CA2005546A1 - Silicone modified polyurethanes - Google Patents

Abstract

ABSTRACT
Silicone modified polyurethane compositions having low surface energy characteristics comprise a polyurethane matrix in which 1-30% of a silicone compound is dispersed. The low surface energy of surface coatings comprised of these silicone modified polyurethanes provides environmentally safe and effective means of managing the effects of marine growth on vessels and static marine structures by the formation of a foulding release surface which enables simple and effective removal of marine organisms without damage to the surface coating. Silicone modified polyurethanes according to the invention also provide a useful alternative to polyester gel coats in fibroglass reinforced plastic boats and the like.

Description

2~55~i T~TLE
Bl Llaone Nod.~f`led Polyureth~ne~
q!h.t~ lnv~ntl~n r~l~t~s to no~rel ~llloDno mo~
po~ r~chAne~ ~ho slllaon~3 mocll~led polyuro'chano~ fln~
5 partlcular u~e ~B co~tlng oompo~ition~ An~ e~peclally aB
m~rin~ palnt~. q!he polyure~hane~ aan al~o be moul~e~ o~ oa~t to orm a vari~ty oi~ arl:iclss or fllm~. ~h~ ~ilicone mo~l~le~ ~?olyuret,hane~ havs low ~ur~ace energy an~ thu~ ~ave ~oo~ ~nt~-oti~ propartle~ makl~g them ~ult~ble ~or ~ouling 10 releA~e paint aompoji~ion~ ana antl-gra~fitl palnt mp~B~ oy~s .
P~ote~tlv~ oating compo~ltlon~ ~uch a~ p~int~ are ever lnore~lng ln thelr complexlty due ln par~ ~o ~ha large ~arlety o ~u~st,rate~ whlch nee~ to be coat~d. Dlver~e ~rtlcle~ or ~r~uxe~ ~uch a~ publl~ bulldlngs, ~lrcr~
~n~ m~rine ve~sels o~ten re~gul~e regular palntinc,~ t:o re~
e~Ylronmental attack an~ to provl~e An ~e8thetia appearAn~e.
wi~h l~rge b~il41ng~ in paLticular~ maln~enanae o~ the ex~e~lo~ ~rface 1~ both expen~lve and ~im~ a~n~mlng ~n~ nny re~u~tion ln the main~enanae o a bull~lng (le. cle~ning or ~lntlng thereo$) 1~ tino~ a~van~age.
M~nag~me~ of ~rfaces expo~e~ to a marine environmon~ 1~ a ma~or problem in~o~ar a~ the cos~ o~
managemont o~ m~rine growth~ are concerned. ~e~ween hull cl~anln~ operatlon~, marln~ gxowths contrlbute g~estly to hull drag and ~n~rea~s~ ~u~l consumption. For s~atlc marlne ~o~s'~
. 2 ~tr~ctur~ uch ~ oll rlgs, marlno growth~ can contrlbut~
to aoxro~lon problem~.
~ arlou~ ~ttt~mpt~ h8ve b~en m~e to overcome the prob~em~ a~ocl~ted with marlne growth a~ cleaning i6 bo~h tlme aon~umlng ~n~ ~xp~n~lve. One common ~etho~ i3 tO
p~ovi~ a paint: comprl~lng ino.rgania or organome~alllc compoun~ whlch exhlbl~ cont~olled releas~ propertl3~ ~rom the sur~Qa~ o~ the paint ~hereby prov~lng ~he palnted ~U~ACe wlth ~oxlc propertie~. A ~erlou6 dl~vantage of thi~ ~yp~ of p~nt however, 18 ~hat the inorganlo or organomet~lllc aompound~ ~re leached out: o~ the p~lnts lnto the water ~stem~ ~na aan re~ul~ ln pollutlon o~ marine organlsm~ ana cre~tu~e~ ~ well a~ aoa~tal or ~nland WAter~
whe~e ~ larg~ number o boat~ ~re u~ed.
15~he ma:Lntenance o~ palnted ~ur~aa9~ suoh a~ the wall~ on bulldln~ ha~ al~o become an lnarea6lng problem ~ue ln par~ to tht~l lnarea~ed le~ of pollutlon in ~he onvlronment~ An addi~lonal pLoblem a~featlng the malntenance o~ paln~o~ suL~~e~ 1~ v~ndal~m in tl~e orm of gr~fitl.
~r~ffiti on palr~te~ wall~ i8 normally oarrie~ out us~ng ~ro~ol pAlnt ~an3, liqui~ pal~t, lnks, ~elt p~ns or the llko. By ~ar ~he most common form o~ graffltl 1~ u~lng A~ro0ol ~pxay paint cans. Prevlously i~ ha~ been ~lt~lault ~ -to remove ouc~ ~ra~lt~ ~rom painteA ~ur~aces as the aero~ol p~nt 1~ formulate~ to a~here ~trongly tO most ~ur~ace~. ~o romove euch gra~lt~ it i~ ne~essary ~o ~ th~ vlgorously :

~,. ", " :' , ' ' . ' - ' ' ' ' . . ~ .:: .:

0 ~ ~ 6 ~crub the paint ~ork with th~ al~ o ~olv~n~s or to repalnt th~ whole ~urfaa~, both o~ whlch ~re timo con~Uming ~nd ex~n~lve.
~ he u~ o~ toxinB to con~rol the ~ouling of 5 unaer~ter at~ucture~ by m~rlne lif~ 1~ unacoeptable.
Alt~rnatlve non-toxi~ low ~ur~ae energy ao~tings ha~e be~n de~elop~ ~nd ~1ela ~rialle~ over t~e la~t deca~e. ~hese aoatlng~ h~ve prc,~e~ ~ucces~ul ~B foullng ~elease coatlng6, ho~r their UBO to aAte has been 11mlted beo~use o~
di~ ultie~ wlth applicatlon, ~urability and re~lRtance to abra~ion.
Yet anotho~ ~orm o paln~e~ surf~ce compr~ses partlales o polytetrafluoroethylene (~TEFLONI'(tra~e mar~)) boun~ in ~ palnt matrlx to confer low frlction quali~es to a p~lnto~ ~urfaae. ~ow friation ~ur~Aae~ may bo deslrable ~o r~duao w~r ln plp~ or aon~uitB c~rrylng flulds, in p~rti~ul~r ~lui~ wl~h 8011~ in ~u~penslon~ 8~mil~rly, ln the h~n~llny o~ partloula~e materialR such a~ graln~
pow~ro~ chemic~l materi~l an~ the .llke, the lnn~r ~urfAce of ~tor~ge hop~er~, nllo~, road and rail freight contalners may bo aoated wl~h ~ PTFE contalning pain~ ln an endeavour to lmprove the 10w charaoteristlc~ of the p~r~t cul~te mat~r~al oYer th~ nu~ac~ of th~ con~ner.
~olym~lc ~ompoBition~ cont~lning antl~ p or hn~ lock ~yent~ ~re known ln the art an~ ar~ commonly u3~d a~ moul~ rele~e ~ent~. ~y}inAlly, th~ polymer compoqltion .,~ ,:, ~', `~ :', 2~

~ont~in~ ~n amount of ~illoone oll which blee~a out rom the compoaitlon ~o p,rovl~e ~he moul~ relea3e prop~r~le~. ~h~
~te o~ ~leeding of the slliaone oil c~n ~e controlle~ by the ~l~oo~lty o~ ~he oll. The ~illcone i~ not bound wi~ln the S polymerlc m~t~ix ~nd can migrate ~o ~he 8u~ce of ~he aompo61tlo~. Whlle thl~ e~irable ~or ~ould rele~e pro~ertles, ~uch "ble~din~" of th~ fiiLlcone oompoun~ from the polymerla ao~pos~tlon re~ult~ 11 dif~iculty ln an ~ppllca~ion of a p~ot~ctlve or ~ecoratlve ~ur~aae 1ni6h to ~he moul~ed a~ial~. A ur~her dl~a~vantage with the~e compe~l~ions 1~
th~t w~le ~h~ pre~enoe o~ the ~iliaono oQmpound At or ne~r ~h~ sur~ce o~ ~he polymer compositlon can con~er ~lexlblll~y ~nd xe~lst~nce to weatherlng, the6e p~opertles a~e rela~ively ~hort li~e~ ~ue to the con~lnual "~leedlng".
lS Un~te~ Stat~6 Pa~en~ 4,500,688 dl~close~ a melt proco~0~ble p~eutlo-interpenetrRtlng ne~work of slllcon~ ln ~h~mo~la~ mt~t~ . q!h~ aompo~ lon 1~ ~o~me~ f rom ~p~r~ bataheo o~ thermopl~stlc pellet8, one of whloh aon~aina u vlnyl ~llox~ne complexe~ witll a pl~lnum cataly~t ~n~ the o~hRr cont~lnlng a ~llicone hydrl~e àompo~itlon. The lnterpenet~tlng netwox~ 16 formed by mlxlng and extrudlng the pellet~ ln a su~table pla~tlc~ extruder. Th~re 1~ no ~clo~ure of the uBe o~ llgul~ componen~ and the u~e of the ~omp~on~nts ~ ~o~t~ng~.
~nlto~ 8tntes Patent No. 4,302,553 ~scrlbe~ an inte~pen~tra~lng networ~ o~ ch~laally dt~ersnt cro~llnklng , ~ . . - . --. ~, - ~ - . , :
, .. . .

