CA1161586A

CA1161586A - Anaerobically curing rubber adhesive compositions

Info

Publication number: CA1161586A
Application number: CA000360082A
Authority: CA
Inventors: James P. Moran, Jr.; Barbara B. Logvin; Frederick F. Newberth
Original assignee: Henkel Loctite Corp
Current assignee: Henkel Loctite Corp
Priority date: 1979-10-19
Filing date: 1980-09-11
Publication date: 1984-01-31
Also published as: DE3039323C2; GB2060669B; IT8049832A0; CH656888A5; GB2060669A; SE8007228L; AU526311B2; IT1144012B; ES8202858A1; AU6298680A; BR8006239A; JPS5665065A; DE3039323A1; FR2467875B1; ES495958A0; NL8005771A; FR2467875A1

Abstract

ANAEROBICALLY CURING RUBBER ADHESIVE COMPOSITIONS
ABSTRACT OF THE DISCLOSURE
There is provided a rubber adhesive composition which is cold vulcanizable and comprises a rubber copolymer and an anaerobic monomer. The polymerized product possesses rubberlike properties. Such compositions are useful in the form of a sheet, tape, ribbon or latex, are solvent and pressure resistant and are used for sealing, gaskets, adhe-sives and as support members. The formed products may be coated with a thin polymeric layer.

Description

111~1586 ~ ~

u~re~ ' ~l~, I ~naerobically ~&~ adhesives compositions are known and their uses have become prosressively moxe important in ¦ industry 25 sealants, gaskets and for their adhesive properties.
I Anaero~ic sealants and adhesives are conventionally i applied i~ a form from w~ter-like to light-weight grease consistency. The c~mposition in this form "wets" the surface to be bonded.
There are disadvantages to the conventional anaerobic compositions presently on the market for certain uses thereof.
The areas of application of anaerobic compositions can be vastly increased if the composition is in a form having solid characteristics. In addition many areas of a,~plication, such as gaskets, requires that the polymerized (cured) compositionb-e resistant to sol~ents and retzin flexibility.
Synthetic rubbers have many of these desired properties ~ut their use is limited due to the relatively drastic means necessary to cure rubber, such as, hiSh temperatures or ! irradiation.
I This invention combines rubber technology and , anaerobic technology to obtain a rubber composition which is ¦l, curable under anaerobic conditions.
, An anaerobic system is usually defined as a system which remains stable in its compounded form in the presence of oxygen, but which polymerize5 to a higher polymeric state in the absence of oxygen. This, in effect, means that the presence ~f oxygen hinders or delays polymerization (curing).
I Preferably anaero~ic curing occurs at ambient temperatures; however, the rate of polymerization is a function ! , i ~1 'L16~586 I ~

of the monomer, initiator, and whether or not i~hi~itors and/or accelerators are present. Thus, the term anaerobic curing, has . been and is used to refer to p~lymerization that occur~ also at higher than ambient temperatures, the prime factor being t~at the-cuxing is inhi~itive ~y the presence of ox~gen but takes p~ace in its a~sence or is reduced concentration of oxygen.
Elevated temperatures and/or metals will also accelerate the pol~meriza~i~n.

~UMMARY OF THE INV~NTION
~ccording to the present invention, there is provided anaerobically curing Tu~ber compositions which can be applied preferably fr~m or as sheets, tapes and the like and which, when cured( ha~e rub~er an~ flexible characteristics.
For convenience *he curing process of the compositions of this invention will be termed "cold vulcanization" an~ is defined as a process of curing, by anaerobic means, of liquid .
long-chain segmPnts or un~ulcanized sum into polymeric material ¦ of high m~l~cular weight ~aving appropriate values of crosslink density to secuxe the rubberlike properties. The rub~erlike properties (ru~er elasticity) are all those properties from a 20 ¦1. high elastic response to a tough flexi~le material of high modules. A definition of ~ubber elasticity is found i~
F.W. Billmeyer's Textbook o~ Polymer Science (Jo~n WilPy & Sons, ~our*h Printing, 1966) t p. 189.
The composition o~ this invention inc~udes a syn*he*ic

2~ ~ubber composition in c~mbination-wi'h one or more anaerobic resins, ~ne or more initiators, an acceleratox and an inhibitor.
The synthetic rub~er composition may also oontain ~illers such as titanium dioxide, glass, nylon fi~ers and/or Teflon.

