CA2087914A1 - Non-aqueous coating compositions from polyethylene terephthalate - Google Patents
Non-aqueous coating compositions from polyethylene terephthalateInfo
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- CA2087914A1 CA2087914A1 CA 2087914 CA2087914A CA2087914A1 CA 2087914 A1 CA2087914 A1 CA 2087914A1 CA 2087914 CA2087914 CA 2087914 CA 2087914 A CA2087914 A CA 2087914A CA 2087914 A1 CA2087914 A1 CA 2087914A1
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- anhydride
- glycol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Life Sciences & Earth Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Sustainable Development (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
ABSTRACT
Coating compositions derived from the alcoholycic of polyothylene terephthalate.
Coating compositions derived from the alcoholycic of polyothylene terephthalate.
Description
93 WED 12:3.~ ID:CO~I-EXE~_UTI~ rEL 1`~ 6-'l6b-zl43 pQ22 pi~3 2 ~ ~ 7 9 :3 ~
NON-AQUE:Qu~ COATIN~ cOM~ITION~ FRO~ P0I.YETHYLE ME~` ~13R~PHT~LATE
R. Tomko D. S~yr~
W. Lesney M. Rao .A~.:~U~KVUNl~ U~ rnEi lS~
Thi~ ~nvention rel~t~s to n~vel coatinc~ composition3 which uti~ize polyethylene terephth~late (P~'r) aæ ~ ~aw m~terial for pxoducing the ~ilm-for~ning resin for su~h coatinys. Most lo p~o~ ly, tho I'E~ ~c rooyalod or :~ccl~3imcd rET f~om pl~ tio tlr~ o~ su~h ~ two-litcr hovc:ragc bottloc.
Pl~ ~.h ~5 p~:rr ;~ nl~n~ fnr ;lhnl~t 7-R w~;~l~t r~rrL~n1, ~n~l about ~0 volum~ p~ent, of th~ wo~ld's solld waste. As a result, muc:h legiSl~tibn h~s been propv~d and~or adoPted re~uirin~3 ~he reayczling OL' plastlc:s.
PET iB the prim~xy ingredient i~l ~lastic el:r tic~ u~ a~i tw(~
liter be~rera~e b~t~;le:~ Rnd the lik~. In the u.~ E~ ; the pla~:tic most often ~ecycled. The l~iggest uses for recycled PET are ~æ flber~; in c~rpeting and insulation. ~ecycled PET i6 also used in hatllroom equipmen~ and blow-molded b~ttles.
~xooe~ea ~or re~ycling P~T beverage bottles into u3able ~aw )p~44;o~ o~ 7r~n~ r~g ~ o~ yoa t~ oc~ a ~l'C ~I~W~ .
~or ex~mple, ~a3tman Chemicals Pu~ atio~ No. N-~62A ~ntitled Un aturated Pol.~e6ter Resin~ ~ased 011 Reclaimed Polyethylene T~r~p~ha~e ~ L_~Qy~q~ Bottles, ~alendine et al. ~19~4), te~ohe~ a prooe~ ~o~ converting PET b~v~rc~ge bo~tle~ into use~ul int~mad1ate~ ~or the ~ynt:lle~i~ oE un~aturate~ pol~e~ters. ~he un~ar,ur~lt~ p~ly6~6~c~ 3 ar~ ~ur~n~L- Cau~llC ~3 ~13~;tUl e~s L-~W
, , .r~"~ ' 9~3 lJ~ 2 ~ ~3 I L) COI I--F`~ ~:CIJT I I.IE I EL ~IO C~ 5~ 3 ~ F~
f~ '~1 4 7~
m~terialB for produclng unreinor~ed cle~r Cc~tings ~nd ~iber~
gla~ r~inforcsd laminates.
A ~econd Ea~:tman ChemiOal~ Publi~ation, No. ~1-2923, e~ti.tled ~ m Re~lalmed YolYP~ h~nQ~ halate, (1~87) teache~ the re~lam~tion o~ PET for produc~ion of Aromatic polyes~er polyol-~ which are useful in rna~ing ricJid p~lyur~than~
polyi.30cyanurate ~oams U.5. Patent ~,223,0~ (C~rlstro~ et al.) teaches the use o~
t~e di~sti~n product o~ p~ly~l~c~lc-,O tcrop~h~l~tO ~crap~ wlth organic polyol ~or the produotion o~ ri~id polyure~h~ne foam~.
~ .~. P~ten~ 4,417,001 ~Sv~ 1,) t~ L~ Li~l o~ low smok~ isocyanur~te modified polyure~hane f~ams w~lch ~e prep~red fro~ p~lyol~ which ~re th~ dige~tion product o~ ~ige~tin~
polyal~ylene ~erephthalate s~raps and or~anic pol~ol~.
U.5. Patent 4,048,104 (Svoboda et al.~ teache~ the prep~ra~i~n o~ polyi~o~yanate prepolymers an~ polyurethane adhe3ive~ and Eoams wherain the prepolymers ~:re prEJparE3d by re~titlg ~rgania polyl60~yan~te wi~h polyol~ which ~re the ~ige~tio~ product of polyalkylen~ ~erephthalate ~craps ~nd org~nic polyols.
~U~A~ 0~ TH~ INVENTI~N
~ his inven~ion relates to novel coa~ing composi-tion~ which u~ilize PET a~ a X`aw materia~ fo.r produclng the ~ilm-~ormillg re~in ~r ~UCh ~oating~. Prerer~bly, ~h~ pr~n~ inv~ntion ~ t~s to lo~ ~i.d vHlue~ non~a~u~oUs~ ~lir or bake dr~y ~oa~ing~ deriv~d from rQalaimed PET and to a prO~eF.~ ~or p~oducing ~uoh coa~irl~. uslng . , '' Sf~ 2~ 3 I~JED 12~ co~ E~;EcllT iSE TEL 1~ :21~ f_.f,-21~ Z? P05 ~
~ 2~
reclaimed PET b~ne~it~i the ~nvironn,~r)t by ~educitlg t1l~ am~unt of ~;olid waste dump~d at land~llls. U~;in~ reclaimec~ PE~ benefit~ this p~oce~s in that it i~ a relatively in~xpensive raw material wh;ch, as i~ ~hown herein, produces an excellen~ col~ti1lg Gomposition.
~n ~ocordance wit:~1 -the present itlV~n~iOn, PET resln (o~ an equ1valent polyalXylene terephtha1ate re~in3, typieally having a structure a~3 ~nown ln FlgUre l:
O o 10 ~i~ure I OH~CH2C~2-o-C~ C-03CH2C}12011 n~100 i~ fir~t dlgested into lower molecul~r weight polymeric units throu~7h an alcoholy~;is re~ction. ThP. rlig~ nn l~rnAIIr~t nf ~h~
15 ;al~h~lyo ~ 7 ~c~ ~ion i~3 then f~r-th~3r ~eact;e~l wlt~ nn n~ S d-~unctional r~3ac~ant, an anhydride or an isocyanat~ to yleld a resin cotnpositio~ suitable ~or use in coating composl'cions~ By varying the a~un~3 and type~ o~ aciA~, isocyanate or hydroxy-~urlctional reactantE: according ~o the te~chlngs herein, one can formulate. a 20 variet~ of c:oatings sy~tems i ncludin~ polyure-th~r1es, high acid value, water-reducible cc>ating~ and low acid value, solvent-based coatin~s. Additionally, fu~ther chemical modi~ications are appllo~ble And ~re further exe~npli~ied h¢rein.
Aocordingly, it i8 ~n obj~ct of t:hi~ invention to teach the 25 u:s~ o~ polye'chyl~ne ~rephthalate a~i a ~aw mate~ial fo~ the production o~ coating compo~itic:n~.
' L~ 3a l L,t'pt . r~ 5~ 70~ ~lall ~(J,~13 ~:34 ~lo .()~ P.~3 1~ is a ~rth~ o~l~ct of this in~ention t:a t~ach no~
air nnri ba~e dry coatir1~J colnpositlons whic~ utiliZ~ reclaimed ~E~r a~ a r~w material.
l`hese and other o~ject~ will hecom~ mor~ r~adily ~ppar~nt ~r~m the det~iled descripti~n, ~xa~pl~ and clai1n~ whlch eollow below.
DeTAI~EG DESCRIP~ION OF TIIE IN~tE2~TION
As statcd ~bov~, the prcsen~ ln~en~.lon rcl~tes to novel r~on-aqueous. coating composition~ compri~ing rET as t11e starting ~ateri~ll eOr the proc1u~tion b~ a fil~-for~ing resin.
l. PE~ ~OURC2 The ~tual so~1rce of PET us~le her~in is not o~ critical ~mport~nce to this invention. "Virgin" P~T, ~hat is P~T whic~h is a~lmercially produced specificall~ as a raw n~aterial, is a~cept~ble Prom a c:hcmic~l standpo~.nt for USQ herein I.ikew;.se, r~cycl~d or r~ol~im~ PE~r tF. a~ceptable ~rom a chemic~al stan~oil1t. At th~J
tlme ot thls ap~l:icatior., there a~ advant~ges to t}l~ ~n~ironmcnt ~r~dl~ction o~ solid waste) ~n~ to the eCO~01~icS o~ this proces~
. (recy~oled PE'r ls much l~ss expensive than virgin ~q') by us.ln~3 ; ro~ led or rcclai~ed PE~i and, there are no perf~rmarlce di~adva~ta~es~to usiny recycled PEI' ver~Us vir~in PET. As ~
~onsequence, recy~led or rec.Laimed PET i8 a preEerr~d ~t~rting mat~ri~l though l~ ~hould be appreclat~d that any s~urce oE
~el~tlvely pur~ PET i9 acc~t~ble.
Typi~lly, ~h~ ~ourc~s foL PET are n~any and varLed. one ~o~Jrc~ ~f olther ~lr~in vr ~bcycled P~l' is mat~lrial ~ro~
R4 -~ R4 ''; ' ., :
'' ' ' ~
' '' ', ' "' '', ~) l P ~ J P ~j r r -:1 . .? I t~ f) - I ~ ~ h ~ O . ~ ;~ 1 8 ~ i l! . O ;~ ~ F . O ~
f~ 8r~
~olym~ ma~ acturels. A ~ec~n~ ~ource c~f P~,~J 1s ex~:e~;s E~l r ~r~Jn~
th~ op~ri~tion~ of th~ bcv¢ra~e bottL~3 man~lf~lct~2rers. i~ t~lird ~ou~c~, ls privatc ¢n~ pr~neur~; deal lng ln recl;~llmecl PE'r. A f~lurth ~oll~.ce ls ~om~ nity recla~natlLon ancl recyclin~ cent~r:s. t~ pref~-r~d 5 ~;~urce Or PET l.q r~yc:led PET be~ert~go bottles.
~ or purposes of this invention, the PET ~ ould be provi~ecl in ~ con~minut~d form. It can be fl~keci, graJ~ul~t~ t o~r.d to ~3 powdel~ or pellQti~ed. Praferred i~ fl~ cl PE'r. T]-e only corl~;traint placl3d on the PET at t~lis po1nt is that lt is rel~t.i~ely 10 pure; th~t i6, th~re ~hc>uld not be ~ lQvel of impurities above a}~out: vn~ ~1) w~l~ht p~rC~11t nor should ther~ bc a~ y appreciAhl~3 lcve. of impl~ritic~s whi~h ~re ch~mlcally re~:tive wit~in this pJ~oC~e~;s. F~ET whlch i.s acceptable tor tlse herei~1 ~3ho~Jld hav~3 the t'~ owing ah~lracterl stic.s:
Intrlnslc vlf~cosity 0. ~5-0. 75 - M~is~.~rf~ ~cl . 09~
~ Lo?: ed PE:I' conterlt <~ OOpprn High ~0n6i.ty Poly-et~ylQnQ ~13L)PE) clOOppm Adhe~ive~ c50O~ m Alumi num ClOp~m 2~ C!}l~I8TRY OF PET
PET 1~ npril3ed of rep~atln-J units of ethy1eoe qlycol an;i tere~)htha~ic acid connecte~l by cster 1in,ca~s~ Fiyu~e I, above, ~5 shows a typical P~T mo1ecu1e. E~ch rep~c-t:Ln~ unit of PET has a weignt ~v-ara~e mol~culAr wo1clht of 1~ with one equiv~1ent ~f et:hy1~ne g1yco1 and on~3 equiva1etlt of terephthAl.tc acld. By raa~l:ir\~J P~T with ~ith~ ~n alcohol or wlth an ~ICi~l, it il!; po~i~lb1 t;c re~ c~ thcl av~r~ga ch~ln l~ng~.h Oe t:he ~F,'r nlc~1ecu10~.
> ~ 4 , . ,., .:, , ", : .
: ;, . . :
J~ 2~)-'9~ ED 1, :~13 ID:COII-EXFCUTIUE rEL i`lO:ZI~ 2kl~ t~
( , .
. Alooholy~ls of P~T
~n~ cheml~l.ry o:t P~l' 15 ~uch the~t e~n e~qullibrium exlss;~3 b~twee~ PE~, water, ~th~len~ ~lycol (E~) an~ ~es~sphthalic ~oid ~TPA) . ~hls aquilibrium ~akes it possible t~ ~b~antially revers~
the polym~rizatlon pro~e~s and depolymers ze PET inSto its star~ing m~erial~. The E~t~sars Chemiaal publications ~ite~ ~bove refer to the procs3ss of depolymseri~ing PET as ~lycolysiS~. That prooe5s .oom~rise~ the catalytic re~ction o~ PET with a polyol. As ~urther de~inad and exemplified below, it should be apprs~ciated that o hydroxy-funotional ~naterial~ ha~i~g OH f~nct~ion~lity ~rea~er or le~s than two can be eEfec-tivPly utili~ed in the pr~.s~n1; p~ocess;
thu6, the prese~t pro~e~ is h¢rein referred to a~s "alcoholy~i~5'.
Ih th~ ~ontext of ~he present inven~ion, refere~ce to "~ ohol"
~hould be under6tood to refer to ~oth mono- and poly-funotional 15 alcohols unloss speciflc~ t~ught otherwis~.
~h~ numbe~ o~ O~ e~uival~n~ Ero~ the alcohol should be equ~l to, or ln excess o~, the numbe~ of equivalen-ts of ethylene gly~ol from the PET. Pre~eral~ly, ~he ra~io oi~ equivalent~ 6hould be betwe~ out 1:1 t.o ~h~l.lt ~1, more. ~refe.r~ly ~hnllt. I~ h~llt.
Zo 1. 5 :1 mc les ~f OH equivalent~ per mole of PET ~
8uitabl~ catalys~s ~or al~oholysis of PET inclucle the traclitional ~r~nses~e~ ation catalys~: inc~udiny ~tannous octoate, c::alcium hydroxld~, c~ m ~onna~e, lithium hy~roxide., bA~iU~l hy~roxi~ dlum hyd:rox.ide, ~odiulll m~thoxide, mangane~
25 ~ ,t~3 tetrahydrn~ nd polymeria di.oryanotin Cat~:,1Y6,t6~L 5Ue'tl as d~b~.yl tln ~id~ ~r~d~mo ~ t, Qv~ilabl~ from M~ Ch~mi~al~).
, ~
:', ~ . .' ':
S~ ` . . . ?~ Er~ ~I~!--E~ T 1"~ ~
~ ~ U ~ 3 ~
Most pre~erred i~ dlbutyl tin oxide. IP used, the catalys~ should bç~ pr~3s~nt in an ~mo~lnt of from a~out 0. 2 weight % to ~out 1. 5 weight % based upon th~ total w~ig~t o~ the ~ET and al~ohol.
When PET and a alcohol are react~d togeth~r in the pr~s~nc~
of ~he above cataly6t ~nd heat, tha high molecular weight PET
m~l~ d~r~ ;o o~ r t~ ir~ W 5'~
aocompliehed ~hrough chaln attack and excll~nge `oy thc al~ohol with the ethylene glycol units of -~h~ PET mole~ule. This ~ttack ~d exchan~e con~inUe~ ~o occur ~ntil a new equili~rium is established b~tween the PET, the ~horter ~hain leng~h PET, the ~horter chain len~h PET sub~tltuted wit~ the alcohol, the alcohol and ethylene glycol. Fi~ure II shows the typical produc-ts of alcoholysis of PET W~th a repre~entative polyol:
Figure I~
~ o HO-R-C O-R'--OH ~ Ho-R"-OH ~ Ho-R-C-o-R"-oli ~ ~lo~R'-OH
A8 ~an be ~een from Figure II, subsequent ~o alcohvlysis all ~lnQ~ning PET x~agm~nt~ nl~d prod~lct~l in ~lLlibri~lm th~wi~h ~r~
hydroxyl ter~inated As described ~urthe~ bQlow, they can be reaatod with aold~, anhydrlde~, fatty acids, isocyanate6 cand the like to ~o~m excellent coating compositions.
Alcoh~l~ ror u~e ln Al~oholy~is o~ PET
ry~lc.~ly~ ~hO ~lo~l-ola wlll h~v IIU~J~- ~v~y~ mol~
2~ w~igh~ o~ b~low about ~000 and typiaal numbQr av~raga molecular w~lgh~ will ran~e ~rum ~ tt 30 ~.~ a~u~. ~o~o, an~ ecl~.ly 100 . , .
~ N- c'O-- ~ Wt L~ l c ~ l I U ~ t.X.tl~.U ! I ~Jt I tL !~(U c~ l b--~bt.~ lc~' ~
to 7~bout 400. Mothod6 of pr~paring al~hole ar~ w~11 kn~wn ih -the :~Y~ d ~7. O~ m~ hc~ r~~ r~ ~h~ G~1 ~h~ a ~ a ~rlt r~~
to the pr~ctic:e of this invel tion.
5uitable al~ohols lnalud~ the Cl-C22 linear and br~nched ~atura~ed and unsaturated alcohol~ includin~, ~or exampl~, me~hanol, sthanol, propanol, 'outanol, hexa~ol, linoleyl ~lcohol, tr1methylolpropane diallyl ether, allyl alco~ol, 2-mercapto ethanol and ~-he like. Additionally, usei~ul alcohols ln~lude the IIY~L~XY--r~ ctiol~al Foly~-t~rs;, poly~t~3-s, p~lyu~-eth~nes, polyaaprolacton~;, otO. a~ gQnor~lly discu~:.ad in S:~tic~n~
th~ough a.l.e. below.
a.1.a. saturated ~nd ~nsat~r~ted p~lyol~ lude gly~erol, castor oil, ethylene glycol, dipropylene glycol, 2,2,4~trimethyl 1,3-pentanediol, n~opentyl glycol, l,~-ptvpanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, ~,3-butanediol, 1,5-pontanediol, l,~-h~xan~diol 7 2, 2-dim~thyl-~, 3 -propanediol, Bisphenol A tetraethoxylate, dodecahydro Bisphenol A, 2,2~-thio ~i~th~nol, di~ethylol propionic acid, acetyl~nic diol~, hydroxy-terminat~d polybutadiene, 1,4 cyclohexanedi~ethanol, 20 1,2-cyclohexanedimethanol, 1,3-cyclohexanedi~eth~hol, if3(2-hyd~oxy~thoxy)cyalohexane, trimethylene glycol, -tetra ~thylQno ~l~ool, ~ontnmothyl~no ~ly~ol, hox~m~thylon~ ~31y~
doa~mo~hylono glyool, ~iothylone glyuol, triothylana c,llyvol~
t~tr~ yl~n~ ~ly~ vL~u~l~yl~ ly~vl, l,~ c~
25 1,~-benzeno~lethanol, ~ nethyl 2-et~lyleneh~xAn~-1,3-diol, 3-~ut~n~ diol, and pol~ol~ eu~h a~ trim~hylol~than~, ~"' ' ' .
trimethy101~opane trim~thylo1prop~n~ mono~llyl ~3~ `e7?
tri~othylolh~-7X.3ne, trir~thy101propan~, 1,2,~.-b~tanctr1~ YC~LO1, p,~ntaery~llrlto1, dipent~erythritol, e~o~, ~ b. Po1yether polyol~ c~rc~ w~11 known in thc clrt .~nd dr~ cor,ve~)ient1y p~ep~red by the re~ctiorl J~ a diol or pc~lyol witl;
thc corre3pond1ng ~lky:Lene oxide~ Tllr~se mclteria1s ,-~r~o~merc~ 11y availab]e ancl mny be prepa~cl ~y ~ ~nown ptocess ~uch as, for n:~n~ple, t:hc~ proce~s~. dcsoribed in F,ncYc~o~erii~ c~ h~mic~1 ~o~ c~ly~ Volume 7, p~ye6 257-262, publlshed L~y ~htt~sci.?nc-e Pub1i~;hers, Inc., 19~ cn.~re~en~a~ive ~am~ s incllldc t~l~
po~propy]ene eth-~r c~1ycols and pc)ly~thylene ethe~ g1ye~ such ae.
tllos~. ~,3-~et~ as N:rAX Po1yols from Union Ca~bi~e ~or~oratio ~ .l.o. Another u~eru1 c~ s of hydlox~ cc.io,~
pc.1~nrs are t.~l~ose pr~p~r~d by co1ld~ c~tion po1ym~ c~tion r~.~c:t:inr t~chniqlles as ar~ we31 known in tl~Q ar~. ~np.r~2selltclt1v~
c<-ndenq3~ion po~ym~riz~tion 1~a~t.i.ons incluc1e po1y~ter~ rc~p~1ec ~y th~ condenf;~tion o~ polyhyd~ic alc~ohols an-l po;,yc.~rhoxy!.lc a~idr or anhyd~ides, with o~ wltho~t the inclus10rl o~ drying oll~
sem:L-~1rying oi~, or nc~n-~ry1~g oil ~Atty ~cids. 8y adjuc.ting t.he 2~ st4~c~l10metry o~ the a1cohols ~nd th~ aaitls Whil~ maint~linin-J ~n ~Xc~..5 of hydroxyl grouE~, hydroxy-functlon~l pc)1yest,ers Can ~e readily produced to provid~ a wide rang~ o~ de~irecl mol~?cul~1r weight6 ~n~ ~erfbrm~nce characte~istics.
Tlle polycsL~r E)olyoLs are d~rlv~d l-rorn one c~r mar~ Elro~lat.i~
25 an~lJvr aliE)~I~tio pol~cal.boxy.l..ic ~a:Lcl.~, th~ an~ d~?~ t:h~?r~of, ar,c~
~ne or Dlore a.ll~ atl.cJ and/c~r ~rom~:ic p~ly~ c,~arl~c)xy~
.;
,''' ',' ' :'' ' ~.
J6~1-al3~ l/FD IZ:.la ID ~n~l E~ECUrl~)E rEL ~o:al6 566-21~13 I~O.. Fl. ~--aaid~ includ~ the satur~ ar~d uns ?.turated polycarboxylic acids and the d~rivativefi thereof, ~uch as malei c acid, fu~ ic acid, ~:ucc: .~ n lc. ~ ç .~ ci lp .~ icl, n ~ n~ ~r)t~ n f!
dic:!arboxylia a/:~id. 'L'h6~ carboxyl iQ aalds al~:o inalude the aromatlc 5 polycarbox~lic acid~, ~uch as pl~th~lic acid, isophkhalic ac:id, tt.~rF2E~hth;~l 1a ;~ci.d, etc. Anhy~r~r~eF~ e~ m~le~n ;Inhyr3rl~
p~thal~c anhydride, trimellitic anhydride, or Nadic ~Sethyl Anhydrid~ (brand nam~ rOr methyl bicyclo t 2 . 2 . l ]
h~pt;c~--2, ~)--d~ cAa-l~oxyli~: n~hy~ lc i~~ lbL~ 11 al~ 4e~ u~
Reprç~sontativ~3 saturated and unsaturated polyol~ which can be reacted in stoic::hiometric ex~ess with th~ carboxylic acids to produce hydxoxy-~ullctional polyesters include the diols taught in a . l. a . and a . l . b ., above .
Typica~ly, the reaction bet~een the polyols and the polycarboxylic a~ids i5 conducted ~t about 120-C to ~bou-t ~Q0C in the pre~ence of an e3teri~ication ~at~ly~it such as dibu~yl tin oxide .
a.l~d. Ac~di~lonally, hyciroxy-funotional polyllle~ can ~e pr~pared by the ~ih~ op~nin~ rQao~ioh c)f ~poXid~E; and/or 20 polyepoxide~i; with primary or, pr~3ferably, seoondary amines or ~olyamine~ to Produce hydroxY-fUnC~ional polyrner~ Repre:en~.~tive aTnine~ an~ p~lyamines include ethanol amine, N-methyle~hah~l amln~, dl~n~thyl am~n~ ~ Q~hylene diam:ine, i~ophor~ne di~mine, ~to .
Rspre~enta~lv~: polyspoxides lnclude tho~e pxeparF3ù by c:onden61rlg 25 n p~lyhyclrlo alc~hol or polyhydric ph~nol with ~n epihalohydrin, ~uc~h ~e ~pl~hl~rohydrin, u~ua:lly uncle~ alk~line c~ondition~. Some , ~ ? 4 r~ ? 1~ T 1 E I ; ~ f,h - I, ~ 3 l, ,~J ~3 ~ 3 of th~;c~ corl~ler~satlr n product:~: ar~ avAllahlra collltr131c i;~11y n~d~r.~ 3 1 f~
dcsLr~natlo~ t EPo~l ~`ron~ Shr~ll Chomlo~l ~'vmE)~ny, ~nd mr~thods ~f pr~p~r~t.ion ~re rQprl3sentc~ti~"aly taur3ht in U.S. ~,~tel-ts ~,592,5Go;
2, 5~, 9F~5 ~ 2, 6~4, 694 .
S a.1.~. ~ther u~Cul hydroxy~furlctior,z~l pol~me~-~; c~r~ be pLepa~ed by tho reactic~n o~ an r~lxc:es of at l~ast ~rne al~ o~lol, X~
aa t:hose ~epre~ent~ltively r~e~c~lblod ~bove, ~ h .isocya~ .e. to prc,duce ~ydroxy-runction~l urethAncs. Rr.~;r~sent~ttive ~not;o-~uncl:ion~l i.s~Jcy~ndte~ clu~lr~ ~llyl isor. yanatr~ ~nrl tolulyl 10 i~ocyan.~te. ~?c:prr sent~tive polyisocy.snates i~c~ r.ie th~ ali~h~tic c~ pr~ullr~; S~IC~I a9 ethylene, trimethylenc, tet~-.tmetllyl~ne, pe,ttantethylene, hexamethyle~lra, 1,2-propyl~lie, 1~2-butylene~
2,3~butylene, 1,3-butyleno, ethylidene Rnd but.ylld~ne ~.iisocyanatr~s, th~ cyclo~lkylene COl:lpOUh~3s s~loh as 3~ cy3n~to methyl-3,5,5-tL-lmet~ .yclohexyli60cyan.~tr, ~ntl tne cyclopentalte, 1~3-cyc~ohexflne~ Al'id ~ ~CyGlOheXrll~e dii.~oc~ na~.~as; the flrom ltic ~ompounds ~uch a.s ht-pheny1.elle, p-pl~enylene, 4,~ diphenyl, 1,5-nz~phth~ a ?In~ -n~phtl~.lIe~na diiE;o~ y~ ;.ttes: the a].iE~hntic-arom~t:ic comprJl~ncls suç s 20 ~,4'-dlph~nylene methAne, 2,4- or 2,~ toluene~ I'-tol~lidine, ~r~
1,4-xy~ylene di.;socyanat~s; benzen~ 1,3-bis (l-i~ocyan~to-1-mcth~l ethyl) J thc nuol~r 6ub.c;titut.ed arvri~ati~ coinpou~ uc:h dS
dia~ lln~ dl laocyanate, 4, 4 ' ~dipllenyl~ther di.lfiocyanAt~ ~nd a~lorodi~llenylen~ di.L~o~y~n~ste; the trii~ol~y~r~cltes such a~3 trlphenyl n~ot.hane~ ',4''-tr.Li~l~cy~nclte, 1,3,5-krll~oc~ydll~t~
~n7.ene an~l 2,4,6-t~:iiso~y~ te tolu~ne~ an~ tr~lsocyarltltfa Il f~4 - ) fl4 ' ~' ' :
~ 22-93l~ED12~ CO~ E~E~UTI~E TELI~O;~ 7~,-Z~ 2P~
2~7'~
s~lch a0 4,4'-diph~nyl dim~3thyl me~han~-2/2l~srs~-t~traisocyanatQ;
th~ polymeriz~d polyisooyanates such as tolylene dii~ocyanate dimers ~nd tr~m~rG, and o~.her variou~ p~lyl~ocyanat~ containing b~ur~ , ureth~n3, and/or allophan~te linkage~. The i~ocyall~t~s and th~ alcohol~. are typiaally r~acted at tan~peratures of 25C to abou~
l50C to form the hydroxy-funational polymers.
E~p~ially pr~rrod hydroxy-ful~ation~l ~at~riala in th~
r~r7~tlr~ n~ 1~h i q i nv~nt -i ~7n z~r~ m~n~--flln~t~ n;~ l r~hnl ,c: ~:tl~h ~.c tr~methylolp~opane dlallyl ether and allyl a].cohol; and diols and triQl~ such as e~hylene ~lycol, dipropylene glycol, 2,2,4-trimethyl 1,3-pentanediol, neopentyl glycol, 1,~-propanediol, 1,3-propanediol, 1,4-bu-tanediol, 1,3-butanediol~ 2,3-butanediol, 1,5-p~ntanediol, 1,6-hex~nediol, 2,2-~imethyl-1,3-prOpane~iOl, 1,4--cyclohexa7leclim~t.h~nol, 1, 2-eyclohexan~a~im~athanol, 1,3-~y~ ~x~ tl~ (2-lly~L~Lll~xy)~y~lull~
trimethylene glyool, t~tra mekhylene glycol, pen~a~ethylens gly~ol, hexamethylene gl~col, ~ecamethylene glyool, dle-thylane gly~ol, triethylenQ glycol, tetraethylene glycol, ~or~ornylene ~lycol, ~ bel~z~n~dim~thnnol, 1,4 -benz e n ~d~h~ h ~ 1, 2,4-dimothyl-~-cth~lonohcxanc-l,3-diol, 2-bu~n~-1,4-diol, and polyols such a~ trimethylolethane, trimeth~lolpropane, tri~eth~lolpropane monoallyl e~he~, trime~hylolhexahe~
triethylolpropane, 1~,4-but~n~riol, ~ly~erol, penta~ryth~it~l, dip~llta~rythri.tolJ and mixtur~s th~reo~.
~5 MOG~ pr~err~d ar~ trimethylolpropane ~lallyl ~t.her, propylQne ~l~ool, ~thylene ~lycol, dietllylene glycol, and mixtures thereo~.
, .
. , J~ ~Q-'q3 I,IEtl l2~a~ O~ EXE,-U`rlllF TEL ~`~0 2l6-'.C~ 2L~3 t11~122 Pla -It ~hould b~ ~pp~ci~ted tlla~ other alcohols ~hould be con3idsred equlv~lents o~ tho~e nam~d here:Ln.
b. E~urt~ eElc:tio~ of th~ Alooholy~ Protluct~
As discuss~d ~ ly abov~, the p~oduct of the alcuholysis reaction ls furthe~ ~eacted ko produce a polyester p~oduc~t u~eul ln a coating compo~ition. Sin~e the alcoholy3is reaction products ~re hyd~oxy-~unctional, they can be ~ur~her reacted with anhydrid~, aclds, fat:~ ac.ids and isocyan~tes including those taught h~low to produce exceptional coat.i"g compositlon~. By 10 controlling the level~ and amounts of x~actants, a~ d~ us ~d below, on8 can formula-t~ either high aoid value or low a~id value ~y ~ems rom the ~lcoholysis reaction produc-ts. The p~oducts of su~h ~action~ lnolude alkyd~ and pol~esters which can be ai~ or bake dried or Which can be furkher mixed, reaGted or tnodifled to 1~ r,reake di~per~ion~ o~ emul~ion polymers using the alkyd~ or polyesters as dispersing medi~ and acrylic modifiQd alXyds and poly~33tsrs .
Suit~ble ~cid-f~nctional ma-terials include mono-fun~tion~l ~ u~ e~ i a, c;rcJtc)~ l i~ a ~ a~ J~ vi-~y z~ ~n ~ld run~1-lur~ ty ~ v~r~ v~ two~ p~lt~
aaid, auccinic aoid, adipic acid, azelaic acid, maleic acid, ~umaria acid, trim~llitic acid, trime~ic acid, naphthal~ne ~;llO~lrll;)OXyllc ~lClQ~ arooxy~ n~ecl polyo~l~aalerle, ~enzopnenone tet.rn~nxboxyll~ cl1allhy~xide, ~ clicabclxy d1phelloXy e~hane, ~nd ~B tho hydroxy carboxylic acid~ of pi~al~one. oth~r ~itabl~ ~id~
include the sa~ur~d ac;id~ ~uch ~ b~tyric, capro~c, ¢~pryllc, ,'. :'.'' , .
.... J~ 20-'93 WED 12:~16 ID:CO~~EXECIJTIIJE TE L 1~l0:~15~ 66--21~l3 ~c2 Pi5 ~, J ~
~ pric, lauric, myristic, palmitic:, stearic, lZ-hydroxy~;te~ric, arachidic, behenic ~nd lignoceric acid~; the unsaturated acids sucll pal~itoleio, ol~i~, rlcinol~io, linc~lel~, linolehic, ~leo~te~ri~, licaric, gadoleic ahd Qra~ic acid~; and th~ oil~ tand thcir fatty acid~) ~uch a~ canola, rapes~ed, castor, dehydrated ca~tor, coconut, cof~e, corn, cottonse~d, fi~, lard, linseed, vticica, palm ~ernal, peanut, perilla, sa~lower, ~oya, ~un~lower, ~llow, tung, walnut, vernonia, tall and m~nhaden oil~ and blends and mixtures o~ natural ~nd synthetic oils ~nd fatty Acids, - 10 p~rtiaularly thoae oils and fatty acid~ with high iodir~e nun~er~.
P.epresentative anhydrid~s include, phthalic anhydride, 3-ni~rophthalic anhydride, ~-nitrophth~ anhydri~le, 3-flourophthalic e~l~hydrid~, 4 chlorophthalie ~nhydride, t~trachlo~ophthalic anhydric~e, tetra bro~nophth~lic anhydrlde, ~etr~ydroph~hall~ anhydride, hexahydro phthalic anhydride, ~e~hylhexahydrophthalic anhydride, ~UCCitliO an}lydride, dode~nylsuccinic anhydride, oc~ylsuccinic anhyd~id~, maleic anhydride, dichloromaleic anhydrid~, gl~lt~ic anhydrlde, adipic anhydridc, ohlorendic anhydrl.de, lt~conic anhydride, ~it~a¢orlic anhydride, endo~methylenetetrahydrophthalla anhyclride, c y c l o h e x a n e ~ a x b o x y l 1 ~ ~ n h y d r i d e , 4 - a y c 1 o h e xe n ~ ~ 1 , 2 -d i c a r b o x y l l c a n h y d r i d e , 4-~thyl-4-qy~loh~xen~-1,2 dicarboxylic anhydr.ide, b o r n e n Q - 2 , 3 - ~ i c ~ r b o x y 1 i c a n h y d r i d e , ~$ 1,4~ayclo}l~xacllene~ dica~b~xylic ~nhydride, -- Y~ WeL~ 4~ lU:UJII~ UI IV~ ItL ~U:~'lb--~t~
- ~ 3 g 7 .~ ~ ~
1~3~y~lopentan~dicar~oxyllc anhydrlde, diglycolio acid anhydride, and the lik~.
Other u~e~ul anhydrides include those anhydrides having A ~ree carboxyl ~roup ln a~ditio~ to the anhydride ~oup such as trimellitic anhydride, acon.itic anhydride, 2,6,7 naphthalene tricarboxylic anhydride, 1,2,4-butane tricarboxy~ic anllydride., 1,3,4-cyclopentane tricarboxylic anhydride, and the liX~.
It should be Apprec.i~t~d thnt other ~cid5 ~nd anhydrides ~hould be con~dered ec~ivalen~s of those named herein.
The aoid- ~ anhydride functional material will generally have a number average molecular we~ght below about 200V. Preferably ~h~.
aaid- or anhydride-~funa~ional nla-terlal will have ~ num~er average molecular weight o~ b~l ow abou~ 4 00. Typioal nu~ber aver~e molecular weight6 oP these materi~ls will ran~ f rom about 96 to about 400.
E~peoially preferred ~ids ah~ anhydrides include the vegetable ~atty acid~ de~c~lbed above and trimelletic anhdyride.
. High ~ Low Aaid vAlue ~ro~uat~ using the AlOoholysi~
Roaation Pro~u~ts ;,r~ A~ ~t~ed ~bD~e, th~ alcohol~sis re~ction products are ~urther rea¢ted with aaid or ~nhydride ~unctlonal mat~ial~ to produc~
either high or low acid vallle produot~. ~or purpo~ of the ~r~s~nt invention, the term "hi~h ac.icl value" i~ meant ~o be those r!~mp~sltion~ h~v1n~.7 ~old vr~lu~ c3rea~r ~h~n l~out 30. ~he ter~i "low acid val ~l~t~ is m~nt to be ~ a ~ompo~ ns haviny aai.~
lo~r than ~o~ ~0. C~mpo~ition~ h~ving acid values , .': " ' ' '.
Jh~ 20~ 3 l~JED IC':'18 Irl:~O~ E~;ECUTI~)E rEL 1~ 6-5f~ 2l'l3 t-l~lZ2 P17 batw~en about 20 ar~d a~out ~o tend to exhi}~ cl-~ract~ti~;~ic~: of both high and low acid valu~3 produat5 And, thu6, are not cat~gori~ed as ~it;her high acid valu~3 or low acid value, although it should be ~ppreciated thllt with some: tri~l and errcr such 5 co~apo~ltions may be acc~3pta~le itl eitl~er c~ateS~o~y.
As a guldeline, in order to for~nulat~e an alcoholysis reaction }~rn~lr~ l-n ~1 h;~h ~ r~ P nf h~ h~1~ n~l A)~ llt fi~;, thc.
~ollowing stoichiometric proportlons (in mole~; of e~uival~nt:s) of m~t~rlalE; ~hould be u~;ed. For ~ach mole of YET used, ~rom about 10 1. 1 t~ bout 1. 5 moles of OH should :l~e used in the alcoholysis reaotion, ~ollowed by furth~r reaction with about 1. O to about 1. ~
mole~3 of acid or anhydride. Preferably, the moles of OH to PET
should be abou~ 1.15:1 to ahout 1.3S:1 and the moles o~
acid/anhydride to P~T ~hould be abo~t 1. O :1 ~o about 1~10 :1 for 15 su~h hi~her acid value products.
In ordex t~ formulate an ~lcoholysis reaGtion produc~ ts: a low aaid value of less than ~bout 20, the following s1:oichlom~ric propor~lons (in moles of equivalents) of materials should be us~d.
~or ~3ach mole of PET used, l~rom about 1. O to abou~ 1. 35 mol~3s o~
20 OA ~:hould be used ln the alcoholysis reaction, vllot~red by further reac~tion witn about t~.~iO to about 0.75 moles o~ acid or anhydride.
Pr~laP~rably~ the moles of o~ t:o P~T should ~e about 1:1 to fl~OUt 1.2~:1 And the moles o~ acid/anhydridQ to PE'~ should be abo-lt 0.50~1 tn A~out 0.65:1.
~5 ~. Fln~l Co~tl~g Prclduata ' ~ , . ;
:
. J~ 2~ wE~ 12~ u~-Ex~ Jrl~lE rEL ~`io:2l6~5~;f~-zl'l3 ~1~2Z Pl8 The products of Sec~tion 2 . c. can b~ U~3d by themselve , in ccmbin~io~ ith oth~r w~:Ll known coatings aclditiv~s, includi.ng p1~ment~, flrw ~n~, c~ta1y~t~, Ai~ nts, ~h1v~nt~, u1tr~vio1et light ab~o~b~rs, and th~ 11k~, or can be. fu~ther mixecl, r~acted o~
modi~ied ~ de6cribed be10w~
The high acid va1ue produ~ts (that is, acid va1ues ~reater than about 30) of Se~tion 2.c., or such products in combin~tion with the above-described additive~, can ~ perBed o~ ~educed in ~ater once neutra1ized with a weak b~e solution such as a tertia~y amine in water. Neutra1ization techniques are well known in the co~tings art. In a pre~erred embodiment, the high acid value ~roducts of Section 2 . c. o~n be redu~ed in water and thereafter ~exv~ a~ the 6tabilizing media ~or the emu1sion po1ymeriz~tion oP
acrylic and other ethy~ enioa11y unsatu~ated monvmer~/ inc1~ding ~yl.ic ~dditioll mon~mers, o1i~ne~ a~ld polym~r~: parti~ula~ly o~
or more ~lkyl ~st~r~q ~f ~ryl1~ ~ nr m~hArryl~r ~r.i~-optiona11y to~ethe~ with ~ne or more other e~hy1enica11y un~3aturated monomers.
Suitable acxylic e~3ter~i lnclude methyl (meth~ ~cryl~te, ethyl 20 (Jneth)acrylate, propyl ~meth)acrylata, butyl (meth)acrylate, hydroxy ~thyl (m~th)acrylate, 2-ethyl hexyl (math)aaryl~te, ~crylonltrlle, a~ryla~lde, vlnyl poly~ers suoh a~ polymer~ oi'vinyl e~er6 of inorg~ni~ or o~g~ni~ acid~, includ~.rlq vlnyl chlori~le, vl~lyl ~oekat~, vinyl proplon~t~, vi.nyl tolu~ne, eka., ~tyren~., anc~
Z5 m~ xtu~ s thf3reoP .
, n ~,! m l . e q J I I I P P t . I E I: ~1 6 - 'i G 6 - 17 (~ 1 ), .3 ~ f (n-~
~ v ? 7 ~
E~ul~ic>rl pc)ly~n~:ri~,ltion r~actLon ccn~lt l(--n:~ are t~e] l kr)~ a in kh~ art al)d Call illClllCl~ ~he proced-lrc~: t:a~yl~t in O . S . E~dt~?~
4,116,903, incc~rpor~ted h~reln by r~ference a.<, wall ag thc proc~dur~:, t~ught in the ~xr~mplQs holow.
~Ill low acid value product~; (thAt is, acid value~; It~r~i th~ln ~bout 20i of ~uch ~sction~ or such pl'~llCt.~ itl ccmhination w.itl~ tile Dbove-ù~sc~ibe~ ~clditi~e~;, c,ln b~ r~d-lced in uolv~ t~i ~;ucll ~JS
xyl~ , tolue:)e, b~nzene, mine~al spirlts and the 1ilce. ~-~c):
prc~ducts c~n ~hot~ `oc allowe~l to air dry or ~orce(l to dry by bc~'cirlcJ
0 AS i~ wcll known in th~. art. ~ mino, ur ec~u.iv~l~l~t, agc!rl~:
wou~d pr~tc~ahly };e addcd to f,acili~dte ~ryincJ in th~d bake ~r~
~;y~ten~C;, In a prefer~e~l embodimetlt, thF~ w acid value product~:
of ~ectiol~ 2,c, can be dir.~ctly modified ~.ith e(cryl~c monomers, oliqomers all~ po:lyme~rs to pro~.ll.lce ~ir ~ry, ~ake and wat~r-~ducibl~
coatinys.
Sultabl~ ac~rylic monomer~ li.gom~rs an~l polym~r~ inc.l.~cle tho~:~ a~rylic, vinylic and ethylenically ~Ins~turat~d m~t~ric~
tau~ht to be ufi~ul with the high acld val~le pro~uct~i as wel]. as the acl-ylia acids thernse]ves such as acrylic acld"nt?.thacrylic acl~
2a and itacor-ic acid.
.[n an~ her E)referr~d embvd11n(!nt~ eit.h~r the high or the 1C-JW
aai(l va1uc products of Section 2.c. ~an be furt~leI m~ 'ied by d~ect flc~ryl i.c modieication. t)ir~ct acr~lic mv:llfl.ci.~ti.-JIl i5 typically c~nducted undor c:orl(litl~ns al~so well knt~wn in ~he ~rt, including th~ pr~ced~lr,3s t~u:~ht in V.s. Patent.~ 4,735,'J~5 and .
lB
,:
.. :
.7~ .JED 1~ 51 lC~CO~I E``'ECUrll-lE lEL ~`lr~ .~215-5~ '1 13 2 ti , ~,~73,2~1, inCorporated ~le~ein ~y reEerQnoe, a~ well ~s by the pro~dllr~s taught in the ~ nples below.
When acrylic modifyl~g the low aci~ value produc~, the 1ncorporatlon of A high level of aeid-~unc~ional acrylic materials S w111 enable th~ ~inal, acrylic-modi~ied Goating produc~ to be rsd-lcible ln water or other aqueou~ ~y6t~m~. Gene~lly, a~o~lnts o~ acid-~'unctional acr~lic material~ ~reater than about 1.0~ by welght of ~he total ~mo~nt o~ acrylic and ~other ethylenically un~aturated m~terials w111 res~lt in a coating ~omposition whicll i~ wate~ reducible. ~mounts less thah the above will generally r~sult in ~oating~ which are not water reducible.
~ he coatings o~ this inventiOn can also be blehded with other acrylic resins, alkyds, poly~ers and coatin~ resin sys~e~s.
~ he coatings of thi~ inv~ntion m~y ~ypic~lly be ~pplied to : 15 any substrat~ ~u~h a8 met~l, pla~tlc~ wood, ~nd qla~3~ by b~ushing~
dipping, roll coa~ing, flo~ coa~in~, spraying or other me~hod ~onventionally ~mplo~ed in the coating industry.
ReprQsentative opacifying pigmen~.inolu~e white pigment~ such a~ tlt~ium dloxide, zinc oxide, antimony oxlde, ~tc. and org~ic ~ inorganic chxom~ic pigmen~s suCII as iron oxide~ carbon black, phthalooyanine blue, etc. The coatingS may also oon-tain extender p~gment~ such as aalcium carbonate, clay, silic~, tala, ~tc.
~ he ~ollowing example9 have been ~elected to illustr~te ~cl~ic emhodiments and prac~ice~ o~ advant~g~ to a more comple~e u~der~kandllly ~ the invqntloll. Unle~s otherwise ~tate~, "parts"
~all8 part~ w~l~ht ~nd "percent" i~ pe~cen~.-by~weigh~.
20- 13 l`J~C! 1?:5~ ID:CQN-EXECUTIOE TEL. ~`lC1:216-~66-21'13 l~k~ P21 ~ ~ ~ 7 ~
r.~r~ur~Ly~:~c c~
~ h~gh c,c~ld ~c~ ., w~L.s.L Le~l~v.L~ . w acaordin~ to t~.he followin5:t procedur~:
A 3 l, ~ k~d round b~t;tom flA~k Qquippod with ~ nort gAG I
~nechanical st1rrer, 13arr~tt tubR and Frledrich I s ac~nden~;er was trlmetltylolpropane d i ~llyl ether, 5 . 3g o~ dibutyl tin vxi~e o~oly~t ~n~l 37~ ~tylcne. 5~hc ~l~t~nt2 wo~ ec~t~:~;l t~ ~ao~ Ql~
un~il all con~QTl~s had melted and ~ clear ~olution was obtained.
The solution was cooled to ~Z5F ~nd ~90. 4g o~ tri~elletie ~nhydride, 344.~g dehydrated ~a~tor oil fatty acid and 65.8g ~1J1~ U11 f~Ly ~lv wire ~dded. T~le con~ents were nea~ea ~o ~70F ~nd held for an aeid value o~ between 60-~5 and a vi5c05ity le~s than lo,QOOcp~ at 90~ i~ propylene gly~ol monop~opyl ether.
Ona~ r~ach~, heat waB removed and the contents allowed to cool.
rhe final resin product had an NVM of 89.~5/ a viscosity o~ 5300cps (u~ing Brook~ield LVT-~3, 12rpm), acid v~lue ~ 6~, Mz o~ 428~, Mw Qf 19~1, Mn of 103~ and Pd of 1.~7.
The resin was further reduced in w~ter by combining ~hP resin, wa~er and triethylamine in ~h~ following amounts:
65g o~ re~in 65g o~ water .lg o~ triethyla~nine.
~XAMPhE ~I: A~CO~IOLYSI~ OF PET
A high a~id ~lue, wat~r xeducible re~in w~ prepared ~cording to ~ho ~llowlny pxocedure:
2n .~, . , J~ 2~-'93 1.IED l? ~ cn~-ExEcur ll~!E rEL ~lO 216-'~66-21~ 2 P22 ( ,..3~7~ ~
A 31, 4~nec)ced round bottom ~ k e~uipped with ine.rt gas, m~chanical ~tirrer, Ba~rett t~be ~nd Friedrich~S c~ndenser w~
charged with 54~.~g o~ polyethylen~ tereph~halate, 735.3g of trimethylolpropane diallyl ether, 5.3g o~ di~utyl tin oxide ue~t~lyo t ;~nd 55g xylene. ~ cc~ntent~3 were l~ e~ 4 60F ~r~d h~ld until all cont~nt~ had melted and a clear sOlu~ion wa~ obtained.
The solution wa~ aooled to 325F and 290.0g o~ ~imelletic anhydride a~d 409. 5g o hlgh content linolaic fatty acid ~Prifac 8~60) were add~d. The con~bhts were h~at~d to 470F and held for an a~id ~lue o~ ~etween 80-B5. Once r~a~h~d, he~t was rehloved and the content~
wed to cool. ~h~ final re~in product had an NvM of ~5.25, a ~is~osity o~ 18, ~OOCp5 (~sing ~rook~ield LVT#3, lZrpm), aci~ value of B2, MZ o~ 36~9, Mw of 1643, Mn Of 919 ~nd Pd Of 1.79.
EXA~PL~ ALC~HOLYS~S OF P~T
A low aci~ value r~sin wa~ prepared acc~rding tQ th~ following pro~edure:
A 31, 4~necked round bott~m flask eg~lipped with inert gas, me~h~nical ~tirrer, Barrett tube and Friedrich's conden~7er was oh:~rgod w~ ~h 1016 . 7~ o~ poly~thylen~ t~:;L~ tl~ , 414 . 0~ lL
ao prDp~ene gly~ol, sog o~ tlllnethylol~ ne diallyl ether, 5. sg o1 dibutyl t:in c~xide cataly~t and 4 Og xylene . The con~ents were h~ted to 4GOF an~ held until all c~ntqn-t~ h~d melt~d and a clear Yolution wa~; obtained. The ~olutlon w~ c:~ol~fl to 325F ~nd 59. og trim~lleti~ ~nhydr.lLde wa~ added. Th~ nterlt~ Wel'~ heated to ~b 470F ~nd held ~or nn ac:id ~alue of l~ han lO. Once reac:lled, h~a~ w~ r~moved und th~ contnn-t~ ~llow~d t:o cool. T~le ~inal resin .. . . . . .
. . .
J~r~ 1'.5'~ I~'.CC~ ccur~ TC~ ~10.'11~ 5C~ '3'~ 3~
h `~ u 7 ~
product had an NVM of ~9.5, ~ v j~oo~i-ty gr~t~r than ~O,OOOcps (u~ng Brookfield LV'~3, 12rpm), acid valu~ of 4.1~ Mz o~ 218~, Mw of 134~, Mn o~ 84~ ~nd Pd of 1.5~.
I3XAMP~E IV; DIRECT P~CRYLI~ MuU~ A~ C)N
dOOg of the r~Eiin of Example III ~ncl 150g of Propasol (propylene glycol monobutyl ether~ ~era charged te a re~c~ion ve~el and h~ated to ~hn~ n~. Arl~ o th~ co~. o-~r ~ ~, 5 hour pe~iod wa6 ~B6g o~ lneth~l methacrylate, 43y of methacrylic acid, 2~g o~ ~tyrene, sog o~ ethyl hexyl ~rylat~. A secon~ fecd lO o~ 9g o~ t-~utyl perben~oate an~ lOOg of Propasol was added over thQ ~ame time period. Upon complete addition of both ~eed~, a ~h~e of 1. ~g t-butyl per~en~o~te in ~Og o~ Propasol was add~d over a ~.5 hour tim~ pe~iod. Heat was removed and the cont~n~s o~ th~
Yessel ~ilterad.
15 E~AMPLE V: AIR DRY COATI~G FORMULA
. A resin prepared according to ~he pro~edure of Exampl~ I can be ~ormulated to a high solids, ~ol~ent~ba~ed air dry ~oating having NV~ of ~0.55, VoC less t~an 250 g/l as ~ollow~:
Ih a hi~h speed dl~per~er, grtnd:
4~2.6g ReR~n of Ex~ple I
47 . 5 A~o~atio Naph~ha - 7 . 7 Soya I~cithin 202 .~ R~t1le tit~nium dioxi~e Run on high ~or 15 Dinu~s 25 Add 203.9 RQsin o~ Example I
1~.3 ~omatic Maphtha 1~2 1296 Cobalt Catal~t 29 . 5 1~ alc:ium Drier 2.1 Me~h~l ethyl ket~xi~nQ
30 ~1.9 ~roma~ia Napht~la O~S ~e~o~m~r (Byk 0.~2) ~X~MP~E: ~X ~ I~A~E I~Y ENAM~ ~MUhA
~2 : ... : , ,. : .
, . ' ', ~q~.~J~N-20-'93 WED 12:55 . iD:CON EXECUTI~)E TEl NO:Z 16-566 .?.~ 02? P24, . ~.. .
~387~1~
f, A re~3in p~epe~d according to th~3 procedure o~ Example III can b~ formulated ~o a balce dry cs~ating ~aving PVC l~ ~ 5, NVM 80. 9 .
w~ight par gallon 11. 8 lhs/~al an~ ~oC Or 2 . 2~ lb~ al as ~ollows:
'r n ~ h ~ ~h o r~ ~ ~ ;L O p ~ J W l J ly .
S . 17g. lg ~sin of Example I~I
24 ~ O Prnr.a.snl P
423l ~u~ itanillm Run to 7H ~e~an Grinc~) ~:tabll~ze l~0. V Propaso:l P
10 Thindown 241. 5 R~in o~ Exampl,e I~I
13Z. 7 Melamine 80. 2 PropasC~l P
.
- ~. ` .:, . .
, ~3
NON-AQUE:Qu~ COATIN~ cOM~ITION~ FRO~ P0I.YETHYLE ME~` ~13R~PHT~LATE
R. Tomko D. S~yr~
W. Lesney M. Rao .A~.:~U~KVUNl~ U~ rnEi lS~
Thi~ ~nvention rel~t~s to n~vel coatinc~ composition3 which uti~ize polyethylene terephth~late (P~'r) aæ ~ ~aw m~terial for pxoducing the ~ilm-for~ning resin for su~h coatinys. Most lo p~o~ ly, tho I'E~ ~c rooyalod or :~ccl~3imcd rET f~om pl~ tio tlr~ o~ su~h ~ two-litcr hovc:ragc bottloc.
Pl~ ~.h ~5 p~:rr ;~ nl~n~ fnr ;lhnl~t 7-R w~;~l~t r~rrL~n1, ~n~l about ~0 volum~ p~ent, of th~ wo~ld's solld waste. As a result, muc:h legiSl~tibn h~s been propv~d and~or adoPted re~uirin~3 ~he reayczling OL' plastlc:s.
PET iB the prim~xy ingredient i~l ~lastic el:r tic~ u~ a~i tw(~
liter be~rera~e b~t~;le:~ Rnd the lik~. In the u.~ E~ ; the pla~:tic most often ~ecycled. The l~iggest uses for recycled PET are ~æ flber~; in c~rpeting and insulation. ~ecycled PET i6 also used in hatllroom equipmen~ and blow-molded b~ttles.
~xooe~ea ~or re~ycling P~T beverage bottles into u3able ~aw )p~44;o~ o~ 7r~n~ r~g ~ o~ yoa t~ oc~ a ~l'C ~I~W~ .
~or ex~mple, ~a3tman Chemicals Pu~ atio~ No. N-~62A ~ntitled Un aturated Pol.~e6ter Resin~ ~ased 011 Reclaimed Polyethylene T~r~p~ha~e ~ L_~Qy~q~ Bottles, ~alendine et al. ~19~4), te~ohe~ a prooe~ ~o~ converting PET b~v~rc~ge bo~tle~ into use~ul int~mad1ate~ ~or the ~ynt:lle~i~ oE un~aturate~ pol~e~ters. ~he un~ar,ur~lt~ p~ly6~6~c~ 3 ar~ ~ur~n~L- Cau~llC ~3 ~13~;tUl e~s L-~W
, , .r~"~ ' 9~3 lJ~ 2 ~ ~3 I L) COI I--F`~ ~:CIJT I I.IE I EL ~IO C~ 5~ 3 ~ F~
f~ '~1 4 7~
m~terialB for produclng unreinor~ed cle~r Cc~tings ~nd ~iber~
gla~ r~inforcsd laminates.
A ~econd Ea~:tman ChemiOal~ Publi~ation, No. ~1-2923, e~ti.tled ~ m Re~lalmed YolYP~ h~nQ~ halate, (1~87) teache~ the re~lam~tion o~ PET for produc~ion of Aromatic polyes~er polyol-~ which are useful in rna~ing ricJid p~lyur~than~
polyi.30cyanurate ~oams U.5. Patent ~,223,0~ (C~rlstro~ et al.) teaches the use o~
t~e di~sti~n product o~ p~ly~l~c~lc-,O tcrop~h~l~tO ~crap~ wlth organic polyol ~or the produotion o~ ri~id polyure~h~ne foam~.
~ .~. P~ten~ 4,417,001 ~Sv~ 1,) t~ L~ Li~l o~ low smok~ isocyanur~te modified polyure~hane f~ams w~lch ~e prep~red fro~ p~lyol~ which ~re th~ dige~tion product o~ ~ige~tin~
polyal~ylene ~erephthalate s~raps and or~anic pol~ol~.
U.5. Patent 4,048,104 (Svoboda et al.~ teache~ the prep~ra~i~n o~ polyi~o~yanate prepolymers an~ polyurethane adhe3ive~ and Eoams wherain the prepolymers ~:re prEJparE3d by re~titlg ~rgania polyl60~yan~te wi~h polyol~ which ~re the ~ige~tio~ product of polyalkylen~ ~erephthalate ~craps ~nd org~nic polyols.
~U~A~ 0~ TH~ INVENTI~N
~ his inven~ion relates to novel coa~ing composi-tion~ which u~ilize PET a~ a X`aw materia~ fo.r produclng the ~ilm-~ormillg re~in ~r ~UCh ~oating~. Prerer~bly, ~h~ pr~n~ inv~ntion ~ t~s to lo~ ~i.d vHlue~ non~a~u~oUs~ ~lir or bake dr~y ~oa~ing~ deriv~d from rQalaimed PET and to a prO~eF.~ ~or p~oducing ~uoh coa~irl~. uslng . , '' Sf~ 2~ 3 I~JED 12~ co~ E~;EcllT iSE TEL 1~ :21~ f_.f,-21~ Z? P05 ~
~ 2~
reclaimed PET b~ne~it~i the ~nvironn,~r)t by ~educitlg t1l~ am~unt of ~;olid waste dump~d at land~llls. U~;in~ reclaimec~ PE~ benefit~ this p~oce~s in that it i~ a relatively in~xpensive raw material wh;ch, as i~ ~hown herein, produces an excellen~ col~ti1lg Gomposition.
~n ~ocordance wit:~1 -the present itlV~n~iOn, PET resln (o~ an equ1valent polyalXylene terephtha1ate re~in3, typieally having a structure a~3 ~nown ln FlgUre l:
O o 10 ~i~ure I OH~CH2C~2-o-C~ C-03CH2C}12011 n~100 i~ fir~t dlgested into lower molecul~r weight polymeric units throu~7h an alcoholy~;is re~ction. ThP. rlig~ nn l~rnAIIr~t nf ~h~
15 ;al~h~lyo ~ 7 ~c~ ~ion i~3 then f~r-th~3r ~eact;e~l wlt~ nn n~ S d-~unctional r~3ac~ant, an anhydride or an isocyanat~ to yleld a resin cotnpositio~ suitable ~or use in coating composl'cions~ By varying the a~un~3 and type~ o~ aciA~, isocyanate or hydroxy-~urlctional reactantE: according ~o the te~chlngs herein, one can formulate. a 20 variet~ of c:oatings sy~tems i ncludin~ polyure-th~r1es, high acid value, water-reducible cc>ating~ and low acid value, solvent-based coatin~s. Additionally, fu~ther chemical modi~ications are appllo~ble And ~re further exe~npli~ied h¢rein.
Aocordingly, it i8 ~n obj~ct of t:hi~ invention to teach the 25 u:s~ o~ polye'chyl~ne ~rephthalate a~i a ~aw mate~ial fo~ the production o~ coating compo~itic:n~.
' L~ 3a l L,t'pt . r~ 5~ 70~ ~lall ~(J,~13 ~:34 ~lo .()~ P.~3 1~ is a ~rth~ o~l~ct of this in~ention t:a t~ach no~
air nnri ba~e dry coatir1~J colnpositlons whic~ utiliZ~ reclaimed ~E~r a~ a r~w material.
l`hese and other o~ject~ will hecom~ mor~ r~adily ~ppar~nt ~r~m the det~iled descripti~n, ~xa~pl~ and clai1n~ whlch eollow below.
DeTAI~EG DESCRIP~ION OF TIIE IN~tE2~TION
As statcd ~bov~, the prcsen~ ln~en~.lon rcl~tes to novel r~on-aqueous. coating composition~ compri~ing rET as t11e starting ~ateri~ll eOr the proc1u~tion b~ a fil~-for~ing resin.
l. PE~ ~OURC2 The ~tual so~1rce of PET us~le her~in is not o~ critical ~mport~nce to this invention. "Virgin" P~T, ~hat is P~T whic~h is a~lmercially produced specificall~ as a raw n~aterial, is a~cept~ble Prom a c:hcmic~l standpo~.nt for USQ herein I.ikew;.se, r~cycl~d or r~ol~im~ PE~r tF. a~ceptable ~rom a chemic~al stan~oil1t. At th~J
tlme ot thls ap~l:icatior., there a~ advant~ges to t}l~ ~n~ironmcnt ~r~dl~ction o~ solid waste) ~n~ to the eCO~01~icS o~ this proces~
. (recy~oled PE'r ls much l~ss expensive than virgin ~q') by us.ln~3 ; ro~ led or rcclai~ed PE~i and, there are no perf~rmarlce di~adva~ta~es~to usiny recycled PEI' ver~Us vir~in PET. As ~
~onsequence, recy~led or rec.Laimed PET i8 a preEerr~d ~t~rting mat~ri~l though l~ ~hould be appreclat~d that any s~urce oE
~el~tlvely pur~ PET i9 acc~t~ble.
Typi~lly, ~h~ ~ourc~s foL PET are n~any and varLed. one ~o~Jrc~ ~f olther ~lr~in vr ~bcycled P~l' is mat~lrial ~ro~
R4 -~ R4 ''; ' ., :
'' ' ' ~
' '' ', ' "' '', ~) l P ~ J P ~j r r -:1 . .? I t~ f) - I ~ ~ h ~ O . ~ ;~ 1 8 ~ i l! . O ;~ ~ F . O ~
f~ 8r~
~olym~ ma~ acturels. A ~ec~n~ ~ource c~f P~,~J 1s ex~:e~;s E~l r ~r~Jn~
th~ op~ri~tion~ of th~ bcv¢ra~e bottL~3 man~lf~lct~2rers. i~ t~lird ~ou~c~, ls privatc ¢n~ pr~neur~; deal lng ln recl;~llmecl PE'r. A f~lurth ~oll~.ce ls ~om~ nity recla~natlLon ancl recyclin~ cent~r:s. t~ pref~-r~d 5 ~;~urce Or PET l.q r~yc:led PET be~ert~go bottles.
~ or purposes of this invention, the PET ~ ould be provi~ecl in ~ con~minut~d form. It can be fl~keci, graJ~ul~t~ t o~r.d to ~3 powdel~ or pellQti~ed. Praferred i~ fl~ cl PE'r. T]-e only corl~;traint placl3d on the PET at t~lis po1nt is that lt is rel~t.i~ely 10 pure; th~t i6, th~re ~hc>uld not be ~ lQvel of impurities above a}~out: vn~ ~1) w~l~ht p~rC~11t nor should ther~ bc a~ y appreciAhl~3 lcve. of impl~ritic~s whi~h ~re ch~mlcally re~:tive wit~in this pJ~oC~e~;s. F~ET whlch i.s acceptable tor tlse herei~1 ~3ho~Jld hav~3 the t'~ owing ah~lracterl stic.s:
Intrlnslc vlf~cosity 0. ~5-0. 75 - M~is~.~rf~ ~cl . 09~
~ Lo?: ed PE:I' conterlt <~ OOpprn High ~0n6i.ty Poly-et~ylQnQ ~13L)PE) clOOppm Adhe~ive~ c50O~ m Alumi num ClOp~m 2~ C!}l~I8TRY OF PET
PET 1~ npril3ed of rep~atln-J units of ethy1eoe qlycol an;i tere~)htha~ic acid connecte~l by cster 1in,ca~s~ Fiyu~e I, above, ~5 shows a typical P~T mo1ecu1e. E~ch rep~c-t:Ln~ unit of PET has a weignt ~v-ara~e mol~culAr wo1clht of 1~ with one equiv~1ent ~f et:hy1~ne g1yco1 and on~3 equiva1etlt of terephthAl.tc acld. By raa~l:ir\~J P~T with ~ith~ ~n alcohol or wlth an ~ICi~l, it il!; po~i~lb1 t;c re~ c~ thcl av~r~ga ch~ln l~ng~.h Oe t:he ~F,'r nlc~1ecu10~.
> ~ 4 , . ,., .:, , ", : .
: ;, . . :
J~ 2~)-'9~ ED 1, :~13 ID:COII-EXFCUTIUE rEL i`lO:ZI~ 2kl~ t~
( , .
. Alooholy~ls of P~T
~n~ cheml~l.ry o:t P~l' 15 ~uch the~t e~n e~qullibrium exlss;~3 b~twee~ PE~, water, ~th~len~ ~lycol (E~) an~ ~es~sphthalic ~oid ~TPA) . ~hls aquilibrium ~akes it possible t~ ~b~antially revers~
the polym~rizatlon pro~e~s and depolymers ze PET inSto its star~ing m~erial~. The E~t~sars Chemiaal publications ~ite~ ~bove refer to the procs3ss of depolymseri~ing PET as ~lycolysiS~. That prooe5s .oom~rise~ the catalytic re~ction o~ PET with a polyol. As ~urther de~inad and exemplified below, it should be apprs~ciated that o hydroxy-funotional ~naterial~ ha~i~g OH f~nct~ion~lity ~rea~er or le~s than two can be eEfec-tivPly utili~ed in the pr~.s~n1; p~ocess;
thu6, the prese~t pro~e~ is h¢rein referred to a~s "alcoholy~i~5'.
Ih th~ ~ontext of ~he present inven~ion, refere~ce to "~ ohol"
~hould be under6tood to refer to ~oth mono- and poly-funotional 15 alcohols unloss speciflc~ t~ught otherwis~.
~h~ numbe~ o~ O~ e~uival~n~ Ero~ the alcohol should be equ~l to, or ln excess o~, the numbe~ of equivalen-ts of ethylene gly~ol from the PET. Pre~eral~ly, ~he ra~io oi~ equivalent~ 6hould be betwe~ out 1:1 t.o ~h~l.lt ~1, more. ~refe.r~ly ~hnllt. I~ h~llt.
Zo 1. 5 :1 mc les ~f OH equivalent~ per mole of PET ~
8uitabl~ catalys~s ~or al~oholysis of PET inclucle the traclitional ~r~nses~e~ ation catalys~: inc~udiny ~tannous octoate, c::alcium hydroxld~, c~ m ~onna~e, lithium hy~roxide., bA~iU~l hy~roxi~ dlum hyd:rox.ide, ~odiulll m~thoxide, mangane~
25 ~ ,t~3 tetrahydrn~ nd polymeria di.oryanotin Cat~:,1Y6,t6~L 5Ue'tl as d~b~.yl tln ~id~ ~r~d~mo ~ t, Qv~ilabl~ from M~ Ch~mi~al~).
, ~
:', ~ . .' ':
S~ ` . . . ?~ Er~ ~I~!--E~ T 1"~ ~
~ ~ U ~ 3 ~
Most pre~erred i~ dlbutyl tin oxide. IP used, the catalys~ should bç~ pr~3s~nt in an ~mo~lnt of from a~out 0. 2 weight % to ~out 1. 5 weight % based upon th~ total w~ig~t o~ the ~ET and al~ohol.
When PET and a alcohol are react~d togeth~r in the pr~s~nc~
of ~he above cataly6t ~nd heat, tha high molecular weight PET
m~l~ d~r~ ;o o~ r t~ ir~ W 5'~
aocompliehed ~hrough chaln attack and excll~nge `oy thc al~ohol with the ethylene glycol units of -~h~ PET mole~ule. This ~ttack ~d exchan~e con~inUe~ ~o occur ~ntil a new equili~rium is established b~tween the PET, the ~horter ~hain leng~h PET, the ~horter chain len~h PET sub~tltuted wit~ the alcohol, the alcohol and ethylene glycol. Fi~ure II shows the typical produc-ts of alcoholysis of PET W~th a repre~entative polyol:
Figure I~
~ o HO-R-C O-R'--OH ~ Ho-R"-OH ~ Ho-R-C-o-R"-oli ~ ~lo~R'-OH
A8 ~an be ~een from Figure II, subsequent ~o alcohvlysis all ~lnQ~ning PET x~agm~nt~ nl~d prod~lct~l in ~lLlibri~lm th~wi~h ~r~
hydroxyl ter~inated As described ~urthe~ bQlow, they can be reaatod with aold~, anhydrlde~, fatty acids, isocyanate6 cand the like to ~o~m excellent coating compositions.
Alcoh~l~ ror u~e ln Al~oholy~is o~ PET
ry~lc.~ly~ ~hO ~lo~l-ola wlll h~v IIU~J~- ~v~y~ mol~
2~ w~igh~ o~ b~low about ~000 and typiaal numbQr av~raga molecular w~lgh~ will ran~e ~rum ~ tt 30 ~.~ a~u~. ~o~o, an~ ecl~.ly 100 . , .
~ N- c'O-- ~ Wt L~ l c ~ l I U ~ t.X.tl~.U ! I ~Jt I tL !~(U c~ l b--~bt.~ lc~' ~
to 7~bout 400. Mothod6 of pr~paring al~hole ar~ w~11 kn~wn ih -the :~Y~ d ~7. O~ m~ hc~ r~~ r~ ~h~ G~1 ~h~ a ~ a ~rlt r~~
to the pr~ctic:e of this invel tion.
5uitable al~ohols lnalud~ the Cl-C22 linear and br~nched ~atura~ed and unsaturated alcohol~ includin~, ~or exampl~, me~hanol, sthanol, propanol, 'outanol, hexa~ol, linoleyl ~lcohol, tr1methylolpropane diallyl ether, allyl alco~ol, 2-mercapto ethanol and ~-he like. Additionally, usei~ul alcohols ln~lude the IIY~L~XY--r~ ctiol~al Foly~-t~rs;, poly~t~3-s, p~lyu~-eth~nes, polyaaprolacton~;, otO. a~ gQnor~lly discu~:.ad in S:~tic~n~
th~ough a.l.e. below.
a.1.a. saturated ~nd ~nsat~r~ted p~lyol~ lude gly~erol, castor oil, ethylene glycol, dipropylene glycol, 2,2,4~trimethyl 1,3-pentanediol, n~opentyl glycol, l,~-ptvpanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, ~,3-butanediol, 1,5-pontanediol, l,~-h~xan~diol 7 2, 2-dim~thyl-~, 3 -propanediol, Bisphenol A tetraethoxylate, dodecahydro Bisphenol A, 2,2~-thio ~i~th~nol, di~ethylol propionic acid, acetyl~nic diol~, hydroxy-terminat~d polybutadiene, 1,4 cyclohexanedi~ethanol, 20 1,2-cyclohexanedimethanol, 1,3-cyclohexanedi~eth~hol, if3(2-hyd~oxy~thoxy)cyalohexane, trimethylene glycol, -tetra ~thylQno ~l~ool, ~ontnmothyl~no ~ly~ol, hox~m~thylon~ ~31y~
doa~mo~hylono glyool, ~iothylone glyuol, triothylana c,llyvol~
t~tr~ yl~n~ ~ly~ vL~u~l~yl~ ly~vl, l,~ c~
25 1,~-benzeno~lethanol, ~ nethyl 2-et~lyleneh~xAn~-1,3-diol, 3-~ut~n~ diol, and pol~ol~ eu~h a~ trim~hylol~than~, ~"' ' ' .
trimethy101~opane trim~thylo1prop~n~ mono~llyl ~3~ `e7?
tri~othylolh~-7X.3ne, trir~thy101propan~, 1,2,~.-b~tanctr1~ YC~LO1, p,~ntaery~llrlto1, dipent~erythritol, e~o~, ~ b. Po1yether polyol~ c~rc~ w~11 known in thc clrt .~nd dr~ cor,ve~)ient1y p~ep~red by the re~ctiorl J~ a diol or pc~lyol witl;
thc corre3pond1ng ~lky:Lene oxide~ Tllr~se mclteria1s ,-~r~o~merc~ 11y availab]e ancl mny be prepa~cl ~y ~ ~nown ptocess ~uch as, for n:~n~ple, t:hc~ proce~s~. dcsoribed in F,ncYc~o~erii~ c~ h~mic~1 ~o~ c~ly~ Volume 7, p~ye6 257-262, publlshed L~y ~htt~sci.?nc-e Pub1i~;hers, Inc., 19~ cn.~re~en~a~ive ~am~ s incllldc t~l~
po~propy]ene eth-~r c~1ycols and pc)ly~thylene ethe~ g1ye~ such ae.
tllos~. ~,3-~et~ as N:rAX Po1yols from Union Ca~bi~e ~or~oratio ~ .l.o. Another u~eru1 c~ s of hydlox~ cc.io,~
pc.1~nrs are t.~l~ose pr~p~r~d by co1ld~ c~tion po1ym~ c~tion r~.~c:t:inr t~chniqlles as ar~ we31 known in tl~Q ar~. ~np.r~2selltclt1v~
c<-ndenq3~ion po~ym~riz~tion 1~a~t.i.ons incluc1e po1y~ter~ rc~p~1ec ~y th~ condenf;~tion o~ polyhyd~ic alc~ohols an-l po;,yc.~rhoxy!.lc a~idr or anhyd~ides, with o~ wltho~t the inclus10rl o~ drying oll~
sem:L-~1rying oi~, or nc~n-~ry1~g oil ~Atty ~cids. 8y adjuc.ting t.he 2~ st4~c~l10metry o~ the a1cohols ~nd th~ aaitls Whil~ maint~linin-J ~n ~Xc~..5 of hydroxyl grouE~, hydroxy-functlon~l pc)1yest,ers Can ~e readily produced to provid~ a wide rang~ o~ de~irecl mol~?cul~1r weight6 ~n~ ~erfbrm~nce characte~istics.
Tlle polycsL~r E)olyoLs are d~rlv~d l-rorn one c~r mar~ Elro~lat.i~
25 an~lJvr aliE)~I~tio pol~cal.boxy.l..ic ~a:Lcl.~, th~ an~ d~?~ t:h~?r~of, ar,c~
~ne or Dlore a.ll~ atl.cJ and/c~r ~rom~:ic p~ly~ c,~arl~c)xy~
.;
,''' ',' ' :'' ' ~.
J6~1-al3~ l/FD IZ:.la ID ~n~l E~ECUrl~)E rEL ~o:al6 566-21~13 I~O.. Fl. ~--aaid~ includ~ the satur~ ar~d uns ?.turated polycarboxylic acids and the d~rivativefi thereof, ~uch as malei c acid, fu~ ic acid, ~:ucc: .~ n lc. ~ ç .~ ci lp .~ icl, n ~ n~ ~r)t~ n f!
dic:!arboxylia a/:~id. 'L'h6~ carboxyl iQ aalds al~:o inalude the aromatlc 5 polycarbox~lic acid~, ~uch as pl~th~lic acid, isophkhalic ac:id, tt.~rF2E~hth;~l 1a ;~ci.d, etc. Anhy~r~r~eF~ e~ m~le~n ;Inhyr3rl~
p~thal~c anhydride, trimellitic anhydride, or Nadic ~Sethyl Anhydrid~ (brand nam~ rOr methyl bicyclo t 2 . 2 . l ]
h~pt;c~--2, ~)--d~ cAa-l~oxyli~: n~hy~ lc i~~ lbL~ 11 al~ 4e~ u~
Reprç~sontativ~3 saturated and unsaturated polyol~ which can be reacted in stoic::hiometric ex~ess with th~ carboxylic acids to produce hydxoxy-~ullctional polyesters include the diols taught in a . l. a . and a . l . b ., above .
Typica~ly, the reaction bet~een the polyols and the polycarboxylic a~ids i5 conducted ~t about 120-C to ~bou-t ~Q0C in the pre~ence of an e3teri~ication ~at~ly~it such as dibu~yl tin oxide .
a.l~d. Ac~di~lonally, hyciroxy-funotional polyllle~ can ~e pr~pared by the ~ih~ op~nin~ rQao~ioh c)f ~poXid~E; and/or 20 polyepoxide~i; with primary or, pr~3ferably, seoondary amines or ~olyamine~ to Produce hydroxY-fUnC~ional polyrner~ Repre:en~.~tive aTnine~ an~ p~lyamines include ethanol amine, N-methyle~hah~l amln~, dl~n~thyl am~n~ ~ Q~hylene diam:ine, i~ophor~ne di~mine, ~to .
Rspre~enta~lv~: polyspoxides lnclude tho~e pxeparF3ù by c:onden61rlg 25 n p~lyhyclrlo alc~hol or polyhydric ph~nol with ~n epihalohydrin, ~uc~h ~e ~pl~hl~rohydrin, u~ua:lly uncle~ alk~line c~ondition~. Some , ~ ? 4 r~ ? 1~ T 1 E I ; ~ f,h - I, ~ 3 l, ,~J ~3 ~ 3 of th~;c~ corl~ler~satlr n product:~: ar~ avAllahlra collltr131c i;~11y n~d~r.~ 3 1 f~
dcsLr~natlo~ t EPo~l ~`ron~ Shr~ll Chomlo~l ~'vmE)~ny, ~nd mr~thods ~f pr~p~r~t.ion ~re rQprl3sentc~ti~"aly taur3ht in U.S. ~,~tel-ts ~,592,5Go;
2, 5~, 9F~5 ~ 2, 6~4, 694 .
S a.1.~. ~ther u~Cul hydroxy~furlctior,z~l pol~me~-~; c~r~ be pLepa~ed by tho reactic~n o~ an r~lxc:es of at l~ast ~rne al~ o~lol, X~
aa t:hose ~epre~ent~ltively r~e~c~lblod ~bove, ~ h .isocya~ .e. to prc,duce ~ydroxy-runction~l urethAncs. Rr.~;r~sent~ttive ~not;o-~uncl:ion~l i.s~Jcy~ndte~ clu~lr~ ~llyl isor. yanatr~ ~nrl tolulyl 10 i~ocyan.~te. ~?c:prr sent~tive polyisocy.snates i~c~ r.ie th~ ali~h~tic c~ pr~ullr~; S~IC~I a9 ethylene, trimethylenc, tet~-.tmetllyl~ne, pe,ttantethylene, hexamethyle~lra, 1,2-propyl~lie, 1~2-butylene~
2,3~butylene, 1,3-butyleno, ethylidene Rnd but.ylld~ne ~.iisocyanatr~s, th~ cyclo~lkylene COl:lpOUh~3s s~loh as 3~ cy3n~to methyl-3,5,5-tL-lmet~ .yclohexyli60cyan.~tr, ~ntl tne cyclopentalte, 1~3-cyc~ohexflne~ Al'id ~ ~CyGlOheXrll~e dii.~oc~ na~.~as; the flrom ltic ~ompounds ~uch a.s ht-pheny1.elle, p-pl~enylene, 4,~ diphenyl, 1,5-nz~phth~ a ?In~ -n~phtl~.lIe~na diiE;o~ y~ ;.ttes: the a].iE~hntic-arom~t:ic comprJl~ncls suç s 20 ~,4'-dlph~nylene methAne, 2,4- or 2,~ toluene~ I'-tol~lidine, ~r~
1,4-xy~ylene di.;socyanat~s; benzen~ 1,3-bis (l-i~ocyan~to-1-mcth~l ethyl) J thc nuol~r 6ub.c;titut.ed arvri~ati~ coinpou~ uc:h dS
dia~ lln~ dl laocyanate, 4, 4 ' ~dipllenyl~ther di.lfiocyanAt~ ~nd a~lorodi~llenylen~ di.L~o~y~n~ste; the trii~ol~y~r~cltes such a~3 trlphenyl n~ot.hane~ ',4''-tr.Li~l~cy~nclte, 1,3,5-krll~oc~ydll~t~
~n7.ene an~l 2,4,6-t~:iiso~y~ te tolu~ne~ an~ tr~lsocyarltltfa Il f~4 - ) fl4 ' ~' ' :
~ 22-93l~ED12~ CO~ E~E~UTI~E TELI~O;~ 7~,-Z~ 2P~
2~7'~
s~lch a0 4,4'-diph~nyl dim~3thyl me~han~-2/2l~srs~-t~traisocyanatQ;
th~ polymeriz~d polyisooyanates such as tolylene dii~ocyanate dimers ~nd tr~m~rG, and o~.her variou~ p~lyl~ocyanat~ containing b~ur~ , ureth~n3, and/or allophan~te linkage~. The i~ocyall~t~s and th~ alcohol~. are typiaally r~acted at tan~peratures of 25C to abou~
l50C to form the hydroxy-funational polymers.