2~:)1)5~6 s polymer~ whlah aO ~ot rea~t together. Irhe ~truatur~ 10 ~e~crlbe~ aB ent~ngle~ ma~ro~yllc polym~rl~ ohal~.
The paten~ close~ the fon~ation of a macrocyllc ~truc~ul-e ~omprls~ng poly (~imethyl8iloxane) an~ poly 5 (urethi~ne-urea) wherein aqueou~ ~mulslon~ of crosfi-llnXed poly~re~hi~e an~ hyarvxy teLminated poly tdlme~hyl8iloxane) Are ln~rmlxe~ to ~orm an homogenou~ mixture wlth ~ulphuL- ~n~ -~
zls~c oxide a~ c~:o~-llnklng i~yents an~ butylate~l buspl~enol A
a~ An an~iox~nt. The mix~Ure 13 cu~e~ At elevate~

10 temperi~tures or ~roun~ 120C whereby cros~llnkln~
e~ecte~ ~y ch~i.n exten~on ol~ 1:he re~pactlve polyurethane an~ ~?c~ly (dimethyl~iloxan~ ) polylller~ .
ESuropean p~1:en1: ~ppllcal:lon 329375 ~ ;ClOBeB a compositlon to control milrine foullng. The compo~ ion :
15 inclu~e~ il aur~ble polyoL~g~no~lloxanel an agent a~pable of ou~ing t~lo polyorgano~lloxane to i~n el~ omer, polylBoay~nate nr~ polyol . The aure~ po~ ymer aompo~Ltion ha~ a low ~ur~a~e energy due to the polyorg~no~iloxane eli~stomer whioh provi~es ~ ~oullng releAse. ~he ~Q speailaatlon ~urther ~a~es that the c~re~ ~ro~uat gener~lly aon~lst~ of ~ontc~ln~ of polyurethane wl~in a notwork of cro~a-link~d pol~organoalloxane. Th~ amoullt of polyurethane .;:
BhOUl~ not exase~1 ~0% by wel~ht a6 lt l~ 8tRte~ that above t~ value the compo~i~lon wlll not glve a s~fficlently low 2S ~ur~ae snergy to prevent marlne ~ouling. I~ l~ ther~for~

evl~ent th~t the oompo~l~lon o~ European patent ~peci~oatlon ' X~0~i5~Çi . . ..
329375 is ~lraotea to ~ ~rethRne mo~l1ad poly~lloxane wlth the urethane a~ ~:he mlnor oompon~nt.
It has now been toun~ ~urpr~1ngly that ~ cone n~o~l~ie~ poly~hQno~ ~vl~y low 6Ul'~C~ ~ne~y c~n ~e S ~orme~ wlth a ma~or amount o~ polyur~thane ~n~ a mlnor amount of poly~ xan~.
In one ftorm the inventlon re~ in ~ curable llqui~ ~lllcone modl~led polyur~thane compri~ing ta) a polyol, ~b) ~ polyi~ooyan~te o~ polyl~othlocyanate, (c) poly~llox~ne ~omprl~lng ~lllcon~ hydrlde group~ and (~) an un~a~ur~te~ poly~ilox~ne, wh~rein the amount o~t (c) and (~) i~ batweon 1 to 30% ~y weigh~ o~ ~he poly~rethane.
~n ~no~her form, the lnventlon resl~es ln a cur~ liqui~ sllicone modified polyurethan~ oomprl~lng ~) ~ po1yol, (b) ~ ~olyifiocyana~e or polyl~othlocyanate, (a) 1-30% by w~l~ht oit the polyu~ethane of a oro~-linknb1e an~
un~turAt~ or~no~lloxAne polymer aomprlslng 611icone hya~i~o g~oup~.
In yet ~nother ftorm, tlle inven~lon re~l~es in a me~ho~ or forming ourablo liqul~ ~llicono mo~l~ied polyur~th~no~ ~omprl~lng premlxlng the unsatur~ted poly~ lox~ne an~ poly~iloxane COmpL~l~lnq alllcone hydride gro~ lng ~he mixture to the polyol, and ~d~lng the polyl~oay~ ox polyl~othiocy~n~te.
2S The ~ Laone mo~i~led polyur~thane~ can be b1Qn~e~
w~-th othor re~ln~ or flll~r~ ~o 70n~er ~e31rable prop~rties 0'3~:6 ~u~h ~a lnar~al ~ ~lexlblllty or #trength to the ~llicone mo~l~le~ po~yux~th g. For exAmE~le, pitch or tar cAn be lncorpoxatRd into .9 sil~aon~e modifle~ polyure~hane compoaltlo~ to pro~ide ~ r~a~e~ flexibillty an~ durablli~y to the com~o~tl~n o~ co~ti~j 3 prepare~ ~here~rom.
q~h~ on~ ocllfle~ polyu2;ethane~ ~an î~a cured by the a~itlon of ~at~lyst~ andtor heatlng. The ahoice Of the cAt~ly~ varles ~ependlng on the type o~ compon~nt u~e~
Typlo~lly, a m~tal c~talyst such as ~2P~C16 i~ u~ed to polymerls~ t~ poly~iloxane componont6. Alternatively, frse ra~lcal pro~ucl~g oataly~ u~h as organlc or lnorganlc p~oxlde~ c~n be used wlth the appllcat~on of heat to genQra~e ree rn~icals. PolymerlsatLon o~ the polyl~ocyanate or poly~othlocy~nate component wlth a polyol i8 well ~nown lS ln th~ art, an~ c~n be c~talysea by any sultable oataly~
~ataly~t~ ~or thLs type o~ polymeri~atlon OomprlSe tertiary aminec or motal ~lt3 or miXtUreB thereo~. ~he type of oa~ly~ta Al~ the condltlons to react the i~ocyanate ox l~othlooya~te wlth the poly~l wlll be well appar~nt to a per~on ~kill~ ln t~e art.
~ ha platlnum a~t~lyst can Gonvenlen~y ~e premlxed w~th ~he uns~turAted pol~siloxane b~fore ad~itlon to the remalnlng ~ompound~ althougll ~his 1~ not es~en~ial~ It 1~
pr~orre~ t~ th~ platlnun~ a~ yBt ~.8 n~t premlxed with the ~5 poly~lloxane aompri~lng the ~lllcone hy~rlde groups. ~f a ~r~e r~lo~l cat~ly~t 1~ u~e~, the~e can suitably be premlxed ~esarib~d above howe~er, a~dl~ionsl cars ne~a~ t~ be t~ken that ~h0 ~talyl~t doec no~ aecompo~e l.~;to free raalcAl~
~rom~tur~ly. I~ ~ o~t~lyst i~ uned ~o ~romot~ ths reac~ion ~e~ween the poly~ocyana~e or pol-.iaothlocyan~te an~ the polyol, lt i~ pr~aferr~d that ~hl~ lB a~de~ lmme~i~tely ~rior to curing~
~ha un~aturated polyBiloxane i~ sultably s~l~cted ~om ~thylenicall.y un~urate~ components su~h a~ hexenyl or ~rom other terminally unsaturated g~oup~, although other 1~ ~orm3 o~ u~tu~ation are also envi~aged. The remalning sub~tltuen~s on the poly~lloxans are preferably alky~ groups ~n~ an e~peclally pre~erred al~yl group 18 the me~hyl group.
I~ow~ve~, lt is ~l~o env~saged tha~ groups ~uch ~s ~romatic g~oup~, long oh~n alkyl gxoup~ o~ cycloalkyl groups can advan~A~oou~ly be used. ~ pre~e~ed unsaturatea polyslloxane 1~ ~ vlnyl en~ groupe~ polydime~hyl~iloxane.
~he ~ bone hydri~ contalnlng polyslloxane 1~
pxe~erAbly a polymethylslloxane contalning a numbor of ~Ll~aone hy~rl~e g~up~ ~long the backbone o~ the polymer~
~t 1~ al30 po~ible for the hy~rl~e an~ the un~t~ra~o~ group to be present on the s~ne siloxane polymsr okbone .
Altorn~ ely, lt 18 also po66ible ~o employ a ~one~-compo~ent~ organo6iloxane component. ~he organosiloxane woul~ be r~qul~e~ to be capa~le of oross-linklng pre~erably ln a non-condens~tlon raactlon in the pre~enoe o~ a catalyst.

