CA1074486A - Polyurethane composition having easy re-entry property - Google Patents
Polyurethane composition having easy re-entry propertyInfo
- Publication number
- CA1074486A CA1074486A CA220,625A CA220625A CA1074486A CA 1074486 A CA1074486 A CA 1074486A CA 220625 A CA220625 A CA 220625A CA 1074486 A CA1074486 A CA 1074486A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- diisocyanate
- solid
- nco
- triol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06C—LADDERS
- E06C7/00—Component parts, supporting parts, or accessories
- E06C7/14—Holders for pails or other equipment on or for ladders
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Ladders (AREA)
- Supports Or Holders For Household Use (AREA)
Abstract
ABSTRACT
This invention is directed to liquid polyurethane prepolymer compositions having free NCO groups, made from organic diisocyan-ate; aliphatic triol; and liquid organic plasticizer material compatible with the composition which has an NCO content of about 1.2-2.5%. This prepolymer composition is cured with a solution composition of urethane curing agent; liquid organic plasticizer compatible with the cured composition; and an organo-metallic catalyst, effective at ambient temperature, to a solid having resiliency; a waterproof solid (metal, plastic paper, or the like) interface; but crumbling under shearing force applied to the surface of interior of the solid, permitting easy break-away reentry into a cable splice, into an embedment, into an encapsulation, or to a surface coated with said solid. Compo-sition, package and method description is presented.
This invention is directed to liquid polyurethane prepolymer compositions having free NCO groups, made from organic diisocyan-ate; aliphatic triol; and liquid organic plasticizer material compatible with the composition which has an NCO content of about 1.2-2.5%. This prepolymer composition is cured with a solution composition of urethane curing agent; liquid organic plasticizer compatible with the cured composition; and an organo-metallic catalyst, effective at ambient temperature, to a solid having resiliency; a waterproof solid (metal, plastic paper, or the like) interface; but crumbling under shearing force applied to the surface of interior of the solid, permitting easy break-away reentry into a cable splice, into an embedment, into an encapsulation, or to a surface coated with said solid. Compo-sition, package and method description is presented.
Description
~17~36 1 This inven~ion relates to liquid polyure~hane prepolymer compositions; also to solid polyurethane compositions having easy reentry property; also to a package of liquid polyurethane prepol~mer composition an.d of a liquid curi.ng solution therefor;
and also to a method of encapsulatingO emhedding or suxface protective coating a solid article to whic~ future access (re-entry) is desired~
Since approximately 1955, when the initial use of plastic shea~h telephone cables beg~n to be used ~y the operating tele-phone companies in the United States, there have been a variekyof m~hods and kechni~ues concerning the protection of splice connections. ~hese have varied from such devices as hermeti-cally sealed metal and plastic cases, to multiple layers of tape wrappings; adaptation of lead sleeving, plastic and metal de~ices ha~ing rubber and neoprene grommets, as well as total encapsulation in ma~y varied closures using such diversified fillers as paraffin, wax, tar, epoxy, and polyurethane, to mention a ew. More recently, there have been a nwmber of attempts to utilize polye~hylene jelly and variations of this type ma~erial for wa~erproof encapsulation of wire connections -yet remain somewhat reentera~le.
The ever increasing application of buried wire and ~able has brought about ~he requirements to develop a more foolproof : closure method for both new splicin~ as well as repair of damaged wire a~d cable that would result in extremely high waterproo~ integrity, yet not invol~e undue cost for materials nvr excessive time in labor required to do ~he work. To date, for one reason or another~none o~ the closures nor materials . .-offered met all of the demanding requirements of the operating telephone compa~ies. Namely, 1) very low cost; 2) exkremely : -~imple; 3) l~w labor; 4) quickly reenterable; 5) safe o~ any type plastic insulated wire~ .
, . ,: ' ''.' . :
'~7~16 1 The mat~rial whic~ most nearly met th~ above x~quirements was developed a few years ago and is a soft cable jelly, com-mercially available as ICKYPIC II Cable Jelly. Unlike other jellies~ this material could be safely used on older poly-e~hylene insulated conductor~, as well as on the newer poly-propylene insulated conductors. Thi9 meanl: that it could be applied on all existing plastic sheath cables used since 1955 in the telephone industry throug~out the United States. Although hig~ly successful, it had a distinct disadvantage in that work-men, generally speaking, abhorred the use o~ any jelly-type material because in each case it was soft and sticky, and has a propensity to quickly transfer to workmens' tools, clothes, o~her pieces of materials, etc. While meeting many desirable r~quirements as previousl~ mentioned above, it was obviousl~ not the final solution for waterproo encapsulation of telephone cable and service wire splices.
A. ~IQUID POLYUR~TH~E PREPOLYMER COMPOSITI~N:
Prepolymer A
The liquid polyurethane prepolymer composition of the in-vention compri~es an ~CO (isocyanate) group containing compo-sition made from:
(a) organic diisocyanate:
~b) aliphatis txiol of a molecular weight of about 1500- .
60~0, D o~~t~ the ~CO/~H ratio of said diisocyanate and said triol charged is a~out 1.0-1.6; and ~C~
~ liquid, organic plasticizer material essentially inert to ~CO reaction and essentially compatible wi~h the diisocyanate- -triol reaction product;
~ said organic plasticiæer being present in a~ amount to provide a composition having an ~CO content o about 1.2-~.5%;
and
and also to a method of encapsulatingO emhedding or suxface protective coating a solid article to whic~ future access (re-entry) is desired~
Since approximately 1955, when the initial use of plastic shea~h telephone cables beg~n to be used ~y the operating tele-phone companies in the United States, there have been a variekyof m~hods and kechni~ues concerning the protection of splice connections. ~hese have varied from such devices as hermeti-cally sealed metal and plastic cases, to multiple layers of tape wrappings; adaptation of lead sleeving, plastic and metal de~ices ha~ing rubber and neoprene grommets, as well as total encapsulation in ma~y varied closures using such diversified fillers as paraffin, wax, tar, epoxy, and polyurethane, to mention a ew. More recently, there have been a nwmber of attempts to utilize polye~hylene jelly and variations of this type ma~erial for wa~erproof encapsulation of wire connections -yet remain somewhat reentera~le.
The ever increasing application of buried wire and ~able has brought about ~he requirements to develop a more foolproof : closure method for both new splicin~ as well as repair of damaged wire a~d cable that would result in extremely high waterproo~ integrity, yet not invol~e undue cost for materials nvr excessive time in labor required to do ~he work. To date, for one reason or another~none o~ the closures nor materials . .-offered met all of the demanding requirements of the operating telephone compa~ies. Namely, 1) very low cost; 2) exkremely : -~imple; 3) l~w labor; 4) quickly reenterable; 5) safe o~ any type plastic insulated wire~ .
, . ,: ' ''.' . :
'~7~16 1 The mat~rial whic~ most nearly met th~ above x~quirements was developed a few years ago and is a soft cable jelly, com-mercially available as ICKYPIC II Cable Jelly. Unlike other jellies~ this material could be safely used on older poly-e~hylene insulated conductor~, as well as on the newer poly-propylene insulated conductors. Thi9 meanl: that it could be applied on all existing plastic sheath cables used since 1955 in the telephone industry throug~out the United States. Although hig~ly successful, it had a distinct disadvantage in that work-men, generally speaking, abhorred the use o~ any jelly-type material because in each case it was soft and sticky, and has a propensity to quickly transfer to workmens' tools, clothes, o~her pieces of materials, etc. While meeting many desirable r~quirements as previousl~ mentioned above, it was obviousl~ not the final solution for waterproo encapsulation of telephone cable and service wire splices.
A. ~IQUID POLYUR~TH~E PREPOLYMER COMPOSITI~N:
Prepolymer A
The liquid polyurethane prepolymer composition of the in-vention compri~es an ~CO (isocyanate) group containing compo-sition made from:
(a) organic diisocyanate:
~b) aliphatis txiol of a molecular weight of about 1500- .
60~0, D o~~t~ the ~CO/~H ratio of said diisocyanate and said triol charged is a~out 1.0-1.6; and ~C~
~ liquid, organic plasticizer material essentially inert to ~CO reaction and essentially compatible wi~h the diisocyanate- -triol reaction product;
~ said organic plasticiæer being present in a~ amount to provide a composition having an ~CO content o about 1.2-~.5%;
and
-2-7~
said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged. Here-inafter, the aforesaid prepolymer composition will be referred to as "Prepolymer A".
Prepolymer Al--A more specific liquid polyurethane prepolymer composition of the invention comprises an NCO group containing composition made from:
(a) aromatic diisocyanate;
(b) polyoxypropylene derivatives of alkanetriol where alkane has 3-6 carbon atoms, having a molecular weight of about 1500-6000;
the NCO/OH ratio of said diisocyanate and said triol derivative charged is about 1.3; and (c) liquid, plasticizer ester of (i) alkanol, alkanediol oxyalkylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkanedioic acid, said ester is essentially compatiL~le with the diisocyanatP-triol derivative reaction product, and has a viscosity of not moxe than about 75 centipoises at about 20C
said ester being present in an amount to provide a com~
position having an NCO content of about 1.5-1.8~ and a viscosity : :
of about 1300-1800 centipoises at 21.1 C (70 F) . Hereinafter the aforesaid more specific prepolymer composition will be re-ferred to as "Prepolymer Al".
Prepolymer A2::
A particular exemplary liquid polyurethane prepolymer composition of the invention comprises an NCO group containing composition made from: .
~ 3 ~
:
: . . . . . .
.
' ': .`, :' ` :, , ~L~7~6 (a) tolylene diisocyanate, about 7.1 weight parts;
(b) polyoxypropylene derivative of trimethylolpropane, of molecular weight about 4500, about 68.1 weight parts; and - .
.
-':~
.: - , . . ~........... ' . ' :
: , . : ' ,, ; ~
~44~
1 ~c) dioctyl adipate, about 24.9 weight parts;
said compositiQn having an ~CO content of about 1 ~ o~ 7~
weight percent and a viscosity of about ~ centipoises at 21.1C (70F). Hereinafter the aforesaid exemplary prepolymer composition will be referred to as "Prepol~mer A2".
B. THE CURI~G SOLUTION COMPOSITIO~:
Curin~ Solution B:
Curing solution composition for use with Prepolymer A con sists essentially of:
~a) a curing agent, in a curing amount, for the polyure-thane prepolymer composition of Prepol~mer A selected from khe class consisking of polyols, organic diamines and aminoalkanols;
(b) liquid, organic plasti~izex material essentially inert to ~CO reaction and essentially compatible with cured, solid polyure~hane comp~sition o~ this invention; and (c) organo-metallic cong?ound e:Efective for catalyzing the ambient temperature reaction of iso~anate groups and h~droxyl or amine groups, and soluble in said plasticizer (b~ ~bove. . :
HereinaEter, the aforesaid curing so:Lution co~position will be ~0 referred to as "curing solution Curinq solution Bl:
A more specific curin~ solution composition of t~e inven tion consists essentially o~
~ a) a curing agent, in a curin~ amount, ~or ~he polyure-khane pxepolymer composition of Prepolymer A selected from the class o aromatic di~mines, alip~atic diamines and ~minoalkanols;
(b1 liquid, plasticizer ester o~ ~i) alkanol, alkanediol, oxyalkylenediol, or polyoxyalkylenediol and (ii~ alkanoic acid or alkanedioic acid, said ester is ~ssentially compatible with the cured, solid polyure~hane composition of this invention; and (c) a soluble organo-me~allic compsund effective for caka-: lyzing ~he ambient temperature reaction of isocyanate groups with 1 hydro~yl or amine groups. Hereinafter, the aforesaid more sp ci~ic curing solution will be referred to as "curing solution Bl".