- 2 =~

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! In one embodiment of this invention the anaerobically curing rubber composition is formed into a tape or ribbon and may be coated with nylon or another polymer. A tape or ri~bon is defined as an article of manufacture in which the width is , less than the elongated d~mension.
In general the synthetic rubber has a molecular weight of about ~0,000 to 500,000 and is present in a range from about 30 to about 80% by weight based on the total weig~t of the total . composition. The anaerobic monomer, which must be soluble or completely miscible with the synthetic rubber is present in a range of from about 70 to about 20% by weight based on the total weight of the resin.
Pillers, when present, are in the range of from about 5 to about 20% by weight of titanium dioxide, glass ar,dJor nylon fibers and from about 0% to about 10~ by weight of Teflon.
~oth weights are ~ased on the total weight of synthetic rubber. .
One or more initiator, in a total amount in the range of about 0.1 to about 7% b~ weight of the weight OI the anaerobic monomer is incorporated into the composition.
Accelerators, when present, are in the range of about ¦ 0.1 to about 7% by weight.
i Inhibitors are present in the range of about 2~ to about 1000 ppm DESCRIPTION OF T~E INVENTION AND ITS PREPERR~D ~MBODIMRNTS
The present invention relates to compositions which when cured anaero~ically attain rubberlike properties.
As used in this invention, the term anaerobic monomer is a monomer having at least one end preferably two, polymer-(~ y ~L16~5~6 ~ zable acrylate ester moieties, normally at the ends of a back-¦ ! ~one which.will pol~merize or cure in the presence of an initiator upon the substantial exclusion of oxygen or air.
One of the most preferred groups of anaexo~ic monomers, , which can be used in this invention, are the polyacrylates esters ¦ which have the following general formula~ .
~2c = c c o [ (c~21 ~ J c = c~2 wherein Rl represents a radical selected from the group consist-ing of hydrogen, lower alkyl of from one to about four carbon atoms, hydroxyalkyl of from one to about four carbon atoms, ' and ~ O
-- CH2 - 0 -- C ~ CH2 ~
. R

wherein R is a radical selected from the group consisting of hydrogen, halogen and lower alkyl of from one to about four -carbon atoms; R is a radical selected ~rom the group consisting o~ hydrogen, hydroxyl and . O

¦- O - C - C = CH~
. R2 m is an integer equal to at least 1, e.g. from l to about 15 or I higher, and preferably from 1 to about 8 inclusi~e; n is an 'i integer equal to at least l, e.g. 1 to about 2~ or more; and p ~s one of the following: t lo .

- 4 ~ I

11615~3fi j 1 ~he polyacrylate esters utilized in accordance with the invention and corresponding to the above general formula , are exempli ied by but not restricted to the ollowing materials:
, di, tri- and tetramethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, polyethylene glycol dimethacrylate, di(pentamethylene glycol~dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol di-(chloroacrylate), diglycerol diacrylate, diglycerol tetramethacrylate r tetramethylene dimethacrylate, ethylene dimethacrylate, meopentyl glycol diacrylate, trimethylol propane triacrylate, the reaction product of hydrogenated Bisphenol A with 2,4-tolylene diisocyanate and 2-hydroxy-me~hacrylate, and the reaction product of methylene-diphenylis~cyanate and 2-hydroxy-methac.rylate or 3-hydroxy-methacrylzte. The foregoing monomers need not be in the pure state, but may comprise commercial grades in which inibitors or stabilizers, such ~s quinones are included. .
i ~50noacryl2te esters, particularly those esters in . which the non-acrylate portion of the ester contains a hydroxyl, ¦ mercapto, or amino group, or other reactive substitutent which j serves as a site for potential cross-lin~ing with itself and/or the synthetic rubber compound~
The choice of anaerobic monomer that can be utilized in this invention is dependent upon the particular synthetic rubber selected. The anaerobic monomer must be soluble or 2~ ! completely miscible with the synthetic rubber composition.
Solubility or miscibility of monomer in the rubber may be easily determined as foll~ws: (1) i the synthetic rubber ~, _s a liquid and the anaerobic monomer is a liquid, then visual 1.
i .