.:- g The polyol component CAn be cho~en from any oompo~n~ comprl~.lng ~t lea~ two hy~roxy grou~3 which are re~c~lve ~o isooyan~te or l~othlocyana~e groupc. Suita~le polyol~ lnclu~ hy~roxy (meth)acrylic Raid~ or ~ter~
ther~of, polye~tars, polyether~, polythloether~, polyacstal~, polyoarbos~tes, ]oolyester-amiae~ all o~ whioh contain at le~t two re~otive ~ydroxy group3. Branched polyalkyl~ wlth ~t~x ~n~ ether crroups may also be u~od. The~ polyol~ may ~e provL~e~ wLth ~ditional ~unctionality ~uch a~ amino, th~ol, or e~r~oxy:Llc group8.
~ he pOlyl~OCy~nAte or poLyl~othlooy~nate oan ln~lu~e ~cycllo, cycllc, cycloalLph~tlc or ar~matia aompoun~. A~itlonally the i~ocyanate or lsothiocyanate can h~ provl~e~ wlth hetero ato~s in a~di~ion to t~e isocyRn~te or l~othlooy~nate nitrogen, and can al~o lnclude un8aturated l~ooyan~t~ or i~oth~oayanAte~ Polyphenyl-polyme~ylenes polyl~oa~nnAte An~ polyl~o~hio~yanat~ lncluding carbodlimido, allophAnate, i~oayanusa~e, ur~hane, aaylated ~rea, ur~a or b~lr~t g~o~p~ ~n~ polyi~ooyAn~te pr~polymers or any mixtur~
2~ o ~he abo~e may be Gultable gor th~ lnventlon.
~ he oonlai~esed useul r~tlo of poly~ilox~ne to poly~e~h~ne i3 between 1 - 30% by we~g~t w~th ~ preferred rat~o of ~bout 10% by weight poly#itoxans to polyurethane.
The silfoon~ modlfled polyurethane~ of the inven~lon onn be prepare~ by ad~ixing the polysllo~ane, polyol an~ polyi~o~y~n~te ln any order. ~hus, the 2~30S5~6 polyurethan~ ~an be preparca by ~dmlxlng the poly~iloxane cont~ln~ ng hy~rld.e group~, the un~a urat~a poly~lloxRne, the p~lyol ~In~ the polyi60ayarlate together ln approprlat~
~mount~. Altern~tlvely, the poly~illoxane~ can be premixQd ~n~ a~O.e~ to the polyol a~1:er which the polyl~ocyEInate 18 ~aded. ~n ~ ~urther alt~rnRtlve method, on~ o~ the polyollox~ne compon~nt~ can lae p~emixed wil:h t:he polyol while tha othsr o the poly~qilox~ne componen~ can be pr~mlx~ with the polyi~oay~na'ce or polyl~othiocy~nate ~nd ~he two prem~xtur~ n be ~dmlxed 'co~ther. In yet ~nother method, ~h~ poly~lloxanali~ oan be premixe~ with the polyisocyana~e ~d tho polyol ~o~ the~eto.
~ho poly~ h~no c~n ~o in tl~ n ~ ln~l~
aom~?onont propolymer compo~ltlon aontalnln~ the polyol anâ
polyl~oay~nA~e or in tha orm o~ a two componan'c ~ompo~itlon containing the polyol an~ polyi~ocyanate a~ ~eparate aomponentc. In A ~lmllar mal~ner, the polysilox~nec can be in ~he ~o~m of a ~in~lo aomponent prepolymer oon~alnlng both 3110x~no~ or ~ two ~omponen~ aomposl~lon contalning the poly~ilox~ne co~pxieing hy~rl~e groups and the un~a~urated poly~llox~ne ~e~pec~ively. The polyurethane ~n~
polyslloxane can be ~dm$xed in any o~ ~he abova manner~, for lnstan~e, the two oomponent ~olyurethane c~mposltlon c~n be mlxed wl~ e ~ingle or two component poly~lloxane or vlce ::
v~r~a. -The invention will be more fully illustrated by 0 ~ ~'3~1~

: . 1 1 -reference to the :eollow$ng exampl~ ~n~ comparltlv~ ex~mpl~

~he aompon~n~ o~ ~he oomposi~on~ are l~ent~fle~ a~ follo~s:
~ A bra~ohe~ hydrvxy ~ontalnlng polye~ter 801~ by BAY~R AUqTRA~IA
LTD.
- A hy~roxy cont~inin~ polyacryl~t~ ~:
~ol~l by 13;~YER AUS~ IA LTD. .-DESMO~?HEN 670 - A sllghtly branclle~ hydroxy .;
~ .
containlng polye~ter ~ol~ by BAYER

~US~RA~IA ~D. :

E8MOPHEN 90QU - A branah~d ~Iydroxy aontaln~n~

polyether ~ol~ ~y BA~ AUS~RA~IA

~D, ~ESMOPHEM A160 - A hy~roxy aontalning polyaaryl~t~
. . ~ _ ~o~d by ~AY~R AtJ~TR~ A ~TD, DB5MODUR ~15 - An ali~ha~l polyi~o~yanAt~ ~ol~ by :. .:
BAYER AUSTRALIA LTD.
D~MODUR ~?5 - An a~omatla polyleocyan~e eold by ~ :
BAYER AUSTRA~IA LTD.
BEIAMITE 8ILICONE_~ - Un~aturate~l poly6110xe~n~
llquld ~ol~ by Bramlte Li~lt sRA~ E S~ICON~ 2018 - PART B - Poly~lloxane ll~ul~
~ ContRlning 6~ licone hy~rlde group~
~old ~y Bramlte ~lmlted ~ D~21s5 - t reactlv~ unsatura~ced. sillcore ~0055~

having ~lllcone hydrid.e groups manu~otur~3d by BR~MXT~ LIMI~ED.
9~ 2 0 6 3 - A ~ one o~ l ha~tlng a ~rl sco s ity of 1000 c~ntlatoke~
~.~A - UnBatU~at:e~d poly~lloxan~ llquld Bold by D0~1 CORNING .
J~E:D~D~_B - ~olysilox~ne liquld con~inlng ~llloone hy~r~de groups aold by DOW
CORNING .
~~R~V615~ - Liquld 811icone rubber ~old by THE
GEN~RAII E~ECT~IC COMPA2tY.
~61~ - ~lgui~ ~ilicone rubber sold by ~HE
GENBR~ E~ECTRIC COMPANY.
MQ~AFLOW ~SI~ MC~DI~E~ - A ~low an~ levelllng Bgent sold by MON8AN~o AUSTRA~IA I,TD.
- ~ wettlnç~ ~nd ~i~persion agent ~old by HATRICK Aus/rRAr~IA LTD.
RUTIL~ ~HD2 - . A xu'cile pigmonl: ~old by ~OXIDE
AU8T~ALIA ~?TY L~D.
~A~C T~1~ - Hy~rou~ Magnealum S~licate aola by COMMERC~A~ MlN~ S ~TD. ~ :
=~CHri-RRRII - A barlum sulate extena~r ~old ~y A ~rIcToR I ~GGO & CO PTY ~TD .
r, ~r - ~ ve~e~abl~ oil ~old by HARCROS ~ -:
CHEMICALS P~ ~TD, SPEC~ PI~C~ NO. 4 - ~ pitch ~ol~ by THE SWIFT WATT8 ::
~''.,"' '':
"'~ ;:: '''''' :
,,' ;''~'~ "',"'' ,~., ,~ ., ;....

' '' ""';' - 2(~)S~4~
: 13 WIM~ER COMPANY.

S~3i~ PAr~ we~t~
1. Da~mophen 651 67~ ln a 1:1 mlxture o~ m~hoxy propyl acetata ~nd xyl~n3 28 2. MoaA~low 5% in methoxy propyl~cet~te 3. ~k P-104~ 1 4. ~utlle R-HD2 24 5. Solvent (e~ual ra~io~ o~ methyl 160butyl . :~
~etone, me~hylethyl ~etone, me~hoxy propyl ~cetat~ and tolu3ne) lG
G. lQ:l r~tio of Bramite 2018 part A ~oontalnln~
a Pt ~t~ly~t1 An~ Bramite 201~ part B 8 1~ Com~on~n~ B
Deqmo~ur N75 75% in methoxy propyla~etate 22 ~he un~atur~e~ poly~llox~ne (Bramlte 2018 par~ A) .;
aont~lnt-ng ~ platlnum c~tAlyGt an~ the poly~llox~ne ~0 ~ompr~tng sllicone hy~ri~e group~ (Bx~mite 2018 part ~) are . . .
p~emlxe~ ln ~ho ~pecifled ratlo (10~ he mtx~ure 1~ added ~o the ~em~ln~ng compouna~ o~ component A ~nd 1~ mixea or 3- lOmln8 ~t am~ient tempera~ures usin~ low shear mlxlng.
Thl~ !mixture 18 le~t a~ ~mblent kemper~ture~ ~or 2-4 wee~ os untll ~he viaao~ity of the mlx~ure no longer i~crea~ea.
Componont B 1~ a~e~ to the mlx~ure, with stlrrlng to form 2~155~16 . 1~
tha ~illcone moal~le~ polyurethana~.
~he mlxt~:e ~n be ~pplled to a ~ur~a~e a~l cur~a to o~m a oo~tlng. ~ naoa~a~y, a ~olven'c mlxtu~e can he u'clllz~ a thlnnlng mlxture to facllit~te the ~or~ 1;1On of S ~or~'clnçl.

EXAMP~E 2 Componont l Part,e (~weiqht ~, 1. De~mophan ~365 6S% ~n ~ 3: 1 r~l~lo o~
bu~yl~c~tate Xylene 41 2. Mo~a~low 5% in methylpropylaoetate 3. ~y~ P-1048 4. ~utlle R-HD2 ~4 5. ~olvent - s~ual ratloB of methyl l~obutyl Xetone, methyl ethyl Xetone, methyl propyl .:
ac~tate An~ 1:01~3n~ 8 6. Br~ml~ 2018 p~rt A (oontn~nlng ~ Pt c~t~ly~t) :
an~ E~r~mlte ~0 18 par1: B ln a 10 :1 ra1:lo 8 ~ .~

7, Br~m~e Slllaone 2063 1 : ~:
20 5~Q~ `
1. De~mo~ur N75 IG

The m~tho~ of axample 1 is u~e~ w~ th the exceptlon .` .
that ths ad~ltion o~ the Bramlte 8111con 2063 ~lui~
25eïimiIIa'ces the ~3g~slrement o~ leavlng the mlxturs fo~ ~-4 ~ ;
weeX~ an~ componen1: B 0~ 1:he example can be ~mmc~lataly : ::: :
~: `:: ::;:

:~
~dded.