Curinq solution B2:
A particular exemplary curing solutio.il of the inventionconsists essenti~ly of:
(a) ~,N,~'vN~-tetrakis(2-hydroxypropyl) ethylene diamine curing agent, about 2.7 weight parts;
(h) liquid, plasticizer 2,2,4-trimet~yl-l, 3-pentanedlol diisobut~rate, about 9703 weight parts; and ~ c) a soluble lead catalyst, suc~ as lead octoate, about O.04 weight parks. Hereinafter, the aforesaid exemplary curing solution will be referred to a~ "curing solution B2".
C. ~ sIrIo~:
The solid, polyure~hane composition of the invention possesses structuxal strength against re~o~di~g forces and also possesses the ~aracteristic of crumbling under shearing force appli~d to ~he surace of the solid or from ~he interior of ~he solid, permitting t~e solid to ~e removed from anoth~r ~ ~:
2a solid object e~capsulated by, or embedded in, or pro~ective coated on a surace khereof, o~ said solid polyurethane; the solid polyuretllane composition consists essentially of, (I) a:Eoresaid prepolymex A; and aforesaid curing solultion B: ~
said prepo~ymer P~ and said curing solution B when intermingl~d ~-cure~ at am~ient tempexatures, to solid polyuret~ane composi-; tion possessing ~he afor~said crumbling characteristic, A more specific solid po~yurethane eompo~ition of the in-vention, possessing ~he hereinabove set forth characteristics, consists essentially of (S) aforesaid prepolymer Al; and (I~) aforesaid curing solution Bl~ in an amount to produce ~37~6 1 a solid polyurethane comæosition ha~ing a Shore hardness of about 7~15 in a time of not more than about 30 minutes at about 20C and possessed o~ th~ aforesaid crumbling characteristic.
A particular exemplary solid polyurethane composition of the invention~ possessing the hereinabove set forth character istics~ consists essentially of:
(I~ aforesaid prepolymer A2; and (II~ aforesaid curing solution B2, and w~en abouk equ~l weight parts of tI) a~d (II) are intermingled at about 21olQC
a ~olid polyuxethane, having a Shore hardness of about 10, is obtained in about 10 minutes.
D T~E TWO-PART P~CKAG~ ASSEMBLY
_, _ In another aspect, the invention is directed to a two~part package asse~bly adapted for produ~ing a solid polyurethane composition ~hen ~he contents of ~he ~wo parts are intermingled, which assembly consists essential~y of:
(I) a first package part conta:ining aforesaid Prepolymar A; and (II) a second package part containing aforesaid curing solution ~.
In a more specific a~pect, the ~wo-part package assembly is adapted to produce a solid polyurethane composition w~en the contents of the two parts are intermingled, which as~em~ly consiæts essentially o~:
(I~ a firsk package part containing aforesaid Prepolymer A; and (II) a second package part containing aoresaid curing solution Bl, in an ~mount to produca a solid polyurethane compo-sition havin~ a Shore hardness of about 7-15 in a time of not more than ~bout 30 minutes at about 20C.
A particular exemplary two-part package assemhly adapted for producing a solid polyure~hane composition wh~n khe contents ~7~6 1 of the two parts are intermingled, which assembly consists essenti~lyof:
(I~ a first pac~age part containing aforesaid Prepolymer A2; and (II3 a second package part containing a~oresaid curing solution B2; and when about e~ual weight parts of (I) and (II) are intenmingled at about 21.1C; a solid polyurethane, having a Shore hardness of about lO is obtained in a~out lO minutes.
E. METHOD OF E~CAPSUhATIO~ AND THE LIK~.
.
A method of encapsulating a cable splice, or capping a cable end, or embedding a solid article, or protective coating a surface with a solid waterproof resilient reenterable poly- . ;
urethane which method comprises~
(1) intermingling to form a flowable liquid composition; ~;.
(I) aforesaid Prepolymer A;
(II) aforesaid curing solution B; and (2) placing said liquid composition into contact with the outer surfaces of said splice, or end, or article, or :~:
surfa~e~ at ambient temperature for ~he time needed for the liquid composition to cure to a solid having the a~oresaid characteristics.
A more specific method of the invention comprises:
~1) intermingling to form a flo~able liquid composition;
(I) aforesaid Prepol~mer Al; and ;
(II) aforesaid Prepol~mer B1, in an amount to produce a solid polyuret~ane composition having a Shore hardness of about 7 15 in a time o~ not more than about 30~minutes at about 20C
and posses~ed of the afore described crumbling c~aracteristic; ..
and ~2) placing said liquid composition into contact with surface described hereinabove at ambient temperatuxe for ~he time needed for ~he liquid composition to cure to a solid having the - ' , ' ~
~7~8~
1 aforesaid characteristics.
A particular exemplary method of the invention compri~es:
(1) intermingling to form a flowable liquid composition;
(I) aforesaid prepolymer A2, and (II) aforesaid prepolymer B2; and when about equal parts by weight of (I) and (II) a~e intermingled at about 21.1C, a solid polyure~hane having a Shore hardness o a~ou~ 10 is o~tained in about 10 minutes;
(2~ placing said liquid composition into contact wi~h surface ~escribed hereinabove at ambient temperature for the time needed for the liquid composition to cure to a solid having the aforesaid chara~teristics.
DESCRIPTION A~D EX~MPLE
P~ r ~9a~ ' ' The liquid polyurethane prepslymer c omposition of ~he :
invention m~y be prepared from any suitable organic diisocyanate.
Particular classes used include: aromatic diisocyanates; ali-phatic diiso~yanates; cycloaliphatic diisocyanates; and hetero-cy d ic diisocyanates.
Illustrative aromatic diisocyanates are: (it is to be understood "diisocyanate" must be read at the end of each of the following terms) tolylene; tolidine; xylylene; phen~lene, napht~ylene; dianisidine; l-chloro-2~4-phenylene; 3,3'-dimethyl-; 4,4'-dip~enylmethane; 4,4'-diphenylmethane;3,3'-dimethyl-4~4'-biphenylene; 3,3'-dimet~oxy-4,4~-biphenylene, 2,2'5,5'-terameth~l-4,4'-biphen~lene; 4,4'-diphenylisopropylidene; 3,3'-dimethyl-4, 4'-diphenyl; 3,3'-dimethoxy-4,4'-diphen~
Illustrative aliphatic diisocyanates are: (it is to be ~:
understood "diiso~yanate" must be read at the end of each of : :
the following~erms) methylenebis (cyclohexylisocyanata) lno di term] methylene 7 ethylene; trimethylene; tetxamethylene;
hexamethylene; 18 carbon atty acid dimer.
,~ ,, ~aD7~ 6 1 I llustrati~e cycloaliphatic diisocyanates are: cyclohexylene diisocyanat2, 1-isocyanato-3-isocanatomethyl-3,5,5-trimethyl cyclo~exane, and isophorone (3,5,5-trimethyl-2-cyclohenen-1-one diiso~yanate).
A typical heterocyclic diisocyanate is furfurylidene diisocyanate.
The triol(s) used in preparing the prepolymer composition of the invention is aliphatic triol of a molecular weight of about 1500 6000, desirably 3000-6000.
A suitable triol is a mixture of castor oil glycerides transesterified to im~rove reactivity with isocyanate groups.
The desired triols are derivatives ~adducts) of a trihydric compound with ~n alkylene oxide~ or mixtuxes thereof, haviny 2-4 carbon a~ms~ such as, e~hylene o~ide, propylene oxide, and bu~ylene oxide.
Preferred are the aliphatic triols which are polyoxyalky lene derivatives of alkanetriol, where the "alkylene" poxtion has 2-4 car~on atoms and the "alkane" portion has 3-10 carbon atoms, Especially preferred are: "alkylene" is propylene; "alkane" has
said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged. Here-inafter, the aforesaid prepolymer composition will be referred to as "Prepolymer A".
Prepolymer Al--A more specific liquid polyurethane prepolymer composition of the invention comprises an NCO group containing composition made from:
(a) aromatic diisocyanate;
(b) polyoxypropylene derivatives of alkanetriol where alkane has 3-6 carbon atoms, having a molecular weight of about 1500-6000;
the NCO/OH ratio of said diisocyanate and said triol derivative charged is about 1.3; and (c) liquid, plasticizer ester of (i) alkanol, alkanediol oxyalkylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkanedioic acid, said ester is essentially compatiL~le with the diisocyanatP-triol derivative reaction product, and has a viscosity of not moxe than about 75 centipoises at about 20C
said ester being present in an amount to provide a com~
position having an NCO content of about 1.5-1.8~ and a viscosity : :
of about 1300-1800 centipoises at 21.1 C (70 F) . Hereinafter the aforesaid more specific prepolymer composition will be re-ferred to as "Prepolymer Al".
Prepolymer A2::
A particular exemplary liquid polyurethane prepolymer composition of the invention comprises an NCO group containing composition made from: .
~ 3 ~
:
: . . . . . .
.
' ': .`, :' ` :, , ~L~7~6 (a) tolylene diisocyanate, about 7.1 weight parts;
(b) polyoxypropylene derivative of trimethylolpropane, of molecular weight about 4500, about 68.1 weight parts; and - .
.
-':~
.: - , . . ~........... ' . ' :
: , . : ' ,, ; ~
~44~
1 ~c) dioctyl adipate, about 24.9 weight parts;
said compositiQn having an ~CO content of about 1 ~ o~ 7~
weight percent and a viscosity of about ~ centipoises at 21.1C (70F). Hereinafter the aforesaid exemplary prepolymer composition will be referred to as "Prepol~mer A2".
B. THE CURI~G SOLUTION COMPOSITIO~:
Curin~ Solution B:
Curing solution composition for use with Prepolymer A con sists essentially of:
~a) a curing agent, in a curing amount, for the polyure-thane prepolymer composition of Prepol~mer A selected from khe class consisking of polyols, organic diamines and aminoalkanols;
(b) liquid, organic plasti~izex material essentially inert to ~CO reaction and essentially compatible with cured, solid polyure~hane comp~sition o~ this invention; and (c) organo-metallic cong?ound e:Efective for catalyzing the ambient temperature reaction of iso~anate groups and h~droxyl or amine groups, and soluble in said plasticizer (b~ ~bove. . :
HereinaEter, the aforesaid curing so:Lution co~position will be ~0 referred to as "curing solution Curinq solution Bl:
A more specific curin~ solution composition of t~e inven tion consists essentially o~
~ a) a curing agent, in a curin~ amount, ~or ~he polyure-khane pxepolymer composition of Prepolymer A selected from the class o aromatic di~mines, alip~atic diamines and ~minoalkanols;
(b1 liquid, plasticizer ester o~ ~i) alkanol, alkanediol, oxyalkylenediol, or polyoxyalkylenediol and (ii~ alkanoic acid or alkanedioic acid, said ester is ~ssentially compatible with the cured, solid polyure~hane composition of this invention; and (c) a soluble organo-me~allic compsund effective for caka-: lyzing ~he ambient temperature reaction of isocyanate groups with 1 hydro~yl or amine groups. Hereinafter, the aforesaid more sp ci~ic curing solution will be referred to as "curing solution Bl".
Curinq solution B2:
A particular exemplary curing solutio.il of the inventionconsists essenti~ly of:
(a) ~,N,~'vN~-tetrakis(2-hydroxypropyl) ethylene diamine curing agent, about 2.7 weight parts;
(h) liquid, plasticizer 2,2,4-trimet~yl-l, 3-pentanedlol diisobut~rate, about 9703 weight parts; and ~ c) a soluble lead catalyst, suc~ as lead octoate, about O.04 weight parks. Hereinafter, the aforesaid exemplary curing solution will be referred to a~ "curing solution B2".