5~

i inspection would show solubility or mQscibility; (2) if the 1- synthetic rub~er has solid characteristics then after mixing the ¦ monomer with the rubbex, the compounded material is placed on 1, paper. An oily wet spot appears on the paper if the monomer 5 ' is not soluble in or completelv miscible with the rubbex.
i The term copolymer as used in this invention are those ¦ commonly ~nDwn synthetic ru~ers copolymers which are preferably polar and of sufficient molecular weight so that its ~iscosity I is sufficiently high to form stable compositions with the i monomers. The preferred copolymers have terminal and/or a I pendant vinyl or reactive sites for possible réactions with , the anaerobic monomers and are preferably unvulcanized gums.
¦, Examples of copolymers or rubbers which may be ¦~ utilized in this invention are acrylonitrile/butadiene copolymers 15 i having reactive terminal groups such as carboxy, mercapto or j amino; polybutadiene; polyisopropene; butadiene/styrene~ poly-urethanes and acrylonitrile/butadiene/styrene.
! - The acrylonitrile/butadiene is available from ! B.F. Goodrich Co. under théir trade name Hycar and the preferred copolymer has an average molecular weight in ~he range of ~rom about 50,000 to about 500,000.
The butadiene-styrene copolymer is designated SBR
¦l and generally has a ratio o~ butadiene to styrene of approximatel !
78:22.
The acrylonitrile/butadiene/styrene copolymers . ., preferably have an average molecular weight of from about 5,000 to about 100,000 and contains from about 1~ percent to about 3j percent acrylonitrile and from about 15 percent to about !

i ~i615~36 ~' ' , 35 percent butadiene.
¦ ~he catalyst or initiator for this system is composed . ' of a peroxy compound and a co-initiator.
I The preferred peroxy initiators are the hydroperoxy ini~iator and most prefera~ly the organic hydroperoxides which have the formula R OOH, w~erein R generally is a hydrocarbon radical containing up to about 18 carbon atoms, preferably an alkyl, aryl or aralkyl radical containing from one to about 12 carbon atoms. Typical examples of such hydroperoxides are cumene hydroperoxide, tertiary butyl hydroperoxide and methyl ethyl ketone hydroperoxide. However, other peroxy initiators, such' as hydrogen peroxide, dihydroperoxides or materials such as certain organic peroxides or peresters which hydrolyze or decompose to form hydroperoxides and di-hydroperoxides and di-hydroperoxides frequently can be used. Examples of such peroxyinitiator~ are benzoyl peroxide and 2,5-dimeth~lhexyl-2,5-dihydro peroxide. These compounds are known in the literature.
¦ Coinitiators which are useful in the present invention I are the known hydrazine derivatives that are capable of , initiating free radical polymerizations at temperatur~s below ! about 100 C., and especially compounds having the formula Rl ~ / - R2 ¦~ wherein R may be selected trDm the Eollowlng radicals:
alkyl, preferably lower alkyl containing 1-6 carbon atoms, either straight chain or branched, more preferably methyl, ethyl or sopropyl: cycloalkyl containing up to about 8 carbon atoms;

, ~.16~l586 alkenyl con~aining up to ab~ut lO, preferably 2-~ car~on atoms;
eycloalkenyl containing up to 10, prefera~ly up to about 6, carbon atoms; aryl, including halo-suos.ituted, aryl, hydroxy-substituted aryl! nitro-su~stituted aryl, and aryl substituted ~y lower alXyl or alkox~ yro~ps cont2ining one to a~out ~ ear~on atoms. R may be hydrogen or any one of the radicals specified for Rl and in addition may ~e an amino or substituted amino group, 0~ 2 carb~nyl group to whieh is eonneeted an ~nreaetive group such as a lower alkyl containing from one to abDut ~ earbo~
atoms.
Representative eompounds according to the above for~ula include, but are ~ot limited t~ aeetyl-2-ph~nylhydrazine/ 1-acetyl-2 ~-tolyl)hydrazine, l-~enzoyl-2-phenylhydrazine, 1-(l'l',l'-trifluoro-acetyl~-~-2phenylhydrazine, l,~-diphenyl-1~ eax~ohydrazid~, l-formyl-2-~henylhydrazine, 1-acetyl-2-(p-bromo-phenyl~hydr,azine, l-aeetyl-2-(p-nitr~phenyl~hydrazine, l-aeetyl .
2-(p-methoxyphenyl)hydrazine, 1-acetyl-2-2(2'phenylethyl~-j hyd~azine and l-aeetyl-2-me$hylhydrazine.
I ~fficacy of the accelerators of this invention ap~ears to require the presence of a prot~n vn eaeh of the ni~rogen at~ms, 1 ~ut no more than one proton on each ni$rogen atom. If this ! criterion ~s met, the p~ecise nature of the ~ groups does not appear to be critical, provided, ~f course, ~hat the ~ sroups may not be selected so as to interfere substantially with the st~rage 2~ properties of the adhesive eomposition Dr with ~he per~rmanee ~f *he accelerator foI its-in*ended purpose. ~hus, the selection o~ specific ~ groups and com~inati~ns thereof is ~eeme~ *o ~e ,a n~tter o~ e~perime~tation and choice It ~qll, of course, be ,.