_omponen~ A ~:3~ L_LL~:L~b9 S 1. De~mophen A36,5 65~ ~n 3-1 ratio o~ hut~laaet~to/Xylene 40 a. ~o~mo~h~n 670 1 :
3. MoAeflo~ 5% ln methoxy propyl ace~a~e 4. ~y~ P-104~ 1 5. RU~ilo R-HD2 24 6. ~olvent-eq~al ratlo~ of methyl l~obutyl ketone, me~hyl ethyl .ketone, methoxy propyl acetate and telue~e ~ ~ .
7. 10:1 ~atio o~ Bramite 2018 part A (oontainlng 8 A Pt aataly~t) ~nd Br~mi~e 2018 part B.

8. Bramito 8111a~n 2063 ~2!~ ",.,. ;~
Pe~mo~ur N73 ~ 75~ ln methoxy p~opyl aoe~te ~6 ~
~ .
Th~ metho~ of example 2 18 use~ to form th~
~lllaone Ino~ifle~ polyurethane~

EXAMPT~E 4 Cgmponent ~ Part~ (~wei~htl.
~. De~mophen 900U 22 2. Rutll~ R-21D2 22 ' .'. ' ' ~ ' ' . ' ' ' ' ' ' ' . '~ ' ` ' . ' ' . ' ' ; ' . ! . . . .. . . . .

Z~

3. ~olvent e~ual r~tlo# of athylglyoola~eta~e, methyl lsobutyl ~etone, ~nd moth~lethyl ke~one 24 4. ~lllaone R~VS15A (con~alnlng ~ ~t c~ly~t) nnA Slllaone RTv6l5a ln a ~0:1 ra~lo lO
~
1. De~mo~ur ~75 - 75~ in e~hyl a~etate. 22 ~h~ eomponent3 Are ~eacted uslng the matho~ of exam~

EXAMP~B 5 ts ~96wel~ht~
1~ D~mop~e~ 900U 14 2 . ~yk P- 104~
3. ~peciAl Pltch No. 4 20 4. ~lc T91s 4 5. Bl~n~ Flxe ~N~ - sacl-~leben 16 6. Castor oil Hy~ro~ena~e~ 2 : ~:
7. 801v~n~ - o~ua~ ratio~ o~ me~hyl 1BO~UtY1 ~eto~
methyl e~hyl k~tone and ~e~hy~ pt~opyl ace~ate l~
8. Sylgar~ 1~4 part ~ (con~al~ing a Pt cataly~t) An~ 9ylg~r~ 184 part B 10: 1 ratio 7 . ~ ~
1. De~mo~ur L75, 75% in ethyl acetate l9 2. ~oluen~ 2 ~he oomponent~ Are re~te~ u~lng the m~thoa of ,~
`" ' .

2~S5 estample 1.

XAMPL~ 6 Co~Ponant A
1. D~mophen ~160 60~ in Xylene 44 2. R~til~ ~-HD2 24 3 . Sol ~nt 2 ~ o o Xylen~ Ana ethyl glycol Qa~t~te 1 2 4. Bramite 2018 Part A tc~ntalnlng Pt cat~ly~t) an~ ~ramite 2018 pArt B ln ~ 10:1 ratlo 4 ~ " .
l. De~mo~ur N75 10 2. ~olu~ne 6 The oomponsnt~ axe ~eacted ~8 ~ n~ th~ m~tho~ o~
exam~

EXAMPLE ?
col!~ponent ~ Pa~t~ welqht) 1. De~mophen ~3~g - 6S% ln bu~yl a~tAte/xyles~ 3: 1 39 2. ~tile ~-HD2 24 3. 501v~nt-equal part6 of methyl l~obutyl Xetone, n~etllyl eth~l ketone, Toluene an~ athyl gly~ol aGo~at~ 15 25 4. Silloone - Brl~mi~a Slliaon~ 2155 6 ~01V55~6 om~onent B
Da~mo~ur ~7~ 7S~ ~n methoxy propyl aoetata 16 ~ h~ aompound~ o~ aomponen~ A ~ere ~ixe~ an~ 50ppm ~relatlva ~o ~he polyslloxane) of a platlnum aa~alyst H2 Pt Cl6 was ad~ed. ~er ~tlxxing a~ ambie~ ~emper~ure for 3-10 mlnut~ ~o~pon~nt B w~ add~ to ~ive th~ s~licono modlfled polyurethanes. :
EXAM1PI.E B
Co~m~on~nt ~ arts ~welql~t) 1. Desmop~on A160 B0~ ln Xylene 44 2. Mo~a~low 5% in methoxy propyl ~cet~te 3. By~ P-1045 .. ..
4, Rutll~ D2 24 5. ~olvent 2:1 r~tlo of Xylene an~ methox~ ~:

propyl aoe~a~o 12 :

6. Slllaone-~r~mite Sllicone 2155 4 :; ~; - ` `.' ~om~n~n~
1. Doomod~r N75 10 2. ~olueno 6 The aomponent6 are r~acted u~ing the metllod o Example 7. :`
'' ~ .

EX~M~LE 9 One paok mo~Letur~3 ourod ey~em l. Ds8modur N75 60 p~rt3 2. Xyl~n~ 30 p~rt3 ~ ;~

X~)S5i~6 :~
:- 19 . Dlbu~ylti~ ~ urate ~. 3 part~
. ~illaon~ R~V615A An~
~illcon~ R~V615B 10:1 ratio 9.7 part~
A~Mixture o ~h~ above compoundy gave a one p~ck mol~ture 5 auro~ ~y8~em.
COM~?ARATIVE E3XAMP~E 1 ~ .
Thls form~ia~lon i~ identical to example 1 wlthout tho ~ram~o 2018 par~ A an~ Braml~e 2~18 par~ ho ~olvan~
oompo~nt l~ lna~o~ee~ to 24 p~rtn.
10 :
COMPARATIVE ~XAMPL~ 2 ~hl~ ~ormulation l~ l~entioal to example 2 wlthout the Br~mlte 2018 pa~ A an~ Bramite 2018 p~t ~ an~ 3ramit~
Billco~e 2063. The ~olvent component ~ inc~eA~e~ to 16 1 5 par~
It l~ belleve~ that th~ R~a~nlte Slllaon~ 2063 a~n ~e p~ lly or totally ~ub~itutea by polyph~nylmo~hyl ailox~n~ ~lui~ or ~luoron~te~ hydro~ar~ wlth low ~urf~e o~orgy.
O~her Hllioone ela~tomor~ ~uch a~ RT~31~0 (~ro~uo~d by DOw CORNING a~ a two pa~t mixture) can ~e use~. ~ho~e ~;
B~ `e oataly~ea ~y dlbu~yl~ln dll~ o o~ e~n~o~
oct~noate. ~ltho~gh the ~ilicon~ ~re o high viocoalty, thinnlng with ap~ropriate solvent~ can be o~rrl~d o~t ~rio~
to lnooxpo~tion ln~o the polyol.
The siliaone modifled polyurethAne~ o~n be orme~

:.: . . - . . .. - . , . : ...

~14 a ~ingle ccmpone~nt ~y lnol~lon o~ ~ poly~lrath~ne ~repolymer which cures by reac~lon Wl'ch ~tmo~ph~rlo mol~ re.
A ~ui~ prepolym3r l~ De~mo~ur ~21 ~ol~ ~y BAYER AU9TRA~IA
LTD. ~lternatlve~y, a one componen~ mo~ rs cure~ one modi~ied polyuret:hane ~an be formed Sa~ed on an ~llphatlo ~olyl#ocyanat~ ~uch ~ Da~mo~ur N75.
Although the a~ove ex~mpls~ have u~ hydroxy ~:
conthlnlng polyaaryla~e~ and other polyol compo~n~ ~old by BAYER AUS~RA~IA, the~e compound~ ma~ be ~ub~titute~ by hydroxy oont~inlrlg polyacrylate~ ~rom HOECH8T AUST~IA LTD
under ~he tra~e mark MACRYNAIJ Stl ~erl~l~ an~ hydroxy contalritln~ poly~oryla~es from CR~Y VA~Y PRODUC~S L~D U.K.
whlch are sol~ ~tn~er the tra~e name S~NOCURE. 91mllarly, an allphatia polyl~ocyanate de~gnate~ aa hartbon A7S 801~ ~y ~ ~:
VICTO~ ~E¢GO A~ID CO PTY hTD lo oonsldo~ed ~ ~ul'cable alt~ natl~r~ to D~modllr N~5.
'rhe ~illcone modifle~ polyur~thane ~y~em o~
exe.mple 3 aon~alning u sm~ll percento.g~ of b~mo~?hen 670 ha0 been u~ed ~o~ coatlng a p~o0.ùa~ ~old by FERRO CORPOE~A~ION
(AUS ;I!) P~ t.'rD un~er the tra~e name VUL~tEM wh~ ch 1~ u~e-d to provl~e ~ ve~y fl~xible ~ubstrato on pOOlB. -Ths ~llloone modl~ied poly~lr~thane compo~ltlon~ of :
exam~?le 5 inaorporating ~;he pitch provlde~ heavy ~uty co~tlngs wltl~ improved w~ath~rlng proper~ n term~ OI ~:
~5 ~10B~ ~e'contlon. Polyuret:hane pltch or tar ~ormulation~ not lncludls~g ~lllcone mo~ ~lcatlon 8u~er from 103~ 0~ g1OB~

