CA1285347C - Grease compatible extended polyurethanes - Google Patents
Grease compatible extended polyurethanesInfo
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- CA1285347C CA1285347C CA000482356A CA482356A CA1285347C CA 1285347 C CA1285347 C CA 1285347C CA 000482356 A CA000482356 A CA 000482356A CA 482356 A CA482356 A CA 482356A CA 1285347 C CA1285347 C CA 1285347C
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- cyclic olefin
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Abstract
ABSTRACT
A plasticized polyurethane gel system comprising the reaction product of an isocyanate compound and a polyol in the presence of a plasticizer compound having a total solubility parameter of between about 9.1 and 10.1.
Said polyurethane systems are cured, crosslinked, non-spewing, grease compatible, and reenterable. This extended polyurethane is further characterized as having superior insulating properties so that it can be used for repairing, encapsulating or reclaiming electrical or telecommunication cables as well as for hard volume encapsulants or general elastomer use.
A plasticized polyurethane gel system comprising the reaction product of an isocyanate compound and a polyol in the presence of a plasticizer compound having a total solubility parameter of between about 9.1 and 10.1.
Said polyurethane systems are cured, crosslinked, non-spewing, grease compatible, and reenterable. This extended polyurethane is further characterized as having superior insulating properties so that it can be used for repairing, encapsulating or reclaiming electrical or telecommunication cables as well as for hard volume encapsulants or general elastomer use.
Description
Technical Field The invention relates to polyurethanes which contain novel pla~ticiæers and which are extended with cyclic olefin~. The~e compositions are for~ulated as grease ~5compatible, non-spewing materials foruse in re~laiming~
encapsulating, or sealing telecommunlca~ion or electrical devices such as cable, as well a~ for other uses.
Background Art It is well-known in the art to e%tend polymers su~h as polyurethanes. ~hi~ extended ~ater~l ~ill then be designated for use fn a de~ired area of utility. Typical of ~uc~ extendinc agents is ~i~eral o~l, su~h mineral oil 25extended poIyurethane~ being disclosed i~ ~.S. Patent Nos~ 3,714,110 and 3,747,037.
It has also been de er~ined that the mineral oil extended polyurethane i5 u3eful in the reclamatlon and protection of insulated electrical ~evices. Such devices ~ay, for example, be underground telephone cable~ which are exposed to fluid contami~ants. ~hese conta~nant~ can seriously impair the electri~al a~d ~echanical prcperties of such a device~ The protectant ~aterial is pu~ped into ~he cable to remove water that has penetrated into lnterior free , :
i3~7
encapsulating, or sealing telecommunlca~ion or electrical devices such as cable, as well a~ for other uses.
Background Art It is well-known in the art to e%tend polymers su~h as polyurethanes. ~hi~ extended ~ater~l ~ill then be designated for use fn a de~ired area of utility. Typical of ~uc~ extendinc agents is ~i~eral o~l, su~h mineral oil 25extended poIyurethane~ being disclosed i~ ~.S. Patent Nos~ 3,714,110 and 3,747,037.
It has also been de er~ined that the mineral oil extended polyurethane i5 u3eful in the reclamatlon and protection of insulated electrical ~evices. Such devices ~ay, for example, be underground telephone cable~ which are exposed to fluid contami~ants. ~hese conta~nant~ can seriously impair the electri~al a~d ~echanical prcperties of such a device~ The protectant ~aterial is pu~ped into ~he cable to remove water that has penetrated into lnterior free , :
i3~7
-2-I . spaces. The material i5 pumped at low vi3cosity to achieve an appropriate distribution and it then ~ure~ in pl~ce to a ~igh viscosity. The cured material acts as a hydrophobic barrier to subsequent water penetration. In another application, this ~aterial may be utilized as an encapqulant for sealing ~ection of cable. In this manner, the material serves to prevent, from the out~et, the pene~ration of fluid contaminants.
A mineral oil extended polyurethane which is useful for this purpo~e is disclosed in U.S. Reissue Patent No~ RE 30,321. That paten~ defines a cured, cross-linXed, mineral oil extended polyurethane prepared from ~pecific polyurethanes and ~oupling agents, the latter being necessary to compatibilize the mineral oil with the cross-linking urethane elastomer.
;~;3 20 Disadvantages of the~e mineral oil extended polyurethane systems were encountered, however, and these are de~cribed iR U~So Patent Mo. ~,163,258. ~here it was stated that, with the earlier mineral oil extended polyure-thanes, the mineral oil would tend to migrate toward any 25grease present in the ~able or device ~n order to be reclaimed or encapsulated. Thi5 grease ls encou~tered more frequently in newer inqulated electrical devices. This migration was shown to cause the for~ation of an oily film at the grea~e interface ~hich tended to decrease the 30reclamation and encapsulant effectivenes~ of the polyurethane. In order to avoid these difficultie~, the patent specifically defined a polyurethane-mineral oil-coupling agent formulation relying on the presence of a polydiene Moiety in the polyurethane struc~ure, ~lineral oil ~2~3~ii3~L~
_ re~ained as the extending agent~ ~ith the stated preference for including some aromatic carbon content therein~
It i~ also known that previous polyurethane compositions have been difficult to re-enter after they have fully cured primarily due to their high c~t strength and aging hardne3s, as well as due to their opaque or cloudy color~ The hlgh cast strength and hardnes~ of these prior art polyurethanes contribute to the difficulty of cutting through or removing cured material from a repaired area. In some applications, the opaque color ~ake~ it difficult for the operator to establish the exact location to reenter a repair. For the~e reason~, clear, ~oft polyurethane gels are preferred. With either the clear or opaque produc~3, the ability of the~e polyurethane~ to be ea~ily reentered i3 important in the repair or encapsulation of insulated electrical or telephone cables when a second splice or connection must be made in the same area a~ the previous repair or encapsulation. ~here are also aituations where the initial repair or encapu~lation i~ improperly made and ha~ to be re-done. For these reasons, the pri~ary concern regarding the physical properties of the~e gels i8 to pro-v~de a polyurethane having a rela~ively low tear 6trength and hardness. Furthermore, it is highly desirable for theae ~aterials to maintain these properties over time.
A vegetable oil extended polyurethane which ~atisfies ~ome of these requirements and prov1des an initially reenterable gel is diaclo~ed in ~.S. Patent No.
~,375,521. There, veget~ble oil e~tended polyurethanes of a ~hree co~ponent ~ystem compri~ing a ~pecific polyurethane, vegetable oil, and ~pecific extending agent ~ di~closed for use in reclamatioD and encapsulatlon applicatioQs, ~o~ever, lZ1~5347 I these vegetable oil extended formulations u~ually provide opaqu~ gel~, and, more importantly, te~d o caus~ cracXing pr ~tressing of ~he polycarbonate connector~ w~ch are u3ually present in the cable unit being reclaimed, encapsu-lated, or repaired. Furthermore, ~ome of these gel ~ormula-tions age harden over time to make reenterability-difficult.
In ~.S. Patent ~o. 4,355,130, a polyalphaolefin extended polyurethane is di~closed which resolve~ the stress cracking problem. Such polyalphaolein extended polyure-thanes comprise specific polyurethanes, a specific polyalphaolefin extender, and, for reclamation and encapsu-1ation purposes, specific ester coupling agent~. ~he coupling agent iR required to compatibiliz~ the formulation ~o that there will be no ~spewing~ of extender from the cured material.
( ~ 20 Generally, the u~e of high amount~ of such coupling agente tends to reduce the el~ctrical characteristic~ of the gels. ~hi~ ig due to the pre~ence of ester or other polar groups within the polyurethane ` .
~tructure. When ~uch polyurethane~ are u~ed ~or the repair 25or encapsulation of electrical device~, they are unable to restore the ~ame electrical characteristic~ because of their higher dis~ipation factorq. Al~o, ~uch formulations are not compatible with ~able grease and the polyalphaoli~in would tend to ~igrate toward any 3uch grease pre~ent in the cable 30 or device to be repaired or encap~ulated.
-l ~5 1~5~7 Thus~ while the art described i~ the above patents represents ~ progression in the technology of reenterable encapsulants, none sati~factor~ly ~olves the problem of oompatibility ~th cable yrea3e. When ~he state of the art encapsulantq are in ~ontact with cable grlea~e~, an incompa-tibility develops as evidenced by an exudation of a liquid either from the grease or the eneapsulantO In some cases, the liquid interface ~ay result from migration of liquids from both the encapsulant and the grease. It has been demon~trated that the presence of a liquld interface between the cable grease and the encapsulant will provide a leak path for water or contaminent~. ~he pre~ence of ~uch contaminant~ then lead~ to the failure of the electrical devices by corrosion.
It i~, therefore, an object of the present i~vention to provide an exten~ed polyurethane gel y~tem 25having improved compatibility with cable greases for ~rarious uses including the reclamation or encapsu}ation of te:Le-communication or fiber optic cable.
It is another ob~ct to provide novel eombinat~ons of pla~ti~izing and e~tending agent3 for ~uch polyurethane gel sy~tems which likewise improves upon physical propert~es of the polyurethane3 of the prior art.
: -6-It i~ a further object to provide extended polyurethane formulations which are defined in a~cordance 5with ~peclfic end use appli~ation~.
It ha~ now been found that by utilizing cyclic olefins as the first extending agent or polyurethanes along with a specified pla~ticizer compound, the resulting systems 1nare compatible with c2ble greases and thu~ are well ~uited for a number of end use applications including telecommunication cable reclamation and encapsulation or a~
general polyurethane ela3tomers. Such cyclic olefin extended polyurethane~ compri~e a ~pecified polyurethane, a ~cy~lic olefin, and, a specified plasticizer co~pound. If desired, a ~econd extender can al~o be used.
~ he cyclic olefins of the present invention are characterized by excellent compatibility with the 0polyurethane, a broad vi~co~ity range, good electrical properties, and the absence of cracking or stres~ing tendencie~ on polycarbonate connector~. ~t i~ particularly in the area of compatibility with polyurethane and electrical properties that the~e polyurethanes e~hibit 25significant improvement~ over prior art extender and ester coupling agent ~y~tem When u~ed in the area of reclamation and encapcu-lation, the polyurethanes of the present invention provide 30excellent performance characteri~tics~ They pQssess the low viscositie~ neces~ary for initial introduction into the cable and the ~billty to retain these low ~isco~itie~ for period of time ~ufficient to enable t~e~ to f~ll the length of the free ~paces in the cable or form a completely 35 encapsulating cover. They al30 possess the ability to ~2~
displace and/or repel fluid contaminants and ~ure in place to form a gel-like urethane Rtructure which neither ~pews 5forth nor exude~ the plasticizer. Thi~ gel structure has sufficient rigidity to provide an e~cellent protective barrier, ye~ can be readily cut and removed if re~entry is de~iredO The polyurethane are non-corrosive to copper ~ire and compatible with the conventionally used polycarbonate connector~ and other polymeric material~ utilized in cable manufacture. The system i~ also convenient to handle and apply in the field.
The polyurethane which i~ used in the~e formula tions is generally prepared by reacting approximately ~toichiometric amounts of an organic polyisocyan~te with a polyol. In a preferred embodime~t, the organic polyi~ocyanate i8 a polyisocyanate prepolymer which is in turn prepared by reacting an exces~ of an polyi~ocyanate ~compound with a polyol in a manner well known in ~he art.
The polyisocyante prepolymer i5 then reacted ~ith the polyol in the presence of the cyclic olefin and the ~pecified pla~ticizer compound and, optionally, any second extenders to form the cyclic olefin e~tended polyurethane~ ~n a 25second embodiment, the organic polyi~ocyanate i5 a polyisocyanate compound which directly react~ with the polyol in the pre~ence of the cyclic olefin and the specified plasticizer compound and, optionally, any ~econd extenders to form the ~yclic olefin exte~ded polyurethane.