Ii . .
appreciated by those skilled in the art that optimum selection jDf R groups may depend upon the curable ester m~nomer or mixture 'of monomers, as well as the initiator or optional co-accelerator lused.
i ~he accelerators may ~e used in concentrations from . ah~ut D. 001 to about 10 percent or more ~y weight based on the total composition. Below t~is lower limit, little effect will be o~served. ~he upper limit is not critical since significant Improvement usually will not be found above concentrations of about ~ by weight. As a practical matter, a concentration range o~ 0.1-2.0% by weight will provide optim~,l o~er-all bene~it and this range is therefore especially preferred.
¦ Accelerators are also frequently used in the compos-¦itions of this invention. Examples include organic amides such 1~ las formamide and succinimide and the likej tertiary amines such ~as tri~utyl amine and triethylamine and the like, aromatic .
tertiary amines such as dimethyl p-toluidine and the like; and ' organic sulfimides, such as ~enzoic sulfimide and the like.
I~Accelerators when present are in the range of from about 0.1 2D t~ a~out 7 % by weight, and pre~era~ly between 2 and 3 ~ by ! weight.
Sta~ilizers or inhibitors utilized in this invention incl~de ~enzoquinone, naphthaquinone, hydr~quinones, monomethyl ¦ ether of hydroguinone, sterically hindered phenols and the like.
2~ I ~he concentration of inhi~i~ors is in the range of from ak~ut ; ~ ZS to a~ou. 1000 ppm.

I' . .

g _ .

~L6~6 The products of this invention can contain any other ingredient which does not materially change the anaerobic properties or interfere with the processing of the compos-itions. Examples of such additional ingredients are filters, such as titanium dioxide, Teflo ~ glass, nylon fibers and the like which for convenience are usually added to the copolymer; coloring agents, plasticizers, and the like.
The compositions or products of this invention can be prepared in a number of ways, as for example, in the form of films, tapes, sheets or coated on a releasable backing. The composition may be extruded, rolled or deposited from a solution, slurry or latex, depending upon the use intended for the product and the physical properties of the compounded formulation. The solution, slurry or latex may be utilized "as is" without an intermediate deposition on another backing, such as a paint.
The products formed from the compositions of this invention have particular utility when applied, as a tape, to threaded members such as pipe fittings. In this app-lication it replaces the presently used Teflon tape and gives superior results as to sealing and is resistant to the effects of pressure and solvents. In curing, the product will retain its flexible characteristic and if applied to threaded members, such as pipe threads, the cured product will provide both a sealing and locking function.
For convenience in storage and use, the products of the compositions of this invention may be coated with a thin layer of a polymeric material, such as nylon. The polymeric coating while sufficiently thick to permit rolling the tape and preventing its sticking to itself it is still thin enough to permit air to permeate through the coating to the tape.
When coated with a polymeric coating, the coating material should be soluble in alcohol and is usually deposited on the unvulcanized polymeric composition from an aleoholie solution preferably methanol. Nylon 6-12 (DuPonts Elvamide~ 8061) and nylon 12-12 (Vestamid~ X1874, X2191 and X2302) have been utilized for eoatings.
The produets of the invention diselosed herein, regard-less of whether in their natural or preapplied form, are shelf stable items eapable of withstanding normal storage and shipping eonditions. They will not polymerize (eure) as long as maintained in reasonably thin sheets (such as about one half ineh or less) and in contaet with air or other sup-plies of oxygen. When eonfined between non-porous surfaees or otherwise placed in an oxygen-free atmospher, euring of the eomposition oceurs. The eured product has the eharae-teristics of a vuleanized rubber and may eonsist of the reaction product of the copolymer and monomer, the eomplete intermeshing of the eopolymer in the polymerized monomer or a combination of both.
The polymerized product, which has the charaeteristies of a vulcanized rubber is distinguishable from the unpoly-merized reaction produets by its extraetibility. The unpolymerized reaction products are soluble in organie solvents whereas the polymerized produet is insoluble in or non-extraetible by organie solvents. The polymerized produet is at least 75~ and preferably 80~ non-extraetible.
The product form after curing retains its flexibility, ~6~S~g~