C. ~ sIrIo~:
The solid, polyure~hane composition of the invention possesses structuxal strength against re~o~di~g forces and also possesses the ~aracteristic of crumbling under shearing force appli~d to ~he surace of the solid or from ~he interior of ~he solid, permitting t~e solid to ~e removed from anoth~r ~ ~:
2a solid object e~capsulated by, or embedded in, or pro~ective coated on a surace khereof, o~ said solid polyurethane; the solid polyuretllane composition consists essentially of, (I) a:Eoresaid prepolymex A; and aforesaid curing solultion B: ~
said prepo~ymer P~ and said curing solution B when intermingl~d ~-cure~ at am~ient tempexatures, to solid polyuret~ane composi-; tion possessing ~he afor~said crumbling characteristic, A more specific solid po~yurethane eompo~ition of the in-vention, possessing ~he hereinabove set forth characteristics, consists essentially of (S) aforesaid prepolymer Al; and (I~) aforesaid curing solution Bl~ in an amount to produce ~37~6 1 a solid polyurethane comæosition ha~ing a Shore hardness of about 7~15 in a time of not more than about 30 minutes at about 20C and possessed o~ th~ aforesaid crumbling characteristic.
A particular exemplary solid polyurethane composition of the invention~ possessing the hereinabove set forth character istics~ consists essentially of:
(I~ aforesaid prepolymer A2; and (II~ aforesaid curing solution B2, and w~en abouk equ~l weight parts of tI) a~d (II) are intermingled at about 21olQC
a ~olid polyuxethane, having a Shore hardness of about 10, is obtained in about 10 minutes.
D T~E TWO-PART P~CKAG~ ASSEMBLY
_, _ In another aspect, the invention is directed to a two~part package asse~bly adapted for produ~ing a solid polyurethane composition ~hen ~he contents of ~he ~wo parts are intermingled, which assembly consists essential~y of:
(I) a first package part conta:ining aforesaid Prepolymar A; and (II) a second package part containing aforesaid curing solution ~.
In a more specific a~pect, the ~wo-part package assembly is adapted to produce a solid polyurethane composition w~en the contents of the two parts are intermingled, which as~em~ly consiæts essentially o~:
(I~ a firsk package part containing aforesaid Prepolymer A; and (II) a second package part containing aoresaid curing solution Bl, in an ~mount to produca a solid polyurethane compo-sition havin~ a Shore hardness of about 7-15 in a time of not more than ~bout 30 minutes at about 20C.
A particular exemplary two-part package assemhly adapted for producing a solid polyure~hane composition wh~n khe contents ~7~6 1 of the two parts are intermingled, which assembly consists essenti~lyof:
(I~ a first pac~age part containing aforesaid Prepolymer A2; and (II3 a second package part containing a~oresaid curing solution B2; and when about e~ual weight parts of (I) and (II) are intenmingled at about 21.1C; a solid polyurethane, having a Shore hardness of about lO is obtained in a~out lO minutes.
E. METHOD OF E~CAPSUhATIO~ AND THE LIK~.
.
A method of encapsulating a cable splice, or capping a cable end, or embedding a solid article, or protective coating a surface with a solid waterproof resilient reenterable poly- . ;
urethane which method comprises~
(1) intermingling to form a flowable liquid composition; ~;.
(I) aforesaid Prepolymer A;
(II) aforesaid curing solution B; and (2) placing said liquid composition into contact with the outer surfaces of said splice, or end, or article, or :~:
surfa~e~ at ambient temperature for ~he time needed for the liquid composition to cure to a solid having the a~oresaid characteristics.
A more specific method of the invention comprises:
~1) intermingling to form a flo~able liquid composition;
(I) aforesaid Prepol~mer Al; and ;
(II) aforesaid Prepol~mer B1, in an amount to produce a solid polyuret~ane composition having a Shore hardness of about 7 15 in a time o~ not more than about 30~minutes at about 20C
and posses~ed of the afore described crumbling c~aracteristic; ..
and ~2) placing said liquid composition into contact with surface described hereinabove at ambient temperatuxe for ~he time needed for ~he liquid composition to cure to a solid having the - ' , ' ~
~7~8~
1 aforesaid characteristics.
A particular exemplary method of the invention compri~es:
(1) intermingling to form a flowable liquid composition;
(I) aforesaid prepolymer A2, and (II) aforesaid prepolymer B2; and when about equal parts by weight of (I) and (II) a~e intermingled at about 21.1C, a solid polyure~hane having a Shore hardness o a~ou~ 10 is o~tained in about 10 minutes;
(2~ placing said liquid composition into contact wi~h surface ~escribed hereinabove at ambient temperature for the time needed for the liquid composition to cure to a solid having the aforesaid chara~teristics.
DESCRIPTION A~D EX~MPLE
P~ r ~9a~ ' ' The liquid polyurethane prepslymer c omposition of ~he :
invention m~y be prepared from any suitable organic diisocyanate.
Particular classes used include: aromatic diisocyanates; ali-phatic diiso~yanates; cycloaliphatic diisocyanates; and hetero-cy d ic diisocyanates.
Illustrative aromatic diisocyanates are: (it is to be understood "diisocyanate" must be read at the end of each of the following terms) tolylene; tolidine; xylylene; phen~lene, napht~ylene; dianisidine; l-chloro-2~4-phenylene; 3,3'-dimethyl-; 4,4'-dip~enylmethane; 4,4'-diphenylmethane;3,3'-dimethyl-4~4'-biphenylene; 3,3'-dimet~oxy-4,4~-biphenylene, 2,2'5,5'-terameth~l-4,4'-biphen~lene; 4,4'-diphenylisopropylidene; 3,3'-dimethyl-4, 4'-diphenyl; 3,3'-dimethoxy-4,4'-diphen~
Illustrative aliphatic diisocyanates are: (it is to be ~:
understood "diiso~yanate" must be read at the end of each of : :
the following~erms) methylenebis (cyclohexylisocyanata) lno di term] methylene 7 ethylene; trimethylene; tetxamethylene;
hexamethylene; 18 carbon atty acid dimer.
,~ ,, ~aD7~ 6 1 I llustrati~e cycloaliphatic diisocyanates are: cyclohexylene diisocyanat2, 1-isocyanato-3-isocanatomethyl-3,5,5-trimethyl cyclo~exane, and isophorone (3,5,5-trimethyl-2-cyclohenen-1-one diiso~yanate).
A typical heterocyclic diisocyanate is furfurylidene diisocyanate.
The triol(s) used in preparing the prepolymer composition of the invention is aliphatic triol of a molecular weight of about 1500 6000, desirably 3000-6000.
A suitable triol is a mixture of castor oil glycerides transesterified to im~rove reactivity with isocyanate groups.
The desired triols are derivatives ~adducts) of a trihydric compound with ~n alkylene oxide~ or mixtuxes thereof, haviny 2-4 carbon a~ms~ such as, e~hylene o~ide, propylene oxide, and bu~ylene oxide.
Preferred are the aliphatic triols which are polyoxyalky lene derivatives of alkanetriol, where the "alkylene" poxtion has 2-4 car~on atoms and the "alkane" portion has 3-10 carbon atoms, Especially preferred are: "alkylene" is propylene; "alkane" has
3-6 carbon a~ms; and the d~rivative m~lecular wPight is about 4000-5000.
Illustrati~e alkanetriols are: glycerol (1,2,3~propanetriol);
butanetriol; pentanetriol; hexanetriol; trime~hylolethane; tri-me~hylolpropane; and triet~ylolpropane.
The ~CO/OH ratio of the diisocyanate charged and the triol charged to the prepol~mer reaction is about 1.0-1~6 and preferably is about 1O3.
m e prepolymer composition of th~ invention includes a liquid, organic plasticizer material essentially inert to iso-cyanate (NCO) and essentially compatible with t~e prepolymer ! product itself~ "Compati~le" is used herein in ~he sPnse o "ability ~o becomé and to remain ~lended with" the liquid pre-_g_ 8~
1 polymer and the solid pol~ure~hane o~tained by reaction of the prepolymer, either self-reaction or with a curing agent. Many compounds accepted as excellent plasticizers exhibit blooming, or exudation~ or slight separation from the solid composition (even liquid composition) on long storage, particularly at higher amhient temperakures (temperatures commonly prevalent in the atmosphere or in buildings)~ The term "essentially compatible"includes such plasticizer materials.
It is preferxed that the plasticizer component be n~utral, ine~t to isocyanate, have low volatility, and relatively low viscosityO that is, not more t~an about 75 centipoises (cps) at 20C. A vast nu~ber of suitable plasticizer matexials are listed in Modern Plastics Encyclopedia, 1973-74 Edition.
A preferred plasticizer material is an ester of alip~atic hydroxy compound and aliphatio carbox~lic acid or aromatic car~oxylic acid. Especially preferred plasticizer materials are the esters of (a) alkanol~ alkanediolO oxyalkylenediol, or poly-oxyalkylenediol and (b) alXanoic acicl or alkaned~oic acid.
; Especially preferred ester compounds axe: dio~tyl adipate which has a ViSCQSity of about 12 cps and a boiling range of --~ about 214C at 5 mm Hg pressure; and 2,2,4-trimethyl-1,3-pentane-R ~ `so6~fyrQ~
diol ~bhh~Y~o~#~be. Other plasticizers of roughly these charac-teris~ics appear in said Modern Plastics Encyclopedia listings.
Inertness to ~CO is essential in order to produce a "water-white"prepolymer and solid polyure~hane composition. ~ven slig~t reactivity causes a white cloudiness to show i~ the product;
this may not be detrimental for many applications o~ the pre-polymer and/or solid polyure~hane composition of ~he invention.
The liquid polyurethane prepolymer composition (prepolymer and plasticizer) has an ~CO content o about 1.2-2.5%. The amount of ~CO present determines~ in ~he main, the speed with which gelationtakes place on intermingling the prepolymer compo-.
. '': , , . . .. - , , 1 sition and the curing solukion. Lower ~C0 contents favor faster times. with the components of prepolymer A2 and curing solution B20 it has been observed that 1~2~2.5% ~C0 .~orresponds roughly to about 5-60 minutes gelation time at a 70~F (21~1C)o A preferxed ~C0 content of the prepol~mer composition is about 1~4-2~/o~ For encapsulation of cable splices and cable end capping~ an N~O con~ent of about 1.5-108% is particularl~
preferred.
The bulk (major portion) of the weight sum of the triol, diisocyanate, and plasticizer charged to the prepolymer reaction is provided by the triol. Adjustments can be made in the vis-cosity of the prepolymer composition by ~ontrollingtheamount of plasticizer charged. For cable work and like usage, suf-ficient plasticizer is present to provide a composition having a viscosity of about 1300-1800 cps at 70F (21.1C), B ~ 5~ Y~ Y~
r The liquid organic plasticizer material component of the curing solution is of the same scope as the p~asticizer material present in the prepolymer COlnpOSitiOn. It is preferred ~hat the pa~tlcular plasticizar ma~.erial in the curing solution be the same as the plasticizer in the prepolymer ~omposition, for example, if the prepolymer composition includes dioctyl adipate plasticizer then it is pre~erred that the curing solution include dioctyl adipate pla~ticizer. ~ :
An organo-metallic compound effective ~or catalyzing the : ambient temperature xeaction of isocyanate groups and hydxoxyl ::
groups or amino groups, which is soluble in the plasticizer com-ponent, is present in the curing solution. A large number o~
suitable organo-metallic compounds are ~nown to be effective.
