Note: Descriptions are shown in the official language in which they were submitted.
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
- 1 0
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~
12
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.
EXAMPLE 1
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.
EXAMPLE 3
_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~
16
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
17
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
18
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~
:.: . . - . . .. - . , . : ...
S546
~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
21
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~
`' '~ ` ~'
' ~.' ',
:: :
-:
... . . ..
.:
':.'... '
.. .
' '
' - ' ',
.,
" ' '
~ ...... . , . ..... , ,.. .. .. ., ~ ,, ~ . :
ZO~
23
r~
~ ~ ~ v ", " ~ ~ " R
~ ~A~ O~
4 ' ~
~ O ~
~ , ' '`
n
1 ~ N ~1 ~ N
. N ~ N ~ ~ ~ ~ ~ ~r O
~ . ~
lu
Z~15~46 ;~
2~ .
,, ~
. -
' :.
~ o
f~ N
~ O ~ _I O ~ --I N
r o ~ ~ ~ ~ ~
~ ~ ~ o '~
r~ O ~
N ~ _ ~ ~ ~ N N . ~
a ~ ~ ~ ~ ~ ~ N r~
~3 ,~ 0 0
5~! i3 i~ ~ ~ ~ ~
Ç
~ ,, ~ X ~
,E 80 ~ o `~
. . . -
O ~ N p
2~o~
~ ~ OD
~ ~ ~ o
~ o a~ ,
~ ` : :
a r~ r
..
., ,'
I 1
.. . ...
~ ~ ' ~ ~ ;
m
a a ~ ~ ~ a
e~ U~ ~
~ ~;
I ~ ~ ~
8 ~
~ L~ R O ~ 1 ~ C ,~ ,G ~
X~55'~
~1 26
....
~, '
.
;./ (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.
. . .~
'~'jl .
,~ .
~....
:;
. ., ~
,.,~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 :
!,`
'~'''~'',''
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~.
~';
:` 5
~.~
' .
~ !
~:;
55~
i`~ 35 ::
., 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.
,~ '
,i; :-.
::
-; :
." ' .
~ 36
;,i.l. : :
.. ; .
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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,;~
~, .
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~ ~
~ . `!
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"` `I .
., .
5~1~
j`". 37
` !
to inhlbit p~3~ 3e~ra~1~n.
~ 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~
. Z :
` ;`.,! . `.:
' ~; . : . :
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
,
., ,~ .
: ^;
, ~
~ /i
: .
- .:.. i ~ ., , . ~ .
.. ".. : - .. ,- . . :: . . -, . . . :
..... ~ .,. ~ , . . . . . . . . . ..
,:,.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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Z~)~)S5~16
-: 40
v~ n~ moD.1 ~lc~tion,3 mAy b~ ma~o ~o th~ e,xan~ple~ wl'~hout
; ~
d~r~lng ~om ~h~ ~p~ rlt ~nd ~oope ~f the i~v~3ntlon a8
lef lnaa. ln t~ ap~?en~e~l elain~ .
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