is also directed to a method of bonding substrates at a bond site comprising placing the above described adhesive at the bond site so as to form a bond.
Suitable isocyanates include any readily addition polymerizable ethylenically unsaturated mono-isocyanate. Examples include vinyl isocyanate and vinylbenzene isocyanate. Preferred are isocyanato acrylates of the formula:
Rlo " . ~, `. "~ H2C-C-C-O-R2-N=C=O
wherein R1 is a hydrogen or a carbon chain of from 1 to :
:
29,323-~ -2-.
i _3_ ll 72~92 5 carbon atoms and R2 is a carbon chain of rom 1 to 7 caxbon atoms. More preferred is 2-isocyanatoethyl acrylate. Most preferred is 2-isocyanatoethyl meth~
acrylate (IEM).
The products of polyamines and isocyanates - have an unusually long shelf life. Unlike other poly-active hydrogen compounds, polyamines react readily with isocyanate moieties, without the ne~d for added catalyst. It is believed that this lack of catalyst in the amine/isocyanate reaction contributes to the long shelf life of these adhesives.
In this conte~t, "polyamine" is intended to mean any polyac~ive hydrogen compound wherein an average greater than one of the active hydrogen moieties is provided by amine groups. A polyamine may generally be illustrated by the formula:
wherein R3 and R4 are each a hydrogen or an organic group and R5 is an organic group. Aminated polyglycols are examples of suitable polyamines. Other examples include ethylenediamine, 1,4-butylenediamine, 1,2- and 1,3-diaminopropane, 1,7-diaminohexane, diaminobenzene and diaminotoluene. Interestingly, experiments with ~` Jeffamine~ polyamines showed that polyamines with higher molecular weight produced adducts with lower viscosity.
~ Trademark ';
, 29,323-F -3-~`
., - ;
In formulating an adhesive according to the ; invention, the isocyanate and polyamine should be reacted in a ratio such that the reactant is capable of being addition polymerized to a substantially solid material. Since suitable polyamines specifically include those compounds having 3 or more active hydrogen moieties per molecule, in defining reaction ratios it is important to specify ~hether equivalent ratios or molecular ratios are being used. It is generally desirable, from a toxicological standpoint, to have a slight excess of active hydrogen moiety. From an adhesive standpoint, it is desirable to have at leas~ 1 molecule of isocyanate for each molecule of polyamine.
An excess of isocyanate is not unduly harmful to the adhesive properties. Preferably, there should be about one equivalent of isocyanate for each equivalent of polyamine.
To be useful as an anaerobic adhesive, the ; isocyanate-polyamine reac~ion product requires a free radical generating means capable of initiating addition polymerization of the reaction product. Any free radical generating means such as a peroxygen compound, an azo compound, a W source and/or a heat source which ~ is suitably employed in the addition polymerization of ;~ 25 ethylenically unsaturated monomers is suitably employed in the practice of this invention. Examples of such free radical generating means and conditions of use are set forth in U.S. Patent No. 3,043,820. Preferred free radical generating means are chemical initiatars, especially the peroxygen compounds such as hydrogen peroxide and the entire class of organic peroxides and ., hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxidP. Such initiators or other free radical 29,323-F -4-:' .1 7~7g2 ~5-generating means are employed in a curing amount, thatis, an amount sufficient to cause the desired polymeri-zation of the reaction product. In ~he case of the hydroperoxides, such are preferably employed in amounts as low as 0.01 weight percent based on the weight of the reaction product, more preferably from 1 to 10 weight percent.
Although not re~uired, it is often preferable to employ an accelerator in combination with the initi-ator. Accelerators are compounds which are believed toassist in the breakdown of the initiator and increase the rate of initiator breakdown. Typical accelerators include tertiary amines such as N,N'-dimethylaniline;
N,N'-dimethyl-p-toluidene; triethylamine; and imides such as benzoic sulfimide. Such accelerators may be used in quantities of 0.01 to 15 percent by weight, based on the weight of initiator, with 0.1 to 7 percent being preferred.
Metal ions are particularly effective and ~0 useful accelerators. While metal ions may be specifi-cally added to the composition, a trace amount will possibly be present as an impurity. In any event, if the a &esive is applied to a metal substrate, the substrate will provide the metal ion source. The application of the adhesive to a metal is particularly advantageous in that it delays the breakdown of the initiator until the adhesive is actually being used.
Exa~ples of effective metal ions include Cu , Fe Cr++ and V++. The metal ions need be present only in catalytic (trace) amounts.
29,323-F -5-Because the aforementioned initiators or combination of initiator and accelerators promote polymerization quite well, it is generally required to employ an inhihitor to prevent premature polymerization.
~xamples of such inhibitors are antioxidants including phenols such as 2,6-di-tert-butyl-4-methylphenol (Ionol~), quinones such as benzoquinone, hydroquinones and other compounds that are known to inhibit addition polymeriza tion of ethylenically unsaturated monomers.