30 The more common are khe phenate, chlorophenate, naphthenate, oleate, linoresinate ~ ethylhexanoate, acetylacetonate, butoxide, sal~s of lead, iron, tin, co~alt, vanadium, titan~um, copper, 1 zinc~ ~hromium, manganese and ca~mium~ Sol~ble lead salts, su~h as, lead octoate, lead naphthenate, lead oleate, and lead linoresinate, are pxeferred catalysts for use in this invention.
The ~mount of catalyst present is relatively smalls it will be dependent on the t~pe and amount of curing agent and the time of gelation desired. In general, the lead catalyst will be present in about O~Ol-l~/o of the total curing solution;
and commorlly O.01-0.3%~
The curing solution includes a curing agent, either a poly-ol, an organic diamine, or amino alcohol.
The organic diamines include the atomatic, aliphatic and cycloaliphatic diamines. Illustrative are~ benzidine, phenylene, diaminP.-methylenebis(chloroanilirle), diaminodiphenylmethane, ~imek~ylene diamine, tetramethylene diamine, hexamethylene diamine~ tetrame~hyl-l 9 3-butanediamine, and diethylcyclohex~l . diamme.
The ~minoal~ohols such as ~minoalkanols are Xno~n curing agents. Illustrative are ethanolamine, dimethylethanol~mine, aminobenzyl alcohol, and M~ON',~'-tetrakis~2-hydroxypropyl)-ethylene diamine~ ~
Sufficient curing agent is used to o~tain a solid poly- :
ure~hane composition. The amount used wi~l ~ry with the MCO
content of the prepolymer composition and ~he particular curing agent, but, in general, ~he curing agen~ usage will range from about 1% to 5% ~y weig~t of the curing solution.
The plasticizer, cuxing ~ent and organo-metallic compound ~:
are mat~hed to provide a solution o~ the three components. The plasticizer is present, in effect, 100 parts minus the amount of curing agent present as the usual catalyst usage is tin~.
The "Cured'' Solid P ~ :
Encapsulation and the ~ik ~ , .
, ~ , . .
1 In preparing the prepolymer composition/ it is customary to blend ~he plasticizer component and the isocyanate component befor~ adding the triol~ The isocyanate removes an~ sli~hk amount of water which may be dissolved in t:he plasticizer.
Anhydrous materials do not need this precautionO The three components are intermingled at about 150-170F ~65.6-76.7c), a typical prepolymer reaction tempexature. ~he product is a viscouS9 liquid having a color from water-white to pale yellow.
The curing solution may require heating to about 40C
(104~ to bring all the diamine and catalyst into solution.
The prepolymer composition and the proper amount of curing sol~tion are rapidly intermingled at ambient temperature.
The blend is ~hen applied (placed in contact with) the surface of the object which is to be encapsulated, embedded, or coated as the case may be. The blend i~ maintained in place ~or the time needed for the liquid to gel. There is no significant exotherm in the reaction.
~ he solid polyurethane pro~uct is usually crystal-cleare some xeactio~s may produce a white cloudinessO
Th~ solid product i~ wate~pxoof and an electrical insula~or.
Tha solid product does adhere to the metal, plastic, paper or such, interface and provides a wa erproof interface. The solid product has resiliency; a mass dropped on a hard surace will rebou~dO
The unique property of this solid product is its response to shearing foxce applied to a sur~ace, such as~ rubbing a finger on th~ surface. And its response to the shearing fo~ce of a wire e~3edded in a ~c~c of ~he solid product and being withdxawn ~hrough the ~lock. The solid crumbles in response to shearing force and breaks up into small pieces. The interface ~etween the solid product and the o~her sur:Eace easily ~leaves wi~h some crur~ling o:E the adjacent solid product surace, freeing -:L3 ~7~ !36 1 the o~her surface of all of the solid prsductO Metal wires, plastic coated wires, paper coated wires~ pull through the encapsulating solid product clean and are ready for "working".
The crumbled material does not stic~ to Skill or clothing, so presents no clean up problems~ a~ do all the prior art re-enterable cable materials. Lony storage tests indicate ~his crumbling property does not change with age.
Another very desirable property of the solia product is its abili~y to be added to itselfO Fresh liquid composition applied to solid product appears to have perfect cohesion, effecting an absolute marriage of ~he old solid and ~he resh solid at the interface. This property means that partial re- ~ -entry into a splice encapsulated by the solid product is satis-factory; it is not necessary to remove the entire encapsulating material.
Another benefit lies in ~he fact that this product is neither expanding nor shrinking on solidification.
The ~wo-Paxt Package The aforedescribed prepolymer composition and the a~ore-described curing solution must be packaged separately for hand-ling, shipping and storage. T~erefore, a two-part package is necessary and the two parts are nonmally handled and stored together and are spoken herein as a "two-part package asse~blyl'.
When ~he consumer wishes to prepare a batch o liquid blend for encapsulation or other use, the necessary amount of each part o ~he package asse~bly is measured out and ~he two amounts are intermingled and the blend is placed in contact with the surface to be pxotected and/or insulated. Usually ~he two-pa~t package is sized so that ~he entire contents of each part are used in a single blending operation. It is desirable that the closure on at least the prepoly~er compo~ition package part be air-tight to pxevent ingress of atmospheric moisture which re-~7~
acts with composition. The package may be any conventional container, such as, removable lid can, screw cap bottle, sealed can when the entire contents are to be used in a single blending operation, sealed plastic or metal tubes for very small jobs, and the like containers.
Especiall.y useful for small or medium applications in the fie].d is the unitary two-part plastic package assembly dis-closed in U.S~ patent 3,639,952. This unitary plastic package comprises an elongated tubular plastic film open-ended container provided with a removable means placed transversely across the container at the midlength thereof to form two separate tubular portions, the desired amount of aforesaid prepolymer composition is placed in one portion whose open end is then sealed; and the desired amount of aforesaid curing composition i5 placed in the other portion whose open end is then sealed, whereby said two compositions are maintained separate until the separating means is removed; the two compositions are then intermingled within the plastic film container, and the blended flowable liquid composition is taken therefrom prior to gelation of the liquid `composition, and placed into contact with the surface to be protected and/or insulated by the cured solid polyurethane pro-duct composition. ;-~ Example A prepolymer composition of the invention was prepared from the following components, 2,4-tolylene diisocyanate, 7.1 weight parts; polyoxypropylene derivative of trimethylolpropane, 4500 molecular weightl 68.1 parts; and dioctyl adipate, 24.9 parts.
The diisocyanate and the adipate were placed in a vessel and heated at 163-170F (71.1-76.7C) for one hour. Then the triol was added to the vessel and the contents intermingled for two hours at the same temperature.
The prepolymer composition had an NCO content of 1 weight percent. It had a density of 8.30 lbs/gallon (US) and is sub-stantially colorless. It had to be stored under a dry nitrogen atmosphere.
The curing composition was prepared from the following components: 2,2,4-trlmethyl-1, 3-pentanediol diisobutyrate, 97.3 weight parts, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene diamine, 2.7 parts; and lead octoate catalyst, 0.04 weight parts.
The three components were brought into solution by mixing at 100-110 F t37.3-43.3 C). The curing solution was clear in color~ had a density of 7.95 lbs/gal (US) and a viscosity of about 40 cps at 70 F (21.1 C).
One part by weight of the prepo]~mer composition and one part by weight of the curing solution was thoroughly inter-mingled to form a homogeneous blend. The ~lend was applied to a bundle of plastic coated copper wires in an in-place filling.
The blend gelled in 9-10 minutes at 700F (21.1C); another blend of the same composition gelled in 35 minutes at 40F
(~ ~C) Some of the blend was placed in a gelling dish made of aluminum with rough vertical sides, 2.5 inches in diameter by 0.5 inches deep. The dish was filled to about 0.25 inches.
There was no noticeable exotherm on curing. Also no noticeable expansion o~ shrinkage in volume of the material placed in the ~kl .
~ - 15 -. . .
' :' . . , : ' ~
: .
... .
. ' .' . ' '' ' ~' '. ~' '~- '' ,': ' ' .
.
, dish. After curing, the solid was as close to colorless as the term water-white connotes. The solid depressed slightly under finger pressure but rebounded on release of pressure.
The solid did not stick to the skin when pressed by the finger.
The solid did adhere to the metal tightly and formed a watertight interface. However, the metal foil easily peeled away from the solid polyurethane and the bottom contact was easily overcome and the solid polyurethane disc slipped out of the dish.
It was observqd the edges of the disc were rough from crumbling of the wall as the metal foil was peeled away. Rubbing - 16a -' ' ' ',' " ' '. ' ' ''. ' ' ~
, . . , , , ., , , ~
~t~'7~
1 ~he disc surface with fingers caused substantial crumbling of the material. Shearing force easily bro~e chunks from the edges of the disc.
However, the disc when dropped several feet onto a hard floor did not shatter or brea~ up. The disc bounced. When dropped on an edge, the disc bounced much like a ru~er ball.
A test on the embedded (encapsulated) plastic coated wires revealed that the wires pulled sideways cut through the solid polyurethane mass and the plastic surface was free of the encapsulating material. The encapsulating solid broke up into pieces easily, these pieces did not stick to sXin, clothing, or to other surfaces on wh~ h ~hey lay.
Tests showed that the solid polyurethane product is a good electrical insulator~
While the pa~ticular polyurethane composition h~ving easy r0entry property herein shown and disclosed in detail is fully cap~ble of attaining the objects and providing ~he advantages hereinbefore stated, it is to be understood ~hat it is merely illustxative of the presently preferred embodiment of the i~en-tion and ~hat no limitations are intended to the detail of ::
construction or design herein sh~wn other than as defined in ~he appended claimsO
.
Illustrati~e alkanetriols are: glycerol (1,2,3~propanetriol);
butanetriol; pentanetriol; hexanetriol; trime~hylolethane; tri-me~hylolpropane; and triet~ylolpropane.
The ~CO/OH ratio of the diisocyanate charged and the triol charged to the prepol~mer reaction is about 1.0-1~6 and preferably is about 1O3.
m e prepolymer composition of th~ invention includes a liquid, organic plasticizer material essentially inert to iso-cyanate (NCO) and essentially compatible with t~e prepolymer ! product itself~ "Compati~le" is used herein in ~he sPnse o "ability ~o becomé and to remain ~lended with" the liquid pre-_g_ 8~
1 polymer and the solid pol~ure~hane o~tained by reaction of the prepolymer, either self-reaction or with a curing agent. Many compounds accepted as excellent plasticizers exhibit blooming, or exudation~ or slight separation from the solid composition (even liquid composition) on long storage, particularly at higher amhient temperakures (temperatures commonly prevalent in the atmosphere or in buildings)~ The term "essentially compatible"includes such plasticizer materials.
It is preferxed that the plasticizer component be n~utral, ine~t to isocyanate, have low volatility, and relatively low viscosityO that is, not more t~an about 75 centipoises (cps) at 20C. A vast nu~ber of suitable plasticizer matexials are listed in Modern Plastics Encyclopedia, 1973-74 Edition.
A preferred plasticizer material is an ester of alip~atic hydroxy compound and aliphatio carbox~lic acid or aromatic car~oxylic acid. Especially preferred plasticizer materials are the esters of (a) alkanol~ alkanediolO oxyalkylenediol, or poly-oxyalkylenediol and (b) alXanoic acicl or alkaned~oic acid.
; Especially preferred ester compounds axe: dio~tyl adipate which has a ViSCQSity of about 12 cps and a boiling range of --~ about 214C at 5 mm Hg pressure; and 2,2,4-trimethyl-1,3-pentane-R ~ `so6~fyrQ~
diol ~bhh~Y~o~#~be. Other plasticizers of roughly these charac-teris~ics appear in said Modern Plastics Encyclopedia listings.