~"', 2~0~ l6 wlthl~ Glx month~ o~ expo~ur~.
~ he ~lliaone modlf~ polyux~thane~ o~ the ~x~mple~ aan b~ unplgmen~ed ~nd the~e ~ormulatlo~ u~ually have W ~tRblllze~r~ pre~ent a~ well as the lev~lllng agent MODAFLOW. Suitable ~tablllzers inc1ude Tlnu~ln 292 an~
Tlnu~n 900 (~racle ma~ CIBA-GEIGY AUSTRALIA ~ A 10%
Bolutlon 1~ xylen~ an~ whlch ~e a~de~ in ~wo p~rts and ~ou~
part~ re~pectivH1y to ~he ~ormula~ion.
An alkern~tive m~thod o~ forn~lng the ~lllcone mo~i~lea polyurethane composltion8 of the ex~mple~ 1~ to premlx the polyol ~n~ poly~ soayana~e or polyi~othlo~y~nate at ~n~bi~nt tam~er~Ure together w~th ~he deslre~ ~ol~nt mlxture and aadltlv~ u~ng low Bhear mixlng con~lt~onB~ ~e uns~turat~ poly~lloxane (aontaining plAtinum o~taly~t) ~nd the poly~iloxane aontalnlng ~lllcone hy~rlde group~ are premixed and -t;hèn ad~ed ~o the polyol/loo~y~nat~ or l~othlo¢yanate n~lxture oveL ~ peLlo~ of 3-10 mlnute~ ~t ambient temperat-lr~s an~ u3ing low ~hear mlxing oonditlon~.
~his mixture oan be ap~lled to a ~u~tr~ts ln the ~orm o~
aoatin~ to ¢ure ~t room temper~t~r~.
~ able l ll~t~ ~arlou~ propertia~ o~ certaln o~ the exempli~le~ Lcone modlfle~ polyurethane~ aompared wlth ~den~iaal polyurethanes not cont~lnlng ~111cone. Unlo~
otherwl~ ~peclied, th~ ~lllaon~ mod~le~ poly~re~hane coating~ have ~een teste~ to Aus~rallan Stan~ax~ 2G02-~aints ~or ~teel ~tru~ture~: f~l1 glos~ poly~rethanes. The .'' ' `', ' ' 1. . ", ",.......................... .. ....

... . ~ : -: . ~: . . . , -'ce~ wer~ car:rl0d out ln Raaoxdanao wl~h A~l~tr311An 6~1nd~rd~ 1580 - Method~ o~ 're~ or P~nts an~ Rel~tMa'cerial~
`' '~ ` ~' ' ~.' ', :: :

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;./ (1) ~2602 :~e~ulro~ ~e3~1ng ~o AS15~0-214.1.
.1 5 ~2) A82602 ~e~uir~3 tofl~lng wlthtn 24 hour~ o~ :
~ appllcat1on o ~e~con~ co~tlng. ~`hl8 wa~ ex~ended to 7 daya ;l "normal'~ curln~, the 24 hour cure tlme b~ing ln~ufflclen~.
.. , (3) Uslng ~ black enamel p~int that ~lght commonly b~
~ u~a ~o~ g~Q~ltl p~rpo3~ eOa Cl*te~ 7 aA
,;;', .

Mo~i~le~ aoa1lng~ osn b~ ap~lle~ ~y bru~hlng, convont~onAl !; alr ~raying ~n~ rollex coating without Any evldenae of fllm ~e~eatc. The p~esence o~ the ~ilicone al~3 ~he ~low, eprea~ing, l~velllng and 1A~P1ng proper~le~ aomp~o~ ~o ~he unmodl~ aoatlng.
2. Po~_llfo ~ hi~ t~s~ W~B o~rsl~ ~u~ ~B~oL~1n~ ~o ~1500-2~.2 ;!~ (consistenay - F~ow Cup) ollowing the procedure outl~n~d in ~ 20 A8260~. Both th~ ~lllcone mod~ fie~ polyurethane And ~he ',~ polyurethane c~Ating~ wera thlnned u~lng ~pr~ylnq thlnner~
. .~ .
80 a~ to glve ~ flow tlme o~ 22 ~econds. A~ter a perlod o~ 3 hours at 25C, flow ti~e wa~ me,~Fure~ ~t 23-24 ~econdG or ., .
both the ~licone modlfie~ polyurethanes ~n~ t~e unmodl~led polyurethanes. The re~,ult~ ~nalcate ~u~tability o~ both y~,t~mc wi~h re~pect to pot ll~e ,~nd lndlreatly ~ugge~t~

J :

:,i `''~' ., , ZO05~
.i .
::. 27 mlnlmal, ~ any, reaatlon ~etwe~n the ~ cone ~nd polyurath~ne ~om~02~en'~.
i' 3~
,i Thl~ ~est lnalc~t:e~ m~ nimal dl~e~nco b~weQn ~e ~llloone mo~l~ie~ anO. ~Imnodl~le~ polyureltl~ane~. In~ ec~ly thl~
I. sugge~t~ some dsg~e of curlng bE the ~llicone ha6 occurre~
.. ` pLior to ~ition o~ polyisocy~nat~ aomponent.
f 4, Bon~l t25~'c Thl~ ~e~ aon~ldered an indic~tion o ~lexibllll:y Rnd ~hs~lon o~ the ao~tlng6.
5. ~ t~
The curlng propertls~ ol~ 1;he polyureth~nes 1~ a~e3~ed by measurln~ the sor~tch re~i~tanoe; the fllm h~ving ~ured for 7 Clny~ ln aaaor~nas with ~S1580-403; 1 shotlld wlth~t~n~ a los.d o~ 1. Sky. The s~ratch re~l6tl:anoe o the pro~uct o~ Ex~mpl~ 1 tly ~own from all ol:h~r aoating~ trialle~.
6. ~1~
Due to th~3 p~oblem o adherencs oi~ p~e~ure-~en01tlve ~c~pe over cut~ maâe l~n the i~m (see AS1580-40~. 4 Adh~ion-oro~
?.0 cut) the lcnlfe t~3B1: me1:hod wao u6ed. A r~'cing of 4 r~pre~ent~ ~rAce peoling~ or removal ~long lnoioiona, in ot:her wor~ lh~lon to the ~b~tr~te io Yory good .~ 7. ~eooat~s~q ~ro1~0~tl~n A ~t~and.ar~ curs pe~iod o E 7 ~ays wac u6~d . ~e~ul~s cl~arly :~ 2~ ~how the abil~ty OE the oillcone modifie~ ~olyurekhaneo to b~
~e~o~
`i ~ ,.:

:'~ ' ' ' ; .~
. ~
`~. ;;'' ~i .:`', 2~5~i4~ :
~ . -: 28 , 8.~vercoatlng pXo ~-`! ~ v~rta~lon o~ 7 ~boY~ wa~ u~e~ to ex~mine th~ ~feot oL' -~
, 5 ap~lying a ~laak en~mel palnt ~ha~ mlghk be u~ by grAffltl '!I .
r~l Arti~ts . R~a~u1~3 olearly ~mon611;rate the ~ nablll'cy of the , black enamel te ~.~here to the ~l:L~oone modlfi~d polyureth~ne 'j aoatin~3. The ~name~ film, when Appll~d ~o the ~llicone :;
.~ modi~ie~ polyurethane co~tlng6~ show~d conslderable ~llm .:; 10 ~eec~s ~ue ~o fi~h-~yeing, e~c.
. ~
~' 9 :.: ~he abraslon xeei6tanoe o~ all ~he coatin~s wa3 excellent.
,:
~'$~ 10. ~ rrlot~
l The test methoa u~ed 16 a varlatlon of AS~M ~i4581 ln ~hat a $' 500gm vertloal loa~ wa~ plaaed on e~ch oo~ed coupon ~hrough ~l a 9.~mm diameter ~te~l ball. The aoatod coupon ~ampla wa~
moun~e~ on a ~1At ~teel plate that could ~vana~ on low ;! ~rlatlon bearlngs. ~he plate wa~ pulle~ ~OrW~rd ~t a ~P-9d ~!~ 0~ 50mm~mlnu~e by the aro~-head ~f a JJ ~loyd t~tlng ., .
0 maehine by ~ ans o~ ~ nylon cor~. The force Le~ulred ~o ;~ propel the plate was measured by me~nB of a load cell.
,.,~
Re~u~ clea~ly ~how a ~lgni1cant reduotlon ln sur~ace .j frlc~ion coe~iclent of the ~llcone mo~l~le~ polyur~th~ne coatl~g~, ~!, 25 ~1. Gl0~3 (60 expo~ura h~ad2 :j Specular glo~ was measure~ ~or those ~ample~ prepareA ~o~
: i .
, .. ~ ..
~, ;
. .