forms a seal which withstands 1500 to 2500 psi pressure and is ,resistant to solvents. These characteristics are retained over . la wide temperatuIe range of fr~m about -6~ to a~out 400~ F.
¦ While curing will normally take place at room , temperature, the time required to. achieve curing can be shortened ¦by su~je~ting the assembly containing the composition to moderate temperatures, such as from about 100~ F. to ab~ut 200~ F.
The sodium salt of ethylenediamine-tetraacetate, when used in the formulation, may be added either to the monomer composition or to the copolymer-monomer composition.
EXAMPLES
The following Examples are given to demonstrate typical compositions within the scope of the in~ention discl~sed herein, and methods of preparation and use of these compositions. The Examples are not intended to be limitations upon the invention.
~nless stat~ed to the contrary, all ratios and percentages in the Examples are on a weight basis.

An anaerobic curing polymerizable monomer formulation was prepared ~y mixing the ingredients describea in Table 1 in the approximate pr~portion indicated.
i TABLE 1 Ingredient Weight (Gms) I Polyethyleneglycol dimethacrylate 100 (aver2ge molecular weight 330) l-Ace~yl -2- phenylhydrazine 0.~02 ~enzoic sulfimide l.Ç
cumene hydroperoxide 3.0 1,4-p-Naphthaquinone solution 0.2 (100 ppm in methanol) ~'a6~5~6 To a mixture consisting of 50 grams acrylonitrile/
butadiene (Hyca ~ 1492) and 20 grams of titanium dioxide, blended in a Waring blender, was added 25 grams of the mixture of Table I and 1 gram of a solution of sodium ethylenediaminetetraacetate (73.5% methanol, 23% water and

3.5% sodium ethylenediaminetetraacetate).
The resultant mixture was processed in a rubber roll mill until the lumps disappeared and then extruded through a slit die about 20 mil thick. The extruded material was then passed through modified heated chill rolls (only one roll was heated) having a gap approximately 0.003 mils.
The resultant material, which was in a ribbon form about 0.002 to 0.250 inches thick, was applied to a release paper strip and wound on takeup spools.

A copolymer - anaerobic monomer mixture was prepared according to the directions of Example 1.
The resultant mixture was extruded through a slit die about 20 mil thick. The extruded material was then passed through modified heated chill rolls as in Example 1.
On leaving the chill roll (calender rolls) the material was passed through a nylon 6-12 solution (6-7~ nylon 6-12, in methanol) and then through a column of air heated to about 52C. The methanol was evaporated in the heated air process coating the rubber tape with a layer of nylon about 0.5 to 1.0 mil thick and the coated tape was then wound on a paper spool without any paper layer separating the layers of tape.

~ .. ..
~' 6~

i .
To use the tape, the tape is placed on the threads and stretched to break the nylon coating.

E~AMPLE 3 ~ o a mixture co~sisting-of 50 grams acrylonitrile/
, butadiene (Hycar 1492), 19.5 grams of titanium dioxide and 0.5 grams Teflon, blended in a Waring blender was added 30 grams of the mixture of Table 1 and 1.5 grams of a solution of sodium ethylenediaminetetraacetate (73.5~ methanol, 23~ water and 3~5 sodium ethylenediaminetetraacetate).
The resultant mixture was processed in a rubber roll mill until the lumps disappear and then extruded through a sllt die about 20 mil thick. The extruded material was then passed ¦ through a modified heated chill roll as in Example 1.
! On leaving the calender rolls the material was passed I through about a 6 to 7% nylon 6-12 solution (in methanol) and then thro~gh a column of air heated to about 52~ C. The me~hanol .
was e~aporated in the heated air process coating the ru~ber tape i with a layer of nylon.
I ~his tape, in its uncured state has a shelf life in , excess o~ one year. In its cured state, the tape has a percent elongation of 470~, a bulk tensile strength of 981 psi and has an operating range OL from about - 65~ F. to about 400 F.
The tape was applied to a 3~8 inch malleable iron T
joint and torqued to 30 ft:-lbs. and subjected to stress tests ~5 with the following results:
~ a) seals, after immediate assembly, or when cured ~4 and 48 hours, did not leak when subjected to hydraulic ~ressure exceeding 2000 psi;