E~p~ially pr~rrod hydroxy-ful~ation~l ~at~riala in th~
r~r7~tlr~ n~ 1~h i q i nv~nt -i ~7n z~r~ m~n~--flln~t~ n;~ l r~hnl ,c: ~:tl~h ~.c tr~methylolp~opane dlallyl ether and allyl a].cohol; and diols and triQl~ such as e~hylene ~lycol, dipropylene glycol, 2,2,4-trimethyl 1,3-pentanediol, neopentyl glycol, 1,~-propanediol, 1,3-propanediol, 1,4-bu-tanediol, 1,3-butanediol~ 2,3-butanediol, 1,5-p~ntanediol, 1,6-hex~nediol, 2,2-~imethyl-1,3-prOpane~iOl, 1,4--cyclohexa7leclim~t.h~nol, 1, 2-eyclohexan~a~im~athanol, 1,3-~y~ ~x~ tl~ (2-lly~L~Lll~xy)~y~lull~
trimethylene glyool, t~tra mekhylene glycol, pen~a~ethylens gly~ol, hexamethylene gl~col, ~ecamethylene glyool, dle-thylane gly~ol, triethylenQ glycol, tetraethylene glycol, ~or~ornylene ~lycol, ~ bel~z~n~dim~thnnol, 1,4 -benz e n ~d~h~ h ~ 1, 2,4-dimothyl-~-cth~lonohcxanc-l,3-diol, 2-bu~n~-1,4-diol, and polyols such a~ trimethylolethane, trimeth~lolpropane, tri~eth~lolpropane monoallyl e~he~, trime~hylolhexahe~
triethylolpropane, 1~,4-but~n~riol, ~ly~erol, penta~ryth~it~l, dip~llta~rythri.tolJ and mixtur~s th~reo~.
~5 MOG~ pr~err~d ar~ trimethylolpropane ~lallyl ~t.her, propylQne ~l~ool, ~thylene ~lycol, dietllylene glycol, and mixtures thereo~.
, .
. , J~ ~Q-'q3 I,IEtl l2~a~ O~ EXE,-U`rlllF TEL ~`~0 2l6-'.C~ 2L~3 t11~122 Pla -It ~hould b~ ~pp~ci~ted tlla~ other alcohols ~hould be con3idsred equlv~lents o~ tho~e nam~d here:Ln.
b. E~urt~ eElc:tio~ of th~ Alooholy~ Protluct~
As discuss~d ~ ly abov~, the p~oduct of the alcuholysis reaction ls furthe~ ~eacted ko produce a polyester p~oduc~t u~eul ln a coating compo~ition. Sin~e the alcoholy3is reaction products ~re hyd~oxy-~unctional, they can be ~ur~her reacted with anhydrid~, aclds, fat:~ ac.ids and isocyan~tes including those taught h~low to produce exceptional coat.i"g compositlon~. By 10 controlling the level~ and amounts of x~actants, a~ d~ us ~d below, on8 can formula-t~ either high aoid value or low a~id value ~y ~ems rom the ~lcoholysis reaction produc-ts. The p~oducts of su~h ~action~ lnolude alkyd~ and pol~esters which can be ai~ or bake dried or Which can be furkher mixed, reaGted or tnodifled to 1~ r,reake di~per~ion~ o~ emul~ion polymers using the alkyd~ or polyesters as dispersing medi~ and acrylic modifiQd alXyds and poly~33tsrs .
Suit~ble ~cid-f~nctional ma-terials include mono-fun~tion~l ~ u~ e~ i a, c;rcJtc)~ l i~ a ~ a~ J~ vi-~y z~ ~n ~ld run~1-lur~ ty ~ v~r~ v~ two~ p~lt~
aaid, auccinic aoid, adipic acid, azelaic acid, maleic acid, ~umaria acid, trim~llitic acid, trime~ic acid, naphthal~ne ~;llO~lrll;)OXyllc ~lClQ~ arooxy~ n~ecl polyo~l~aalerle, ~enzopnenone tet.rn~nxboxyll~ cl1allhy~xide, ~ clicabclxy d1phelloXy e~hane, ~nd ~B tho hydroxy carboxylic acid~ of pi~al~one. oth~r ~itabl~ ~id~
include the sa~ur~d ac;id~ ~uch ~ b~tyric, capro~c, ¢~pryllc, ,'. :'.'' , .
.... J~ 20-'93 WED 12:~16 ID:CO~~EXECIJTIIJE TE L 1~l0:~15~ 66--21~l3 ~c2 Pi5 ~, J ~
~ pric, lauric, myristic, palmitic:, stearic, lZ-hydroxy~;te~ric, arachidic, behenic ~nd lignoceric acid~; the unsaturated acids sucll pal~itoleio, ol~i~, rlcinol~io, linc~lel~, linolehic, ~leo~te~ri~, licaric, gadoleic ahd Qra~ic acid~; and th~ oil~ tand thcir fatty acid~) ~uch a~ canola, rapes~ed, castor, dehydrated ca~tor, coconut, cof~e, corn, cottonse~d, fi~, lard, linseed, vticica, palm ~ernal, peanut, perilla, sa~lower, ~oya, ~un~lower, ~llow, tung, walnut, vernonia, tall and m~nhaden oil~ and blends and mixtures o~ natural ~nd synthetic oils ~nd fatty Acids, - 10 p~rtiaularly thoae oils and fatty acid~ with high iodir~e nun~er~.
P.epresentative anhydrid~s include, phthalic anhydride, 3-ni~rophthalic anhydride, ~-nitrophth~ anhydri~le, 3-flourophthalic e~l~hydrid~, 4 chlorophthalie ~nhydride, t~trachlo~ophthalic anhydric~e, tetra bro~nophth~lic anhydrlde, ~etr~ydroph~hall~ anhydride, hexahydro phthalic anhydride, ~e~hylhexahydrophthalic anhydride, ~UCCitliO an}lydride, dode~nylsuccinic anhydride, oc~ylsuccinic anhyd~id~, maleic anhydride, dichloromaleic anhydrid~, gl~lt~ic anhydrlde, adipic anhydridc, ohlorendic anhydrl.de, lt~conic anhydride, ~it~a¢orlic anhydride, endo~methylenetetrahydrophthalla anhyclride, c y c l o h e x a n e ~ a x b o x y l 1 ~ ~ n h y d r i d e , 4 - a y c 1 o h e xe n ~ ~ 1 , 2 -d i c a r b o x y l l c a n h y d r i d e , 4-~thyl-4-qy~loh~xen~-1,2 dicarboxylic anhydr.ide, b o r n e n Q - 2 , 3 - ~ i c ~ r b o x y 1 i c a n h y d r i d e , ~$ 1,4~ayclo}l~xacllene~ dica~b~xylic ~nhydride, -- Y~ WeL~ 4~ lU:UJII~ UI IV~ ItL ~U:~'lb--~t~
- ~ 3 g 7 .~ ~ ~
1~3~y~lopentan~dicar~oxyllc anhydrlde, diglycolio acid anhydride, and the lik~.
Other u~e~ul anhydrides include those anhydrides having A ~ree carboxyl ~roup ln a~ditio~ to the anhydride ~oup such as trimellitic anhydride, acon.itic anhydride, 2,6,7 naphthalene tricarboxylic anhydride, 1,2,4-butane tricarboxy~ic anllydride., 1,3,4-cyclopentane tricarboxylic anhydride, and the liX~.
It should be Apprec.i~t~d thnt other ~cid5 ~nd anhydrides ~hould be con~dered ec~ivalen~s of those named herein.
The aoid- ~ anhydride functional material will generally have a number average molecular we~ght below about 200V. Preferably ~h~.
aaid- or anhydride-~funa~ional nla-terlal will have ~ num~er average molecular weight o~ b~l ow abou~ 4 00. Typioal nu~ber aver~e molecular weight6 oP these materi~ls will ran~ f rom about 96 to about 400.
E~peoially preferred ~ids ah~ anhydrides include the vegetable ~atty acid~ de~c~lbed above and trimelletic anhdyride.
. High ~ Low Aaid vAlue ~ro~uat~ using the AlOoholysi~
Roaation Pro~u~ts ;,r~ A~ ~t~ed ~bD~e, th~ alcohol~sis re~ction products are ~urther rea¢ted with aaid or ~nhydride ~unctlonal mat~ial~ to produc~
either high or low acid vallle produot~. ~or purpo~ of the ~r~s~nt invention, the term "hi~h ac.icl value" i~ meant ~o be those r!~mp~sltion~ h~v1n~.7 ~old vr~lu~ c3rea~r ~h~n l~out 30. ~he ter~i "low acid val ~l~t~ is m~nt to be ~ a ~ompo~ ns haviny aai.~
lo~r than ~o~ ~0. C~mpo~ition~ h~ving acid values , .': " ' ' '.
Jh~ 20~ 3 l~JED IC':'18 Irl:~O~ E~;ECUTI~)E rEL 1~ 6-5f~ 2l'l3 t-l~lZ2 P17 batw~en about 20 ar~d a~out ~o tend to exhi}~ cl-~ract~ti~;~ic~: of both high and low acid valu~3 produat5 And, thu6, are not cat~gori~ed as ~it;her high acid valu~3 or low acid value, although it should be ~ppreciated thllt with some: tri~l and errcr such 5 co~apo~ltions may be acc~3pta~le itl eitl~er c~ateS~o~y.
As a guldeline, in order to for~nulat~e an alcoholysis reaction }~rn~lr~ l-n ~1 h;~h ~ r~ P nf h~ h~1~ n~l A)~ llt fi~;, thc.
~ollowing stoichiometric proportlons (in mole~; of e~uival~nt:s) of m~t~rlalE; ~hould be u~;ed. For ~ach mole of YET used, ~rom about 10 1. 1 t~ bout 1. 5 moles of OH should :l~e used in the alcoholysis reaotion, ~ollowed by furth~r reaction with about 1. O to about 1. ~
mole~3 of acid or anhydride. Preferably, the moles of OH to PET
should be abou~ 1.15:1 to ahout 1.3S:1 and the moles o~
acid/anhydride to P~T ~hould be abo~t 1. O :1 ~o about 1~10 :1 for 15 su~h hi~her acid value products.
In ordex t~ formulate an ~lcoholysis reaGtion produc~ ts: a low aaid value of less than ~bout 20, the following s1:oichlom~ric propor~lons (in moles of equivalents) of materials should be us~d.
~or ~3ach mole of PET used, l~rom about 1. O to abou~ 1. 35 mol~3s o~
20 OA ~:hould be used ln the alcoholysis reaction, vllot~red by further reac~tion witn about t~.~iO to about 0.75 moles o~ acid or anhydride.
Pr~laP~rably~ the moles of o~ t:o P~T should ~e about 1:1 to fl~OUt 1.2~:1 And the moles o~ acid/anhydridQ to PE'~ should be abo-lt 0.50~1 tn A~out 0.65:1.
~5 ~. Fln~l Co~tl~g Prclduata ' ~ , . ;
:
. J~ 2~ wE~ 12~ u~-Ex~ Jrl~lE rEL ~`io:2l6~5~;f~-zl'l3 ~1~2Z Pl8 The products of Sec~tion 2 . c. can b~ U~3d by themselve , in ccmbin~io~ ith oth~r w~:Ll known coatings aclditiv~s, includi.ng p1~ment~, flrw ~n~, c~ta1y~t~, Ai~ nts, ~h1v~nt~, u1tr~vio1et light ab~o~b~rs, and th~ 11k~, or can be. fu~ther mixecl, r~acted o~
modi~ied ~ de6cribed be10w~
The high acid va1ue produ~ts (that is, acid va1ues ~reater than about 30) of Se~tion 2.c., or such products in combin~tion with the above-described additive~, can ~ perBed o~ ~educed in ~ater once neutra1ized with a weak b~e solution such as a tertia~y amine in water. Neutra1ization techniques are well known in the co~tings art. In a pre~erred embodiment, the high acid value ~roducts of Section 2 . c. o~n be redu~ed in water and thereafter ~exv~ a~ the 6tabilizing media ~or the emu1sion po1ymeriz~tion oP
acrylic and other ethy~ enioa11y unsatu~ated monvmer~/ inc1~ding ~yl.ic ~dditioll mon~mers, o1i~ne~ a~ld polym~r~: parti~ula~ly o~
or more ~lkyl ~st~r~q ~f ~ryl1~ ~ nr m~hArryl~r ~r.i~-optiona11y to~ethe~ with ~ne or more other e~hy1enica11y un~3aturated monomers.
Suitable acxylic e~3ter~i lnclude methyl (meth~ ~cryl~te, ethyl 20 (Jneth)acrylate, propyl ~meth)acrylata, butyl (meth)acrylate, hydroxy ~thyl (m~th)acrylate, 2-ethyl hexyl (math)aaryl~te, ~crylonltrlle, a~ryla~lde, vlnyl poly~ers suoh a~ polymer~ oi'vinyl e~er6 of inorg~ni~ or o~g~ni~ acid~, includ~.rlq vlnyl chlori~le, vl~lyl ~oekat~, vinyl proplon~t~, vi.nyl tolu~ne, eka., ~tyren~., anc~
Z5 m~ xtu~ s thf3reoP .
, n ~,! m l . e q J I I I P P t . I E I: ~1 6 - 'i G 6 - 17 (~ 1 ), .3 ~ f (n-~
~ v ? 7 ~
E~ul~ic>rl pc)ly~n~:ri~,ltion r~actLon ccn~lt l(--n:~ are t~e] l kr)~ a in kh~ art al)d Call illClllCl~ ~he proced-lrc~: t:a~yl~t in O . S . E~dt~?~
4,116,903, incc~rpor~ted h~reln by r~ference a.<, wall ag thc proc~dur~:, t~ught in the ~xr~mplQs holow.
~Ill low acid value product~; (thAt is, acid value~; It~r~i th~ln ~bout 20i of ~uch ~sction~ or such pl'~llCt.~ itl ccmhination w.itl~ tile Dbove-ù~sc~ibe~ ~clditi~e~;, c,ln b~ r~d-lced in uolv~ t~i ~;ucll ~JS
xyl~ , tolue:)e, b~nzene, mine~al spirlts and the 1ilce. ~-~c):
prc~ducts c~n ~hot~ `oc allowe~l to air dry or ~orce(l to dry by bc~'cirlcJ
0 AS i~ wcll known in th~. art. ~ mino, ur ec~u.iv~l~l~t, agc!rl~:
wou~d pr~tc~ahly };e addcd to f,acili~dte ~ryincJ in th~d bake ~r~
~;y~ten~C;, In a prefer~e~l embodimetlt, thF~ w acid value product~:
of ~ectiol~ 2,c, can be dir.~ctly modified ~.ith e(cryl~c monomers, oliqomers all~ po:lyme~rs to pro~.ll.lce ~ir ~ry, ~ake and wat~r-~ducibl~
coatinys.
Sultabl~ ac~rylic monomer~ li.gom~rs an~l polym~r~ inc.l.~cle tho~:~ a~rylic, vinylic and ethylenically ~Ins~turat~d m~t~ric~
tau~ht to be ufi~ul with the high acld val~le pro~uct~i as wel]. as the acl-ylia acids thernse]ves such as acrylic acld"nt?.thacrylic acl~
2a and itacor-ic acid.
.[n an~ her E)referr~d embvd11n(!nt~ eit.h~r the high or the 1C-JW
aai(l va1uc products of Section 2.c. ~an be furt~leI m~ 'ied by d~ect flc~ryl i.c modieication. t)ir~ct acr~lic mv:llfl.ci.~ti.-JIl i5 typically c~nducted undor c:orl(litl~ns al~so well knt~wn in ~he ~rt, including th~ pr~ced~lr,3s t~u:~ht in V.s. Patent.~ 4,735,'J~5 and .
lB
,:
.. :
.7~ .JED 1~ 51 lC~CO~I E``'ECUrll-lE lEL ~`lr~ .~215-5~ '1 13 2 ti , ~,~73,2~1, inCorporated ~le~ein ~y reEerQnoe, a~ well ~s by the pro~dllr~s taught in the ~ nples below.
When acrylic modifyl~g the low aci~ value produc~, the 1ncorporatlon of A high level of aeid-~unc~ional acrylic materials S w111 enable th~ ~inal, acrylic-modi~ied Goating produc~ to be rsd-lcible ln water or other aqueou~ ~y6t~m~. Gene~lly, a~o~lnts o~ acid-~'unctional acr~lic material~ ~reater than about 1.0~ by welght of ~he total ~mo~nt o~ acrylic and ~other ethylenically un~aturated m~terials w111 res~lt in a coating ~omposition whicll i~ wate~ reducible. ~mounts less thah the above will generally r~sult in ~oating~ which are not water reducible.
~ he coatings o~ this inventiOn can also be blehded with other acrylic resins, alkyds, poly~ers and coatin~ resin sys~e~s.
~ he coatings of thi~ inv~ntion m~y ~ypic~lly be ~pplied to : 15 any substrat~ ~u~h a8 met~l, pla~tlc~ wood, ~nd qla~3~ by b~ushing~
dipping, roll coa~ing, flo~ coa~in~, spraying or other me~hod ~onventionally ~mplo~ed in the coating industry.
ReprQsentative opacifying pigmen~.inolu~e white pigment~ such a~ tlt~ium dloxide, zinc oxide, antimony oxlde, ~tc. and org~ic ~ inorganic chxom~ic pigmen~s suCII as iron oxide~ carbon black, phthalooyanine blue, etc. The coatingS may also oon-tain extender p~gment~ such as aalcium carbonate, clay, silic~, tala, ~tc.
~ he ~ollowing example9 have been ~elected to illustr~te ~cl~ic emhodiments and prac~ice~ o~ advant~g~ to a more comple~e u~der~kandllly ~ the invqntloll. Unle~s otherwise ~tate~, "parts"
~all8 part~ w~l~ht ~nd "percent" i~ pe~cen~.-by~weigh~.
20- 13 l`J~C! 1?:5~ ID:CQN-EXECUTIOE TEL. ~`lC1:216-~66-21'13 l~k~ P21 ~ ~ ~ 7 ~
r.~r~ur~Ly~:~c c~
~ h~gh c,c~ld ~c~ ., w~L.s.L Le~l~v.L~ . w acaordin~ to t~.he followin5:t procedur~:
A 3 l, ~ k~d round b~t;tom flA~k Qquippod with ~ nort gAG I
~nechanical st1rrer, 13arr~tt tubR and Frledrich I s ac~nden~;er was trlmetltylolpropane d i ~llyl ether, 5 . 3g o~ dibutyl tin vxi~e o~oly~t ~n~l 37~ ~tylcne. 5~hc ~l~t~nt2 wo~ ec~t~:~;l t~ ~ao~ Ql~
un~il all con~QTl~s had melted and ~ clear ~olution was obtained.
The solution was cooled to ~Z5F ~nd ~90. 4g o~ tri~elletie ~nhydride, 344.~g dehydrated ~a~tor oil fatty acid and 65.8g ~1J1~ U11 f~Ly ~lv wire ~dded. T~le con~ents were nea~ea ~o ~70F ~nd held for an aeid value o~ between 60-~5 and a vi5c05ity le~s than lo,QOOcp~ at 90~ i~ propylene gly~ol monop~opyl ether.
Ona~ r~ach~, heat waB removed and the contents allowed to cool.
rhe final resin product had an NVM of 89.~5/ a viscosity o~ 5300cps (u~ing Brook~ield LVT-~3, 12rpm), acid v~lue ~ 6~, Mz o~ 428~, Mw Qf 19~1, Mn of 103~ and Pd of 1.~7.
The resin was further reduced in w~ter by combining ~hP resin, wa~er and triethylamine in ~h~ following amounts:
65g o~ re~in 65g o~ water .lg o~ triethyla~nine.
~XAMPhE ~I: A~CO~IOLYSI~ OF PET
A high a~id ~lue, wat~r xeducible re~in w~ prepared ~cording to ~ho ~llowlny pxocedure:
2n .~, . , J~ 2~-'93 1.IED l? ~ cn~-ExEcur ll~!E rEL ~lO 216-'~66-21~ 2 P22 ( ,..3~7~ ~
A 31, 4~nec)ced round bottom ~ k e~uipped with ine.rt gas, m~chanical ~tirrer, Ba~rett t~be ~nd Friedrich~S c~ndenser w~
charged with 54~.~g o~ polyethylen~ tereph~halate, 735.3g of trimethylolpropane diallyl ether, 5.3g o~ di~utyl tin oxide ue~t~lyo t ;~nd 55g xylene. ~ cc~ntent~3 were l~ e~ 4 60F ~r~d h~ld until all cont~nt~ had melted and a clear sOlu~ion wa~ obtained.
The solution wa~ aooled to 325F and 290.0g o~ ~imelletic anhydride a~d 409. 5g o hlgh content linolaic fatty acid ~Prifac 8~60) were add~d. The con~bhts were h~at~d to 470F and held for an a~id ~lue o~ ~etween 80-B5. Once r~a~h~d, he~t was rehloved and the content~
wed to cool. ~h~ final re~in product had an NvM of ~5.25, a ~is~osity o~ 18, ~OOCp5 (~sing ~rook~ield LVT#3, lZrpm), aci~ value of B2, MZ o~ 36~9, Mw of 1643, Mn Of 919 ~nd Pd Of 1.79.
EXA~PL~ ALC~HOLYS~S OF P~T
A low aci~ value r~sin wa~ prepared acc~rding tQ th~ following pro~edure:
A 31, 4~necked round bott~m flask eg~lipped with inert gas, me~h~nical ~tirrer, Barrett tube and Friedrich's conden~7er was oh:~rgod w~ ~h 1016 . 7~ o~ poly~thylen~ t~:;L~ tl~ , 414 . 0~ lL
ao prDp~ene gly~ol, sog o~ tlllnethylol~ ne diallyl ether, 5. sg o1 dibutyl t:in c~xide cataly~t and 4 Og xylene . The con~ents were h~ted to 4GOF an~ held until all c~ntqn-t~ h~d melt~d and a clear Yolution wa~; obtained. The ~olutlon w~ c:~ol~fl to 325F ~nd 59. og trim~lleti~ ~nhydr.lLde wa~ added. Th~ nterlt~ Wel'~ heated to ~b 470F ~nd held ~or nn ac:id ~alue of l~ han lO. Once reac:lled, h~a~ w~ r~moved und th~ contnn-t~ ~llow~d t:o cool. T~le ~inal resin .. . . . . .
. . .
J~r~ 1'.5'~ I~'.CC~ ccur~ TC~ ~10.'11~ 5C~ '3'~ 3~
h `~ u 7 ~
product had an NVM of ~9.5, ~ v j~oo~i-ty gr~t~r than ~O,OOOcps (u~ng Brookfield LV'~3, 12rpm), acid valu~ of 4.1~ Mz o~ 218~, Mw of 134~, Mn o~ 84~ ~nd Pd of 1.5~.
I3XAMP~E IV; DIRECT P~CRYLI~ MuU~ A~ C)N
dOOg of the r~Eiin of Example III ~ncl 150g of Propasol (propylene glycol monobutyl ether~ ~era charged te a re~c~ion ve~el and h~ated to ~hn~ n~. Arl~ o th~ co~. o-~r ~ ~, 5 hour pe~iod wa6 ~B6g o~ lneth~l methacrylate, 43y of methacrylic acid, 2~g o~ ~tyrene, sog o~ ethyl hexyl ~rylat~. A secon~ fecd lO o~ 9g o~ t-~utyl perben~oate an~ lOOg of Propasol was added over thQ ~ame time period. Upon complete addition of both ~eed~, a ~h~e of 1. ~g t-butyl per~en~o~te in ~Og o~ Propasol was add~d over a ~.5 hour tim~ pe~iod. Heat was removed and the cont~n~s o~ th~
Yessel ~ilterad.
15 E~AMPLE V: AIR DRY COATI~G FORMULA
. A resin prepared according to ~he pro~edure of Exampl~ I can be ~ormulated to a high solids, ~ol~ent~ba~ed air dry ~oating having NV~ of ~0.55, VoC less t~an 250 g/l as ~ollow~:
Ih a hi~h speed dl~per~er, grtnd:
4~2.6g ReR~n of Ex~ple I
47 . 5 A~o~atio Naph~ha - 7 . 7 Soya I~cithin 202 .~ R~t1le tit~nium dioxi~e Run on high ~or 15 Dinu~s 25 Add 203.9 RQsin o~ Example I
1~.3 ~omatic Maphtha 1~2 1296 Cobalt Catal~t 29 . 5 1~ alc:ium Drier 2.1 Me~h~l ethyl ket~xi~nQ
30 ~1.9 ~roma~ia Napht~la O~S ~e~o~m~r (Byk 0.~2) ~X~MP~E: ~X ~ I~A~E I~Y ENAM~ ~MUhA
~2 : ... : , ,. : .
, . ' ', ~q~.~J~N-20-'93 WED 12:55 . iD:CON EXECUTI~)E TEl NO:Z 16-566 .?.~ 02? P24, . ~.. .
~387~1~
f, A re~3in p~epe~d according to th~3 procedure o~ Example III can b~ formulated ~o a balce dry cs~ating ~aving PVC l~ ~ 5, NVM 80. 9 .
w~ight par gallon 11. 8 lhs/~al an~ ~oC Or 2 . 2~ lb~ al as ~ollows:
'r n ~ h ~ ~h o r~ ~ ~ ;L O p ~ J W l J ly .
S . 17g. lg ~sin of Example I~I
24 ~ O Prnr.a.snl P
423l ~u~ itanillm Run to 7H ~e~an Grinc~) ~:tabll~ze l~0. V Propaso:l P
10 Thindown 241. 5 R~in o~ Exampl,e I~I
13Z. 7 Melamine 80. 2 PropasC~l P
.
- ~. ` .:, . .
, ~3
Claims (17)
1. A non-aqueous coating composition comprising the reaction product of:
a. polyethylene terephthalate with an alcohol in the presence of a catalyst;
b. followed by the reaction of the product of step a with a member of the group consisting of acid- and anhydride-functional materials;
wherein the resultant composition has an acid value less than about 15.
a. polyethylene terephthalate with an alcohol in the presence of a catalyst;
b. followed by the reaction of the product of step a with a member of the group consisting of acid- and anhydride-functional materials;
wherein the resultant composition has an acid value less than about 15.
2. The coating composition of Claim 1 wherein the alcohol is selected from the group consisting of mono-functional alcohols, diols and triols having number average molocular weights or below about 4000.
3. The coating composition of Claim 2 wherein the alcohol is selected from the group consisting of:
a. the C1-C22 linear and branched saturated and unsaturated alcohols including methanol, ethanol, propanol, butanol, hexanol, linoleyl alcohol, trimethylolpropane diallyl ether, allyl alcohol, 2-mercapto ethanol and mixtures thereof, b. saturated and unsaturated polyols including glycerol, castor oil, ethylene glycol, dipropylene glycol, 2,2,4-trimethyl 1,3-pentanediol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1 , 3 - c y c l o h e x a n e d i m e t h a n o l , 1,4-bis(2-hydroxyethoxy)cyclohexane, trimethylene glycol, tetra methylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, norbornylene glycol, 1,4-benezenedimethanol, 1 , 4 - b e n z e n e d i e t h a n o l , 2,4-diemthyl-2-ethylenehexane-1,3-diol, 2-butene-1,4-diol, and polyols such as trimethylolethane, trimethylolpropane, trimothylolpropane monoallyl ether, trimethylolhexane, triothylolpropane, 1,2,4-butanetriol, glycerol, pentaerythritol, dipentaerythritol, and mixtures thereof;
c) Polyether polyols prepared by the reaction of a diol or polyol with an alkylene oxide, including polypropylene ether glycols and polyethylene ether glycols;
d) polyesters prepared by the condensation of polyhydric alcohols and polycarboxylic acids or anhydrides, wtih or without the inclusion of drying oil, semi-drying oil, or non-drying oil fatty acids while maintaining an excess of hydroxyl groups;
e) hydroxy-functional polymers prepared by the ring opening reaction of epoxides and/or polyepoxides with primary or, preferably, secondary amines or polyamines;
f) hydroxy-functional urethane polymers prepared by the reaction of an excess of at least one alcohol with isocyanates.
a. the C1-C22 linear and branched saturated and unsaturated alcohols including methanol, ethanol, propanol, butanol, hexanol, linoleyl alcohol, trimethylolpropane diallyl ether, allyl alcohol, 2-mercapto ethanol and mixtures thereof, b. saturated and unsaturated polyols including glycerol, castor oil, ethylene glycol, dipropylene glycol, 2,2,4-trimethyl 1,3-pentanediol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1 , 3 - c y c l o h e x a n e d i m e t h a n o l , 1,4-bis(2-hydroxyethoxy)cyclohexane, trimethylene glycol, tetra methylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, norbornylene glycol, 1,4-benezenedimethanol, 1 , 4 - b e n z e n e d i e t h a n o l , 2,4-diemthyl-2-ethylenehexane-1,3-diol, 2-butene-1,4-diol, and polyols such as trimethylolethane, trimethylolpropane, trimothylolpropane monoallyl ether, trimethylolhexane, triothylolpropane, 1,2,4-butanetriol, glycerol, pentaerythritol, dipentaerythritol, and mixtures thereof;
c) Polyether polyols prepared by the reaction of a diol or polyol with an alkylene oxide, including polypropylene ether glycols and polyethylene ether glycols;
d) polyesters prepared by the condensation of polyhydric alcohols and polycarboxylic acids or anhydrides, wtih or without the inclusion of drying oil, semi-drying oil, or non-drying oil fatty acids while maintaining an excess of hydroxyl groups;
e) hydroxy-functional polymers prepared by the ring opening reaction of epoxides and/or polyepoxides with primary or, preferably, secondary amines or polyamines;
f) hydroxy-functional urethane polymers prepared by the reaction of an excess of at least one alcohol with isocyanates.
4. The coating composition of Claim 2 wherein for each mole of polyethylene terephthalate, from about 1.0 to about 1.35 moles of hydroxy functionality and from about 0.50 to about 0.75 moles of acid/anhydride functionality are present.
5. The coating composition of Claim 3 wherein the alcohol is selected from the group consisting of mono-functional alcohols including trimethylolpropane diallyl ether and allyl alcohol, diols and triols including ethylene glycol, dipropylene glycol, 2,2,4-trimethyl 1,3-pentanediol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1 , 3 - c y c l o h e x a e d i m e t h a n o l , 1,4,-bis(2-hydroxyethoxy)cyclohexane, trimethylene glycol, tetra methylene glycol, pentamethylene glycol, hexamethylene glycol, tetraethylene glycol, norbornylene glycol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 2,4-dimethyl-2-ethylenehexane-1,3-diol, 2-butene-1,4-diol, and polyols such as trimethylolethane, trimethylolpropane, trimethylolpropane moncallyl ether, trimethylolhexane, triethylolpropane, 1,2,4-butanetriol, glycerol, pentaerythritol, dipentaerythritol; and mixtures thereof.
6. The coating composition of Claim 5 wherein the alcohol is selected from the group consisting trimethylolpropane diallyl other, propylene glycol, ehylene glycol, diethylene glycol, and mixtures thereof.
7. The coating composition of Claim 1 wherein the acid- and anhydride-functional materials are selected from the group consisting of mono-functional acids, including berzoic, crotonic and sorbic acids; acids having an acrid functionality on average of at least two, including phthalic acid, succinic acid, adipic acid, azelaic acid, maleic acid, fumaric acid, trimellitic acid, trimesic acid, naphthalene dicarboxylic acids, carboxylic acids of piralactone; saturated acids, tetracarboxylic dianhydride, 4,4'-dicarboxy diphenoxy ethane, hydroxy carboxylic acids of piralactone; saturated acids, including butyric, caproic, caprylic, capric, lauric, myristic, palmitic, stearic, 12-hydroxystearic, arachidic, behenic and lignoceric acids; unsaturated acids, including palmitoleic, oleic, ricinoleic, linoleic, linolenic, eleostearic, licaric, gadoleic and eracic acids; oils (and their fatty acids) including canola, rapeseed, castor, dehydrated castor, coconut, coffee, corn, cottonseed, fish, lard, linseed, oticica, palm kernal, peanut, perilla, safflower, soya, sunflower, tallow, tung, walnut, vernonia, tall and menhaden oils; blends and mixtures of natural and synthetic oils and fatty acids, particularly oils and fatty acids with high iodine numbers; anhydrides, including, phthalic anhydride, 3-nitrophthalio anhydride, 4-nitrophthalic anhydride, 3-flourophthalic anhydride, 4-chlorophthalic anhydride, tetrachlorophthalic anhydride, tetra bromophthalic anhydride, tetrahgydrophthalic anhydride, hexahydro phthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, dodecenylsuccinic anhydride, octylsuccinic anhydride, maleic anhydride, dichloromaelic anhydride, glutaric anhydride, adipic anhydride, chlorendic anhydride, itaconic anhydride, citraconic anhydride, endo-methylenetetrahydrophthalic anhydride, cyclohexane-1,2-dicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 1,4-cyclohexadiene-1,2-dicarboxylic anhydride, 1,3-cyclopentanedicarboxylic anhydride, diglycolic acid anhydride; anhydrides having a free carboxyl group in addition to the anhydride group, including trimellitic anhydride, aconitic anhydride, 2,6,7-naphthalene tricarboxylic anhydride, 1,2,4-butane tricarboxylic anhydride, 1,3,4-cyclopentane tricarboxylic anhydride; and mixtures thereof.
8. The coating composition of Claim 7 wherein the acid- and anhydride-functional materials are selected from the group consisting of the vegetable fatty acids of Claim 7 and trimelletic anhydride.
9. A coating composition comprising:
a. the reaction product of polyethylene terephthalate with an alcohol in the presence of a catalyst;
b. wherein the composition of step a is further reacted with a member of the group consisting of acid- and anhydride-functional materials to produce a composition having an acid value less than about 15;
c. wherein acrylic and other ethylenically unsaturated monomers are subsequently polymerized in the presence of the composition of step c.
a. the reaction product of polyethylene terephthalate with an alcohol in the presence of a catalyst;
b. wherein the composition of step a is further reacted with a member of the group consisting of acid- and anhydride-functional materials to produce a composition having an acid value less than about 15;
c. wherein acrylic and other ethylenically unsaturated monomers are subsequently polymerized in the presence of the composition of step c.
10. The coating composition of Claim 9 wherein the alcohol is selected from the group consisting of mono-functional alcohols, diols, and triols having number average molecular weights of below about 4000.
11. The coating composition of Claim 10 wherein the alcohol is selected from the group consisting of:
a) the C1-C22 linear and branched saturated and unsaturated alcohols including methanol, ethanol, propanol, butanol, hexanol, linoleyl alcohol, trimethylolpropane diallyl ether, allyl alcohol and mixtures thereof, b) saturated and unsaturated polyols including glycerol, castor oil, ethylene glycol, dipropylene glycol, 2,2,4-trimethyl 1,3-pentanediol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1 , 3 - c y c l o h e x a n e d i m e t h a n o l , 1,4-bis(2-hydroxyethoxy)cyclohexane, trimethylene glycol, tetra methylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, norbornylene glycol, 1,4-benzenedimethanol, 1 , 4 - b e n z e n e d i e t h a n o l , 2,4-dimethyl-2-ethylenehexane-1,3-diol, 2-butene-1,4-diol, and polyols such as trimethylolethane, trimethylolpropane, trimethylolpropane monoallyl ether, trimethylolhexane, triethylolpropane, 1,2,4-butanetriol, glycerol, pentaerythritol, dipentaerythritol, and mixtures thereof;
c) Polyether polyols prepared by the reaction of a diol or polyol with an alkylene oxide, including polypropylene ether glycols and polyethylene ether glycols;
d) polyesters prepared by the condinsation of polyhydric alcohols and polycarboxylic acids or anhydrides, with or without the inclusion of drying oil, semi-dryadding oil, or non-drying oil fatty acids while maintaining an excess of hydroxyl groups;
e) hydroxy-functional polymers can be prepared be the ring opening reaction of epoxides and/or polyepoxides with primary or, preferably, secondary amines or polyamines;
f) hydroxy-functional urethane polymers prepared by the reaction of an excess of at least one alcohol with isocyanates.
a) the C1-C22 linear and branched saturated and unsaturated alcohols including methanol, ethanol, propanol, butanol, hexanol, linoleyl alcohol, trimethylolpropane diallyl ether, allyl alcohol and mixtures thereof, b) saturated and unsaturated polyols including glycerol, castor oil, ethylene glycol, dipropylene glycol, 2,2,4-trimethyl 1,3-pentanediol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1 , 3 - c y c l o h e x a n e d i m e t h a n o l , 1,4-bis(2-hydroxyethoxy)cyclohexane, trimethylene glycol, tetra methylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, norbornylene glycol, 1,4-benzenedimethanol, 1 , 4 - b e n z e n e d i e t h a n o l , 2,4-dimethyl-2-ethylenehexane-1,3-diol, 2-butene-1,4-diol, and polyols such as trimethylolethane, trimethylolpropane, trimethylolpropane monoallyl ether, trimethylolhexane, triethylolpropane, 1,2,4-butanetriol, glycerol, pentaerythritol, dipentaerythritol, and mixtures thereof;
c) Polyether polyols prepared by the reaction of a diol or polyol with an alkylene oxide, including polypropylene ether glycols and polyethylene ether glycols;
d) polyesters prepared by the condinsation of polyhydric alcohols and polycarboxylic acids or anhydrides, with or without the inclusion of drying oil, semi-dryadding oil, or non-drying oil fatty acids while maintaining an excess of hydroxyl groups;
e) hydroxy-functional polymers can be prepared be the ring opening reaction of epoxides and/or polyepoxides with primary or, preferably, secondary amines or polyamines;
f) hydroxy-functional urethane polymers prepared by the reaction of an excess of at least one alcohol with isocyanates.
12. The coating composition of Claim 11 wherein for each mole of polyethylene terephthalate, from about 1.0 to about 1.35 moles of hydroxy functionality and from about 0.50 to about 0.75 moles of acid/anhydride functionality are present.
13. The coating composition of Claim 12 wherein the alcohol is selected from the group consisting of mono-functional alcohols including trimethylolpropane diallyl ether and allyl alcohol;
diols and triols including ethylene glycol, dipropylene glycol, 2,2,4-trimethyl 1,3-pentanediol, neopentyl glycol, 1,2-propane diol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1 , 3 - c y c l o h e x a n e d i m e t h a n o l , 1,4-bis(2-hydroxyethoxy)cyclohexane, trimethylene glycol, tetra methylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, norbornylene glycol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 2,4-dimethyl-2-ethylenehexane-1,3-diol, 2-butene-1,4-diol, and polyols such as trimethylolethane, trimethylolpropane, trimethylolpropane monoallyl ether, trimethylolhexane, triethylolpropane, 1,2,4-butanetriol, glycerol, pentaerythritol, dipentaerythritol; and mixtures thereof.
diols and triols including ethylene glycol, dipropylene glycol, 2,2,4-trimethyl 1,3-pentanediol, neopentyl glycol, 1,2-propane diol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1 , 3 - c y c l o h e x a n e d i m e t h a n o l , 1,4-bis(2-hydroxyethoxy)cyclohexane, trimethylene glycol, tetra methylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, norbornylene glycol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 2,4-dimethyl-2-ethylenehexane-1,3-diol, 2-butene-1,4-diol, and polyols such as trimethylolethane, trimethylolpropane, trimethylolpropane monoallyl ether, trimethylolhexane, triethylolpropane, 1,2,4-butanetriol, glycerol, pentaerythritol, dipentaerythritol; and mixtures thereof.
14. The coating composition of Claim 13 wherein the alcohol is selected from the group consisting trimethylolpropane diallyl ehter, propylene glycol, ethylene glycol, diethylene glycol, and mixtures thereof.
15. The coating composition of Claim 9 wherein the acid- and anhydride-functional materials are selected from the group consisting of mono-functional acids, including benzoic, ocrotonic and sorbic acids; acids having an acid functionality on average of at least two, including phthalic acid, succinic acid, adipic acid, azelaic acid, maleic acid, fumaric acid, trimellitic acid, trimesic acid, naphthalene dicarboxylic tetracarboxylic dianhydride, 4,4'-dicarboxy diphenoxy ethane, hydroxy carboxylic acids of piralactone; saturated acids, including butyric, caproic, caprylic, capric, lauric, myristic, palmitic, stearic, 12-hydroxystearic, arachidic, behenic and lignoceric acids; unsaturated acids, including palmitoleic, oleic, ricinoleic, linoleic, linolenic, cleostearic, licaric, gadoleic and eracic acids; oils (and their fatty acids) including canola, rapeseed, castor, dehydrated castor, coconut, coffee, corn, cottonseed, fish, lard, linseed, oticica, palm, kernal, peanut, perilla, safflower, soya, sunflower, tallow, tung, walnut, vernonia, tall and menhaden oils; blends and mixtures of natural and synthetic oils and fatty acids, particularly oils and fatty acids having high iodine numbers; anhydrides, including, phthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, 3-fluorophthalic anhydride, 4-chlorophthalic anhydride, tetrachlorophthalic anhydride, tetra bromophthalic anhydride, tetrahydrophthalic anhydride, hexahydro phthalic anhydride, methylhexahydrophthalic anhydride, hexahydro phthalic anhydride dodecenylsuccinic anhydride, octylsuccinic anhydride, maleic anhydride, dichloromaleic anhydride, glutaric anhydride, adipic anhydride, chlorendic anhydride, itaconic anhydride, citraconic anhydride, endo-methylenetetrahydrophthalic anhydride, cyclohexane-1,2-dicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 1,4-cyclohexadiene-1,2-dicarboxylic anhydride, 1,3-cyclopentanedicarboxylic anhydride, diglycolic acid anhydride; anhydrides having a free carboxyl group in addition to the anhydride group, including trimellitic anhydride, aconitic anhydride, 2,6,7-naphthalene tricarboxylic anhydride, 1,2,4-butane tricarboxylic anhydride, 1,3,4-cyclopentane tricarboxylic anhydride; and mixtures thereof.
16. The coating composition of Claim 15 wherein the acid- and anhydride-functional materials are selected from the group consisting of the vegetable fatty acids of Claim 15 and trimelletic anhydride.
17. The coating composition of Claim 9 wherein the acrylic and other ethylenically unsaturated monomers are selected from the group consisting of acrylic esters, including methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hydroxy ethyl (meth)acrylate, and 2-ethyl hexyl (meth)acrylate; acrylonitrile; acrylamide;
vinyl esters of inorganic or organic acids, including vinyl chloride, vinyl acetate, vinyl propionate, vinyl toluene; styrene; acrylic acids, including acrylic acid, methacrylic acid and itaconic acid; and mixtures thereof.
vinyl esters of inorganic or organic acids, including vinyl chloride, vinyl acetate, vinyl propionate, vinyl toluene; styrene; acrylic acids, including acrylic acid, methacrylic acid and itaconic acid; and mixtures thereof.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82466592A | 1992-01-23 | 1992-01-23 | |
| US07/824,665 | 1992-01-23 | ||
| JP3784792A JP3293646B2 (en) | 1992-01-23 | 1992-02-25 | New non-aqueous dispersion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2087914A1 true CA2087914A1 (en) | 1993-07-24 |
Family
ID=26377001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2087914 Abandoned CA2087914A1 (en) | 1992-01-23 | 1993-01-22 | Non-aqueous coating compositions from polyethylene terephthalate |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0558906A1 (en) |
| JP (2) | JP3293646B2 (en) |
| CA (1) | CA2087914A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6534624B2 (en) | 2000-02-23 | 2003-03-18 | Kansai Paint Co., Ltd. | Process for producing alkyd resins |
| US6686399B1 (en) | 1999-10-07 | 2004-02-03 | Kansai Paint Co., Ltd. | Process for producing alkyd resin |
| US6803389B2 (en) | 2000-09-06 | 2004-10-12 | Kansai Paint Co., Ltd. | Process for producing polyester resin |
| US6887909B2 (en) | 2001-03-30 | 2005-05-03 | Kansai Paint Co., Ltd. | Processes for producing aqueous alkyd resin dispersions |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5858551A (en) * | 1997-01-31 | 1999-01-12 | Seydel Research, Inc. | Water dispersible/redispersible hydrophobic polyester resins and their application in coatings |
| US8476364B2 (en) * | 2007-03-29 | 2013-07-02 | Beaulieu Group, Llc | Polymer manufacturing process |
| JP5826988B2 (en) * | 2009-10-02 | 2015-12-02 | 太陽ホールディングス株式会社 | Curable resin composition |
| JP5656533B2 (en) * | 2010-09-28 | 2015-01-21 | 大日本塗料株式会社 | Resin composition for paint |
| CN105358607B (en) * | 2013-07-10 | 2019-01-11 | 哈利玛化成株式会社 | The manufacturing method of the alkyd modified silicone acrylic copolymer of oxidative cure type |
| PL3099726T3 (en) | 2014-01-27 | 2020-09-21 | Swimc Llc | Water-reducible coating composition |
| US10450410B2 (en) * | 2014-04-23 | 2019-10-22 | Sun Chemical Corporation | Process for preparing polyester resins from polyethylene terephthalate and energy curable coating compositions |
| WO2019079597A1 (en) | 2017-10-18 | 2019-04-25 | Talaco Holdings, LLC | Aromatic polyester polyether polyols derived from polyethylene terephthalates, polyurethanes made therefrom and useful materials comprising same |
| US11578165B2 (en) | 2019-01-21 | 2023-02-14 | Talaco Holdings, LLC | Methods of making foams exhibiting desired properties from aromatic polyester polyether polyols derived from polyethylene terephthalates and foams made therefrom |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1669104A1 (en) * | 1967-07-08 | 1969-10-30 | Albert Ag Chem Werke | Process for the production of stoving enamels |
| DE1923922A1 (en) * | 1969-05-10 | 1970-11-19 | Reichhold Albert Chemie Ag | Process for the multi-stage production of curable fatty acid-modified polyester resins based on terephthalic acid esters and telomerizates |
| BE791281A (en) * | 1971-11-12 | 1973-03-01 | Jaeger Fabrik Chem Ernst | METHOD FOR MANUFACTURING A COATING AGENT |
| JPS5323876B2 (en) * | 1973-03-22 | 1978-07-17 | ||
| US4873281A (en) * | 1987-09-29 | 1989-10-10 | Ppg Industries, Inc. | Stable water-solubilized polyester/acrylic resins made utilizing hydrocarbon waxes and low acid value polyesters |
-
1992
- 1992-02-25 JP JP3784792A patent/JP3293646B2/en not_active Expired - Fee Related
-
1993
- 1993-01-22 EP EP19930100991 patent/EP0558906A1/en not_active Withdrawn
- 1993-01-22 CA CA 2087914 patent/CA2087914A1/en not_active Abandoned
- 1993-01-25 JP JP4430293A patent/JPH069923A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6686399B1 (en) | 1999-10-07 | 2004-02-03 | Kansai Paint Co., Ltd. | Process for producing alkyd resin |
| US6534624B2 (en) | 2000-02-23 | 2003-03-18 | Kansai Paint Co., Ltd. | Process for producing alkyd resins |
| US6803389B2 (en) | 2000-09-06 | 2004-10-12 | Kansai Paint Co., Ltd. | Process for producing polyester resin |
| US6887909B2 (en) | 2001-03-30 | 2005-05-03 | Kansai Paint Co., Ltd. | Processes for producing aqueous alkyd resin dispersions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05279408A (en) | 1993-10-26 |
| JP3293646B2 (en) | 2002-06-17 |
| JPH069923A (en) | 1994-01-18 |
| EP0558906A1 (en) | 1993-09-08 |
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