.`.3, ,,, ~

r,,~ 6 ~ 29 . .! ~
., .: ~o~el,e,rate,d Q W w~,~th,~,rlnq. All coatlngs met the mlnimum , ", e~EUlremHnt of A,~326~2, in tha'c spe,aular gl,~a~ ~h,sll no~ be 3a~ than ~5 glo3~ ~unitJ.
' 12. Duxabll~x ; S A~t~3r a w~a,atherlng parlo~ of 12 n~onths, proper~y ~e~ec~s ~ucl~
.`~ a~ e~o~lon, cracking, cheakl~g, flaXlnq an~ pe~ling, '`'1 ;;;~ delamlna~lon, ruEtlng with bllste~s, rusting and blls~erlng J
., we~e no~ ob3~ve, an~d the highest rating o~ 10 WAB no~e~.
.~ The,~e result~ ar,e to ~e expe"~e~ an~ th~ mlnimum requirement ; ! 1 0~ A~2602 is that a rAting o~ 10 be a~a~sd ~uring the fl~st .. , 48 mo~ths. ~e~ult~ ~o show th~t no adve~Ys e~ec~s are, . noted ~or the 31llcone modlfi,s~ polyuretllnne ~ystem6.
13. ~ r~billty (Q'~Y ao,celer,~e,~ wea~h~srln~ - dOO hou~
h" coatlng~ were æub~ected to acaeler~ed weatherln,g 'U8 lng a .j 15 fluore,~a~nt ultraviole~ tUV) an~ c,on,~,an~atlon appa~atu~ to ;¦ 3imula~e the de~erloratlon aaused by sunlight and wa~er a3 r,~ln o~ ~ew. ~e,peat~ad ayales of 4hrs U'~ light followed by 4'hx3 aon~e~satlon were used. Re~ul~e lndicat,3 t'hat ths . 311~aone mo~;L~L~d polyure~hane~ o~ ex~imple~ 2,~ an~ 8 : 20 p~rform b~tex, ln t~rms o~ g~o~ retentlon than Comp~r~tlve Exampls 2 or ~xamplo 1. .

The interl~r ~rfaca of ~VC pipes of 6 me~res ln length, 50mm :~:~
~ iaineter, were ooatea with the pro~uct of Comparatlve .-l 25 Exa~ple 2 ~n~ o ~xample 2. On~ pipe was l~t uncoate~
Pro~sus~ ~rop ~n~ me~ure~ o~er a 5 mot~e ~l~tance, ~elocity .. : .

'''```'1 ` .~

o~ the wat~r belng measure~ at 4.0m/s, nomlnal ~low belng ; 7.34 kg/~, Pr3~l3ure axop ~or th~ PVC plpe wa~ lOOmm Hg.
~e~ult~i ha~ be,an corracte~ to a diamet~r o~ 50.0 mm~
R~iults 6ugge~t that the ~lllcone moRl le~ polyurethane ., 5 ~o~ting wl~l al~o effect a reduction ln drag Por s~llln~
~ Ve#~9l ~ ~n~ other m~rin~ crA~, no~ ~o men~lon ~mproving the '~ o~lo~enay o~ pumpin~ ~y~t~m~, et~
lS, . W~t r re~istan~e ~ :~
~n thls te~ .he e ~ectlvene~i o~ th~ 6ilicone-modlfied i.~
, 10 polyux~thAne coa~ting of ~x~mple 2 in lmpxovlng the water ;,,!, re~ii6tallce ratlng (wi~h respect to bli6terlng) o~ ~ gel-'1 aoa~e~ l~mlnate wa~ a~certalne~. The proce~u~e di~f~red to ., AS1838 ln that a t~mperature of 65C wa~ malntained for 300 '~ hour~ Qn~ not 100C for 100 hour6. T~e gel-coat lamlna~e wa~ know~ to havl~ a degr~ ion ratlng of 5 or, afi as~e~ed ~; ~y ASl$~0-481.2, a rating of ~C. ~he slllcon~ moAi~lefl .~ polyurethane coating fiigni~lc~n~ly imp~oveA the bll~ter ~tlng of th~ ~el~eoat and ~howe~ ~n improvement with re6peot to tl~e polyur~hnne ~ys~em o tho compRratlve ~x~mple8. It ;~ 20 should be no~ hat the~ wa6 no ~lgn of bll~erlng or any o~her ~llm ~e~ect when c~ting~ were applied ~o polye~er DMC
~ough moul~e~ c~mpound) p~nel~. Ro~ults ln~icAte lmproved water xe~ ana~ of the ~ilicone modlfled coatlng and ''d ~ ~uggeBtfl that ~he applica~lon of ~uch coatinge to fib~glass ves~el3 wlll provi~e inc~eased protsc~on wlth re~pect to o~mo~
':
`: :

, .~

t~s~6 -. 31 . 16. Durabllit ~
':t ~hes~ ~3tc we~e aarrled out in an ~ro~ of h~i~vy ~oullng ac~lvity An~ where temperature of the w~ter ~emainfi temperate. Unmo~lied polyurethane an~ ~lllcone modi~led ~:~ S polyuxe~h~ne ~as~ panel~ allowe~ to ~lt ln thls envi~nment ' ox a totnl of 12 months, ~how ~ullng very mucl~ to the s~me .3 degree. The ~ oona mo~le~ u~eth~ne coating~ ars non-. .~
~oxlc a~ w~ll th~rofore foul. However, on claanlng the te~t panel~ lt 1~ observed that th~ ~ilioone modlfled "- ,1 ~ 10 polyurethane c~a~ing~ are easlly cleanea with no evl~ena~ of . ;1 :; ln~ivl~u~l ~efect~ wherea~ e unmodl~ie~ coa~lng3 are gulte : .:
dl~lcul~ ~o clean an~, where barnaoles have been pre~ent, d~m~go ~o ~ho ooa~lng occuro.
17. ~ .:
'' 'i1 15 Re~ult~ we~e obtalned a~t:er plagues were prepare~
pproxlm~'coly lmm thlak.
.:1 18. ~ ,~
Q~ults ln~iaa~o ~n inarease ln flexiblllty o~ the ~illoone ;:
'~ modl~ polyureth~ne. ~hese value~ can be compared wl~h an ;j~ 20 unpign~ented Rillcone ela~omer (110%), ~he unplg~ente~
polyurethal~e~ of Comparatlve Example~ 1 or 2 (59~) and ~he ~ unplgment~ sllioone modi~led polyure~hanes o~ Example~ 1,2,3 ;~ ~n~ 8 ~66%).

`'.
''''~,.

~7 : 2C3~ 6 19. e~r ~tren~th ~i~ RQ~ult;s lndla~te ~ !leO~eaBO ~n t~ar ~trength for the ~licon~
.; :,.;
:~....... mo~i~lo~ polyureth~ne~. ~he~e re~ults s~n be compA~ed wi~h ..;.
an unplgmente~ ~;ilioone ela~tomer (6.7), the unplgment~
., ; j, 5 polyurethAne~ of Comp~rative Examples 1 or ~ (12.~) ana the ;.;:
~., unplgme~to~ ~Lllco~ modi~le~ polyu~ethanes oP Examplee 1, 2, 3 . . .
an~ ~ (11.5 , ~ 20. ~
Tes~ aas~rle~ ou~ on coating6 s}~r~yed un~er optlmum ... . .
:, ~ 10 condit Lon~ wlth r,a~pec'c to thlnning o~ palnt system. Surface ~i.
x'cure W~!18 ~s~e3 3ed u~lng ~ T~ylor Hob~on Taly~u~ mea~urlng ~r~ ce wh~l ah d~awR ~ stylu~ needle over a maa~u~a~ l~nyth of ooatlng, 21. _urab;Llit~ =
~,~ 15 weathetr~ nq - 1, 000 hou~
~e~ul'c~ ln~llaat~ an impxovem~nt ln glo88 xe~entlon o~ ~he ~illcon~ mo~ d poly~ th~ne~.

Pnrt~ ouLArly ~d~ran~ageou~ pLopeL~tie~ o~ ~oatlng~
~, 20 prepareA ~rom the ~lllcone modlf led polyureth~ne~ of ~he `-~ '1 , examE~l~o arG ll~t~CI below:
O~
;, E?~ ~E~3~
~,;, 1 ClooA ll~ht etabilll;y; glo~ retentlon;
;~ ~ out~oor xeslstanca, ~nd chemlcal re~i~tanoe.
~-~ 25 2 Excollent ~ouling release p~cpertles w~en .~j used as a m~rlne p~lnt.
. . .~
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,.,~i ; 20~553~6 ~,3 . ~ ~
.~ 3 Sx~Llent fouling r~laa~e propert~e~, good ~ lex~ bill~-y, :~ 4 Goo~ ouling rele~e p~opertle~ an~ ~ntL-~' aorro ~ lon proper'c le ~ .
~xcellenl: ~ nduatrlalac>atlngs, he~vy duty ,.~,~ ' m~rlno 3o~tlngE
6 Good. re~i~t~nce to w~thering, wate~, , a.e1;ergen1; ~olu1;lon~ and chemioele.