The organic polyi~ocyanate compound3 which can be used for the preparat~on of the polyi~ocyanate prepoly~er or reaction with the polyol to form the polyuretha~e contemplate any organic polyi~ocyanate having 2 or more NCO
groups per molecule and no other ~ubst~tutent~ c~pable of ~Z~i347 reacting with the hydroxy groups of the polyol. ~his would include aliphatic polyiso~yanates, cycloaliphati~
~olyisocyanates, or aromatic polyisocyanates~ ~ypical of such polyisocyanate compound~ are 3-isocyanatomethyl-3,5,5 -trimethyl-cyclohe~yl isocyanate ( IPDI ), toluene diisocyanate (TDI), 4, 4' diphenylme~hanediisocyanate (MDI), polymethylene polyphenylisocyanate, 1, 5 naphthalene diisocyanate, phenylene diisocyanates, 4, ~' -methylene bis-(cyclohexylisocyanate), hexamethylene diisocyanate, biure~ of hexamethylene diisocyanate, 2, 2, 4 --trimethylhexamethylene diisocyanate and combinations thereof, as well as related aromatic, aliphatic, and cycloaliphatic polyisocyanates which may be ~ubstitutecl with other organic or inorganic groups that do not adversely affect the course of the reaction.
~he term ~aliphatic~, as used herein, includes ~.20those carbon chains w~ich are substanti~lly non-aromatic in : nature. They may be saturated or unsaturated, unbranched, branched, or cyclic in configuration and may contain ~ubsti-tuents which do not ~dversely affect ~igration. Such ali-phatic isocyanates generally have an eguivalent ~eight of from 60 to 160 and a viscosity of 1 to 1500 centipoises at 25-C~ ~xemplary of the liguid long chain aliphatic polyiso-cyanates are dodecyl diisocyanate, tridecyl diisocyanate, and the like. Polymethylene polyphenyl i~ocyanate is commercially available from Mobay Chemicals under the trade-mark Mondur MRSo Two preferred compounds, ~ondur MRS and MRS-10, are dark-brown liquids having a slight aro~atic ordor. Specifically Mondur MRS has an NCO ~ontent of 31.5%, an amine equivalent of 133, a viscosity of 200 mPa-S at 25-C, and a density of 1.24 g/cc, while Mondur ~RS-10 has an 35NCO content of 31.9%, an amine equivale~t of 13~, a ,,.
viscosity of 80 mPa-~ at 25~C and a density of approximately 1.24 g/cc. Diphenyl methane diisocyanates are commercially ~vailable in a ~tabilized liquid form from Up~ohn under ~he trademark I~onate 143L or from ~obay under the tr~demark ~ondur CD. Specifieally, Isonate 143-L i~ a llght yellow, modified diphenyl-methane dii~ocyanate having an ~C0 content o 29. 2 weight percent~ an i~ocyanate equi.valency of 144, an 0acidity value of less than 0.030 and a vi~co~ity of 35 cps at 25~C, while Mondur CD i8 a light-yello~ modified 4,4' diphenylmethane diisocyanate having an NC0 content of 29.3 weight percent and ~ viscosity of les~ than 100 mPa-s at 25C. Various polyarylene polyiso~yanates are con~ercially available from Upjohn under the trademark PAPI, of which PAPI 94 i~ typical. PAPI g4 i8 a polymeric methylene diisocyanate containing approximately 98~ of 4,4' i60mer with the remainillg 2% being the 2, 4 ' isomer. PAPI 94 ha3 a NCO content of approximately 2.
Suitable polyol~ for reaction with the previously described organic polyisocyanate~ include those known to be useful for the preparation of polyurethanes gels having about 2-8 hydroxyl group~. Tho~e polyol~ having about 2-4 25hydroxyl groups are preferred. Typical e~ample~ include c~stor oil, polyether polyol~, polyester polyol~, hydro%yl bearing homopolymers of diene~, hydroxyl bear~ng eopo:Lymers of dienes, and combinations thereof. Such polyols generally have an equivalent ~eight of from 30 to 6000 and a viscosity 30of from 1 to 20,000 centipoi~es at 25 to 60-C. The higher equivalent weight material~, ~.e., tho~e having equivalent weight~ above about 250, are generally preferred.
~ne polyol which may be u~ed in the preparation of 35these cyclic olef în extended polyurethane i~ c~tor oil, a ;i3~7 ~1 o--comoound primarily compcsed of ricinolein, wnieh is a glyceride of ricinolei~ acid. A typical castor oil ~omprises a mixture of about 70~ pure glyceryl triricinoleata and about 30% glye~ryl diricinoleate -monoleate or mo~olinoleate and is available from CasChem, *, Inc. as DB Oil.
Suitable polyether polyol~ lnclude aliphatic ~lkylene glycol polymers having an alkylene u~it c^~pose~ of at le~st two c~rbon atoms. ~hese aliphatic alkylene glycol polymers are e~emplified by p~lyoxypropylene glyco} and polytetramethyle~e ether glycol. Also, trifunctional compou~ds exemplifiea by the reaction product o~ tri~ethyol propane and propylene oxide may be employed. A typical polyether polyol i~ available ~rom ~nion Carbide under ~e desig~ation ~iax PPG-425. Speciically, ~ia~ PPG-425, a copolymer of a co~e~tio~al pol~ol a~d a ~i~yl ~onom~r, ha~
an average hydroxyl ~umber of 263, an acld numbes of 0.5, and a ~i co~ity o~ 80 co~tistoke~ at 25C.
~ he general erm poly~ther polyol~ al30 i~clude~
polymer~ which are o~t~ seferr~d to as ami~ based polyol~
or polymeric polyols. ~yplcal amin~ ba3ed polyol~ include sucro~e-arnine polyol. 8uc~ i~s ~iax E~DE-400 or ~AF-S2~ or amis~e polyol~ such a ~ias ~-475 or ~ 700, all o ~hic~
are available ~rom ~nion Car~ide. A~ one skilled iQ the art would Xrlow, ~here are no free amino hydroge~ in any of the ~ e compo unds .
.
The hydroxyl be3ring homopolymers of dienes or hyd~o:cyl bearing copoly~s~er~ o diene~ are prepared from dienes which include uslubstituted, ~ sub tituted or 2, 3-disubstit~lted 1, 3-dienes <: f up to about 12 c:3r~on atomq .
* Trade-mark .; j ~, ~35;347 Preferably, the diene has up to about 6 carbon atoms and the ~ubstituents ln the 2- and/or 3 position may be hydrogen, ~lkyl groups having abou~ l to about 4 carbon atoms~ ~ubstl~
tuted aryl, unsubstituted aryl, halogen, and the lik~
Typical o such dienes are 1,3-butadiene, isoprene, chloro-prene, 2-cyano-l,3-butadiene, 2,3-d;methyl -l,2-~utadiene, and the like. The preferred dienes are l,3-butadiene and isoprene. A hydroxyl terminated polybutadiene i~ available from ~RCO Chemicals under the designation Poly-B~ R-45~T~
Specifically, Poly BD R-45~T ha~ a molecular weight of about 2800, a degree of polymerization of ~0, a hydroxyl function-ality of about 2.4 to 2.6, a hydroxyl number of 46.6r a hydroxyl value of 0.83, and an iodine number o 398.
A wide variety of aromatic and aliphatic diamines may form part of the amine-based polyols, such as ~, ~ bis (2-hydroxypropyl~ aniline and ~,~,N' ,~' ~tetrakis ~2-hydrox-ypropyl) ethylenediamine~ A typical amine-based polyol is aYailable from ~pjohn under the designation Isonol lO0, ?n amber colored l~quid polyol having a molecular weight of 209, a hydroxyl number of 534~ an equi~alent weight of 104.5, an average funtionality of 2.0 and a ~isco~ity of 1450 at 50-C. A typical aliphatic amine~ba~ed polyol is available from BASF under the designation Quadrol, a viscous liquid polyol with four hydroxyl groups, two tertiary nitrogen atoms, a hydroxyl number of 770 and a Yiscosity of 53,000 cps a~ 25-C.
~ he general term polyether polyol~ also includes compounds which are referred to as polyme~ic polyols.
Polymeric polyol~ can be described a3 conventional polyol3 with a stable disper~ion of vinyl polymer~. Por e~ample, U.S. Patent ~o. 4,104,236 aiscloses such polyols with * Trade Mark f ~2~353~7 ~12- -acrylonitrile-styrene polymers; a further typical polyol ic available from Union Carbide under the de~ignation ~iax 24-532. Specifically, ~ia~ 24-32~ a copolymer of a conventional polyol and a vinyl monomer, has an average hydroxyl number of 32 and a viscosity of 1300 centipoise at 25C.
Th2 term polymeric polyols al~o include~ other copmbination polyol~, ~uch a~ graft polyol~ or other synthetic polyol ~ombinations.
The cyclic olefins utilized herein as the first extender~ typically include dipentene, pinene, dicyclopentadiene, and polycyclopentadiene, all o which are commerc;ally availableO The cyclic olefin~ con~i~t of at least one 5 or 6 membered ring with at lea~t one unsaturated bond. In addition to this one unsaturated ring, the compound may include saturated carbon chains, un~aturated carbon chains, satu~ated carbon rings, un~atur~ted c~rbon rings, or combination~ of any of the3e carbon ~tructures.
These cyclic olefins can range from very low ~isco~$tie~, in the case of law molecular ~eight~, tohigh ~isco~ities, in the case opf high polymerization of these c~pounds. ~hese compounds are compatible with polyurethane~ without the use of additional compatibillzer~, ~uch as ester coupling agents. They can also be polymerized with other non-cyclic, unsaturated compound~ to produ~e a material which i~
compatible with polyurethanes.
Ihe polyurethanes of the pre~ent invention ~ay al50 optionally contain a benzenoid co~pound along with the cyclic olef in extender . Typical benzenoid compound~ include toluene and pyrrole, and the~e are al50 compatible with 35polyurethane~ without hte use of ester coupl~ng agents.
~2~347 Both the cyclic olefin and cyclic olefin/benzenoid compourld extended polyurethanes will not e2hibi~ ~pewing of l:he cender and ~re utilized in concentra'ciorl ranging from about 1 - 92 weight pereent of the total estended polyurethan~ ~y~tem.
The pla~tieizer compounds ~hich ~an ~e u~ed in 0thi~ insention ir1clud~ Uly compounds or ~i~:tur~ of compounds having a total ~olubility parameter of between about 9~1 and 10.1. Compound~ ha~ins 301ubillty p rameters higher than 10.1 llr~ too vola ile for u~e in gel formulat~ons, Suitable pla~ti~izer component~ are e~ters ~uch a~
the phthzlate~ or adipate~ having be~ween abou~ ~ ~nd 13 carbon atoms, ~lnce these con~pound~ po~e~s ~olubil$ty parameter~ iEalllng within ~he abo~-de~cribed ~:rit$cal ranges. C~rtain rlcinol~at~ co~pound~ such as glyceryl tri (acetyl r~c~noleate) and ~imilar compound~ ~hich ha~e ~olublli~y p~ram~ter3 ~rithin the ~bo7~-di~clo~d range~, are al~o useful ~nd, 7~ould ~ pref~rred aue to their gre~ter compa~ibllity under ~ wid~ rang~ of ~able filler~ or grea~es wh~Gh ar~ typic~lly encountered in the reda~atlon or 25enc~p~ulatlon of t~lecom~unicatlon or e~ectPlcal cable.