iL161~36 .
~ b~ no leakage occurred when the assembled T's ~cured jfor 24 hoursl, were su~jected to temperatures of from about . 1 200 F. to about 400 F. for a period of 500 hours, and su~jected to pressures of a~out 1500 psi;
5 , c~ no leakage occurred at pressures to 300.0 psi (after the asse~led T's cured for 24 hoursLt when immersed in the following sol~Pnts, at the te~peratures indicated for eight weeks: transmission fluids L300 F.l; motor oil L300 F.~;
50% glycol/water C270~ F~L; gasoline (180~ F. L and air (188 F.~.
d) several T's (cured for 24 hoursL that have been exp~sed to 95% humidity at 100 F. for 1000 hours showed no leaks after pressuring to 2000 psi.
EXAMP~E 4 ~he mixture and process of Example 1 was repeated utilizing t-butylhydroperoxide in place of cumene hydroperoxide.
~XAMPLE 5 ~ o a mixture of 75 gms acrylonitrile/butadiene (Hycar .
149~) and 20 gms titanium dioxide, blended in a Waring blender was added 25 gms of the mixture of Table 1 and 1 gram of a sodium ethylenediaminetetraacetate solution (73.5% methanol), 2~ water and 3.5~ sodium ethylenediaminetetraacetate~.
The resultant mixture was processed in a rubber roll ¦mill and passed through calender rolls into a film material 0.002 inches in thickness.
25 ¦ ~XAMPLE 6 ¦ 1~ 186 grams of a 20~ Hycar 1492 solution, in methylethyiketone, was added in sequence, ensuring complete solution of a compound or mixture before the addition of the - l!
.

5~6 , I' , subsequent compound or mixture, 40 grams triethyleneglycol-! dimethacrylate; 22.~ grams of an 80% solution, in toluene, a dimethacrylate formed from the reaction product of toluen diisocyanate hydrogenated Bisphenol A and 2-hydroxethylmeth-I, acrylate, and 2.4 gr~ns o~ 2,5 dimethyl-hexyl-2,5-dihydroperoxide.
The temperature throughout the addition was maintained below j40 C.
- ~he resultant solut;on was coated onto a release paper land the sol~ent evaporated leaving a dried uncured film 0.002 to 0.010 inches in thickness. Drying of the film (evaporation ~of solvent), should occur at no higher temperature than ~2' C.
i EXA~LE 7 , Acceptable uncured tape and sheet materials are ~,obtained utllizing the following copolymers and anaerobic monomer ,in the procedure of Examples 1, 2 and/~r ~.

Copol~mer M~nomer .

a~ utadiene/methacrylate polyethyleneglycol-having pendente ~nsaturation dimethacrylate 'b~ acrylonitrile/butadiene lauryl methacrylate c)_ butadiene/styrene tetramethyleneglycol-dimethacrylate d) acryloni'rile/butadeiene 3-hydroxypropylmethacrylate ' ha~ing terminal carboxy groups , e) butadiene/styrene ~D% ~tyrene/20~ pentaethy-lene glycoldimethacrylate butadiene~acrylate/ pentaethyleneglycol methacrylate ' dimethacrylate gl acrylonitrile/butadiene 2-hydr~xyethymethacrylate l: ( i, . .
~he processing of the final product by extrusion, llcalendering or deposition from solution is dependent upon ease ¦ of operation and physical properties of the product. Most Iproducts are a gum or pliable solid which can be extruded without jthe use of an excessive amount of force. Should the product . llbe of a nature that is not easily extrudable, then it can be pxocessed through calender rolls or by deposition from solution.

I'.

= 17 - l

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A cold vulcanizable, rubber composition comprising a) about 30% to about 80% by weight of a copolymer selected from the group consisting of acrylonitrile/
butadiene having an average molecular weight of from about 50,000 to about 500,000 and having terminal or pendent vinyl groups, acrylonitrile/butadiene having terminal, reactive carboxy, mercapto or amino groups, polybutadiene, polyisoprene, acrylonitrile/butadiene/styrenes, and butadiene/styrenes;
b) about 70% to about 20% by weight of an anaerobic monomer which is soluble in or miscible with said copoly-mer, said anaerobic monomer having the general formula wherein R1 represents a radical selected from the group consisting of hydrogen, lower alkyl of from one to about four carbon atoms, hydroxy alkyl of from one to about four carbon atoms, and R2 is a radical selected from the group consisting of hydrogen, halogen, and lower alkyl of from one to about four carbon atoms; R3 is a radical selected from the group consisting of hydrogen hydroxyl and m is an integer equal to at least 1; n is an integer equal to at least 1; and p is one of the following: 0, 1;
c) about 0.1 to about 7% by weight of the weight of said anaerobic monomer of a catalyst system comprising a peroxy initiator selected from the group consisting of hydrogen peroxide, hydroperoxides having the general formula R4OOH wherein R4 is a hydrocarbon radical having 1 to 12 carbon atoms selected from the group consisting of alkyl aryl and aralkyl, peroxides, peresters and dihydro peroxides, and as a co-initiator a hydrazine derivative capable of initiating free radical polymerization at temperatures below about 100°C.;
d) about 0.1 to about 7% by weight of an accelerator;
and e) about 25 to 1000 ppm of a stabilizer, said composition being capable of being polymerized, under anaerobic conditions to a high molecular weight material with vulcanized, rubberlike properties, having at least 65% nonextractable solids.