. ~ R~pld ~lx Arylng flnish, goo~ wea~her ,~ . .
.i' 10 re~ anca, llght ~t~bll~ty, ~olvent ana petrol re~l~tance. :-~

A p~r1-lcular Advnntnge o the coatlng~ of the ~:
~x~m2~le~ re~ in thelr low ~ f~ae ~nergy propertleo.
A~v~nt~g~ i~ t~ken o tho~e low ~ux~Aa~
energy propartie~ in tl~e u~ of ~llf aonG modl~ied . polyure~hr~ne ~ompo~ition~ mean~ o~ octlvely and . . :~
~ely manhging the e~fec1:~ o~ m~rlne growl;h on ve~els such ;
commoxal~ .p~ plea~ure c~aft, ferrles an~ tha llk9 a 20 well ~8 ~atia marine struatur~ uch a~ oil rlg~, Je'cty .`` .:: ~':
la8, eto.

lthough these ~ilicone mo~ilfie~ polyur~thane ;;
~ompoun~ ~re lnheron~ly non toxle to marlne organl6m~ Ana .
,~ ~ol;herwi~e preser~e the lntegrlty of the m~ins ~nvironm~nt, 25 thelr low aurf lce en~rgy charaetexi~los ps:ovi~ foullng relea~3 coa1:1ng whlch inhibit~ the deg2~ee of ~ah~ion o~

i :
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'~'''~'','' 2005~4 ~~. 34 . .~ . ;
marlne organi~m~. Thi~ ln turn psrmit~ ~lmple and ~:......... inexpen~l~e un~rWA~er aleanlng ope~atlon~ to be carrlea ou~
.. ~ or othe~wlse 1~8 tims con~umin~ sllpp~n~ of vessel6 ~or removal of tn~ine growth. ~he ~ouldlng rele~ co~in~3 .: 1 i.i; S ~nable r~a~y removal o~ marlne growth by 1~ rlgorour ~:! sc~ub~in~ on hlgh pxes~ure hoslng without ~Amaglng ~he `1 aoa~ing suri~e~ Few organlo ~iubst~nce~ ~dhere wlll to tho ';.' ~ur~aae o~ ~he coating~ and thuis th~ coatlng can be u~ed a~t1-gra~ltl coEItlngei on bull~lng~, ~allway carLi~g~ o~
othsr ~ur~nce~ likely ~o be ~i~flgured by gra~itl ~r~
! j ;,~
In A~dltion ~he~ may be uK~d as anti-Pouling coatings on ~ Itlal~lne ve~selis. Dlr~ plak up 16 re~asa An~ ~here~or~
`r;f" ~ur~ace tracking i~t aleio re~ce~. When used a~ a ~ecor~tlv~
,i! and/or pro~eatlve aoa~ing on buildings, the aoatlngs h~vo ~
'`"4 15 low aoe~lcien~ o fL~lction ~nd together wlth ths roduoed ,; :; .
he~lon o~ ~irt o other p~r~lcles tha ao~tlng 1~ ~a~lly ~lo~nco~ ~y ~in.
Tho ao.~lng~ are more ~lexlblo an~ ~oPtel~ than oonventio~al ~ro~-llnka~ p~in~ coatlng~ and thus exhlblt~
~mprove~ ~oratch ren~nt~nce.
The coating~ ~hile having an anti-s~lc~ ~ur~ace c~n be r~co~t~ wlth a s~con~ coat h~ving goo~ a~e~lon propertle~ ~o ~h~ ~lr~ coat. Thus, it i~ not n~ae~nry to ... ,jj .
rlp the ~lrst co~t. ~urthe~, the coatln~ can be ~pplle~
~lr~c~ly ~o a sub~trate without requlrlng prlmer co~ts or "tl~" ooAt~.

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., In ~n endeMvour ~o ~ert~ln ~ho phy#lcal ~tru~ture o~ th~ ~lllaone ~.odl1~a ~?olyureth~ne oompo~sltlon~, a numbor ~;~ o ~ce~ we~e oar.rie~ out. l`he~a~ t~ include~:-, :, ~xE~Lx~ ~cb;~o~lato~ra~hx T~st~ aonat~c~ced on ., .
both mc~li1e~ and unmo~if 1~ polyurethano ~ya~em~
: .., uggeat that no ln~:eraction occur~ betw~n the ~ ~
.... . .
rethana an~ ~llicone componen1; . 'rhe modl~led gy~t~3m 3howsd no pse.k~ a3~0clated wtth the ~Y li~on~
componen1: and this wa8 aon~l~er~ to ba e most 10~lnu~ual re~ult. PolyurethAne ~race~ ln both c~ses rer~ l~ontl~
.,.,' :.
'rhe~mal analysis uslng al~erential Bpe~t~al calorlmeter showeCl ~cha~ the 1 ass transitlon #~ e (Tg~ of ~che ~llicons ela~tome~, the moAl~leA and the unmoAl~ied urethan~
1 .,~ ' ~
aarylla aomposltion~ were ~ub~antl~lly i~entl~
, ~ i~l Tect~ Ten~lle elong~tion ~n~ te~r 'i ~
~t~eng~h mea~u~ement~ ~ll Yhowed rodua~ luo~ or 3111cone mo~lle~ ~ys~em~
~¦ 20Whlls not wlshlng to be bo~n~ by ~pecul~lon, -~
lnve~tigatlon~ ~u~ge~t t~at the ~ con~ mod~fl~d polyu~hane~ oS the ln~enklon compri~o ~omalns o~ at loa~
,~.j paxti~lly cur~ poly~iloxanes wlthin ~ netwox~ o~
., polyuro~ane. rt 1 ~ po~ le ~h~t an amount o~ lnter-25p~netratlon ~nd/o~ ch~mlcal bonding oacur~ ~long the lnter~aao ~etween the ~lllcone aomalns ~nd the polyuret~anc.
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7 However, lt l# al~o po~lble th~t ~o~e degr~e o~ ch~ml~ifll ~i coup~ g ocaur~ b,stween the ~illaone ~nd pol~urethane to glve .,.~,. .
cro3~ nk~, andi/or ~raft polymeri or block polymor~.
It 1B ~l~o po~lble th~ he polyol may react wlth S a ~lllcone hy~ricls functlonality to ll~k at lea~it A portlon ~1 o~ the polyurath~lne re~ln to ~he poly0iiloxaine domAln~. ~he ~illcons hya~ide containlng poly3110xan~ m~y ~e~ict wl~h a , polyol to form pol~ir 3e~m~nt3 whlch may i~ig~regat~ lnto ., ml~aelle-llk~ Ela~lcles wi~h ~illaone polymer ohoiin~
exten~lng into ths ~urroun~ing polyur~thAn~ m~trlx.
It 1~ also oon~ orad ~hat the re~pectlve ~nsltle3 ,~'~.;
an~i pol~i~ltle~ o~ the pOly~ oXaneB an~ the polyol may hi~ve a pro~ouna bea~ing on the typ~ o~ pxod~ct ~ormo~i. The ~I polyslloxane~i tyE~ioally have a low solublllty in th~ polyol ~ii 15 anc~ ~olvent~ and thus tend to ~olm ~n emul~lon or aolloid~l ",~j pen~lon of ~ine droplets of the ~ on~ ln the p~lyol ,"
upon mlxin~. ~he hydroxy oont~lnlng poly~ryl~te~ (eg.
e~mophen ~365) oan ~orm an emul~lon wlth the un~tur~ted poly~iloxane ~e~. Br~mite 2018 Part A~ an~ ~lllcon~ hy~
20 aont~ining poly~loxane (eg. ~rAmi~e 2018 ~ar~ B) wh~ch 13 ~ table ~or ~ period o abou~ thrae weoks ~fter whlch time !ij ~ppreciable phas~a ~paratlon ha~ occurr~. In ~hia example ;:~
~;i it ~a~ obs3rve~ that th~ ~en~lty of the poly~iloxAne~ ~nd ,~
Bo~v~nt~ app~oxlmate~ ~he denslty of the polyol and lt 1~
~5 hell~v~ ~ha~ thl~ con~ribute~ to th~ ~t~b~ y of the ~mul~lon. A~d~tlon of a~ lves ~uch a~ plgmont~ ~ppoar ~180 .j "
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~ As the polyurethane ~y~tem compri~e3 a polyol wlth :'` a numb~r o~ hy~roxyl group~ whlah normally rea~ wlth th~

~ ocysnate group~ iB pos~lble th~t ~ome of these hydroxyl .,,.,,l~j i, 5 group~ react with hydrosil~ne functio~ roup8 to che~nlcally ,;j ~ bon~ th~ ~llicone aomaln~ wlthln the polyurethane matrlx.

.:. Alternatively, th~e could be forme~ pol~mer ohaln~i h~vlng a , . . .
`' polyureth~ne ~unction at one en~ and a elllcone fun~tio~ at ~.`,~,1 . ~, ~he o~her. ~ ~ur~her po~tulatlon 1~ that ~hrough lnhlbltlo~
~ 10 of polymerlsatlon o~ the silicone menomer~, the proportlon o~
uncro~-lln~ed ~lllcone monomer may be free to migrate th~ough the polyurethane matrix. ~hat being the case, it 13 ~i llkely through ~ur~ce ten~ion efect~, that there occur~

. ." ~
greater aonaentration o ~ilicone n~onomeri near th~ ~xpo~ed ,r,: 15 ~urface o~ the polyurethane m~trix. ~hl~ concon~rA~lon m~y ~;; ~hen allow aro~ llnklng o ~he ~llicone monomer~ in ~' lntarp~netrAt~n~ network a~ ~t~ria islh~bl~lon 18 r~duced.
Althouyh thore i6 no ~e~inite ~ nce to aup~oL^t ~ny par~iaul~r po~t~latlon of the Mo~oaul~r ~truatur~ o~ ~he : 20 ~lllaone mo~l~le~ polyurethan~ sy~tem~ aaaor~ln~ 1o ~he ~: invsntion, the I~O~t likely ~t~uatuxs i8 b~lie~e~ to comprl~e ;-` ! mlcelle-llke donlain~ of silicon~ polymer wl~h ~illcone ~.~ chaln~ ex~ending lnto the ~urrounding polyurethAne matrlx.