Inertness to ~CO is essential in order to produce a "water-white"prepolymer and solid polyure~hane composition. ~ven slig~t reactivity causes a white cloudiness to show i~ the product;
this may not be detrimental for many applications o~ the pre-polymer and/or solid polyure~hane composition of ~he invention.
The liquid polyurethane prepolymer composition (prepolymer and plasticizer) has an ~CO content o about 1.2-2.5%. The amount of ~CO present determines~ in ~he main, the speed with which gelationtakes place on intermingling the prepolymer compo-.
. '': , , . . .. - , , 1 sition and the curing solukion. Lower ~C0 contents favor faster times. with the components of prepolymer A2 and curing solution B20 it has been observed that 1~2~2.5% ~C0 .~orresponds roughly to about 5-60 minutes gelation time at a 70~F (21~1C)o A preferxed ~C0 content of the prepol~mer composition is about 1~4-2~/o~ For encapsulation of cable splices and cable end capping~ an N~O con~ent of about 1.5-108% is particularl~
preferred.
The bulk (major portion) of the weight sum of the triol, diisocyanate, and plasticizer charged to the prepolymer reaction is provided by the triol. Adjustments can be made in the vis-cosity of the prepolymer composition by ~ontrollingtheamount of plasticizer charged. For cable work and like usage, suf-ficient plasticizer is present to provide a composition having a viscosity of about 1300-1800 cps at 70F (21.1C), B ~ 5~ Y~ Y~
r The liquid organic plasticizer material component of the curing solution is of the same scope as the p~asticizer material present in the prepolymer COlnpOSitiOn. It is preferred ~hat the pa~tlcular plasticizar ma~.erial in the curing solution be the same as the plasticizer in the prepolymer ~omposition, for example, if the prepolymer composition includes dioctyl adipate plasticizer then it is pre~erred that the curing solution include dioctyl adipate pla~ticizer. ~ :
An organo-metallic compound effective ~or catalyzing the : ambient temperature xeaction of isocyanate groups and hydxoxyl ::
groups or amino groups, which is soluble in the plasticizer com-ponent, is present in the curing solution. A large number o~
suitable organo-metallic compounds are ~nown to be effective.
30 The more common are khe phenate, chlorophenate, naphthenate, oleate, linoresinate ~ ethylhexanoate, acetylacetonate, butoxide, sal~s of lead, iron, tin, co~alt, vanadium, titan~um, copper, 1 zinc~ ~hromium, manganese and ca~mium~ Sol~ble lead salts, su~h as, lead octoate, lead naphthenate, lead oleate, and lead linoresinate, are pxeferred catalysts for use in this invention.
The ~mount of catalyst present is relatively smalls it will be dependent on the t~pe and amount of curing agent and the time of gelation desired. In general, the lead catalyst will be present in about O~Ol-l~/o of the total curing solution;
and commorlly O.01-0.3%~
The curing solution includes a curing agent, either a poly-ol, an organic diamine, or amino alcohol.
The organic diamines include the atomatic, aliphatic and cycloaliphatic diamines. Illustrative are~ benzidine, phenylene, diaminP.-methylenebis(chloroanilirle), diaminodiphenylmethane, ~imek~ylene diamine, tetramethylene diamine, hexamethylene diamine~ tetrame~hyl-l 9 3-butanediamine, and diethylcyclohex~l . diamme.
The ~minoal~ohols such as ~minoalkanols are Xno~n curing agents. Illustrative are ethanolamine, dimethylethanol~mine, aminobenzyl alcohol, and M~ON',~'-tetrakis~2-hydroxypropyl)-ethylene diamine~ ~
Sufficient curing agent is used to o~tain a solid poly- :
ure~hane composition. The amount used wi~l ~ry with the MCO
content of the prepolymer composition and ~he particular curing agent, but, in general, ~he curing agen~ usage will range from about 1% to 5% ~y weig~t of the curing solution.
The plasticizer, cuxing ~ent and organo-metallic compound ~:
are mat~hed to provide a solution o~ the three components. The plasticizer is present, in effect, 100 parts minus the amount of curing agent present as the usual catalyst usage is tin~.
The "Cured'' Solid P ~ :
Encapsulation and the ~ik ~ , .
, ~ , . .
1 In preparing the prepolymer composition/ it is customary to blend ~he plasticizer component and the isocyanate component befor~ adding the triol~ The isocyanate removes an~ sli~hk amount of water which may be dissolved in t:he plasticizer.
Anhydrous materials do not need this precautionO The three components are intermingled at about 150-170F ~65.6-76.7c), a typical prepolymer reaction tempexature. ~he product is a viscouS9 liquid having a color from water-white to pale yellow.
The curing solution may require heating to about 40C
(104~ to bring all the diamine and catalyst into solution.
The prepolymer composition and the proper amount of curing sol~tion are rapidly intermingled at ambient temperature.
The blend is ~hen applied (placed in contact with) the surface of the object which is to be encapsulated, embedded, or coated as the case may be. The blend i~ maintained in place ~or the time needed for the liquid to gel. There is no significant exotherm in the reaction.
~ he solid polyurethane pro~uct is usually crystal-cleare some xeactio~s may produce a white cloudinessO
Th~ solid product i~ wate~pxoof and an electrical insula~or.
Tha solid product does adhere to the metal, plastic, paper or such, interface and provides a wa erproof interface. The solid product has resiliency; a mass dropped on a hard surace will rebou~dO
The unique property of this solid product is its response to shearing foxce applied to a sur~ace, such as~ rubbing a finger on th~ surface. And its response to the shearing fo~ce of a wire e~3edded in a ~c~c of ~he solid product and being withdxawn ~hrough the ~lock. The solid crumbles in response to shearing force and breaks up into small pieces. The interface ~etween the solid product and the o~her sur:Eace easily ~leaves wi~h some crur~ling o:E the adjacent solid product surace, freeing -:L3 ~7~ !36 1 the o~her surface of all of the solid prsductO Metal wires, plastic coated wires, paper coated wires~ pull through the encapsulating solid product clean and are ready for "working".
The crumbled material does not stic~ to Skill or clothing, so presents no clean up problems~ a~ do all the prior art re-enterable cable materials. Lony storage tests indicate ~his crumbling property does not change with age.
Another very desirable property of the solia product is its abili~y to be added to itselfO Fresh liquid composition applied to solid product appears to have perfect cohesion, effecting an absolute marriage of ~he old solid and ~he resh solid at the interface. This property means that partial re- ~ -entry into a splice encapsulated by the solid product is satis-factory; it is not necessary to remove the entire encapsulating material.
Another benefit lies in ~he fact that this product is neither expanding nor shrinking on solidification.
The ~wo-Paxt Package The aforedescribed prepolymer composition and the a~ore-described curing solution must be packaged separately for hand-ling, shipping and storage. T~erefore, a two-part package is necessary and the two parts are nonmally handled and stored together and are spoken herein as a "two-part package asse~blyl'.
When ~he consumer wishes to prepare a batch o liquid blend for encapsulation or other use, the necessary amount of each part o ~he package asse~bly is measured out and ~he two amounts are intermingled and the blend is placed in contact with the surface to be pxotected and/or insulated. Usually ~he two-pa~t package is sized so that ~he entire contents of each part are used in a single blending operation. It is desirable that the closure on at least the prepoly~er compo~ition package part be air-tight to pxevent ingress of atmospheric moisture which re-~7~
acts with composition. The package may be any conventional container, such as, removable lid can, screw cap bottle, sealed can when the entire contents are to be used in a single blending operation, sealed plastic or metal tubes for very small jobs, and the like containers.
Especiall.y useful for small or medium applications in the fie].d is the unitary two-part plastic package assembly dis-closed in U.S~ patent 3,639,952. This unitary plastic package comprises an elongated tubular plastic film open-ended container provided with a removable means placed transversely across the container at the midlength thereof to form two separate tubular portions, the desired amount of aforesaid prepolymer composition is placed in one portion whose open end is then sealed; and the desired amount of aforesaid curing composition i5 placed in the other portion whose open end is then sealed, whereby said two compositions are maintained separate until the separating means is removed; the two compositions are then intermingled within the plastic film container, and the blended flowable liquid composition is taken therefrom prior to gelation of the liquid `composition, and placed into contact with the surface to be protected and/or insulated by the cured solid polyurethane pro-duct composition. ;-~ Example A prepolymer composition of the invention was prepared from the following components, 2,4-tolylene diisocyanate, 7.1 weight parts; polyoxypropylene derivative of trimethylolpropane, 4500 molecular weightl 68.1 parts; and dioctyl adipate, 24.9 parts.
The diisocyanate and the adipate were placed in a vessel and heated at 163-170F (71.1-76.7C) for one hour. Then the triol was added to the vessel and the contents intermingled for two hours at the same temperature.
The prepolymer composition had an NCO content of 1 weight percent. It had a density of 8.30 lbs/gallon (US) and is sub-stantially colorless. It had to be stored under a dry nitrogen atmosphere.
The curing composition was prepared from the following components: 2,2,4-trlmethyl-1, 3-pentanediol diisobutyrate, 97.3 weight parts, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene diamine, 2.7 parts; and lead octoate catalyst, 0.04 weight parts.
The three components were brought into solution by mixing at 100-110 F t37.3-43.3 C). The curing solution was clear in color~ had a density of 7.95 lbs/gal (US) and a viscosity of about 40 cps at 70 F (21.1 C).
One part by weight of the prepo]~mer composition and one part by weight of the curing solution was thoroughly inter-mingled to form a homogeneous blend. The ~lend was applied to a bundle of plastic coated copper wires in an in-place filling.
The blend gelled in 9-10 minutes at 700F (21.1C); another blend of the same composition gelled in 35 minutes at 40F
(~ ~C) Some of the blend was placed in a gelling dish made of aluminum with rough vertical sides, 2.5 inches in diameter by 0.5 inches deep. The dish was filled to about 0.25 inches.
There was no noticeable exotherm on curing. Also no noticeable expansion o~ shrinkage in volume of the material placed in the ~kl .
~ - 15 -. . .
' :' . . , : ' ~
: .
... .
. ' .' . ' '' ' ~' '. ~' '~- '' ,': ' ' .
.
, dish. After curing, the solid was as close to colorless as the term water-white connotes. The solid depressed slightly under finger pressure but rebounded on release of pressure.
The solid did not stick to the skin when pressed by the finger.
The solid did adhere to the metal tightly and formed a watertight interface. However, the metal foil easily peeled away from the solid polyurethane and the bottom contact was easily overcome and the solid polyurethane disc slipped out of the dish.
It was observqd the edges of the disc were rough from crumbling of the wall as the metal foil was peeled away. Rubbing - 16a -' ' ' ',' " ' '. ' ' ''. ' ' ~
, . . , , , ., , , ~
~t~'7~
1 ~he disc surface with fingers caused substantial crumbling of the material. Shearing force easily bro~e chunks from the edges of the disc.
However, the disc when dropped several feet onto a hard floor did not shatter or brea~ up. The disc bounced. When dropped on an edge, the disc bounced much like a ru~er ball.
A test on the embedded (encapsulated) plastic coated wires revealed that the wires pulled sideways cut through the solid polyurethane mass and the plastic surface was free of the encapsulating material. The encapsulating solid broke up into pieces easily, these pieces did not stick to sXin, clothing, or to other surfaces on wh~ h ~hey lay.