2. A composition of Claim 1, wherein said copolymer is acrylonitrile/butadiene having terminal or pendent vinyl groups and having an average molecular weight of from about 50,000 to about 500,000.

3. A composition of Claim 2, in which there is a filler in an amount in the range of about 5% to about 20% by weight based on the total weight.

4. A composition of Claim 1, wherein said peroxide initiator is cumene hydroperoxide and said co-initiator is 1-acetyl -2- phenylhydrazine.

5. A composition of Claim 4, wherein the accelerator is selected from the group consisting of organic amides, tertiary alkyl amines, aromatic tertiary amines and organic sulfimide.

6. A composition of Claim 5 wherein the accelerator is an organic sulfimide.

7. A composition of Claim 6 wherein the organic sulfimide is benzoic sulfimide.

8. A composition of Claim 7, wherein said stabilizer is selected from the group consisting of benzoquinone, naph-thaquinone, hydroquinone, nonomethyl ether of hydroquinone and sterically hindered phenols.

9. A composition of Claim 8, wherein the stabilizer is naphthaquinone.

10. A composition of Claim 9, in which the anaerobic monomer is polyethylene glycol dimethacrylate.

11. A composition of Claim 10, wherein said polyethylene-glycol dimethacrylate has an average molecular weight of about 330.

12. A composition of Claim 11, wherein the copolymer is present in the range of about 60 to about 75% by weight.

13. A composition of Claim 12, wherein the anaerobic monomer is present in the range of about 20 to about 50%
by weight.

14. A composition of Claim 13, wherein the filler is selected from the group of titanium dioxide in the range of about 5 to about 20% by weight and polytetrafluoro-ethylene in the range of about 0 to about 10% by weight and said total weight of filler does not exceed about 20%
by weight, said weight being based on the total weight of the composition.

15. A composition of Claim 14, wherein said filler is a mixture of titanium dioxide in the range of about 18 to about 19.5% by weight and polytetrafluoroethylene in the range of about 0.5 to about 2% by weight.

16. A composition of Claim 14, wherein the filler is titanium dioxide in the range of about 18 to about 20% by weight.

17. An article in the form of a ribbon having a thickness in the range of from about 0.002 to about 0.250 inches, for use as a sealant and formed from a cold vulcanizable, rubber composition comprising a) about 30% to about 80% by weight of a copolymer selected from the group consisting of acrylonitrile/
butadiene having an average molecular weight of from about 50,000 to about 500,000 and having terminal or pendent vinyl groups, acrylonitrile/butadiene having terminal, reactive carboxy, mercapto or amino groups, polybutadiene, polyisoprene, acrylonitrile/butadiene/styrenes, and butadiene/styrenes;
b) about 70% to about 20% by weight of an anaerobic monomer which is soluble in or miscible with said copolymer;
c) about 0.1 to about 7% by weight of the weight of said anaerobic monomer of a catalyst system;
d) an accelerator; and e) a stabilizer, said composition being capable of being polymerized, under anaerobic conditions to a high molecular weight material with vulcanized, rubberlike properties, having at least 65%
nonextractable solids.

18. An article according to Claim 17 wherein the anaerobic monomer has the general formula wherein R1 represents a radical selected from the group consisting of hydrogen, lower alkyl of from one to about four carbon atoms, hydroxy alkyl of from one to about four carbon atoms, and R2 is a radical selected from the group consisting of hydrogen, halogen, and lower alkyl of from one to about four carbon atoms; R3 is a radical selected from the group consisting of hydrogen hydroxyl and m is an integer equal to at least 1; n is an integer equal to at least 1; and p is one of the following: 0, 1;
and said copolymer is acrylonitrile/butadiene having terminal or pendant vinyl groups and having an average molecular weight of from about 50,000 to about 500,000.

19. An article according to Claim 18 wherein the catalyst system comprises comprising a peroxy initiator selected from the group consisting of hydrogen peroxide, hydro peroxides having the general formula R4OOH wherein R4 is a hydrocarbon radical having 1 to 12 carbon atoms selected from the group consisting of alkyl aryl and aralkyl, per-oxides, peresters and dihydro peroxides, and as a co-init-iator a hydrazine derivative capable of initiating free radical polymerization at temperatures below about 100°C.

20. An article according to Claim 19 wherein said peroxide initiator is cumene hydroperoxide and said co-initiator is 1-acetyl -2- phenylhydrazine.

21. An article according to Claim 20 wherein the acceler-ator is selected from the group consisting of organic amides, tertiary alkyl amines, aromatic tertiary amines and organic sulfimide and wherein the accelerator is an organic sulfimide.

22. An article according to Claim 21 wherein the organic sulfimide is benzoic sulfimide.

23. An article according to Claim 22 wherein said stabilizer is selected from the group consisting of benzoquinone, naphthaquinone, hydroquinone, nonomethyl ether of hydroquinone and sterically hindered phenols.

24. An article according to Claim 23 wherein the stabilizer is naphthaquinone.

25. An article according to Claim 24 in which the anaerobic monomer is polyethylene glycol dimethacrylate.

26. An article according to Claim 25 wherein said poly-ethylene-glycol dimethacrylate has an average molecular weight of about 330.

27. An article according to Claim 26 wherein the copolymer is present in the range of about 60 to about 75% by weight.

28. An article according to claim 27 wherein the anaerobic monomer is present in the range of about 20 to about 50%
by weight.

29. An article according to Claim 28 wherein the filler is selected from the group of titanium dioxide in the range of about 5 to about 20% by weight and polytetrafluoroethylene in the range of about 0 to about 10% by weight and said total weight of filler does not exceed about 20% by weight, said weight being based on the total weight of the compos-ition and wherein said filler is a mixture of titanium dioxide in the range of about 18 to about 19.5% by weight and polytetrafluoroethylene in the range of about 0.5 to about 2% by weight.

30. An article according to Claim 29 wherein the filler is titanium dioxide in the range of about 18 to about 20 by weight.

31. An article according to Claim 30 in which said ribbon is coated with a polymeric coating in a thickness of from about 0.5 to 1 mil, said coating permitting air to reach the rubber composition.

32. An article according to Claim 31, wherein the poly-meric coating is nylon 6-11.

33. An article according to Claim 17 in the form of a sheet having a thickness in the range of from about .002 to about .015 inches, for use in the preparation of gasketing material or as a support material.

34. An article according to Claim 18 in the form of a sheet having a thickness in the range of from about .002 to about .015 inches, for use in the preparation of gasketing material or as a support material.

35. An article according to Claim 19 in the form of a sheet having a thickness in the range of from about .002 to about .015 inches, for use in the preparation of gasketing material and as a support material.

36. An article according to Claim 20, in the form of a sheet having a thickness in the range of from about .002 to about .015 inches, for use in the preparation of gasketing material and as a support material.

37. An article according to Claim 21, in the form of a sheet having a thickness in the range of from about .002 to about .015 inches, for use in the preparation of gasketing material and as a support material.

38. An article according to Claim 22 in the form of a sheet having a thickness in the range of from about .002 to about .015 inches, for use in the preparation of gasketing material and as a support material.

39. An article according to Claim 23 in the form of a sheet having a thickness in the range of from about .002 to about .015 inches, for use in the preparation of gasketing material and as a support material.

40. An article according to Claim 24, in the form of a sheet having a thickness in the range of from about .002 to about .015 inches, for use in the preparation of gasketing material and as a support material.

41. An article according to Claim 25 in the form of a sheet having a thickness in the range of from about .002 to about .015 inches, for use in the preparation of gasketing material and as a support material.

42. An article according to Claim 26 in the form of a sheet having a thickness in the range of from about .002 to about .015 inches, for use in the preparation of gasketing material and as a support material.

43, An article according to Claim 27 in the form of a sheet having a thickness in the range of from about .002 to about ,015 inches, for use in the preparation of gasketing material and as a support material.

44. An article according to Claim 28 in the form of a sheet having a thickness in the range of from about .002 to about .015 inches, for use in the preparation of gasketing material and as a support material.

45. An article according to Claim 29 in the form of a sheet having a thickness in the range of from about .002 to about .015 inches, for use in the preparation of gasketing material and as a support material.