Veq~table oll~ having total ~olubility ~ar~eter3 falling withi~ the aboY~-identlf$ed r~nge ar~ 30 u~e~ul in thi~ inventiol Kll:hou~ the noed for a colap~tibil$2er or 30coupllng agent. Spe~ preferred co~pound- for can be u~ed ag Z?la3tlcizer~ in ac:cordanc~ th the ~ nt~on are 1 l~ted below, .
~,", _l ;
~l28~30~7 ~A ~--~C ~ 5~
~om~ound'c~unilit~ P~r~met~r diu~de~yl phthalate g 4 OdiisoZe~yl pht~alate 9.5 glyce yl tri (acotyl ric~nole~te) 9.3 dibu yl phthalate 10.1 The specific solubility parameter ranges h~ve bee~
deter~ine~ by weigh~ gain a~a c~nductor pull out tests as shown by the e~amples. Specifi~ally, compound~ havin~ a total solubili~y parameter whi~ result~ in a weight lo 3 or in which a condu~tor cab}e ca~ be easily pulled ou~ are not sati~.actory for u~e i~ thi~ ~nve~tio~.
Al~o, o~e or mo~e o the above-identifiea plas~i-cizers c~n be u~ed in combination without depart~ng fro~ the teachingc of the ~n~e~tion provided that t~ overall solubility re~ain~ in the ~rit~c~l raQge.
e soluhility paramete~ of t~e pla~ticizer compounds ~re deter~inea a- des~ibed i~ the arti~le entitled ~S~lubility Parame~e~ ~ whic~ aooear~ e ~rX-Othmer E~CYCLGP~IA OF C~IC.~L T~C~NOLOG~ upple~ental volume~ second edit~on pace~ 890 to 9It.
In thi3 article, the total s~luhility para~e~er is c~lc~lated from threa i~dividual ~olubility parameters,
A mineral oil extended polyurethane which is useful for this purpo~e is disclosed in U.S. Reissue Patent No~ RE 30,321. That paten~ defines a cured, cross-linXed, mineral oil extended polyurethane prepared from ~pecific polyurethanes and ~oupling agents, the latter being necessary to compatibilize the mineral oil with the cross-linking urethane elastomer.
;~;3 20 Disadvantages of the~e mineral oil extended polyurethane systems were encountered, however, and these are de~cribed iR U~So Patent Mo. ~,163,258. ~here it was stated that, with the earlier mineral oil extended polyure-thanes, the mineral oil would tend to migrate toward any 25grease present in the ~able or device ~n order to be reclaimed or encapsulated. Thi5 grease ls encou~tered more frequently in newer inqulated electrical devices. This migration was shown to cause the for~ation of an oily film at the grea~e interface ~hich tended to decrease the 30reclamation and encapsulant effectivenes~ of the polyurethane. In order to avoid these difficultie~, the patent specifically defined a polyurethane-mineral oil-coupling agent formulation relying on the presence of a polydiene Moiety in the polyurethane struc~ure, ~lineral oil ~2~3~ii3~L~
_ re~ained as the extending agent~ ~ith the stated preference for including some aromatic carbon content therein~
It i~ also known that previous polyurethane compositions have been difficult to re-enter after they have fully cured primarily due to their high c~t strength and aging hardne3s, as well as due to their opaque or cloudy color~ The hlgh cast strength and hardnes~ of these prior art polyurethanes contribute to the difficulty of cutting through or removing cured material from a repaired area. In some applications, the opaque color ~ake~ it difficult for the operator to establish the exact location to reenter a repair. For the~e reason~, clear, ~oft polyurethane gels are preferred. With either the clear or opaque produc~3, the ability of the~e polyurethane~ to be ea~ily reentered i3 important in the repair or encapsulation of insulated electrical or telephone cables when a second splice or connection must be made in the same area a~ the previous repair or encapsulation. ~here are also aituations where the initial repair or encapu~lation i~ improperly made and ha~ to be re-done. For these reasons, the pri~ary concern regarding the physical properties of the~e gels i8 to pro-v~de a polyurethane having a rela~ively low tear 6trength and hardness. Furthermore, it is highly desirable for theae ~aterials to maintain these properties over time.
A vegetable oil extended polyurethane which ~atisfies ~ome of these requirements and prov1des an initially reenterable gel is diaclo~ed in ~.S. Patent No.
~,375,521. There, veget~ble oil e~tended polyurethanes of a ~hree co~ponent ~ystem compri~ing a ~pecific polyurethane, vegetable oil, and ~pecific extending agent ~ di~closed for use in reclamatioD and encapsulatlon applicatioQs, ~o~ever, lZ1~5347 I these vegetable oil extended formulations u~ually provide opaqu~ gel~, and, more importantly, te~d o caus~ cracXing pr ~tressing of ~he polycarbonate connector~ w~ch are u3ually present in the cable unit being reclaimed, encapsu-lated, or repaired. Furthermore, ~ome of these gel ~ormula-tions age harden over time to make reenterability-difficult.
In ~.S. Patent ~o. 4,355,130, a polyalphaolefin extended polyurethane is di~closed which resolve~ the stress cracking problem. Such polyalphaolein extended polyure-thanes comprise specific polyurethanes, a specific polyalphaolefin extender, and, for reclamation and encapsu-1ation purposes, specific ester coupling agent~. ~he coupling agent iR required to compatibiliz~ the formulation ~o that there will be no ~spewing~ of extender from the cured material.
( ~ 20 Generally, the u~e of high amount~ of such coupling agente tends to reduce the el~ctrical characteristic~ of the gels. ~hi~ ig due to the pre~ence of ester or other polar groups within the polyurethane ` .
~tructure. When ~uch polyurethane~ are u~ed ~or the repair 25or encapsulation of electrical device~, they are unable to restore the ~ame electrical characteristic~ because of their higher dis~ipation factorq. Al~o, ~uch formulations are not compatible with ~able grease and the polyalphaoli~in would tend to ~igrate toward any 3uch grease pre~ent in the cable 30 or device to be repaired or encap~ulated.
-l ~5 1~5~7 Thus~ while the art described i~ the above patents represents ~ progression in the technology of reenterable encapsulants, none sati~factor~ly ~olves the problem of oompatibility ~th cable yrea3e. When ~he state of the art encapsulantq are in ~ontact with cable grlea~e~, an incompa-tibility develops as evidenced by an exudation of a liquid either from the grease or the eneapsulantO In some cases, the liquid interface ~ay result from migration of liquids from both the encapsulant and the grease. It has been demon~trated that the presence of a liquld interface between the cable grease and the encapsulant will provide a leak path for water or contaminent~. ~he pre~ence of ~uch contaminant~ then lead~ to the failure of the electrical devices by corrosion.
It i~, therefore, an object of the present i~vention to provide an exten~ed polyurethane gel y~tem 25having improved compatibility with cable greases for ~rarious uses including the reclamation or encapsu}ation of te:Le-communication or fiber optic cable.
It is another ob~ct to provide novel eombinat~ons of pla~ti~izing and e~tending agent3 for ~uch polyurethane gel sy~tems which likewise improves upon physical propert~es of the polyurethane3 of the prior art.
: -6-It i~ a further object to provide extended polyurethane formulations which are defined in a~cordance 5with ~peclfic end use appli~ation~.
It ha~ now been found that by utilizing cyclic olefins as the first extending agent or polyurethanes along with a specified pla~ticizer compound, the resulting systems 1nare compatible with c2ble greases and thu~ are well ~uited for a number of end use applications including telecommunication cable reclamation and encapsulation or a~
general polyurethane ela3tomers. Such cyclic olefin extended polyurethane~ compri~e a ~pecified polyurethane, a ~cy~lic olefin, and, a specified plasticizer co~pound. If desired, a ~econd extender can al~o be used.
~ he cyclic olefins of the present invention are characterized by excellent compatibility with the 0polyurethane, a broad vi~co~ity range, good electrical properties, and the absence of cracking or stres~ing tendencie~ on polycarbonate connector~. ~t i~ particularly in the area of compatibility with polyurethane and electrical properties that the~e polyurethanes e~hibit 25significant improvement~ over prior art extender and ester coupling agent ~y~tem When u~ed in the area of reclamation and encapcu-lation, the polyurethanes of the present invention provide 30excellent performance characteri~tics~ They pQssess the low viscositie~ neces~ary for initial introduction into the cable and the ~billty to retain these low ~isco~itie~ for period of time ~ufficient to enable t~e~ to f~ll the length of the free ~paces in the cable or form a completely 35 encapsulating cover. They al30 possess the ability to ~2~
displace and/or repel fluid contaminants and ~ure in place to form a gel-like urethane Rtructure which neither ~pews 5forth nor exude~ the plasticizer. Thi~ gel structure has sufficient rigidity to provide an e~cellent protective barrier, ye~ can be readily cut and removed if re~entry is de~iredO The polyurethane are non-corrosive to copper ~ire and compatible with the conventionally used polycarbonate connector~ and other polymeric material~ utilized in cable manufacture. The system i~ also convenient to handle and apply in the field.
The polyurethane which i~ used in the~e formula tions is generally prepared by reacting approximately ~toichiometric amounts of an organic polyisocyan~te with a polyol. In a preferred embodime~t, the organic polyi~ocyanate i8 a polyisocyanate prepolymer which is in turn prepared by reacting an exces~ of an polyi~ocyanate ~compound with a polyol in a manner well known in ~he art.
The polyisocyante prepolymer i5 then reacted ~ith the polyol in the presence of the cyclic olefin and the ~pecified pla~ticizer compound and, optionally, any second extenders to form the cyclic olefin e~tended polyurethane~ ~n a 25second embodiment, the organic polyi~ocyanate i5 a polyisocyanate compound which directly react~ with the polyol in the pre~ence of the cyclic olefin and the specified plasticizer compound and, optionally, any ~econd extenders to form the ~yclic olefin exte~ded polyurethane.
The organic polyi~ocyanate compound3 which can be used for the preparat~on of the polyi~ocyanate prepoly~er or reaction with the polyol to form the polyuretha~e contemplate any organic polyi~ocyanate having 2 or more NCO
groups per molecule and no other ~ubst~tutent~ c~pable of ~Z~i347 reacting with the hydroxy groups of the polyol. ~his would include aliphatic polyiso~yanates, cycloaliphati~
~olyisocyanates, or aromatic polyisocyanates~ ~ypical of such polyisocyanate compound~ are 3-isocyanatomethyl-3,5,5 -trimethyl-cyclohe~yl isocyanate ( IPDI ), toluene diisocyanate (TDI), 4, 4' diphenylme~hanediisocyanate (MDI), polymethylene polyphenylisocyanate, 1, 5 naphthalene diisocyanate, phenylene diisocyanates, 4, ~' -methylene bis-(cyclohexylisocyanate), hexamethylene diisocyanate, biure~ of hexamethylene diisocyanate, 2, 2, 4 --trimethylhexamethylene diisocyanate and combinations thereof, as well as related aromatic, aliphatic, and cycloaliphatic polyisocyanates which may be ~ubstitutecl with other organic or inorganic groups that do not adversely affect the course of the reaction.