Tests showed that the solid polyurethane product is a good electrical insulator~
While the pa~ticular polyurethane composition h~ving easy r0entry property herein shown and disclosed in detail is fully cap~ble of attaining the objects and providing ~he advantages hereinbefore stated, it is to be understood ~hat it is merely illustxative of the presently preferred embodiment of the i~en-tion and ~hat no limitations are intended to the detail of ::
construction or design herein sh~wn other than as defined in ~he appended claimsO
.
Claims (35)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An NCO group containing composition, which comprises liquid polyurethane prepolymer, made from:
(a) organic diisocyanate;
(b) polyoxypropylene derivative of an alkanetriol where the alkane has 3 - 6 carbon atoms, having a molecular weight of about 1500 -6000;
the NCO/OH ratio of said diisocyanate and said triol charged being about 1.0 - 1.6; and (c) liquid, organic plasticizer material essentially inert to NCO reaction and essentially compatible with the diisocyanate-triol reaction product;
said organic plasticizer being present in an amount to provide a composition having an NCO content of about 1.2 - 2.5%; and said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged.
(a) organic diisocyanate;
(b) polyoxypropylene derivative of an alkanetriol where the alkane has 3 - 6 carbon atoms, having a molecular weight of about 1500 -6000;
the NCO/OH ratio of said diisocyanate and said triol charged being about 1.0 - 1.6; and (c) liquid, organic plasticizer material essentially inert to NCO reaction and essentially compatible with the diisocyanate-triol reaction product;
said organic plasticizer being present in an amount to provide a composition having an NCO content of about 1.2 - 2.5%; and said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged.
2. The composition of claim 1 wherein said NCO/OH ratio is about 1.3.
3. The composition of claim 1 wherein said NCO content is about 1.4 - 2.0%.
4. The composition of claim 1 wherein said diisocyanate is selected from the class consisting of aromatic diisocyanate, aliphatic diisocyanate, cycloaliphatic diisocyanate, and hetercyclic diisocyanate.
5. The composition of claim 4 wherein said diisocyanate is tolylene diisocyanate.
6. The composition of claim 4 wherein said diisocyanate is diphenylmethane diisocyanate.
7. The composition of claim 4 wherein said diisocyanate is methylenebis (cyclohexylisocyanate).
8. The composition of claim 4 wherein said diisocyanate is hexamethylene diisocyanate.
9. The composition of claim 4 wherein said diisocyanate is cyclohexylene diisocyanate.
10. The composition of claim 1 wherein said polyoxypropylene has a molecular weight of about 4000-5000.
11. The composition of claim 1 wherein said liquid, organic plasticizer material is an ester of aliphatic hydroxy compound and ali-phatic carboxylic acid or aromatic carboxylic acid.
12. The composition of claim 11 wherein (a) said hydroxy compound is alkanol, alkanediol, oxyalkylene diol or polyoxyalkylenediol and (b) said acid is alkanoic acid or alkanedioic acid.
13. The composition of claim 12 wherein said ester has a viscosity of not more than about 75 centipoises at about 20°C.
14. The composition of claim 12 wherein said ester is dioctyl adipate.
15. The composition of claim 12 wherein said ester is 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.
16. An NCO group containing composition which comprises liquid polyurethane prepolymer, made from:
(a) Aromatic diisocyanate;
(b) polyoxypropylene derivative of alkanetriol where alkane has 3-6 carbon atoms, having a molecular weight of about 1500 - 6000;
the NCO/OH ratio of said diisocyanate and said triol derivative charged being about 1.3; and (c) liquid, plasticizer ester of (i) alkanol, alkanediol oxyalkylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkanedioic acid, said ester is essentially inert to NCO reaction and is essentially compatible with the diisocyanate-triol derivative reaction product, and has a viscosity of not more than about 75 centipoises at about 20°C;
said ester being present in an amount to provide a com-position having an NCO content of about 1.5-1.8% and a viscosity of about 1300-1800 centipoises at 21.1°C (70°F), said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged.
(a) Aromatic diisocyanate;
(b) polyoxypropylene derivative of alkanetriol where alkane has 3-6 carbon atoms, having a molecular weight of about 1500 - 6000;
the NCO/OH ratio of said diisocyanate and said triol derivative charged being about 1.3; and (c) liquid, plasticizer ester of (i) alkanol, alkanediol oxyalkylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkanedioic acid, said ester is essentially inert to NCO reaction and is essentially compatible with the diisocyanate-triol derivative reaction product, and has a viscosity of not more than about 75 centipoises at about 20°C;
said ester being present in an amount to provide a com-position having an NCO content of about 1.5-1.8% and a viscosity of about 1300-1800 centipoises at 21.1°C (70°F), said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged.
17. An NCO group containing composition which comprises liquid polyurethane prepolymer, made from:
(a) tolylene diisocyante, about 7.1 weight parts;
(b) polyoxypropylene derivative of trimethylolpropane, of molecular weight about 4500, about 68.1 weight parts; and (c) dioctyl adipate, about 24.9 weight parts;
said composition having an NCO content of about 1 weight percent and a viscosity of about 1300 - 1800 centipoises at 21.1°C (70°F).
(a) tolylene diisocyante, about 7.1 weight parts;
(b) polyoxypropylene derivative of trimethylolpropane, of molecular weight about 4500, about 68.1 weight parts; and (c) dioctyl adipate, about 24.9 weight parts;
said composition having an NCO content of about 1 weight percent and a viscosity of about 1300 - 1800 centipoises at 21.1°C (70°F).
18. A two-part package assembly adapted for producing a solid polyurethane composition when the contents of the two parts are intermingled, which assembly consists essentially of:
(I) a first package part containing an NCO group containing composition, which comprises liquid polyurethane prepolymer, made from:
(a) organic diisocyanate;
(b) polyoxypropylene derivative of an alkanetriol where the alkane has 3-6 carbon atoms, having a molecular weight of about 1500-6000;
the NCO/OH ratio of said diisocyanate and said alkane triol derivative charged is about 1.0 - 1.6; and (c) liquid, organic plasticizer material essentially inert to NCO reaction and essentially compatible with the diisocyanate-triol reaction product;
said organic plasticizer being present in an amount to provide a composition having an NCO content of about 1.2 - 2.5%; and said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged; and (II) a second package part containing a curing solution com-position consisting essentially of:
(a) a curing agent, in a curing amount, for the polyurethane prepolymer composition of (I) selected from the class consisting of polyols, organic diamines and aminoalkanols;
(b) liquid, organic plasticizer material essentially inert to NCO reaction and essentially compatible with the cured, solid polyure-thane composition; and (c) organo-metallic compound effective for catalyzing the ambient temperature reaction of isocyanate groups and hydroxyl or amine groups; and soluble in said plasticizer.
(I) a first package part containing an NCO group containing composition, which comprises liquid polyurethane prepolymer, made from:
(a) organic diisocyanate;
(b) polyoxypropylene derivative of an alkanetriol where the alkane has 3-6 carbon atoms, having a molecular weight of about 1500-6000;
the NCO/OH ratio of said diisocyanate and said alkane triol derivative charged is about 1.0 - 1.6; and (c) liquid, organic plasticizer material essentially inert to NCO reaction and essentially compatible with the diisocyanate-triol reaction product;
said organic plasticizer being present in an amount to provide a composition having an NCO content of about 1.2 - 2.5%; and said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged; and (II) a second package part containing a curing solution com-position consisting essentially of:
(a) a curing agent, in a curing amount, for the polyurethane prepolymer composition of (I) selected from the class consisting of polyols, organic diamines and aminoalkanols;
(b) liquid, organic plasticizer material essentially inert to NCO reaction and essentially compatible with the cured, solid polyure-thane composition; and (c) organo-metallic compound effective for catalyzing the ambient temperature reaction of isocyanate groups and hydroxyl or amine groups; and soluble in said plasticizer.
19. The package of claim 18 wherein said catalyst amount of (II) and the NCO content of said prepolymer composition (I) are adjusted to provide on intermingling and curing a solid polyurethane composition having a Shore hardness of about 5-20 in a curing time of not more than about 60 minutes at about 20°C.
20. The package assembly of claim 18 wherein said curing agent is ethylene diamine.
21. The package assembly of claim 18 wherein said curing agent is N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene diamine.
22. The package assembly of claim 18 wherein said curing agent is polyoxypropylene derivative of pentaerythritol of molecular weight of about 300-450.
23. The package assembly of claim 18 wherein said plasticizer material of (II) is the same as the plasticizer material of (I).
24. The package assembly of claim 19 wherein said plasticizer material in (I) and (II) is 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.
25. The package assembly of claim 23 wherein said plasticizer material in (I) and (II) is dioctyl adipate.
26. A two part package assembly adapted for producing a solid polyurethane composition when the contents of the two parts are intermingled, which assembly consists essentially of:
(I) a first package part containing an NCO group containing composition which comprises liquid polyurethane prepolymer, made from:
(a) aromatic diisocyanate;
(b) polyoxypropylene derivative of alkanetriol where alkane has 3-6 carbon atoms, having molecular weight of about 1500-6000;
the NCO/OH ratio of said diisocyanate and said triol derivative charged being about 1.3; and (c) liquid, plasticizer ester of (i) alkanol, alkanediol, oxyalkylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkanedioic acid, said ester is essentially inert to NCO reaction and is essentially compatible with the diisocyanate-triol derivative reaction product, and has a viscosity of not more than about 75 centipoises at about 20°C;
said ester being present in an amount to provide a composition having an NCO content of about 1.5-1.8% and a viscosity of about 1300 - 1800 centipoises at 21.1°C (70°F); and said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged, (II) a second package part containing a curing solution composition consisting essentially of:
(a) a curing agent, in a curing amount, for the polyurethane prepolymer composition of (I) selected from the class of aromatic diamines, aliphatic diamines and aminoalkanols;
(b) liquid, plasticizer ester of (i) alkanol, alkanediol, oxyalkylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkanedioic acid, said ester is essentially inert to NCO reaction and is essentially compatible with the cured, solid polyurethane composition, and (c) a soluble organo-metallic compound effective for catalyzing the ambient temperature reaction of isocyanate groups with hydroxyl or amine groups, in an amount to produce a solid polyurethane composition having a Shore hardness of about 7 - 15 in a time of not more than about 30 minutes at about 20°C.
(I) a first package part containing an NCO group containing composition which comprises liquid polyurethane prepolymer, made from:
(a) aromatic diisocyanate;
(b) polyoxypropylene derivative of alkanetriol where alkane has 3-6 carbon atoms, having molecular weight of about 1500-6000;
the NCO/OH ratio of said diisocyanate and said triol derivative charged being about 1.3; and (c) liquid, plasticizer ester of (i) alkanol, alkanediol, oxyalkylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkanedioic acid, said ester is essentially inert to NCO reaction and is essentially compatible with the diisocyanate-triol derivative reaction product, and has a viscosity of not more than about 75 centipoises at about 20°C;
said ester being present in an amount to provide a composition having an NCO content of about 1.5-1.8% and a viscosity of about 1300 - 1800 centipoises at 21.1°C (70°F); and said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged, (II) a second package part containing a curing solution composition consisting essentially of:
(a) a curing agent, in a curing amount, for the polyurethane prepolymer composition of (I) selected from the class of aromatic diamines, aliphatic diamines and aminoalkanols;
(b) liquid, plasticizer ester of (i) alkanol, alkanediol, oxyalkylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkanedioic acid, said ester is essentially inert to NCO reaction and is essentially compatible with the cured, solid polyurethane composition, and (c) a soluble organo-metallic compound effective for catalyzing the ambient temperature reaction of isocyanate groups with hydroxyl or amine groups, in an amount to produce a solid polyurethane composition having a Shore hardness of about 7 - 15 in a time of not more than about 30 minutes at about 20°C.