An effective amount of an inhibitor must be added to a useful adhesive formulation. An "effective amount" of an inhibitor is an amount which will prevent premature polymerization of the formulation. Excess inhibitor will cause long cure times. Preferably, the inhibitor is a quinone or a hydroquinone which is preferably employed in an amount in the range from 5 to 10,000 ppm based on the formulation weight, more prefer-ably from 50 to 1,000 ppm~
While a ree-radical initiatox is, in practi-cal terms, a requirement, the other components of theinitiator system are optional. ',ome applications will need none or only some of the other ingredients, but others will require all of them.
The adhesive of the instant invention is 2~ utilizable in a num~er of applications. Uses include adhesives and metal impregnation. Specific applica-tions include locking threaded assemblies, sealing threaded, porous and flanged assemblies, strengthening Trademark 29,323-F -6 ~ 1 72792 cylindrical assemblies and structural bonding. Sub-strates to be bonded include metals, plastics, ceramics and glass. Potential medical applications include tooth and bone cementing sealants.
In applications such as locking the threads of steel bolts and nuts, the oxygen which is present in the adhesive is quickly consumed by the initiator, and the physical barrier of the threads prevents the infu-sion of new oxygen. In other applications or in parti-cular formulations, however, it may be desirable to specifically remove the oxygen from the system. Such removal may be by mechanical means such as a vacuum pump or by chemical means such as an oxygen consuming agent.
Further details of the invention will become apparent in the following examples. In the examples, all percentages are by weight, unless otherwise speci-fied.
PREPARATION OF IEM ADDUCT
IEM-Ethylenediamine Adduct Ethylenediamene (60.0 g, 2 equivalents active hydrogen) and Ionol~ antioxidant (O.15 g) were combined in a reaction vessel. The mixture was at room tempera-ture and IEM (194 g, 1.9 moles) was added over a 1-hour period. The temperature rose to 125C. The final product was a solid which will not melt at 125C.
Trademark 29,323-F -7-~ 1 72~92 Example 1 Shelf Stability of IEM-Poly~ine Adduct Formulation Jeffamine~ D400 polyamine, available from Jefferson Chemical Co., (120.24 g, dried over a molecu-lar sieve3 was blended with 0.11 g Ionol~ inhibitor.
The amine was added dropwise to the IEM at a rate such that the temperature of the reaction mixture did not exceed 50C. An infrared spectograph showed that the reaction was complete. The product was a translucent amber viscous liquid. Accelerated aging tests showed the product to have excellent shelf stability.
The procedure was repeated except that the temperature was not allowed to exceed 30C. The results were slmllar.
The first reaction product was formulated with 2.0 percent cumene hydroperoxide and 500 ppm Ionol~. When placed in an 82C bath, the formulation gelled in 20 minutes.
Comparative Run A
Shelf Stability of IEM-Po~yol Adhesive Formulation IEM (145.2 g) was reacted with tetraethylene glycol (90.0 g) in the presence of 0.235 g zinc octoate and a total of 00227 g Ionol~ and 0.225 g Da~co~ (tri-ethylenediamine). A~ in Example 1, the product was formulated with 2.0 percent cumene hydroperoxide and 500 ppm Ionol~. This formulation gelled in less than 3 minutes when placed in an 82C bath.
~ Trademark -; 29,323-F -8-
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An anaerobic adhesive comprising:
(a) the reaction product of:
(1) an addition polymerizable ethylenically unsaturated isocyanate and (2) a polyamine, wherein the reaction between the polyamine and the isocyanate has been carried out in the absence of an added catalyst; and (b) a polymerization initiator.
(a) the reaction product of:
(1) an addition polymerizable ethylenically unsaturated isocyanate and (2) a polyamine, wherein the reaction between the polyamine and the isocyanate has been carried out in the absence of an added catalyst; and (b) a polymerization initiator.
2. The adhesive of Claim 1 wherein the ethylenically unsaturated isocyanate has the formula:
wherein R1 is a hydrogen or a carbon chain of from 1 to 5 carbon atoms and R2 is a carbon chain of from 1 to 7 carbon atoms.
wherein R1 is a hydrogen or a carbon chain of from 1 to 5 carbon atoms and R2 is a carbon chain of from 1 to 7 carbon atoms.
3. The adhesive of Claim 2 wherein the ethylenically unsaturated isocyanate is 2-isocyanato-ethyl methacrylate or 2-isocyanatoethyl acrylate.
4. The adhesive of Claim 1 wherein the polymerization initiator is a free-radical initiator.
5. The adhesive of Claim 4 wherein the polymerization initiator is a peroxygen compound.
6. The adhesive of Claim 4 wherein the polymerization initiator is an organic peroxide or hydroperoxide.
7. A method of bonding substrates at a bond site comprising placing the adhesive of Claim 1 at the bond site so as to form a bond.
8. The method of Claim 7 including the additional step of removing oxygen from the bond site.
9. The method of Claim 7 including the additional step of applying pressure to the bond site.
29,323-F -10-
29,323-F -10-
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US21599780A | 1980-12-12 | 1980-12-12 | |
| US215,997 | 1980-12-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1172792A true CA1172792A (en) | 1984-08-14 |
Family
ID=22805245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000392075A Expired CA1172792A (en) | 1980-12-12 | 1981-12-11 | Addition polymerizable isocyanate-polyamine anaerobic adhesives |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1172792A (en) |
-
1981
- 1981-12-11 CA CA000392075A patent/CA1172792A/en not_active Expired
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