~he term ~aliphatic~, as used herein, includes ~.20those carbon chains w~ich are substanti~lly non-aromatic in : nature. They may be saturated or unsaturated, unbranched, branched, or cyclic in configuration and may contain ~ubsti-tuents which do not ~dversely affect ~igration. Such ali-phatic isocyanates generally have an eguivalent ~eight of from 60 to 160 and a viscosity of 1 to 1500 centipoises at 25-C~ ~xemplary of the liguid long chain aliphatic polyiso-cyanates are dodecyl diisocyanate, tridecyl diisocyanate, and the like. Polymethylene polyphenyl i~ocyanate is commercially available from Mobay Chemicals under the trade-mark Mondur MRSo Two preferred compounds, ~ondur MRS and MRS-10, are dark-brown liquids having a slight aro~atic ordor. Specifically Mondur MRS has an NCO ~ontent of 31.5%, an amine equivalent of 133, a viscosity of 200 mPa-S at 25-C, and a density of 1.24 g/cc, while Mondur ~RS-10 has an 35NCO content of 31.9%, an amine equivale~t of 13~, a ,,.
viscosity of 80 mPa-~ at 25~C and a density of approximately 1.24 g/cc. Diphenyl methane diisocyanates are commercially ~vailable in a ~tabilized liquid form from Up~ohn under ~he trademark I~onate 143L or from ~obay under the tr~demark ~ondur CD. Specifieally, Isonate 143-L i~ a llght yellow, modified diphenyl-methane dii~ocyanate having an ~C0 content o 29. 2 weight percent~ an i~ocyanate equi.valency of 144, an 0acidity value of less than 0.030 and a vi~co~ity of 35 cps at 25~C, while Mondur CD i8 a light-yello~ modified 4,4' diphenylmethane diisocyanate having an NC0 content of 29.3 weight percent and ~ viscosity of les~ than 100 mPa-s at 25C. Various polyarylene polyiso~yanates are con~ercially available from Upjohn under the trademark PAPI, of which PAPI 94 i~ typical. PAPI g4 i8 a polymeric methylene diisocyanate containing approximately 98~ of 4,4' i60mer with the remainillg 2% being the 2, 4 ' isomer. PAPI 94 ha3 a NCO content of approximately 2.
Suitable polyol~ for reaction with the previously described organic polyisocyanate~ include those known to be useful for the preparation of polyurethanes gels having about 2-8 hydroxyl group~. Tho~e polyol~ having about 2-4 25hydroxyl groups are preferred. Typical e~ample~ include c~stor oil, polyether polyol~, polyester polyol~, hydro%yl bearing homopolymers of diene~, hydroxyl bear~ng eopo:Lymers of dienes, and combinations thereof. Such polyols generally have an equivalent ~eight of from 30 to 6000 and a viscosity 30of from 1 to 20,000 centipoi~es at 25 to 60-C. The higher equivalent weight material~, ~.e., tho~e having equivalent weight~ above about 250, are generally preferred.
~ne polyol which may be u~ed in the preparation of 35these cyclic olef în extended polyurethane i~ c~tor oil, a ;i3~7 ~1 o--comoound primarily compcsed of ricinolein, wnieh is a glyceride of ricinolei~ acid. A typical castor oil ~omprises a mixture of about 70~ pure glyceryl triricinoleata and about 30% glye~ryl diricinoleate -monoleate or mo~olinoleate and is available from CasChem, *, Inc. as DB Oil.
Suitable polyether polyol~ lnclude aliphatic ~lkylene glycol polymers having an alkylene u~it c^~pose~ of at le~st two c~rbon atoms. ~hese aliphatic alkylene glycol polymers are e~emplified by p~lyoxypropylene glyco} and polytetramethyle~e ether glycol. Also, trifunctional compou~ds exemplifiea by the reaction product o~ tri~ethyol propane and propylene oxide may be employed. A typical polyether polyol i~ available ~rom ~nion Carbide under ~e desig~ation ~iax PPG-425. Speciically, ~ia~ PPG-425, a copolymer of a co~e~tio~al pol~ol a~d a ~i~yl ~onom~r, ha~
an average hydroxyl ~umber of 263, an acld numbes of 0.5, and a ~i co~ity o~ 80 co~tistoke~ at 25C.
~ he general erm poly~ther polyol~ al30 i~clude~
polymer~ which are o~t~ seferr~d to as ami~ based polyol~
or polymeric polyols. ~yplcal amin~ ba3ed polyol~ include sucro~e-arnine polyol. 8uc~ i~s ~iax E~DE-400 or ~AF-S2~ or amis~e polyol~ such a ~ias ~-475 or ~ 700, all o ~hic~
are available ~rom ~nion Car~ide. A~ one skilled iQ the art would Xrlow, ~here are no free amino hydroge~ in any of the ~ e compo unds .
.
The hydroxyl be3ring homopolymers of dienes or hyd~o:cyl bearing copoly~s~er~ o diene~ are prepared from dienes which include uslubstituted, ~ sub tituted or 2, 3-disubstit~lted 1, 3-dienes <: f up to about 12 c:3r~on atomq .
* Trade-mark .; j ~, ~35;347 Preferably, the diene has up to about 6 carbon atoms and the ~ubstituents ln the 2- and/or 3 position may be hydrogen, ~lkyl groups having abou~ l to about 4 carbon atoms~ ~ubstl~
tuted aryl, unsubstituted aryl, halogen, and the lik~
Typical o such dienes are 1,3-butadiene, isoprene, chloro-prene, 2-cyano-l,3-butadiene, 2,3-d;methyl -l,2-~utadiene, and the like. The preferred dienes are l,3-butadiene and isoprene. A hydroxyl terminated polybutadiene i~ available from ~RCO Chemicals under the designation Poly-B~ R-45~T~
Specifically, Poly BD R-45~T ha~ a molecular weight of about 2800, a degree of polymerization of ~0, a hydroxyl function-ality of about 2.4 to 2.6, a hydroxyl number of 46.6r a hydroxyl value of 0.83, and an iodine number o 398.
A wide variety of aromatic and aliphatic diamines may form part of the amine-based polyols, such as ~, ~ bis (2-hydroxypropyl~ aniline and ~,~,N' ,~' ~tetrakis ~2-hydrox-ypropyl) ethylenediamine~ A typical amine-based polyol is aYailable from ~pjohn under the designation Isonol lO0, ?n amber colored l~quid polyol having a molecular weight of 209, a hydroxyl number of 534~ an equi~alent weight of 104.5, an average funtionality of 2.0 and a ~isco~ity of 1450 at 50-C. A typical aliphatic amine~ba~ed polyol is available from BASF under the designation Quadrol, a viscous liquid polyol with four hydroxyl groups, two tertiary nitrogen atoms, a hydroxyl number of 770 and a Yiscosity of 53,000 cps a~ 25-C.
~ he general term polyether polyol~ also includes compounds which are referred to as polyme~ic polyols.
Polymeric polyol~ can be described a3 conventional polyol3 with a stable disper~ion of vinyl polymer~. Por e~ample, U.S. Patent ~o. 4,104,236 aiscloses such polyols with * Trade Mark f ~2~353~7 ~12- -acrylonitrile-styrene polymers; a further typical polyol ic available from Union Carbide under the de~ignation ~iax 24-532. Specifically, ~ia~ 24-32~ a copolymer of a conventional polyol and a vinyl monomer, has an average hydroxyl number of 32 and a viscosity of 1300 centipoise at 25C.
Th2 term polymeric polyols al~o include~ other copmbination polyol~, ~uch a~ graft polyol~ or other synthetic polyol ~ombinations.
The cyclic olefins utilized herein as the first extender~ typically include dipentene, pinene, dicyclopentadiene, and polycyclopentadiene, all o which are commerc;ally availableO The cyclic olefin~ con~i~t of at least one 5 or 6 membered ring with at lea~t one unsaturated bond. In addition to this one unsaturated ring, the compound may include saturated carbon chains, un~aturated carbon chains, satu~ated carbon rings, un~atur~ted c~rbon rings, or combination~ of any of the3e carbon ~tructures.
These cyclic olefins can range from very low ~isco~$tie~, in the case of law molecular ~eight~, tohigh ~isco~ities, in the case opf high polymerization of these c~pounds. ~hese compounds are compatible with polyurethane~ without the use of additional compatibillzer~, ~uch as ester coupling agents. They can also be polymerized with other non-cyclic, unsaturated compound~ to produ~e a material which i~
compatible with polyurethanes.
Ihe polyurethanes of the pre~ent invention ~ay al50 optionally contain a benzenoid co~pound along with the cyclic olef in extender . Typical benzenoid compound~ include toluene and pyrrole, and the~e are al50 compatible with 35polyurethane~ without hte use of ester coupl~ng agents.
~2~347 Both the cyclic olefin and cyclic olefin/benzenoid compourld extended polyurethanes will not e2hibi~ ~pewing of l:he cender and ~re utilized in concentra'ciorl ranging from about 1 - 92 weight pereent of the total estended polyurethan~ ~y~tem.
The pla~tieizer compounds ~hich ~an ~e u~ed in 0thi~ insention ir1clud~ Uly compounds or ~i~:tur~ of compounds having a total ~olubility parameter of between about 9~1 and 10.1. Compound~ ha~ins 301ubillty p rameters higher than 10.1 llr~ too vola ile for u~e in gel formulat~ons, Suitable pla~ti~izer component~ are e~ters ~uch a~
the phthzlate~ or adipate~ having be~ween abou~ ~ ~nd 13 carbon atoms, ~lnce these con~pound~ po~e~s ~olubil$ty parameter~ iEalllng within ~he abo~-de~cribed ~:rit$cal ranges. C~rtain rlcinol~at~ co~pound~ such as glyceryl tri (acetyl r~c~noleate) and ~imilar compound~ ~hich ha~e ~olublli~y p~ram~ter3 ~rithin the ~bo7~-di~clo~d range~, are al~o useful ~nd, 7~ould ~ pref~rred aue to their gre~ter compa~ibllity under ~ wid~ rang~ of ~able filler~ or grea~es wh~Gh ar~ typic~lly encountered in the reda~atlon or 25enc~p~ulatlon of t~lecom~unicatlon or e~ectPlcal cable.
Veq~table oll~ having total ~olubility ~ar~eter3 falling withi~ the aboY~-identlf$ed r~nge ar~ 30 u~e~ul in thi~ inventiol Kll:hou~ the noed for a colap~tibil$2er or 30coupllng agent. Spe~ preferred co~pound- for can be u~ed ag Z?la3tlcizer~ in ac:cordanc~ th the ~ nt~on are 1 l~ted below, .
~,", _l ;
~l28~30~7 ~A ~--~C ~ 5~
~om~ound'c~unilit~ P~r~met~r diu~de~yl phthalate g 4 OdiisoZe~yl pht~alate 9.5 glyce yl tri (acotyl ric~nole~te) 9.3 dibu yl phthalate 10.1 The specific solubility parameter ranges h~ve bee~
deter~ine~ by weigh~ gain a~a c~nductor pull out tests as shown by the e~amples. Specifi~ally, compound~ havin~ a total solubili~y parameter whi~ result~ in a weight lo 3 or in which a condu~tor cab}e ca~ be easily pulled ou~ are not sati~.actory for u~e i~ thi~ ~nve~tio~.
Al~o, o~e or mo~e o the above-identifiea plas~i-cizers c~n be u~ed in combination without depart~ng fro~ the teachingc of the ~n~e~tion provided that t~ overall solubility re~ain~ in the ~rit~c~l raQge.
e soluhility paramete~ of t~e pla~ticizer compounds ~re deter~inea a- des~ibed i~ the arti~le entitled ~S~lubility Parame~e~ ~ whic~ aooear~ e ~rX-Othmer E~CYCLGP~IA OF C~IC.~L T~C~NOLOG~ upple~ental volume~ second edit~on pace~ 890 to 9It.
In thi3 article, the total s~luhility para~e~er is c~lc~lated from threa i~dividual ~olubility parameters,
3~
:`jJ
~8~;3~
namely the dispersion componen~r the polar component, and the hydrogen bonding component, a~ follow~:
The values which appear in Table 1 are the tota~
-~olubility parameter Y for the plasticizer compounds listed.
With re~pect to the weight change te~ting, there are different type3 of grea~e~ which ~y be encountered in tele~ommunication cable. The mo~t common i3 FLEXGEL cable filler. FLEXG~L i a reglstered trademark of the We~tern Electr~c Co. Inc~ Por their cable ~illing compound~ for waterprooflng ele~trical cable. Oth~r c~bl~s may have petroleum ielly (PJ1 or polyethylene modified petroleu~
~elly ~PEPJ). PEPJ ~ 8 hi$her ~elt~ng point ~terial than PJ. It ~hould be noted that the rlcinoleate~ ~a~e ~ wider range of comp~tlb~lity with ~ll types of c~ble ~iller~ than 20 the other plas~cizer compound~.
With re~pect to the u~e o4 the~e plasticizer co~pounds in th~ formul~tion3 of th~ pre~nt invention, it should be noted that tho~e co~pound~ ha~ihg a ~olubility paramet~r between about 9.1 and lO,l pro~d~ c}ear nd tran~parent gels which ~re preferred or ap~llc~t~o~ ~her~
reenterab~lity is o~ prl~ry i~portan~. All the polyurethane gels according to this invention are soft with a low tear strength, and these properties are maintained over time to provide desirable reenterable compounds.
1 - :
, 1~8~3a~7 It ~hould further be no~ed hat all the suitable pla ticizer components according ~o the inven'cion are low 5 viscosity liquids at room temperature.
A~ stated her2inabove, a coupling ~gent or compatibilizer quch as an e~ter compound i~ not reauired for the extended polyurethane, but ~uch coupling agents m~y 10 optionally be u~ed in the~e e~tended polyurethanes in ~pecific application~. In the ca~e of highly polymerized cyclic olefin~ coupling agent can be used to lower the Vi E;c05i~:y~ if de~ired. When u~ed, the coupling ~gent may range up to about 50 weight per-:~nt of the total extellded 15 polyurethane. ~uch compound~ are non-r~act~Ye or ~ub tantially non-reactive w~ th th@ polyuethane forming companents. ~ter~ are preferred, and they ~ay b~ ~atur~ted or un~aturated and may b~ aliph~ti~:, cycloal~phat~cg or aromatic aliphatic. Typical ester~ i~clu~e phthalate~ such a~ 2-ethylhexyl phthalate, zand ~xture~ of n-C~, Cl~, and C 11 phthalat~, adip~te~ ~uch as ~ ode~yl adipa e and n-octyl-n-de~yl adlpate, glutara~e~, fumztra~e~ ~ebacat~
c~trate~, and th~ e, a~ well a3 polymeric e~ters such n~
Plastoleirl 9720 from ~mery Iridu~trie~, ~ plasticizer having an acid v~lue o~ 3. 0, a~ hydroxyl ~alue of 20, and a viscQ~ity of 207 centi~toke~ at lO0 F to provide a low volat~ y ~terial havlng good r~ tance to oil ex'craction .
The cyclic olefin extended polyur~thane can ~l~o optionally include othes extender co~pound~ ~hich can b~
u~ed w~th or without a compatibilizer. 1!!1O~t oll~
coomerci~Ily ~a~ lable for rubber proce3~ing ~y be used for oil exten~ion of the extended polyurethane~ o th~
inventlon. When u~ed, the~e extender~ can range up * Trade-mark ~53~7 to 50 weiyht percent of the total extended polyurethane.
Examples of compounds included in ~he term processing oils are listed in U.S~ Paten~ No~ 3,107,224, and they can be classified by sourc~ into the following group~: petroleum oils and asphalts, petroleum wa~e~, coal tar oils and pitches~ esters~ chlorinated hydrocarbons, pine tars and oils, phenols, and resins. All of these commercially available materials are essentially hydrocarbon, that is, at least about 50 weight percent carbon and hydrogen.
Preferably, the oil i5 at least about 75 weight percent or more preferably at least about 90 weight percent carbon and hydrogen. As is apparent from the materials listed, the hydrocarbon chains or rings may be interrupted or ~erminated t5 by non-hydrocarbon groups, for instance, ester, ether, or other oxygen-containins linkages.
Usable processing oils are characterized by a viscosity SSV at 100 ~ of at least 3Q~ and preferably at - 20 least about 70. Petroleum oils are most often u ed in extending natural and synthetic fubber~ as well a3 the polyurethanes of this invention, and yenerally are categorized as paraffinic, napthenic (cycloaliphatic), aromatic, or asphaltic oils. ~owe~er, proces~ing oils which combine the characteristics of two or more of these type~
also may be employed. Viscosities fre~uently vary from about 100 - 600 SSU at lOO~F or 35 - 100 SSU at 210-F
although aromatic and/or asphaltic oils of up to 1000 or 2000 or more SS~ at lOO-F are ~ometimes used.
Coal tar pitch, asphalts, asphaltenes, chlorinated biphenyl ethers, chlorinated waxes, chlorinated oils, rosin es~ers, certain esters and amides of styrene-maleic anhydride resins, courmarone-indene resin~, polybutenes, as ~2~353~7 well as many other processing compounds may be used, either alone or in conjunction with oils as a further e~tender.
Aromatic and chlorinated oils may also be u~ed a~ extenders.
Additional extenders composed mainly of hydrocarbons are asually preferred because of their improved hydrolytic properites, oxidative properties~ and lower cost.
Other extender~ include the low ~olecular weight polybutenes or polyisobutylenes as ~ell as the high boiling fractions o petroleum polymers ordinarily used for lubricants.
Chlorinated aromatic and aliphatic hydrocarbons, aromatic ether~, and phosphorus derivatives are par~icularly advantageouc since ~hey may impart some flame retardance to the finished product. m e additional extender may comprise up to about 40 weight percent of the cyclic slefin extended polyurethane.
In accordance with the extended polyurethanes of- 20 the present invention, finely divided solid fillers which are commonly employed in the art as either reinforcing or inert ~illers can also be utilized. The use of such ~olid fillers applie~ mainly to non-reenterable polyurethanes.
Conventional fillers include carbon black, asphaltenese, silica, silica-alumina~ hydrated silica, zinc oxide, magnesium carbonates, clays, talc, and pulv*rized reclaimed rubber as well as various mineral ~illers which are known in the art. Solid fillers may be employed in the amount of up to 50 weight percent the polyurethane.
The cyclic olefin extended polyurethane of the present invention is generally comprised of from about 10 to 90 parts by weight of an extended polyurethane comprising ~L~8~3~
_1 9 about B to 100 parts by weight of a polyurethane, and about 92 to 0 part by weight of a cyclic olefin, an~ about 90 to 10 parts by weight of a plasticizer compound. Optionally, up to about 50 parts by weight of a coupling agent, up to about 40 parts by weight of an second extender, ana up to 50 parts by weight of a solid iller can be added. The preferred concentration with particular reference to the reclaiming or encapsulating utility comprises about 10 to 50 parts by weight of extended polyurethane as described above, and abo~t 90 to 50 part~ by weight of plasticizer. If amounts less than 10~ polyurethane are used, the resulting gel will have essentially no tear strength at all, while if less than 10~ of plasticizer is used, the re3ulting formulation will not provide the improved properties. The preferred concentration with particular reference to the reclaiming or encapsulating utility comprises about 30 to 40 parts by weight of polyurethane reaction product, about 70 to 60 parts by weight of plasticizer.
If hard, grease compatible formulations are desired, the relative proportions ~ould be about 90 to 50 parks by weight of polyurethane and about tO to 50 parts by weiyht of plasticizer.
The instant cyclic olefin extended materials are preferably prepared at the application site by admixing the resin system with the hardener system. Depending on the desired utility, the resin and hardener are utilized in the required amounts meeting the stoichiometric require~ents.
In a preferred embodiment, the resin component ~omprises the organic polyisocyanate, all or a portion of the ~yclic olefin, at least a portion or all of the plast~cizer and, if present, the benzenoid and coupling agent or other ~2~35347 extenders. The hardener component comprise~ the polyol, and, when present, the remaining portion of the plasticizer a second portion of the same or different coupling agenty any other extender benzenoid compounds, and the remaining portion of the cyclic olefin. The catalyst and optional additives such as fungicides, pigments, anti-oxidants, moisture scavengers, and the like, are generally added to the hardener component. Catalysts are known to those skilled in the art and may comprise, for example, heavy metals ~tilized in amounts of about 0.1 weight percent of the hardener component.
It is also possible to mix all the desired components together in a single batch to prepare the polyurethane and then apply the mixture and allow it to cure to the final product.
As noted, ~he cyclic olefin extended polyurethanes posses~ the desired properties for a range of utilities, with primary emphasis on utilitie~ such as ~rease compatible reenterable encapsulants and reclamants for insulated electrical device~. Initially, these materials are sufficiently fluid to be introduced into the core of a cable or mold surrounding the area of concern and to retain their fluidity for a period of time sufficient to ill all the interior free spaces.
The term "reclamation~ is used to include the 30 situation wherein the polyurethane gel compositions of the invention are injected into damaged telecommunication or electrical cable to displace any fluid contaminants and restore the cable to its initial condition. As the gel 3~t7 -2~-_ cures, it expands and displaces the contaminants in the damaged cable.
The term ~encapsulation" refers to the use of the polyurethane gels of the invention to seal a splice or connection to a cable. In this arrangemellt~ the electrical connections are made to an existing cable, a closure of polyethylene or similar material is made ~round the connection, and the gel composition is injected into the space between the closure and cable, where it expands and cures to form a moisture resistant seal~
In its reclaiming function, the polyurethane will thus displace the liquid penetrants in the free fipaces.
Thereafter~ a stable gel forms within a reasonable period of time to provide a seal against penetration of water or other fluid materials. Where reenterability is desired, the selected polyurethane can be formulated to provide a gel ~hich is sufficiently ~oft qo as to be readily removed. The presence of a cyclic olefin produces a compatible extended polyurethane ~ystem without the u~e of coupling agents, the plasticizer imparts grease compatibility to these compositions.
When lower relative amounts of plasticizers and esters are usedr the insulating properties of the reenterable encapsulant and reclamant are good, particularly with regara to the di~sipation factor and volume resistivity 30 of the material. ~urthermore, there is no exudation of extender~ used and there i5 e~cellent compatibility with materials employed in the cable cons~ruction and ~ith polycarbonante connectors~ In addition, the in~tant extended polyurethanes can be utilized as hard volume ;i3~
~2-(permanent) encapsulants and for general polyurethane elastomeric uses.
Examples The scope of the invention is further described in connection with the following examples which are set forth for the sole purpose of illustrating the preferred embodi-ments of the invention and which are no~ to be construed aslimiting the scope of the invention in any manner. In these examples, all parts siven are by weight unless otherwise specified~
~
The following examples illustrate the preparation of typi~al plasticizer/polyurethane gel sy~tem.q of this invention which are intended for us~ as reenterable reclamants or encapsulants. All components appear i~ parts by weight unles~ otherwise indic~ted.
-23~
Table I - Ty~ical Polyurethane Formula~ion A B C D ~ F
polymethylene 4.8 4.8 4.8 4.8 9.5 ~.8 polyphenyl isocyanate (1) tO castor oil (2) 407 407 4.7 4.7 9.3 4.7 polycyclopentadiene (3)6.5 32.5 16.3~8.7 7.5 1.0 hydroxyl terminated 25.S 25.5 25.525.5 51.2 25.5 polybutadiene (~) diundecyl phthalate - 32.5 ~ - -ditridecyl adipate ~ - - 16.3 - -glyceryl tri (acetyl ricinole~te) ~ - ~8.7 - 22.5 64.0 (l) PAPI 9~ ~rom Up~ohn (2) DB Oil fro~ CaQChem, Inc.
~3) E~copol ~-020 from E~xon ~4) Poly ~D R45 -RT f rom Arco Chemical Polyureth~ne~ we~e then prepared by ~ixing the component~ of each of the above~identlfied formulations.
After curing, 0ach sf ~he~e polyure~hanes were found to be 30 ~oft, cl~ar gels wh~h are ~u~tabl~ for o~e in applications 3uch as the encap~ulation of el~ctrical or ~eleco~unica~ion cabl2.
* Trade-mark ii3~'7 -2~-Each of these formulations was found to have suitable electrical properties for the intended application.
Specifically, dissipation constants ranged from 2.~ to 3.8 and volume resistivities ranged from ~ x lO12 ~o 2 x 1014.
All these values are acceptable for encapsulaton or reclamation compounds.
To de~ermine ~he suitablity of these formulations 1 for grease compatibility, the formulations were then cured on FLEXGEL cable filler, and, after curlng, the weight change of the formulation was measured. Compatible formulations are those which show a weight gain, ~ince this indicates that grease is taken into the formulation.
Incompatible formulations show a weight loss which indi~ates exudation or separation of the extender or plasti~izer from the gel. The tests were repeated for compatibli~y wi,h PE2J
and PJ cable fillers.
~, ~
Table II: Test Results -Formulation % Wei~ht Change FLEXGEL PEPJ P~
A -6.5 -11.2 -9.7 B -4.~ -8.2-10.8 C 72.3 -2.1 -3.2 D ~.3 -9.1 -8.1 E +4.8 +0.4~0.7 F ~6.0 +1.2+2.2 ~2~3~
~r~ 2 She follo~D~ or~ulatlon~ ~llu~triste lt~cal pla~tlci zer/polyureth~ne gel ~y~te~ o~ the! lr~rention ~ih~c~
are intended for u~e as reenterable recl;!lrnanl:~ or encapsul ant~ 0 ~ .31 I J
.
polymethylene polyp)l~nyl 23. 8 23 ~ 823 . 8 3. 0 i~ocyanate ( 1 ) ~Rtor oil ~2) 2.3 _ 2,.3 1.8 diundecyl phthalat~ 12.g 76.2 = 45.2 d~trid~cyl 3~dip~te - - 12. 9 K L M N
hydro:cyl termina~ced 32. 0 320 0 32. 0 13.
polybutad~ene ~ 3 ) ca3tor oil (2) 2.9 5.8 2.g 1.
diundecyl phthalate 65.,1 62.2 65.1 34.8 1 ) PAPI 9û 1 f rom Up john ~2 ) DB Oil f~om CasChem, Inc.
( 3 ) Poly-BI:) R45-HT from Arco Chemicals The following polyurethane gels were then prepared by mixing Resin Sy~tem~3 G, H, I, and J wi~h ~arden~r Syste~s K, L, M, and N, re~pec'cively. AEter c~uring,, cach of l:hese formulatlons were found to be soft, clear g~ which are e~inently ~uitalbla~ ~or u~ ln ~ppll~:ation~ ch ~ the 3~ re~:la~tion o~ cap~ulation o~ tele~:o~un~c~tion cl~ble o1hgn 2 r~ ter~ble for~Dulaltlon l~ ~le~irable.
... .. ... .
~.2853~7 The following for~ulations were then prepared by mixing the followlng components together and allowiny the 5 ~i~ture to cure.
o P Q
polymethylene polyphenyl 5.0 5.5 4.3 isocyanate castor oil (2) - 5.3 10 hydroxyl terminated 45.0 29.2 polybutadiene (3) ditridecyl adipate 50.0 diisodecyl phthalate - 60.0 65.0 polyoxypropylene diol ( 4 ) - - 30. 7 (1 ) PAPI 901 from Upjohllo (2) DB Oil from CasChem, Inc.
53) Po1y-BD R45-HT from Arco Chemicals.
(4~ PPG-2025 from Union Carbide.
TheRe fomulations were also found to be soft, ~lear, gel~, which also would be suitable for reenterable repair applicat;ons.
EXA~PLE 4 The followin~ polymer ~y~tem was p~epared:
~ , Par~
3~ polymethylene polyphenyl isocyanate (1) 13.6 ca~tor oil (2) 13.3 hydroxyl terminated polybutadiene ~3) . 73.1 51) PAPI 901 from Up~ohn.
35 52) D~ Oil from CasChem, IncO
~3) Poly-B~ R45-~T fro~ Arco Chemicals.
3~7 Then~ 65 parts of this polymer sys~m was ~i~ed with 35 part~
of the ollowing plastici~ers to prepare the de~ignated polyurethane formulationsO
Plasticizer ~ormulation d i tr idecyl adipate R
dioctyl adipate s diundecyl phthalate T
soybean oil u 201 mixture of ditridecyl adipate: soybean oil v
:`jJ
~8~;3~
namely the dispersion componen~r the polar component, and the hydrogen bonding component, a~ follow~:
The values which appear in Table 1 are the tota~
-~olubility parameter Y for the plasticizer compounds listed.
With re~pect to the weight change te~ting, there are different type3 of grea~e~ which ~y be encountered in tele~ommunication cable. The mo~t common i3 FLEXGEL cable filler. FLEXG~L i a reglstered trademark of the We~tern Electr~c Co. Inc~ Por their cable ~illing compound~ for waterprooflng ele~trical cable. Oth~r c~bl~s may have petroleum ielly (PJ1 or polyethylene modified petroleu~
~elly ~PEPJ). PEPJ ~ 8 hi$her ~elt~ng point ~terial than PJ. It ~hould be noted that the rlcinoleate~ ~a~e ~ wider range of comp~tlb~lity with ~ll types of c~ble ~iller~ than 20 the other plas~cizer compound~.
With re~pect to the u~e o4 the~e plasticizer co~pounds in th~ formul~tion3 of th~ pre~nt invention, it should be noted that tho~e co~pound~ ha~ihg a ~olubility paramet~r between about 9.1 and lO,l pro~d~ c}ear nd tran~parent gels which ~re preferred or ap~llc~t~o~ ~her~
reenterab~lity is o~ prl~ry i~portan~. All the polyurethane gels according to this invention are soft with a low tear strength, and these properties are maintained over time to provide desirable reenterable compounds.
1 - :
, 1~8~3a~7 It ~hould further be no~ed hat all the suitable pla ticizer components according ~o the inven'cion are low 5 viscosity liquids at room temperature.
A~ stated her2inabove, a coupling ~gent or compatibilizer quch as an e~ter compound i~ not reauired for the extended polyurethane, but ~uch coupling agents m~y 10 optionally be u~ed in the~e e~tended polyurethanes in ~pecific application~. In the ca~e of highly polymerized cyclic olefin~ coupling agent can be used to lower the Vi E;c05i~:y~ if de~ired. When u~ed, the coupling ~gent may range up to about 50 weight per-:~nt of the total extellded 15 polyurethane. ~uch compound~ are non-r~act~Ye or ~ub tantially non-reactive w~ th th@ polyuethane forming companents. ~ter~ are preferred, and they ~ay b~ ~atur~ted or un~aturated and may b~ aliph~ti~:, cycloal~phat~cg or aromatic aliphatic. Typical ester~ i~clu~e phthalate~ such a~ 2-ethylhexyl phthalate, zand ~xture~ of n-C~, Cl~, and C 11 phthalat~, adip~te~ ~uch as ~ ode~yl adipa e and n-octyl-n-de~yl adlpate, glutara~e~, fumztra~e~ ~ebacat~
c~trate~, and th~ e, a~ well a3 polymeric e~ters such n~
Plastoleirl 9720 from ~mery Iridu~trie~, ~ plasticizer having an acid v~lue o~ 3. 0, a~ hydroxyl ~alue of 20, and a viscQ~ity of 207 centi~toke~ at lO0 F to provide a low volat~ y ~terial havlng good r~ tance to oil ex'craction .
The cyclic olefin extended polyur~thane can ~l~o optionally include othes extender co~pound~ ~hich can b~
u~ed w~th or without a compatibilizer. 1!!1O~t oll~
coomerci~Ily ~a~ lable for rubber proce3~ing ~y be used for oil exten~ion of the extended polyurethane~ o th~
inventlon. When u~ed, the~e extender~ can range up * Trade-mark ~53~7 to 50 weiyht percent of the total extended polyurethane.
Examples of compounds included in ~he term processing oils are listed in U.S~ Paten~ No~ 3,107,224, and they can be classified by sourc~ into the following group~: petroleum oils and asphalts, petroleum wa~e~, coal tar oils and pitches~ esters~ chlorinated hydrocarbons, pine tars and oils, phenols, and resins. All of these commercially available materials are essentially hydrocarbon, that is, at least about 50 weight percent carbon and hydrogen.
Preferably, the oil i5 at least about 75 weight percent or more preferably at least about 90 weight percent carbon and hydrogen. As is apparent from the materials listed, the hydrocarbon chains or rings may be interrupted or ~erminated t5 by non-hydrocarbon groups, for instance, ester, ether, or other oxygen-containins linkages.
Usable processing oils are characterized by a viscosity SSV at 100 ~ of at least 3Q~ and preferably at - 20 least about 70. Petroleum oils are most often u ed in extending natural and synthetic fubber~ as well a3 the polyurethanes of this invention, and yenerally are categorized as paraffinic, napthenic (cycloaliphatic), aromatic, or asphaltic oils. ~owe~er, proces~ing oils which combine the characteristics of two or more of these type~
also may be employed. Viscosities fre~uently vary from about 100 - 600 SSU at lOO~F or 35 - 100 SSU at 210-F
although aromatic and/or asphaltic oils of up to 1000 or 2000 or more SS~ at lOO-F are ~ometimes used.
Coal tar pitch, asphalts, asphaltenes, chlorinated biphenyl ethers, chlorinated waxes, chlorinated oils, rosin es~ers, certain esters and amides of styrene-maleic anhydride resins, courmarone-indene resin~, polybutenes, as ~2~353~7 well as many other processing compounds may be used, either alone or in conjunction with oils as a further e~tender.
Aromatic and chlorinated oils may also be u~ed a~ extenders.
Additional extenders composed mainly of hydrocarbons are asually preferred because of their improved hydrolytic properites, oxidative properties~ and lower cost.
Other extender~ include the low ~olecular weight polybutenes or polyisobutylenes as ~ell as the high boiling fractions o petroleum polymers ordinarily used for lubricants.
Chlorinated aromatic and aliphatic hydrocarbons, aromatic ether~, and phosphorus derivatives are par~icularly advantageouc since ~hey may impart some flame retardance to the finished product. m e additional extender may comprise up to about 40 weight percent of the cyclic slefin extended polyurethane.
In accordance with the extended polyurethanes of- 20 the present invention, finely divided solid fillers which are commonly employed in the art as either reinforcing or inert ~illers can also be utilized. The use of such ~olid fillers applie~ mainly to non-reenterable polyurethanes.
Conventional fillers include carbon black, asphaltenese, silica, silica-alumina~ hydrated silica, zinc oxide, magnesium carbonates, clays, talc, and pulv*rized reclaimed rubber as well as various mineral ~illers which are known in the art. Solid fillers may be employed in the amount of up to 50 weight percent the polyurethane.
The cyclic olefin extended polyurethane of the present invention is generally comprised of from about 10 to 90 parts by weight of an extended polyurethane comprising ~L~8~3~
_1 9 about B to 100 parts by weight of a polyurethane, and about 92 to 0 part by weight of a cyclic olefin, an~ about 90 to 10 parts by weight of a plasticizer compound. Optionally, up to about 50 parts by weight of a coupling agent, up to about 40 parts by weight of an second extender, ana up to 50 parts by weight of a solid iller can be added. The preferred concentration with particular reference to the reclaiming or encapsulating utility comprises about 10 to 50 parts by weight of extended polyurethane as described above, and abo~t 90 to 50 part~ by weight of plasticizer. If amounts less than 10~ polyurethane are used, the resulting gel will have essentially no tear strength at all, while if less than 10~ of plasticizer is used, the re3ulting formulation will not provide the improved properties. The preferred concentration with particular reference to the reclaiming or encapsulating utility comprises about 30 to 40 parts by weight of polyurethane reaction product, about 70 to 60 parts by weight of plasticizer.
If hard, grease compatible formulations are desired, the relative proportions ~ould be about 90 to 50 parks by weight of polyurethane and about tO to 50 parts by weiyht of plasticizer.
The instant cyclic olefin extended materials are preferably prepared at the application site by admixing the resin system with the hardener system. Depending on the desired utility, the resin and hardener are utilized in the required amounts meeting the stoichiometric require~ents.
In a preferred embodiment, the resin component ~omprises the organic polyisocyanate, all or a portion of the ~yclic olefin, at least a portion or all of the plast~cizer and, if present, the benzenoid and coupling agent or other ~2~35347 extenders. The hardener component comprise~ the polyol, and, when present, the remaining portion of the plasticizer a second portion of the same or different coupling agenty any other extender benzenoid compounds, and the remaining portion of the cyclic olefin. The catalyst and optional additives such as fungicides, pigments, anti-oxidants, moisture scavengers, and the like, are generally added to the hardener component. Catalysts are known to those skilled in the art and may comprise, for example, heavy metals ~tilized in amounts of about 0.1 weight percent of the hardener component.
It is also possible to mix all the desired components together in a single batch to prepare the polyurethane and then apply the mixture and allow it to cure to the final product.
As noted, ~he cyclic olefin extended polyurethanes posses~ the desired properties for a range of utilities, with primary emphasis on utilitie~ such as ~rease compatible reenterable encapsulants and reclamants for insulated electrical device~. Initially, these materials are sufficiently fluid to be introduced into the core of a cable or mold surrounding the area of concern and to retain their fluidity for a period of time sufficient to ill all the interior free spaces.
The term "reclamation~ is used to include the 30 situation wherein the polyurethane gel compositions of the invention are injected into damaged telecommunication or electrical cable to displace any fluid contaminants and restore the cable to its initial condition. As the gel 3~t7 -2~-_ cures, it expands and displaces the contaminants in the damaged cable.
The term ~encapsulation" refers to the use of the polyurethane gels of the invention to seal a splice or connection to a cable. In this arrangemellt~ the electrical connections are made to an existing cable, a closure of polyethylene or similar material is made ~round the connection, and the gel composition is injected into the space between the closure and cable, where it expands and cures to form a moisture resistant seal~
In its reclaiming function, the polyurethane will thus displace the liquid penetrants in the free fipaces.
Thereafter~ a stable gel forms within a reasonable period of time to provide a seal against penetration of water or other fluid materials. Where reenterability is desired, the selected polyurethane can be formulated to provide a gel ~hich is sufficiently ~oft qo as to be readily removed. The presence of a cyclic olefin produces a compatible extended polyurethane ~ystem without the u~e of coupling agents, the plasticizer imparts grease compatibility to these compositions.
When lower relative amounts of plasticizers and esters are usedr the insulating properties of the reenterable encapsulant and reclamant are good, particularly with regara to the di~sipation factor and volume resistivity 30 of the material. ~urthermore, there is no exudation of extender~ used and there i5 e~cellent compatibility with materials employed in the cable cons~ruction and ~ith polycarbonante connectors~ In addition, the in~tant extended polyurethanes can be utilized as hard volume ;i3~
~2-(permanent) encapsulants and for general polyurethane elastomeric uses.
Examples The scope of the invention is further described in connection with the following examples which are set forth for the sole purpose of illustrating the preferred embodi-ments of the invention and which are no~ to be construed aslimiting the scope of the invention in any manner. In these examples, all parts siven are by weight unless otherwise specified~
~
The following examples illustrate the preparation of typi~al plasticizer/polyurethane gel sy~tem.q of this invention which are intended for us~ as reenterable reclamants or encapsulants. All components appear i~ parts by weight unles~ otherwise indic~ted.
-23~
Table I - Ty~ical Polyurethane Formula~ion A B C D ~ F
polymethylene 4.8 4.8 4.8 4.8 9.5 ~.8 polyphenyl isocyanate (1) tO castor oil (2) 407 407 4.7 4.7 9.3 4.7 polycyclopentadiene (3)6.5 32.5 16.3~8.7 7.5 1.0 hydroxyl terminated 25.S 25.5 25.525.5 51.2 25.5 polybutadiene (~) diundecyl phthalate - 32.5 ~ - -ditridecyl adipate ~ - - 16.3 - -glyceryl tri (acetyl ricinole~te) ~ - ~8.7 - 22.5 64.0 (l) PAPI 9~ ~rom Up~ohn (2) DB Oil fro~ CaQChem, Inc.
~3) E~copol ~-020 from E~xon ~4) Poly ~D R45 -RT f rom Arco Chemical Polyureth~ne~ we~e then prepared by ~ixing the component~ of each of the above~identlfied formulations.
After curing, 0ach sf ~he~e polyure~hanes were found to be 30 ~oft, cl~ar gels wh~h are ~u~tabl~ for o~e in applications 3uch as the encap~ulation of el~ctrical or ~eleco~unica~ion cabl2.
* Trade-mark ii3~'7 -2~-Each of these formulations was found to have suitable electrical properties for the intended application.
Specifically, dissipation constants ranged from 2.~ to 3.8 and volume resistivities ranged from ~ x lO12 ~o 2 x 1014.
All these values are acceptable for encapsulaton or reclamation compounds.
To de~ermine ~he suitablity of these formulations 1 for grease compatibility, the formulations were then cured on FLEXGEL cable filler, and, after curlng, the weight change of the formulation was measured. Compatible formulations are those which show a weight gain, ~ince this indicates that grease is taken into the formulation.
Incompatible formulations show a weight loss which indi~ates exudation or separation of the extender or plasti~izer from the gel. The tests were repeated for compatibli~y wi,h PE2J
and PJ cable fillers.
~, ~
Table II: Test Results -Formulation % Wei~ht Change FLEXGEL PEPJ P~
A -6.5 -11.2 -9.7 B -4.~ -8.2-10.8 C 72.3 -2.1 -3.2 D ~.3 -9.1 -8.1 E +4.8 +0.4~0.7 F ~6.0 +1.2+2.2 ~2~3~
~r~ 2 She follo~D~ or~ulatlon~ ~llu~triste lt~cal pla~tlci zer/polyureth~ne gel ~y~te~ o~ the! lr~rention ~ih~c~
are intended for u~e as reenterable recl;!lrnanl:~ or encapsul ant~ 0 ~ .31 I J
.
polymethylene polyp)l~nyl 23. 8 23 ~ 823 . 8 3. 0 i~ocyanate ( 1 ) ~Rtor oil ~2) 2.3 _ 2,.3 1.8 diundecyl phthalat~ 12.g 76.2 = 45.2 d~trid~cyl 3~dip~te - - 12. 9 K L M N
hydro:cyl termina~ced 32. 0 320 0 32. 0 13.
polybutad~ene ~ 3 ) ca3tor oil (2) 2.9 5.8 2.g 1.
diundecyl phthalate 65.,1 62.2 65.1 34.8 1 ) PAPI 9û 1 f rom Up john ~2 ) DB Oil f~om CasChem, Inc.
( 3 ) Poly-BI:) R45-HT from Arco Chemicals The following polyurethane gels were then prepared by mixing Resin Sy~tem~3 G, H, I, and J wi~h ~arden~r Syste~s K, L, M, and N, re~pec'cively. AEter c~uring,, cach of l:hese formulatlons were found to be soft, clear g~ which are e~inently ~uitalbla~ ~or u~ ln ~ppll~:ation~ ch ~ the 3~ re~:la~tion o~ cap~ulation o~ tele~:o~un~c~tion cl~ble o1hgn 2 r~ ter~ble for~Dulaltlon l~ ~le~irable.
... .. ... .
~.2853~7 The following for~ulations were then prepared by mixing the followlng components together and allowiny the 5 ~i~ture to cure.
o P Q
polymethylene polyphenyl 5.0 5.5 4.3 isocyanate castor oil (2) - 5.3 10 hydroxyl terminated 45.0 29.2 polybutadiene (3) ditridecyl adipate 50.0 diisodecyl phthalate - 60.0 65.0 polyoxypropylene diol ( 4 ) - - 30. 7 (1 ) PAPI 901 from Upjohllo (2) DB Oil from CasChem, Inc.
53) Po1y-BD R45-HT from Arco Chemicals.
(4~ PPG-2025 from Union Carbide.
TheRe fomulations were also found to be soft, ~lear, gel~, which also would be suitable for reenterable repair applicat;ons.
EXA~PLE 4 The followin~ polymer ~y~tem was p~epared:
~ , Par~
3~ polymethylene polyphenyl isocyanate (1) 13.6 ca~tor oil (2) 13.3 hydroxyl terminated polybutadiene ~3) . 73.1 51) PAPI 901 from Up~ohn.
35 52) D~ Oil from CasChem, IncO
~3) Poly-B~ R45-~T fro~ Arco Chemicals.
3~7 Then~ 65 parts of this polymer sys~m was ~i~ed with 35 part~
of the ollowing plastici~ers to prepare the de~ignated polyurethane formulationsO
Plasticizer ~ormulation d i tr idecyl adipate R
dioctyl adipate s diundecyl phthalate T
soybean oil u 201 mixture of ditridecyl adipate: soybean oil v
4:1 mixture of diisodecyl phthalate: soybean oil W
6:7 mixture of dioctyl adipate: mineral oil x 2:1 mixture of 2iisodecyl phthalate: mineral oil y Dioctyl adipate ha~ a to al solubility parameter of 9.U5, ~hich i~ outside the 3cope o ehe invention~ Thu it was used in formulation S a a comparative example. The mineral oil e~tender~ of formulation~ x and Y ~ere al~o u3ed to illustrate ~omparative example~ of pla~t~ci~er material~
which are out~ide of the scope o~ the ~nvention.
. . ~ . .
To determine the suitability of the above formulations for grease compatibility, the formulations were cured on FL~XGEL cable filler and, after ~uri~g, the weight change of the formulat~on was measured. Comp~tible formulation~ ~how a we~ght gain, which inaicat~æ th~t the 35 grea3e i~ taken into the formulation.
Alterna~ely, in~ompatible formulations show a weight loss ~hich indicates an exudation or ~eparation of the ) extender or plasticizer from the gel. Te~t re3ult0 are shown below in Table III.
As a further measure of greas~ compat~bility, an electrical conductor was coated Wil:h FLEXGEL cable filler and encapsulated with the above for~ulations~ After the form~lations cured, the conductor was pulled out of the polyurethane. The force necessary to separate ~he con~uctor from the polyurethane was measured and is al~o listed below in Table III .
Table III Test Results Pull-out Force Formula~ion ~ Wei~ht Chan~(Lbs) _ R ~0.4 4.5 S -1.1 ~.1 T +0.6 6.3 U ~0.4 5.1 V +~.9 5.9 W ~2.0 4.7 X +~.6 5,~
y _5.~ l.8 Z -4.5 ~.0 It is evident from the preceding table that plasticizer~ having a total ~olubility para~eter between about 9.1 and 9.7 or about 8.3 a~d 8.9 are grea~e co~patible, whereas compou~d~ having other solubility 35 parameter~ are not.
;i3~L7 -2~-~XAMPL~ 5 __ _ The following formulation was prepared:
Component Part~
polymethylene polyphenyli~ocyanate (1) A.~
castor oil ~2) 4.6 10 hydroxyl terminated polybutadiene (3) 25.6 glyceryl tri (acetyl ricinoleate) 65 (1) PAPI 901 from ~pjohn (2) DB Oil from CasChem, Inc,
6:7 mixture of dioctyl adipate: mineral oil x 2:1 mixture of 2iisodecyl phthalate: mineral oil y Dioctyl adipate ha~ a to al solubility parameter of 9.U5, ~hich i~ outside the 3cope o ehe invention~ Thu it was used in formulation S a a comparative example. The mineral oil e~tender~ of formulation~ x and Y ~ere al~o u3ed to illustrate ~omparative example~ of pla~t~ci~er material~
which are out~ide of the scope o~ the ~nvention.
. . ~ . .
To determine the suitability of the above formulations for grease compatibility, the formulations were cured on FL~XGEL cable filler and, after ~uri~g, the weight change of the formulat~on was measured. Comp~tible formulation~ ~how a we~ght gain, which inaicat~æ th~t the 35 grea3e i~ taken into the formulation.
Alterna~ely, in~ompatible formulations show a weight loss ~hich indicates an exudation or ~eparation of the ) extender or plasticizer from the gel. Te~t re3ult0 are shown below in Table III.
As a further measure of greas~ compat~bility, an electrical conductor was coated Wil:h FLEXGEL cable filler and encapsulated with the above for~ulations~ After the form~lations cured, the conductor was pulled out of the polyurethane. The force necessary to separate ~he con~uctor from the polyurethane was measured and is al~o listed below in Table III .
Table III Test Results Pull-out Force Formula~ion ~ Wei~ht Chan~(Lbs) _ R ~0.4 4.5 S -1.1 ~.1 T +0.6 6.3 U ~0.4 5.1 V +~.9 5.9 W ~2.0 4.7 X +~.6 5,~
y _5.~ l.8 Z -4.5 ~.0 It is evident from the preceding table that plasticizer~ having a total ~olubility para~eter between about 9.1 and 9.7 or about 8.3 a~d 8.9 are grea~e co~patible, whereas compou~d~ having other solubility 35 parameter~ are not.
;i3~L7 -2~-~XAMPL~ 5 __ _ The following formulation was prepared:
Component Part~
polymethylene polyphenyli~ocyanate (1) A.~
castor oil ~2) 4.6 10 hydroxyl terminated polybutadiene (3) 25.6 glyceryl tri (acetyl ricinoleate) 65 (1) PAPI 901 from ~pjohn (2) DB Oil from CasChem, Inc,
5 ~3) Poly-BD R45-HT from Arco Chemicals This formulation was~then tested for weight change and conductor pullout as described above. The results are summarized below.
Weight change on various cable filler~s FLEXGEL ~5.5 p~pJ +1.6 PJ +0.5 Coated Conductor pull out: 7.0 lbs This sho~ that the ~icinol~ate pl~sticizer 30 imparts the highest degree of compatibility with a variety of commonly encountered cable fillers or greases to the formulation. Other ricinoleate~ having total ~olubility parameter3 within the above di3closed range~ should also ! perform similarly.
:,.
.
Although positive values are preferred for weight change (since this indicates that grease i9 taken in~o the formulation), the formulations having lo~ negative (i.eO -closer to zero) values are also sui~able for many applications.
The results ~how that the novel plasticizing compounds of the invention when added to cyclic olefin 1~ extended polyurethane formulations, improve their grease compatibility by increasing the weight change either to less ne~ative (i.e. - closer to zero) or positive values. Also, compounds that do not possess the disoloRed total solubility ran~e sho~ a lower compatibility with such greases. qhus, polyurethane gels possexsing good electrical properties and improved grease resistants are obtained by this invention.
While it is apparent that the invention herein di~closed is well calculated to fulfill the objec~s above stated, it will ~e appre~iated that numerous modifi~ations and embodiments may be devis~d by those ~killed in the art~
and it is intended that the appended claim~ cover all such modifications and embodiments as fall within the true spirit and scope of the present invention.
Weight change on various cable filler~s FLEXGEL ~5.5 p~pJ +1.6 PJ +0.5 Coated Conductor pull out: 7.0 lbs This sho~ that the ~icinol~ate pl~sticizer 30 imparts the highest degree of compatibility with a variety of commonly encountered cable fillers or greases to the formulation. Other ricinoleate~ having total ~olubility parameter3 within the above di3closed range~ should also ! perform similarly.
:,.
.
Although positive values are preferred for weight change (since this indicates that grease i9 taken in~o the formulation), the formulations having lo~ negative (i.eO -closer to zero) values are also sui~able for many applications.
The results ~how that the novel plasticizing compounds of the invention when added to cyclic olefin 1~ extended polyurethane formulations, improve their grease compatibility by increasing the weight change either to less ne~ative (i.e. - closer to zero) or positive values. Also, compounds that do not possess the disoloRed total solubility ran~e sho~ a lower compatibility with such greases. qhus, polyurethane gels possexsing good electrical properties and improved grease resistants are obtained by this invention.
While it is apparent that the invention herein di~closed is well calculated to fulfill the objec~s above stated, it will ~e appre~iated that numerous modifi~ations and embodiments may be devis~d by those ~killed in the art~
and it is intended that the appended claim~ cover all such modifications and embodiments as fall within the true spirit and scope of the present invention.
Claims (28)
1. A grease compatible cyclic olefin extended polyurethane composition comprising from about 10 to 90 parts of the liquid reaction product of an organic polyisocyanate with a polyol in the presence of a liquid cyclic olefin, the polyisocyanate polyol reaction product being present in a range from about 8 to 99 parts by weight, and said cyclic olefin being present in range of from about 92 to 1 part by weight, and from about 90 to 10 parts by weight of a plasticizer having a total solubility parameter of between about 9.1 and 10.1.
2. The composition according to claim 1 wherein said organic polyisocyanate in selected from the group consisting of aliphatic, cycloaliphatic, and aromatic polyisocyanates.
3. The composition according to claim 2 wherein said organic polyisocyanate is polymethylene polyphenylisocyanate or methylenediisocyanate.
4. The composition according to claim 1 wherein said organic polyisocyanate is a polyisocyanate prepolymer prepared by reacting an excess of a polyisocyanate compound and polyol .
5. The composition according to claim 1 wherein said polyol is selected from the group consisting of castor oil, polyether polyols, hydroxyl-bearing hompolymers of dienes, hydroxyl-bearing copolymers of dienes, and mixtures thereof.
6. The composition according to claim 5 wherein said polyol is a hydroxyl terminated polybutadiene.
7. The composition according to claim 1 wherein the liquid cyclic olefin is polycyclopentadiene, dicyclopentadiene, pinene, or dipentene.
8. The composition according to claim 1 wherein said plasticizer is diundecyl phthalate, diisodecyl phthalate, glyceryl tri (acetyl ricinoleate), or dibutyl phthalate.
9. The grease compatible polyurethane composition comprising about 50 to 90 parts of the liquid reaction product of an organic polyisocyanate and polyol in the presence of a liquid cyclic olefin, the polyisocyanate polyol reaction product being present in a range of from 8 to 99 parts by weight and said cyclic olefin being present in a range from 92 to 1 part by weight, and from about 50 to 10 parts of a plasticizer compound having a total solubility parameter of 9.1. and 10.1.
10. A grease compatible cyclic olefin extended polyurethane gel composition comprising from about 10 to 50 parts of the liquid reaction product of an organic polyisocyanate with a polyol in the presence of liquid cyclic olefin, the polyisocyanate polyol reaction product being present in a range of from about 8 to 99 parts by weight and said cyclic olefin being present in a range from about 92 to 1 part by weight, and from about 90 to 50 parts by weight of a plasticizer having a total solubility parameter of between about 9.1 and 10.1.
11. The gel composition of claim 10 wherein the liquid reaction product is present in the range of from about 30 to 40 parts by weight and the plasticizer compound is present in a range of about 70 to 60 parts by weight.
12. A process for providing a fluid impervious protective seal around an insulated electrical device which comprises introducing the components of the composition of claim 1 into a confined space surrounding the section of a device to be protected and allowing said composition to cure to a gel.
13. A process for providing a fluid impervious protective seal around an insulated electrical device which comprises introducing the components of the composition of claim 9 into a confined space surrounding the section of a device to be protected and allowing said composition to cure to a gel.
14. A process for providing a fluid impervious protective seal around an insulated electrical device which comprises introducing the components of the composition of claim 10 into a confined space surrounding the section of a device to be protected and allowing said composition to cure to a gel.
15. A process for providing a fluid impervious protective seal around an insulated electrical device which \
comprises introducing the components of the composition of claim 11 into a confined space surrounding the section of a device to be protected and allowing said composition to cure to a gel.
comprises introducing the components of the composition of claim 11 into a confined space surrounding the section of a device to be protected and allowing said composition to cure to a gel.
16. The process of claim 12 wherein said composition is used to encapsulate said device.
17. The process of claim 12 wherein said composition is used to reclaim said device.
18. The process of claim 16 wherein said composition contains 30 to 40 parts by weight of liquid reaction product and 70 to 60 parts by weight of plasticizer compound.
19. The process of claim 17 wherein said composition contains 30 to 40 parts by weight of liquid reaction product and 70 to 60 parts by weight of plasticizer compound.
20. An insulated electrcal device comprising a plurality of insulated wire conductors and the cured polyurethane gel of claim 1.
210 An insulated electrical device comprising a plurality of insulated wire conductors and the cured polyurethane gel of claim 9.
22. An insulated electrical device comprising a plurality of insulated wire conductors and the cured polyurethane gel of claim 10.
23. An insulated electrical device comprising a plurality of insulated wire conductors and the cured polyurethane gel of claim 11.
24. A grease compatible polyurethane composition comprising a liquid cyclic olefin and about 50 to 90 parts of the liquid reaction product of an organic polyiscocyanate and a polyol in the presence of about 50 to 10 parts of a plasticizer compound having a total solubility parameter of between about 9.1 and 10.1.
25. The composition according to claim 24 wherein said plasticizer is diundecyl phthalate, diisodecyl phthalate, glyceryl tri(acetyl ricinoleate), or dibutyl phthalate.
26. A grease compatible polyurethane composition comprising from about 10 to 90 parts by weight of the liquid reaction product of an organic polyisocyante with a polyol in the presence of a liquid cyclic olefin, the polyisocyante polyol reaction product being present in a range of from about 8 to 99 parts by weight and the cyclic olefin being present in a range of about 92 to 1 part by weight and about 90 to 10 parts by weight of tridecyl adipate or soybean oil.
27. A grease compatible polyurethane composition comprising about 50 to 10 parts of the liquid reaction product of an organic polyisocyanate and a polyol in the presence of a cyclic olefin and about 50 to 90 parts of a plasticizer compound having a total solubility parameter of between about 9.1 and 10.1.
28. The composition according to claim 27 wherein said plasticizer is diundecyl phthalate, diisodecyl phthalate, glyceryl tri(acetyl ricinoleate), or dibutyl phthalate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/713,378 US4596743A (en) | 1983-11-18 | 1985-03-19 | Grease compatible extended polyurethanes |
| US713,378 | 1985-03-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1285347C true CA1285347C (en) | 1991-06-25 |
Family
ID=24865898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000482356A Expired - Lifetime CA1285347C (en) | 1985-03-19 | 1985-05-24 | Grease compatible extended polyurethanes |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1285347C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111902451A (en) * | 2018-04-05 | 2020-11-06 | 三井化学株式会社 | Polyurethane gel material, polyurethane gel, biomimetic material and manufacturing method of polyurethane gel |
-
1985
- 1985-05-24 CA CA000482356A patent/CA1285347C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111902451A (en) * | 2018-04-05 | 2020-11-06 | 三井化学株式会社 | Polyurethane gel material, polyurethane gel, biomimetic material and manufacturing method of polyurethane gel |
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| MKLA | Lapsed | ||
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