27. A two part package assembly adapted for producing a solid polyurethane composition when the contents of the two parts are intermingled, which assembly consists essentially of:
(I) a first package part containing an NCO group containing composition which comprises liquid polyurethane prepolymer, made from:
(a) tolylene diisocyanate, about 7.1 weight parts;
(b) polyoxypropylene derivative of trimethylolpropane, of molecular weight about 4500, about 68.1 weight parts; and (c) dioctyladipate, about 24.9 weight parts, said composition having an NCO content of about 1 weight percent and a viscosity of about 1300 - 1800 centipoises at 21.1°C (70°F);
and (II) a second package part containing a solution of (a) N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene diamine curing agent, about 2.7 weight parts;
(b) liquid, plasticizer 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, about 97.3 weight parts; and (c) a soluble lead catalyst, about 0.04 parts; and when about equal weight parts of (I) and (II) are intermingled at about 21.1°C, a solid polyurethane, having a Shore hardness of about 10, is obtained in about 10 minutes.
(I) a first package part containing an NCO group containing composition which comprises liquid polyurethane prepolymer, made from:
(a) tolylene diisocyanate, about 7.1 weight parts;
(b) polyoxypropylene derivative of trimethylolpropane, of molecular weight about 4500, about 68.1 weight parts; and (c) dioctyladipate, about 24.9 weight parts, said composition having an NCO content of about 1 weight percent and a viscosity of about 1300 - 1800 centipoises at 21.1°C (70°F);
and (II) a second package part containing a solution of (a) N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene diamine curing agent, about 2.7 weight parts;
(b) liquid, plasticizer 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, about 97.3 weight parts; and (c) a soluble lead catalyst, about 0.04 parts; and when about equal weight parts of (I) and (II) are intermingled at about 21.1°C, a solid polyurethane, having a Shore hardness of about 10, is obtained in about 10 minutes.
28. A solid, polyurethane composition possessing structural strength against rebounding forces and also possessing the characteristic of crumbling under shearing force applied to the surface of the solid or from the interior of the solid, permitting the solid to be removed from another solid object encapsulated by or embedded in or protective coated on a surface thereof of said solid polyurethane, which solid polyurethane composition consists essentially of, (I) an NCO group containing composition, which comprises liquid polyurethane prepolymer, made from:
(a) organic diisocyanate;
(b) polyoxypropylene derivative of an alkane triol where the alkane has 3 - 6 carbon atoms, having a molecular weight of about 1500 -6000;
the NCO/OH ratio of said diisocyanate and said triol charged is about 1.0 - 1.6; and (c) liquid, organic plasticizer material essentially inert to NCO reaction and essentially compatible with the diisocyanate-triol reaction product;
said organic plasticizer being present in an amount to provide a composition having an NCO content of about 1.2-2.5%; and said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged; and (II) a curing solution composition consisting essentially of:
(a) a curing agent, in a curing amount, for the polyurethane prepolymer composition of (I) selected from the class consisting of polyols, organic diamines and aminoalkanols;
(b) liquid, organic plasticizer material essentially inert to NCO reaction and essentially compatible with the cured, solid polyurethane composition; and (c) organo-metallic compound effective for catalyzing the ambient temperature reaction of isocyanate group and hydroxyl or amine groups; and soluble in said plasticizer; said prepolymer composition and said curing composition intermingled cure, at ambient temperatures, to solid polyurethane composition possessing the aforesaid crumbling character-istics.
(a) organic diisocyanate;
(b) polyoxypropylene derivative of an alkane triol where the alkane has 3 - 6 carbon atoms, having a molecular weight of about 1500 -6000;
the NCO/OH ratio of said diisocyanate and said triol charged is about 1.0 - 1.6; and (c) liquid, organic plasticizer material essentially inert to NCO reaction and essentially compatible with the diisocyanate-triol reaction product;
said organic plasticizer being present in an amount to provide a composition having an NCO content of about 1.2-2.5%; and said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged; and (II) a curing solution composition consisting essentially of:
(a) a curing agent, in a curing amount, for the polyurethane prepolymer composition of (I) selected from the class consisting of polyols, organic diamines and aminoalkanols;
(b) liquid, organic plasticizer material essentially inert to NCO reaction and essentially compatible with the cured, solid polyurethane composition; and (c) organo-metallic compound effective for catalyzing the ambient temperature reaction of isocyanate group and hydroxyl or amine groups; and soluble in said plasticizer; said prepolymer composition and said curing composition intermingled cure, at ambient temperatures, to solid polyurethane composition possessing the aforesaid crumbling character-istics.
29. The solid polyurethane composition of claim 28 wherein said catalyst amount of (II) and the NCO content of said prepolymer composition (I) are adjusted to provide on intermingling and curing a solid polyurethane composition having a Shore hardness of about 5 - 20 in a curing time of not more than about 60 minutes at about 20°C.
30. The solid polyurethane composition of claim 28 wherein said plasticizer material of (II) is the same as the plasticizer material of (I).
31. A solid, polyurethane composition possessing structural strength against rebounding forces and also possessing the characteristic of crumbling under shearing force applied to the surface of the solid or from the interior of the solid, permitting the solid to be removed from another solid object encapsulated by or embedded in, or protective coated on a surface thereof of said solid polyurethane, which solid polyurethane composition consists essentially of (I) an NCO group containing com-position which comprises liquid polyurethane prepolymer, made from:
(a) aromatic diisocyanate;
(b) polyoxypropylene derivative of alkanetriol where alkane has 3-6 carbon atoms, having a molecular weight of about 1500 - 6000;
the NCO/OH ratio of said diisocyanate and said triol derivative charged is about 1.3: and (c) liquid, plasticizer ester of (I) alkanol, alkanediol oxyal-kylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkanedioic acid, said ester is essentially inert to NCO reaction and is essentially com-patible with the diisocyanate-triol derivative reaction products, and has a viscosity of not more than about 75 centipoises at about 20°C;
said ester being present in an amount to provide a composition having an NCO content of about 1.5 - 1.8% and a viscosity of about 1300 - 1800 centipoises at 21.1°C (70°F);
said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged; and (II) a curing solution composition consisting essentially of (a) a curing agent, in a curing amount, for the polyurethane prepolymer composition of (I) selected from the class of aromatic diamines aliphatic diamines and aminoalkanols;
(b) liquid, plasticizer ester of (i) alkanol, alkanediol, oxyalkylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkanedioic acid, said ester is essentially inert to NCO reaction and is essentially compatible with the cured, solid polyurethane composition;
and (c) a soluble organo-metallic compound effective for catalyzing the ambient temperature reaction of isocyanate groups with hydroxyl or amine groups, in an amount to produce a solid polyurethane composition having a Shore hardness of about 7 - 15 in a time of not more than about 30 minutes at about 20°C and possessed of the aforesaid crumbling characteristic.
(a) aromatic diisocyanate;
(b) polyoxypropylene derivative of alkanetriol where alkane has 3-6 carbon atoms, having a molecular weight of about 1500 - 6000;
the NCO/OH ratio of said diisocyanate and said triol derivative charged is about 1.3: and (c) liquid, plasticizer ester of (I) alkanol, alkanediol oxyal-kylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkanedioic acid, said ester is essentially inert to NCO reaction and is essentially com-patible with the diisocyanate-triol derivative reaction products, and has a viscosity of not more than about 75 centipoises at about 20°C;
said ester being present in an amount to provide a composition having an NCO content of about 1.5 - 1.8% and a viscosity of about 1300 - 1800 centipoises at 21.1°C (70°F);
said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged; and (II) a curing solution composition consisting essentially of (a) a curing agent, in a curing amount, for the polyurethane prepolymer composition of (I) selected from the class of aromatic diamines aliphatic diamines and aminoalkanols;
(b) liquid, plasticizer ester of (i) alkanol, alkanediol, oxyalkylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkanedioic acid, said ester is essentially inert to NCO reaction and is essentially compatible with the cured, solid polyurethane composition;
and (c) a soluble organo-metallic compound effective for catalyzing the ambient temperature reaction of isocyanate groups with hydroxyl or amine groups, in an amount to produce a solid polyurethane composition having a Shore hardness of about 7 - 15 in a time of not more than about 30 minutes at about 20°C and possessed of the aforesaid crumbling characteristic.
32. A solid, polyurethane composition possessing structural strength against rebounding forces and also possessing the characteristic of crumbling under shearing force applied to the surface of the solid or from the interior of the solid, permitting the solid to be removed from another solid object encapsulated by or embedded it, or protective coated on a surface thereof of said solid polyurethane, which solid poly-urethane composition consists essentially of, (I) an NCO group containing composition which comprises liquid polyurethane prepolymer, made from:
(a) tolylene diisocyanate, about 7.1 weight parts;
(b) polyoxypropylene derivative of trimethylolpropane, of molecular weight about 4500, about 68.1 weight parts; and (c) dioctyl adipate, about 24.9 weight parts;
said composition having an NCO content of about 1 weight percent and a viscosity of about 1300 - 1800 centipoises at 21.1°C (70°F); and (II) a curing solution of (a) N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene diamine curing agent, about 2.7 weight parts;
(b) liquid, plasticizer 2,2,4-trimethyl-1,3-pentanediol dii-sobutyrate, about 97.3 weight parts; and (c) a soluble lead catalyst, about 0.04 parts; and when about equal weight parts of (I) and (II) are intermingled at about 21.1°C, a solid polyurethane, having a Shore hardness of about 10, is obtained in about 10 minutes.
(a) tolylene diisocyanate, about 7.1 weight parts;
(b) polyoxypropylene derivative of trimethylolpropane, of molecular weight about 4500, about 68.1 weight parts; and (c) dioctyl adipate, about 24.9 weight parts;
said composition having an NCO content of about 1 weight percent and a viscosity of about 1300 - 1800 centipoises at 21.1°C (70°F); and (II) a curing solution of (a) N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene diamine curing agent, about 2.7 weight parts;
(b) liquid, plasticizer 2,2,4-trimethyl-1,3-pentanediol dii-sobutyrate, about 97.3 weight parts; and (c) a soluble lead catalyst, about 0.04 parts; and when about equal weight parts of (I) and (II) are intermingled at about 21.1°C, a solid polyurethane, having a Shore hardness of about 10, is obtained in about 10 minutes.
33. A method of encapsulating a cable splice or capping a cable end with a solid waterproof resilient reenterable solid poly-urethane which method comprises:
(1) intermingling to form a flowable liquid composition, (I) an NCO group containing composition, which comprises liquid polyurethane prepolymer, made from:
(a) organic diisocyanate;
(b) polyoxypropylene derivative of an alkanetriol where the alkane has 3 - 6 carbon atoms, having a molecular weight of about 1500 -6000;
the NCO/OH ratio of said diisocyanate and said triol charged is about 1.0 - 1.6; and (c) liquid, organic plasticizer material essentially inert to NCO reaction and essentially compatible with the diisocyanate-triol reaction product;
said organic plasticizer being present in an amount to provide a composition having an NCO content of about 1.2 -2.5%; and said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged; and (II) a curing solution composition consisting essentially of:
(a) a curing agent, in a curing amount, for the polyurethane prepolymer composition of (I) selected from the class consisting of polyols, organic diamines and aminoalkanols, (b) liquid, organic plasticizer material essentially inert to NCO reaction and essentially compatible with the cured, solid polyurethane composition; and (c) organo-metallic compound effective for catalyzing the ambient temperature reaction of isocyanate groups and hydroxyl or amine groups; and soluble in said plasticizer; and (2) placing said liquid composition into contact with the outer surfaces of said splice or end at ambient temperature for the time needed for the liquid composition to cure to a solid having the aforesaid characteristics.