::' The~e ext~n~e~ slllaosle chain~ probably blnd to the ;:, 2~ polyureth~ne ml~tr~x by a comblnation of ahemlaAl bondlng ~-, be~w~en ~illaone hydride and ~he polyol hydroxy groups a~

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is~! 20~ 46 :~- 38 ''., ~,~' -` wcll a~ lnt~rp~ne~rA~ion o~ ~h~ polyu~e~han~ mol~cul~.
., ~he sili~one modi~led polyureth~sn oompo~ltlonR
caor~ln~ ~o ~he lnven~lon may have ap~lic~tio~ in a wl~e range o~ ~iela~. The 311iconQ moal~e~ polyur~han~s hav~
~ij 5pA~ic~lA~ np~llc~tlon ~ ~on t:Qxlc e~vlronmos~t~lly ~1~
`"l ouling releaBe ooa~ing~ ~or marine applica~on~ lnclud~ng ,~ ~1.1 m~nner~ ~ m~rlne ve~cels and marine s~ruc~ures BUCh as ~'1 oil rlgc ~ he llko.
~ a~y ~ut~ coating6 comprl6ing pltch or tar may be ,~, 10 ~sa~ a~ anti-corro6ion coatlng~ ln marlne and land b~sed ~tructur~ p~rticul~rly where mArlns foullng relea~e ,~' propert~ re re~ulr~d.
Other ~pplicatlons include enhanced 81ip coa~ing~
~or contalner~ of par~lcula~e ma~erla~ 8UC~ gr~ln~, 15 cement pow~er8, e.n~ stiaky subst~noes suàh as 6ugar an~
molA~es and where non-toxic low friatlon co~tlng~ are r~uired. ~uch non-toxia low frictlon coatln~ are al~o ~ult~ le ~or the lnte~ior o~ plpe~ and o1;her oon~ult:~. The~e non-~oxla aoA~;in~s aould be u~a ~or example ln the pumplng 20 o~ ~own wat:er or ln l:he ~oo~ inO.u~l:xy suoh a# in oonvey~noing o~ bevor~ges. l~n o~her ~ppll¢ation~ ~u¢h a~ the pumping of '=~ cooliny w~ter ln condenser~ oP power 8ta~clon8, 1~ub~ can1:1al ;~3, lmprovemant in pump eflclancy by re~uction of llea~ lo~e~
~;~ o~n ~e axpeo~
Appl ica ~lon of the ~ cone mod.l~ polyurethane :~ oo~ting~ a~oordlng l:o t:he inven~:lon ln aerol~au~:lo , ., ,~ .
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,:,.i 2(~SS~LÇi : - 39 :, 1l appllcatlon~ i~ expeated to l~afl to lncxease~ ~uel ~avlnys ,-, ~ . ,, ~ue to reduced i~ir ~xi~ig o~ aeroplan~ and the llk~, :
,~ A p~rtlcul~rly i~vantageou~ AppliCRtion of ~he o. ~111oono modi~la~ polyurethane aompo8itiong 1B ln the :;
~;, 5 m~nu~actur~ o ~:Lbreglati6 (FRP) producl~ uch a~ boat8. As ,;.~
n AlternDi~lv~ to aonventional polye~ter gel co~ts, .,,~
;~ cori~po~ltlons ~ccoLaing to t~e lnv~ntion provide a means o~
.' ov~r~omln~, mainy ~ ~he t.ri~i.t.lo-~iq~ gel ~ prohlQm~ ~u~h ~8 `;~
: crAcklng, bli~tering, o~mo~ An~ water absorptlon. The :
.~ 10 great~r flexlbillty a~ lmproved resiEitance to mol~ture : . ,.~ , ;,j ab~orpt~on inpart; lmprovea imp~ t resi6tance, re~l~tance ~o E~br~6iion whlch ot:her~l~a ln more brittle polye~ter gel ^oat~
;~i le~ to ~'~t~r~ cr~ickin0 whleh ln turn flllow~ w~ter to penetrate the gal coat/ibreglass ~t:ruct ure, oft~n with `~15 ~lsa~trou6 e~fect~. At ~hs sams tims~ the low 6urface energy . o~ ~h~ ~ompo~ltlon~ provld4~ ~n envlxomontally ~ouna, non-, tVx~c o~1ing r~3lea3~ ~u~Ace o~ above and below wat~r u~a~
, 1 :j ~n yet ~rth~r mo~l~laatlons o~ the invention ~here ~.~ 20 ar~ provided mould~ble or aastable ~illcone modl~led :.
.' polyurethAno aomposltion~ a~plicable in ~he ~lel~ of !''j`'~ me~lol~e, c~eh ~6 6urglc~1 prosthese~, or in other ~leld6 ~uch ~ ~utomoti~e components, cast ~llm~, poly~erlc ~amln~tee ~OL^ automotive And domes~ic upholstery an~ the ~,' 2~ like. -:
ould be ~ppreciated that ~ar~ou~ othar change~

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Claims (27)

1. A curable liquid silicone modified polyurethane composition comprising (a) a polyol, (b) a polyisocyanate or polyisothiocyanate (c) a polysiloxane comprising silicone hydride groups, and (d) an unsaturated polysiloxane, wherein the amount of (c) and (d) is between 1-30% by weight of the polyurethane.

2. The composition as claimed in claim 1, wherein the amount of (c) and (d) is between 5-15%.

3. The composition as claimed in claim 2, wherein the amount of (c) and (d) is about 10%.

4. The composition as claimed in claim 1, wherein the amount of said polyol is between 10-60%.

5. The composition as claimed in claim 1, wherein the amount of said polyisocyanate or polyisothiocyanate is between 10-20%.

6. The composition as claimed in claim 1, wherein the ratio of (c) to (d) is between 6:1 to 12:1.

7. The composition as claimed in claim 6, wherein the ratio of (c) to (d) is about 10:1.

8. The composition as claimed in claim 1, wherein said polyol is selected from hydroxy containing polyesters, hydroxy containing polyacrylates and hydroxy containing polyethers.

9. The composition as claimed in claim 1, wherein said polysiloxane comprising silicone hydride groups comprises one or more of said silicone hydride groups.

10. The composition as claimed in claim 1, wherein said unsaturated polysiloxane comprises one or more vinyl groups.

11. The composition as claimed in claim 1, wherein said polyisocyanate of polyisothiocyante is selected from aliphatic or aromatic polyisocyanates or polyisothiocyanates.

12. A method of forming a curable liquid silicone modified polyurethane composition as claimed in claim 1, comprising the steps of mixing said polysiloxane comprising silicone hydride groups, and unsaturated polysiloxane and said polyol as a first component and adding said polyisocyanate or polyisothiocyanate as a second component to said first component.

13. A method of forming a curable liquid silicone modified polyurethane composition as claimed in claim 1, comprising the steps of mixing said polysiloxane comprising silicone hydride groups, said unsaturated polysiloxane and said polyisocyanate or polyisothiocyanate as a first component and adding said polyol as a second component to said first component.

14. A method of forming a curable liquid silicone modified polyurethane composition as claimed in claim 1, comprising the steps of mixing said polyol, said polyisocyanate or polyisothiocyanate, said polysiloxane comprising silicone hydride groups and said unsaturated polysiloxane as separate components.

15. A method of forming a curable liquid silicone modified polyurethane composition as claimed in claim 1, comprising the steps of mixing said polyol and said polyisocyanate or polyisothiocyanate as a first component, mixing said polysiloxane comprising silicone hydride groups and said unsaturated polysiloxane as a second component and admixing said components.

16. A method of forming a curable liquid silicone modified polyurethane composition as claimed in claim 1, comprising the steps of mixing said polyol, said polyisocyanate or polyisothiocyanate and said polysiloxane comprising silicone hydride groups as a first component and adding said unsaturated polysiloxane as a second component to said first component.

17. A method of forming a curable liquid silicone modified polyurethane composition as claimed in claim 1, comprising the steps of mixing said polyol, said polyisocyanate or polyisothiocyanate and said unsaturated polysiloxane as a first component and adding said polysiloxane comprising silicone hydride groups as a second component to said first component.

18. A method of forming a curable liquid silicone modified polyurethane composition as claimed in claim 1, comprising the steps of mixing said polyol and said polysiloxane comprising silicone hydride groups as a first component, mixing said polyisocyanate or polyisothiocyanate as a second component and admixing said components.

19. A method of forming a curable liquid silicone modified polyurethane composition as claimed in claim 1, comprising the steps of mixing said polyol and said unsaturated polysiloxane as a first component, mixing said polyisocyanate or polyisothiocyanate as a second component and admixing said components.

20. The composition as claimed in claim 1, comprising 1-25% of a reinforcing agent.

21. The composition as claimed in claim 20, wherein said reinforcing agent is selected from particulate fillers, fibrous fillers and cross-linkable polymeric materials.

22. A coating composition comprising the composition as claimed in claim 1.

23. A non-toxic anti-fouling composition for coating surfaces exposed to a marine environment comprising the composition as claimed in claim 1.

24. An anti-slip coating comprising the composition as claimed in claim 1.

25. An anti-graffiti coating comprising the composition as claimed in claim 1.

26. A moulded article comprising the composition as claimed in claim 1.

27. A cast sheet-like material or laminate comprising the composition as claimed in claim 1.