Synthesis and Characterizations of Reactive Diluents for Polyamidoamine with improved Glass Transition Temperature (Tg) at am ient temperature

Dr! "ipin Shu#la* and $shwin D! %ethwa Atul Ltd. (Polymer-Division) Dist. Valsad, Gujrat (INDIA)

ABSTRACT
T e !resent "or# relates to synt esis and $ ara$teri%ation o& diluent &or e!o'y $uratives, in !arti$ular, rea$tive diluents &or &atty !olyamidoamine ardeners. T e i( vis$osity o& !olyamidoamine e!o'y ardeners re)uires t e use o& a vis$osity redu$in( additive to lo"er t e vis$osity o& $urin( a(ent and allo" more $onvenient !ro$essin(. T e need &or a rea$tive diluent &or i( vis$osity e!o'y $uratives is !rimarily t e result o& ne" and anti$i!ated (overnment re(ulations &or environmentally sa&e !rodu$ts and lo"er emissions. T us, t e e!o'y industry is in need o& a rea$tive diluent &or &atty !olyamidoamine ardeners " i$ "ill redu$e vis$osity, minimi%in( or eliminatin( t e use o& materials " i$ $ontri*ute to volatile or(ani$ $ontent (V+,) level in an e!o'y $oatin( &ormulation. -aterials " i$ $ontri*ute to V+,s are !rimarily nonrea$tive solvents. T ey are $urrently used to o*tain t e a!!ro!riate &ormulation vis$osity &or !aint and $oatin( a!!li$ations. T e rea$tive diluents o& t e "or# are t e amide and.or imida%oline rea$tion !rodu$ts o& lo" mole$ular "ei( t $ar*o'yli$ a$ids and !olyal#ylene!olyamines (or !olyal#yleneamines).T e rea$tive diluents are !re!ared *y $ondensation rea$tion o& t e $ar*o'yli$ a$id and t e !olyal#yleneamine at elevated tem!erature (eneratin( a mi'ture o& unrea$ted !olyal#yleneamine, amides and.or imida%olines. T e rea$tive diluents rea$tion !rodu$ts are used to redu$e t e vis$osity o& i( vis$osity !olyamidoamines. Also dis$losed t at i& "e are usin( t ese $uratives as sole $urin( a(ent "it e!o'y resin (DG/0A), it (ives i( er T( at am*ient tem!erature.

*Corresponding $uthor& 123-2456788585, vi!in9s

u#la:atul.$o.in ;

vi!in93<<<:redi&&mail.$om

'(TR)D*CT')( T e i( vis$osity o& !olyamidoamine e!o'y ardeners re)uires t e use o& a

vis$osity redu$in( additive to lo"er t e $urative vis$osity and !ermit more $onvenient !ro$essin(. T e need &or rea$tive diluents &or i( vis$osity e!o'y $uratives is !rimarily t e result o& ne" and anti$i!ated (overnment re(ulations &or environmentally sa&e !rodu$ts and lo"er emissions. T us, t e e!o'y industry is in need o& rea$tive diluents &or &atty !olyamidoamine ardeners " i$ "ill redu$e vis$osity, minimi%in( or eliminatin( t e use o& materials " i$ $ontri*ute to volatile or(ani$ $ontent (V+,) level in an e!o'y $oatin( &ormulation (Ashcroft, W.R.; 1993). -aterials " i$ $ontri*ute to V+,s are !rimarily non-rea$tive solvents. T ey are $urrently used to o*tain t e a!!ro!riate &ormulation vis$osity &or !aint and $oatin( a!!li$ations (Wilson, A.F.; (1988). Vis$osity redu$in( additives ave involved t e addition o& lo"er vis$osity !olyet ylene amines su$ as triet ylenetetramine (T/TA) or amidoamines (t e rea$tion !rodu$t !olyet ylene amines and mono*asi$ &atty a$ids), or a nonrea$tive !lasti$i%er su$ as ! t alate esters or *en%yl al$o ol, and.or non-rea$tive diluents su$ as tertiary amines, aromati$ et.al.; 1999). T e vis$osity o& t e entire e!o'y &ormulation is sometimes redu$ed *y addin( ali! ati$ (ly$idyl et ers, ydro$ar*on resins or a$rylates to t e resin side. =u$ additives are used to redu$e t e vis$osity o& t e ardener or resin, and t e entire e!o'y &ormulation *ut at t e $ost o& dry time, and.or at t e $ost o& >V sta*ility, and ty!i$ally at i( er system $ost. 0el(ian Patent 884,4<7 (3286) des$ri*es t e synt esis o& 3-aminoal#yl-<-al#yl-<-imida%oline *y t e rea$tion o& nitriles and !olyamines at elevated tem!erature under !ressure A$$ordin( to t e !atent t e !rodu$ts are suita*le as !olye!o'y ardeners. ?o"ever, in $ontrast, t e ,A a*stra$t (,A 86-6786d) states t e !rodu$ts are !lasti$i%ers &or !olye!o'ides (Adrlen, G.H.; 1981). ydro$ar*ons or al$o ols (Zeno Wicks,

<

T e !resent "or# !rovides rea$tive diluents &or !olyamidoamine e!o'y $urin( a(ents, or

i(

vis$osity (@3AAA $!s)

ardeners, a !ro$ess &or !re!arin( t e !rodu$ts o& lo" a$id, as and < su$

rea$tive diluents and $om!ositions em!loyin( t e rea$tive diluents. T e rea$tive diluents are t e amide and.or imida%oline rea$tion mole$ular "ei( t $ar*o'yli$ (or a$ids, su$ as !olyal#yleneamines #encl!d, F.; 19$8). T e rea$tive diluents are !re!ared *y $ondensation rea$tion o& t e $ar*o'yli$ a$id and t e !olyal#yleneamine at elevated tem!erature (eneratin( a mi'ture o& unrea$ted !olyal#yleneamine, amides and.or 8A imida%olines. T e rea$tive diluents rea$tion !rodu$ts are used to redu$e t e vis$osity o& i( vis$osity !olyamidoamines !re!ared &rom a &atty dimer a$id, a mono*asi$ &atty a$id and a !olyal#yleneamine, su$ as t e dimer a$id o& tall oil &atty a$id, tall oil &atty a$id and T/TA (#oe%,&.#.; 19$8). T us, anot er em*odiment o& t is "or# is an e!o'y $urative $om!osition $om!risin( t e rea$tive diluent rea$tion !rodu$t and a !olyamidoamine $urin( a(ent. Bet anot er !i$ture o& t e "or# is an e!o'y $om!osition $om!risin( t e e!o'y $urative $om!osition o& a &atty !olyamidoamine $urin( a(ent and an e!o'y resin, su$ as t e di(ly$idyl et er o& *is! enol A, redu$ed in vis$osity *y t e addition o& t e rea$tive diluent !rodu$t. T e rea$tive diluent &or vis$osity amine i( ardeners a$$ordin( to t e invention !rovides a means to !olyal#ylene !olyamines), a$eti$

aminoet yl!i!era%ine (A/P) and triet ylenetetramine (T/TA) ( o!che, ". and

redu$e or eliminate t e use o& volatile non-rea$tive solvents and.or !lasti$i%ers su$ as di*utyl! t alate, *en%yl al$o ol et$. as vis$osity redu$in( a(ents in e!o'y !aints and $oatin(s. ,onventional routes to redu$e vis$osity and V+, o& !olyamidoamine $ured systems ty!i$ally e'tend dry time *y more t an 4AC. T e *alan$e o& dry time and !ot li&e in a lo"er vis$osity !olyamidoamine.e!o'y system is uni)ue (&arten et.al. 1991). T e rea$tive diluents o& t is resear$ "or# are t e amide and.or imida%oline rea$tion !rodu$ts o& lo" mole$ular "ei( t $ar*o'yli$ a$ids and !olyal#ylene !olyamines (or !olyal#yleneamines). T e rea$tive diluents are !re!ared *y

$ondensation rea$tion o& t e $ar*o'yli$ a$id and t e !olyal#ylene !olyamine at elevated tem!erature (eneratin( a rea$tion !rodu$t mi'ture o& unrea$ted !olyal#ylene !olyamine, amides and.or imida%olines. =uita*le lo" mole$ular "ei( t $ar*o'yli$ a$ids &or ma#in( t e rea$tive diluent are t e ,<-,5 ali! ati$ $ar*o'yli$ a$ids, su$ as !ro!ioni$ a$id and *utyri$ a$id, es!e$ially a$eti$ a$id, and ,5-,3< aromati$ $ar*o'yli$ a$ids, su$ as *en%oi$ a$id, a*eti$ a$id (Dosin). Any !olyal#ylene !olyamine $an *e used to !re!are t e rea$tive diluent su$ as !olyet ylene !olyamines and !oly!ro!ylene !olyamines ('ohnson, R. W.; 198(). ?o"ever, t e !olyet ylene amines are !re&erred, es!e$ially aminoet yl !i!era%ine (A/P), and ot ers su$ (T/TA), as diet ylenetriamine (D/TA), triet ylenetetramine (T/PA), and i( er mole$ular "ei( t tetraet ylene!entamine

!olyet yleneamine oli(omers. In (eneral, t e $ondensation rea$tion !rodu$ts are !re!ared *y rea$tin( and (eneratin( a salt &rom t e $ar*o'yli$ a$id and !olyal#yleneamine, eatin( t e salt and $ondensin( to an amide or an amide.imida%oline mi'ture "it t e elimination o& "ater as illustrated *y t e rea$tion o& a$eti$ a$id and a !olyet yleneamine(Ei(ure - 3). >sin( a$eti$ a$id and !olyet yleneamine &or (eneral illustrative !ur!oses, a!!ro'imately e)ual molar amounts o& a$eti$ a$id and !olyet yleneamine are mi'ed to(et er and eated. T e tem!erature is $ontinually raised t rou( out t e !ro$ess slo"ly drivin( o&& "ater as t e rea$tion !ro$eeds until t e desired amount o& "ater is removed. Va$uum may *e em!loyed to assist in t e removal o& "ater. T e end!oint &or t e rea$tion is " en a !redetermined amount o& "ater as *een removed and.or t e desired imida%oline to amide ratio (ID ratio) as *een rea$ ed. T e imida%oline.amide ratio (ID ratio) is determined *y in&rared s!e$tros$o!y usin( t e C transmission mode and is ty!i$ally re!orted as ID ratio. T e !ea# ei( t o& t e imida%oline *and at 38AA $m-F divided *y t e !ea# ei( t o& t e amide I *and at 385A $m -3 determines t e ID ratio (Ei(ure G < to 7). As "ould *e evident to anyone s#illed in t e art, any rea$tion tem!erature and !ressure may *e used so lon( as it is ade)uate &or t e $ondensation rea$tion to o$$ur and t e "ater &ormed to *e removed. T e &inal rea$tion tem!erature is determined *y t e !olyet yleneamine used, t e !ressure used &or t e rea$tion, and t e amide.imida%oline ratio desired. Parti$ular $are must

*e used i& t e rea$tion is $ondu$ted under redu$ed !ressure to ensure t at t e rea$tion tem!erature is not su$ as to distill out t e !olyet yleneamine. T e ID ratio o& t e &inal !rodu$t is de!endent on t e amount o& "ater ta#en out o& t e rea$tion mi'ture. I& one mole o& "ater !er mole o& a$eti$ a$id is ta#en o&&, t e !rodu$t "ill *e !redominantly, i& not all, in t e amide &orm. I& (reater t an one mole o& "ater, *ut less t an t e ma'imum o& t"o moles, is removed t e !rodu$t "ill *e a mi'ture o& amide and imida%oline. Eor t is invention, it is desired t at at least one mole o& "ater *e removed !er mole o& $ar*o'yli$ a$id used. I& t e !olyet yleneamine used is <-aminoet yl !i!era%ine (A/P) only one mole o& "ater $an *e removed !er mole o& a$eti$ a$id *e$ause A/P $annot &orm imida%oline. All ot er $ommer$ially availa*le !olyet yleneamines su$ !olyet yleneamine oli(omers and mi'tures t ereo& as diet ylenetriamine (D/TA), i( er mole$ular "ei( t ave t e !otential o& &ormin( triet ylenetetramine(T/TA), tetraet ylene!entamine (T/PA),

amide.imida%oline mi'tures, any or all o& " i$ are suita*le &or t is invention. ,om*inin( o& t e lo" mole$ular "ei( t $ar*o'yli$ a$id and !olyet yleneamine may *e $ondu$ted at any !ra$ti$al tem!erature &rom su*am*ient to <6AH ,. T e !re&erred met od is to *e(in t e mi'in( o& t e rea$tants at am*ient tem!erature usin( t e eat o& rea$tion to raise t e tem!erature to a*out t e !oint near " ere t e $ondensation rea$tion *e(ins. Ideally, t e $ondensation rea$tion is $ondu$ted at t e lo"est !ossi*le tem!erature to minimi%e side rea$tions and &ormation o& $olored *odies. T e ty!i$al tem!erature ran(e is 36A to <6AH ,. Atmos! eri$ !ressure to a*out -<5 in$ (56 mm) ?( is t e (eneral o!eratin( !ressure "it t e o!timum *ein( atmos! eri$ !ressure to minimi%e t e loss o& !olyet yleneamine. At i( tem!eratures to"ard t e end o& t e $ondensation rea$tion, !arti$ularly " en redu$ed !ressure is em!loyed, unrea$ted !olyet yleneamine may distill over "it t e "ater &rom t e $ondensation u!settin( t e t ermodynami$ e)uili*rium o& t e !rodu$t mi'. As !olyet yleneamine is removed &rom t e rea$tion mi'ture, t e e)uili*rium "it in t e mi'ture $ an(es leadin( to t e (eneration o& additional &ree !olyet yleneamine and i( er mole$ular "ei( t oli(omers. ,are must *e ta#en to ensure t at si(ni&i$ant )uantities o& !olyet yleneamine are not distilled &rom t e !rodu$t mi'ture. T e &ree unrea$ted !olyet yleneamine remainin( in t e !rodu$t is not detrimental to its !er&orman$e. T e amount o& &ree !olyet yleneamine may ran(e &rom (reater t an A to <6 "t C o& t e !rodu$t. T e rea$tant stoi$ iometry may ran(e &rom A.3 to <.A moles o& lo" mole$ular

"ei( t $ar*o'yli$ a$id !er mole o& !olyet yleneamine. T e rea$tive diluent rea$tion !rodu$t is a mi'ture o& unrea$ted amine, amides and imida%olines de!endin( on t e !olyet yleneamine em!loyed. T e rea$tive diluent rea$tion !rodu$t may *e used to redu$e t e vis$osity o& any!olyamidoamine ardener. T e !olyamidoamine *ased ardener may $ontain any ot er$om!onents (enerally used *y one s#illed in t e art, in$ludin( *ut not limited to amines, !lasti$i%ers, diluents, a$$elerators, !i(ments or &illers. T e !olyamidoamine *ased ardener $an *e used to $ure any !olye!o'ide resin ty!i$ally used in t e art su$ as t e di(ly$idyl et ers o& *is! enol A and *is! enol E, and e!o'y Novala$s. Dea$tive (ly$idyl, ydro$ar*on and a$rylate diluents may *e in$or!orated into t e resin to serve as additional diluents.In$or!oratin( t is ty!e o& rea$tive diluent into a !olyamidoamine ardener redu$es $urative vis$osity, su*se)uently redu$in( solvent demand ne$essary &or ade)uate dilution and im!rovin( solvent dilution e&&i$ien$y.

Raw +aterial *sed

Glacial $cetic $cid (,!R!Grade) Triethylenetetramine (T.T$) 1 22 (DG.1$) Sunmide 345 .! +erc#/ *S$ T)S)0/ %apan $tul ,td!/ "alsad/ 'ndia $ir Products/ *S$

(/.V. I 6.465 e).#(, Vis$osity :<6H, I 3A,22A $!s ,olor I J 3 G) (A.V. I <3AK<A m( L+?.( , Vis$osity :7AH, I 62,AAA $!s, ,olor I 8 G 5 G)

Synthesis of Polyaminoamide
8

A 6AA ml round *ottom &las# e)ui!!ed "it a nitro(en !ur(e, t ermo$ou!le, dro!!in( &unnel, Dean =tar# $olle$tor and $ondenser, va$uum $onne$tion and eatin( mantle "as $ ar(ed "it <<A ( o& T/TA. T e tem!erature "as maintained at am*ient tem!erature. Mit a(itation, 22 ( o& (la$ial a$eti$ a$id "as added over a 4A minute !eriod. T e eat "as a!!lied to t e rea$tion mi'ture to slo"ly raise t e e'ot erm &rom t e addition $aused t e tem!erature to rise &rom <NH ,. to 3<AH ,. A&ter addition "as $om!lete, tem!erature and distill o&& t e "ater &rom t e $ondensation rea$tion. M en t e rea$tion tem!erature rea$ ed <6AH ,., At t is !oint 42 ( o& distillate "as $olle$ted. T e rea$tion mi'ture "as t en $ooled and t e !rodu$t $olle$ted. <NA ( !rodu$t "as o*tained. vis$osity o& 484 $P, an amine value o& 5N2 m( L+?.( and a $al$ulated amine ydro(en e)uivalent "ei( t (A?/M) o& 64.6.

Result and Discussion

5

Ta*le G 3 = o"s &ormulation and !ro!erties o& Polyaminoamides . Imida%oline &ollo"ed *y *at$ no. NAAA3 to NAAA7. In *at$ No. NAAA4, "e too# A,+?O T/TA in <O3 ratio " i$ is not &avora*le &or !rodu$tion o& Polyaminoamides . Imida%oline &or our !resent "or#, *e$ause it (ives very i( vis$ous !rodu$t. T e amine value, vis$osity and P r (!er No.NAAA3,NAAA< and NAAA7 "ere ea$ mi'ed "it undred (rams o& resin) are also s o"n in Ta*le - 3 T e materials !rodu$ed in 0at$ =unmide 4A6 &atty !olyamidoamine in a di&&erent "ei( t ratio and t e vis$osities measured. T e results a!!ear in Ta*le <. In all $ases t e resultin( mi'tures "ere si(ni&i$antly lo"er in vis$osity $om!ared to t e &atty !olyamidoamine.T e *lends o& rea$tive diluent and =unmide 4A6 !olyamidoamine !re!ared in /'!eriments 3 to 33 "ere mi'ed "it a stoi$ iometri$ amount o& 0 33 *is! enol A ty!e e!o'y resin and "e $ e$#ed t e !ot li&e o& all $om!ositions *y =?B+D> Gel Timer (-odel No.3AA, >=A -ade) , T( *y D=,(*y -ettler Toledo ,-odel No.) , T in Eilm Dryin( Time *y Gard$o /le$troni$ >ltra ,y$le Dryin( Time De$order (-odel No.DT-6A<A.<<A), ardness *y s ore D and 0ond =tren(t *y LL+BD Instruments (-odel No. LD6AL). A&ter 3.< our indu$tion !eriod, <A Pm &ilms "ere dra"n on steel Panels. A&ter <7 ours, *y visual measurements o& (loss "ere made to determine $urative.e!o'y resin $om!ati*ility. As results are s o"in( t at " en "e are in$reasin( (radually t e !er$enta(e o& rea$tive diluent *ond stren(t , !ot li&e and t in &ilm dryin( time are de$reases *ut T( and ardness in$reases. T e test results e' i*ited in Ta*le- < s o" t at t e addition o& rea$tive diluents to t e &ormulation lo"ered t e V+, and redu$ed t e t in &ilm set time. A&ter 5 days o& $ure at <6H ,. and 6AC relative umidity, t e &ilms "ere tested &or e'tent o& $ure. T e results s o"n in Ta*le - < s o"s t at t e !resen$e o& t e rea$tive diluent lo"ers t e mi' vis$osity, in$reases t e $urative.e!o'y resin $om!ati*ility, as seen *y in$reased (loss, and e'tent o& $ure "it out si(ni&i$antly a&&e$tin( t e t in &ilm set time.

R.6.R.(C.S
N

Adrlen, G.?.Q RPolyamideSQ >= Patents- 7,<75,7<8Q (32N3). As $ro&t, M.D. R, emistry and Te$ nolo(y o& /!o'y DesinS, $ a!ter <, !!. 42 ; 7A, 0la$#ie A$ademi$ ; Pro&essional, Ne" Bor# (3224).

0ou$ e, ,. and Len$lud, E.Q R?ardeners &or e!o'y resinsSQ >= Patents G 7,AN8,325Q (325N).

Loe*, -.L.Q RPolyamide resin and met od &or manu&a$turin(SQ >= Patents G 7,A5<,873Q (325N).

-arten et.al.Q R>se o& !olyamidoamine as $urin( a(ents &or e!o'y resin and $ura*le mi'ture $ontainin( t ese su*stan$es " ere in t e a$id $om!onent as o'yal#ene re!eatin( unitS Q >= Patent G 6,A35,856Q(3223).

To nson ,D. M. Q RT e $ emistry o& di*asi$ and !oly*asi$ &atty a$idsS in Tournal o& t e Ameri$an +il , emistsF =o$iety Volume 83, Num*er < . Ee*ruary, (32N7).

Mal#er, E.?. and =tarner, M./.Q RPolyamide $urin( a(ent *ased on mi'ture o& !olyet yleneamine and !i!er%ine derivatives. >= Patents G 8,AAN,434Q (3222).

Milson, A.E.Q RPolyamide resin $ontainin( &ree amino (rou! !rodu$ed &rom !olymeri$ &atty a$id.Q >= Patents G 7,54<,288Q (32NN).

Ueno Mi$#s, Tr., Eran# N. Tones, and =. Peter Pa!!as, R+r(ani$ ,oatin(s =$ien$e and Te$ nolo(yS, <nd /d. Miley-Inters$ien$e, Ne" Bor#, (3222).