(1) intermingling to form a flowable liquid composition, (I) an NCO group containing composition, which comprises liquid polyurethane prepolymer, made from:
(a) organic diisocyanate;
(b) polyoxypropylene derivative of an alkanetriol where the alkane has 3 - 6 carbon atoms, having a molecular weight of about 1500 -6000;
the NCO/OH ratio of said diisocyanate and said triol charged is about 1.0 - 1.6; and (c) liquid, organic plasticizer material essentially inert to NCO reaction and essentially compatible with the diisocyanate-triol reaction product;
said organic plasticizer being present in an amount to provide a composition having an NCO content of about 1.2 -2.5%; and said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged; and (II) a curing solution composition consisting essentially of:
(a) a curing agent, in a curing amount, for the polyurethane prepolymer composition of (I) selected from the class consisting of polyols, organic diamines and aminoalkanols, (b) liquid, organic plasticizer material essentially inert to NCO reaction and essentially compatible with the cured, solid polyurethane composition; and (c) organo-metallic compound effective for catalyzing the ambient temperature reaction of isocyanate groups and hydroxyl or amine groups; and soluble in said plasticizer; and (2) placing said liquid composition into contact with the outer surfaces of said splice or end at ambient temperature for the time needed for the liquid composition to cure to a solid having the aforesaid characteristics.
34. A method of encapsulating a cable splice or capping a cable end with a solid waterproof resilient reenterable polyurethane which method comprises:
(1) intermingling to form a flowable fluid composition, (I) an NCO group containing composition which comprises liquid polyurethane prepolymer, made from:
(a) aromatic diisocyanate;
(b) polyoxypropylene derivative of alkanetriol where alkane has 3-6 carbon atoms, having a molecular weight of about 1500-6000;
the NCO/OH ratio of said diisocyanate and said triol derivative charged is about 1.3; and (c) liquid, plasticizer ester of (i) alkanol, alkanediol oxyalkylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkane-dioic acid, said ester is essentially inert to NCO reaction and is essen-ially compatible with the diisocyanate-triol derivative reaction product, and has a viscosity of not more than about 75 centipoises at about 20°C;
said ester being present in an amount to provide a composition having an NCO content of about 1.5 - 1.8% and a viscosity of about 1300 - 1800 centipoises at 21.1°C (70°F) and said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged, (II) a curing solution composition consisting essentially of (a) a curing agent, in a curing amount, for the polyurethane prepolymer composition of (I) selected from the class of aromatic diamines, aliphatic diamines and aminoalkanols;
(b) liquid, plasticizer ester of (i) alkanol, alkanediol, oxyalkylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkanedioic acid, said ester is essentially inert to NCO reaction and is essentially compatible with the cured, solid polyurethane composition;
and (c) a soluble organo-metallic compound effective for catalyzing the ambient temperature reaction of isocyanate groups with hydroxyl or amine groups, in an amount to produce a solid polyurethane composi-tion having a Shore hardness of about 7 - 15 in a time of not more than 30 minutes at about 20°C and possessed of the aforesaid crumbling characteristic; and (2) placing said liquid composition into contact with the outer surfaces of said splice or end at ambient temperature for the time needed for the liquid composition to cure to a solid having the aforesaid characteristics.
(1) intermingling to form a flowable fluid composition, (I) an NCO group containing composition which comprises liquid polyurethane prepolymer, made from:
(a) aromatic diisocyanate;
(b) polyoxypropylene derivative of alkanetriol where alkane has 3-6 carbon atoms, having a molecular weight of about 1500-6000;
the NCO/OH ratio of said diisocyanate and said triol derivative charged is about 1.3; and (c) liquid, plasticizer ester of (i) alkanol, alkanediol oxyalkylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkane-dioic acid, said ester is essentially inert to NCO reaction and is essen-ially compatible with the diisocyanate-triol derivative reaction product, and has a viscosity of not more than about 75 centipoises at about 20°C;
said ester being present in an amount to provide a composition having an NCO content of about 1.5 - 1.8% and a viscosity of about 1300 - 1800 centipoises at 21.1°C (70°F) and said triol providing the bulk of the weight sum of the said diisocyanate, triol and organic plasticizer charged, (II) a curing solution composition consisting essentially of (a) a curing agent, in a curing amount, for the polyurethane prepolymer composition of (I) selected from the class of aromatic diamines, aliphatic diamines and aminoalkanols;
(b) liquid, plasticizer ester of (i) alkanol, alkanediol, oxyalkylenediol, or polyoxyalkylenediol and (ii) alkanoic acid or alkanedioic acid, said ester is essentially inert to NCO reaction and is essentially compatible with the cured, solid polyurethane composition;
and (c) a soluble organo-metallic compound effective for catalyzing the ambient temperature reaction of isocyanate groups with hydroxyl or amine groups, in an amount to produce a solid polyurethane composi-tion having a Shore hardness of about 7 - 15 in a time of not more than 30 minutes at about 20°C and possessed of the aforesaid crumbling characteristic; and (2) placing said liquid composition into contact with the outer surfaces of said splice or end at ambient temperature for the time needed for the liquid composition to cure to a solid having the aforesaid characteristics.
35. A method of encapsulating a cable splice or capping a cable end with a solid waterproof resilient reenterable polyurethane which method comprises:
(1) intermingling to form a flowable liquid-composition , (I) an NCO group containing composition which comprises liquid polyurethane prepolymer, made from:
(a) tolylene diisocyanate about 7.1 weight parts;
(b) polyoxypropylene derivative of trimethylolpropane, of molecular weight about 4500, about 68.1 weight parts; and (c) dioctyl adipate, about 24.9 weight parts, said composition having an NCO content of about 1 weight percent and a viscosity of about 1300 - 1800 centipoises at 21.1°C
(70°F); and (II) a curing solution of (a) N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene diamine curing agent, about 2.7 weight parts;
(b) liquid, plasticizer 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, about 97.3 weight parts; and (c) a soluble lead catalyst, about 0.04 parts and when about equal weight parts of (I) and (II) are intermingled at about 21.1°C, a solid polyurethane, having a Shore hardness of about 10, is obtained in about 10 minutes.
(2) placing said liquid composition into contact with the outer surfaces of said splice or end at ambient temperature for the time needed for the liquid composition to cure to a solid having the aforesaid charac-teristics.
(1) intermingling to form a flowable liquid-composition , (I) an NCO group containing composition which comprises liquid polyurethane prepolymer, made from:
(a) tolylene diisocyanate about 7.1 weight parts;
(b) polyoxypropylene derivative of trimethylolpropane, of molecular weight about 4500, about 68.1 weight parts; and (c) dioctyl adipate, about 24.9 weight parts, said composition having an NCO content of about 1 weight percent and a viscosity of about 1300 - 1800 centipoises at 21.1°C
(70°F); and (II) a curing solution of (a) N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene diamine curing agent, about 2.7 weight parts;
(b) liquid, plasticizer 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, about 97.3 weight parts; and (c) a soluble lead catalyst, about 0.04 parts and when about equal weight parts of (I) and (II) are intermingled at about 21.1°C, a solid polyurethane, having a Shore hardness of about 10, is obtained in about 10 minutes.
(2) placing said liquid composition into contact with the outer surfaces of said splice or end at ambient temperature for the time needed for the liquid composition to cure to a solid having the aforesaid charac-teristics.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US445442A US3895772A (en) | 1974-02-25 | 1974-02-25 | Device for supporting a bucket on a ladder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1074486A true CA1074486A (en) | 1980-03-25 |
Family
ID=23768916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA220,625A Expired CA1074486A (en) | 1974-02-25 | 1975-02-24 | Polyurethane composition having easy re-entry property |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3895772A (en) |
| CA (1) | CA1074486A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE33755E (en) * | 1985-03-19 | 1991-11-26 | Caschem, Inc. | Ester plasticizers for polyurethane compositions |
| USRE33754E (en) * | 1983-11-18 | 1991-11-26 | Caschem, Inc. | Grease compatible extended polyurethanes |
| USRE33761E (en) * | 1985-03-19 | 1991-12-03 | Caschem, Inc. | Ricinoleate plasticizers for polyurethane compositions |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3993307A (en) * | 1975-06-30 | 1976-11-23 | Errico Giacomo J | Tennis ball caddy |
| US4013251A (en) * | 1975-11-24 | 1977-03-22 | Cleveland John P | Paint can holder |
| US4071214A (en) * | 1976-06-14 | 1978-01-31 | Reidy Robert A | Holder for paint cans and the like |
| EP0061358B1 (en) * | 1981-03-25 | 1985-07-17 | Julius Wilhelm Thalmann | Ladder attachment |
| US4403368A (en) * | 1982-02-10 | 1983-09-13 | Harper Orville R | Paint can support for ladders |
| US4534528A (en) * | 1984-01-27 | 1985-08-13 | Michel Rousseau | Paint can holder |
| GB2180874A (en) * | 1985-09-25 | 1987-04-08 | Alan Donald Theaker | Paint tin holder |
| US4787586A (en) * | 1986-05-29 | 1988-11-29 | Crain W Kenneth | Container support device |
| US4899970A (en) * | 1988-12-28 | 1990-02-13 | James Berzina | Paint can hanger |
| GB2237727A (en) * | 1989-11-03 | 1991-05-15 | Lee Michael Farrier | Buckets |
| US5584453A (en) * | 1994-11-22 | 1996-12-17 | Morter; David A. | Apparatus for supporting a container on a ladder rung |
| US5960905A (en) * | 1998-02-23 | 1999-10-05 | Gardner; Brady I. | Ladder accessory device |
| US6848540B2 (en) | 2001-05-14 | 2005-02-01 | Kevin L. Kvam | Ladder accessory holder |
| CA2455919A1 (en) * | 2001-07-30 | 2003-02-13 | Theodore R. Salani | Can caddie and method of forming the same |
| US7143987B2 (en) * | 2001-08-10 | 2006-12-05 | Ted Salani | Can support device for supporting paint cans on a support structure and method of forming the same |
| US9284776B2 (en) * | 2009-10-19 | 2016-03-15 | William Ralph Bond | Entertainment table |
| US8925683B1 (en) | 2012-04-30 | 2015-01-06 | Scott E. Gunsaullus | Utility holding device |
| US11840889B2 (en) * | 2021-08-23 | 2023-12-12 | Johnnie Sterling, JR. | Self leveling one gallon paint can holder-extension ladder attachment |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1246140A (en) * | 1917-04-11 | 1917-11-13 | John D Moritz | Bucket-holder. |
| US1772392A (en) * | 1928-08-30 | 1930-08-05 | Firl Milton | Holder for buckets and other containers |
| US3448956A (en) * | 1967-09-08 | 1969-06-10 | Michael Kuhaneck Jr | Paint can holder |
| US3642240A (en) * | 1970-07-27 | 1972-02-15 | Richard K Hershey | Handy man{3 s tool box and ladder accessory |
-
1974
- 1974-02-25 US US445442A patent/US3895772A/en not_active Expired - Lifetime
-
1975
- 1975-02-24 CA CA220,625A patent/CA1074486A/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE33754E (en) * | 1983-11-18 | 1991-11-26 | Caschem, Inc. | Grease compatible extended polyurethanes |
| USRE33755E (en) * | 1985-03-19 | 1991-11-26 | Caschem, Inc. | Ester plasticizers for polyurethane compositions |
| USRE33761E (en) * | 1985-03-19 | 1991-12-03 | Caschem, Inc. | Ricinoleate plasticizers for polyurethane compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| US3895772A (en) | 1975-07-22 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |