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Investigation of the stability of the modified urea-formaldehyde resin

Article in Polimery -Warsaw- · January 2004

DOI: 10.14314/polimery.2004.049

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POLIMERY 200't,49, nr i 49

S. A. KURTA, S, V FEDORCHENKO, M. V CHABER

Precarpathian University, Deparhent of Chemistry
Pushkina Strect, 4/62, 77-300 Kalush, Ukraine

Investigation of the stability of the modified urea-formaldehyde resin

(UD lvas
Summary
- Commercial KFMT-I5 type urea-formaldehyde resin
modificd with an addition of 4 wt. % of various alcohols (methanol. ethanol,
isopropanol, butanol). Chan8es ofpH,relative viscosity, hot $lation time and
fuec formaldehyde contentduring storage (up to 4 months)were investigated.
Chemical intelPr€tation of the results obtained has been proposed. lt was
found that isopropanol is the most advantageous modifier
- from the point
of vicw of UF uscful propcrties (especially emission of formaldehyde).
Key words: urea-formaldehyde resins, modification, aliphatic aicohols, stor-
age stability.

Urea-fomaldehydc (UF) resins modificd with mono- amounts 4 wt. "/.) or dioctyl phthalatc (DOP as a plasti
hydric and polyhydric alcohols have been well kno\a'n cizer). To this precondensatc, after thc stage of acid con-
for a long time, but influencc of modificrs added ai the densation at pH = 4.3_4.6, the modifier has been add€d
slagc of polycondensation (l -8'7J on UF resins propeF and the resin was heated to 60-90''c during 1-2
ti€s has not bccn sufficicntly fuvcsti8at€d Il_3t' hours.
]t is especially important for thc stabilizatiolr of UF Aftcr the introduction of alcohols to the prcconden-
resins properties durjng long timestora8e, forexample l sate, thc following reactions (1) and (2) took part be
to 4 months. The problem ,as interesting for us, and tween an ur€a and methylol derivatives of urea at th€
additionaily our custońcrs claimcd that they wantcd to stage of ihc acid polycondensation:
gct UF resins with stable properties and technical cha-
racteristiG. At th€ same tim€ thc modificr content in UF HNCH,OIt IINCH,OII
resin should not be hi8h (up to 10 91t, because Breater
amounts of thc moclificls make UF resins very expcn-
co + c.H,.. ,ou:l'Śo
l
co + IJ,o
'
HNCH,OH I tNCHrOC,llr,, I

At the CsC ,,Lukor" \r'r'orks the ureałormaldchyde )

resins arc produced by continuous gas phase method

accodinS to which urea solution interacts with formal-
dehyde rich gases dcrived from the process ofmethanol llNcll:OH HN-CH"-Nlt
.O , rO
; '
oxiclaiion. Thc technological linc of a condensation step r()
r-1,r,
consists of the cascade of the reactors. IJN CI trOC
"H.,,., HNC ,OH IINCH,OH

EXPERlMENTĄL nonłnodificd Ul'lcsjns (2)

ItN_ CHr_ N_ C r_ NH
A laboratory installation enablcd to repeate the work
: Cn CO CO llo
of thc cascadc of reaciors with high accuracy was con-
ItNCHrOC,Hrn,r HNCl.l:OH HNCrl:OtI
structcd for thc modificd resins with stable properties
Production' Addińonally, th€ installation rvas €quiPPed
rĄ'ith a thcrmostat with an autornatjc le8ulatol of tem The first rcaction (1) took place in the weak acid me-
perature and pl'l metcr. dium (pH = 5--{), while the reaction (2) at pH
For our tests lve used crude UF r€situ (preconden- 3.H.5 [5]. As a result of the above processes thc
- modi
=

sates) that wcrc formcd aft€r thc alkahre sta8e of urea fied UF resins werc obtained. This product was then sta-
condcnsaiio with gas fonnaldchyde at the molar ratio bilized with additional urea (to the molar ratio urea:for"
of 1:1.8 and the modifier was introduced at thisstagc [4]. maldehyde equal 'l:1.2) coolcd and analyzed. Modified
This Product has b€en chos€n for our investigations' UF resins were kcpt du ng 4 months. Sampling and
Crudc UF rcsins modification was made by monohy product analysis wcre donc cach month an.l viscosity,
dric alcohols (methanol, ethanol, isopropa nol, butanol at hot gelation time and ftec formaldch)'de conient wcrc
50 POLIMERY 2004,49, nr 1

determined according io [6J. Modified products proper- 170

ties were compared with non-modified KFMT-1s resin,
150
in which the final ratio of wea and formaldehyde was
5
the same: 1:1.2 i7l. 130

RESULTS $ rro l
2

90
pH ofmodified UF resins and
As it is shov/n in Fig. 1,
70
non-modified KFMT-I5 one undergoes the obvious
changes in the cou$e of storage iime. At ihe be$nnin& 0t234
Slorage tinc, monLhs
fol th€ first month of stola8e, PH of aLnost all resins
decreases. ]t is the most obvious for the KFMT-1s resin Fig.3. UF tesin hot &elatin tijne (HGT) dcpendence o stot-
dnd UF reslns modińed bV ethanol' The decrcase is Prac_ age tine; fot sVmbols see FiS. 1
tically the sańe for ihe UF resins, modified by the iso-
propanol orplasiified by dioctyl phthalate DOP Dur
ing the lorger stomge, pH of the resins increase. After 4 An inoease in hot gelation time (HGn of at1 resins
months the highest pH value (exceedlng the initial one) during month of stora8e (Fi8. 3) is connected ł.ith the
1
shows ihe non-modified resin while the lowest (lolver intermoleĆulaT reaciion takir€ P]ace in the structure of
than initial pH) the resinmodified with buianol. the resins and a further reaction of UF resins derivaiives,
- that leads to the considerable inĆreasc h intermolecular
bonds in a resin.llcT order ofihe products ofmodifica-
tion is fo11ov/ing: ethanol > methanol > butanol > iso
propanol so there is no dependence on hydrocarbon
chain length. li seems ethanol shows better reaciivity
towards methylol troups than methanol white tu case of
isoproPanol the sieric hindrances decrease the reaĆiivity'
Lo rer reactivity of a modifier prolonts gelation time.
After 4 months storage HGT values of majoriiy of the
modified products are lower. Only the restu modified
0r211 with isopropanol is an exception.
Slo getimc. nront|s Our supposition is also confirmed by the changes of
fig. 1. UF resitl pH dependence on stonge titne: 1 free formaldehyde content du ng storage time shown in
no,1
nodit'iŁd UF rcsh KFMT-1'; the fesins madit'ied wilh: 2
- Fig. 4.
ethanol,3 1t- b talnl,4-l ethnnol, S
-isapropanol,6
DoP (plasticŁer)
0,6
4
I
2
2 i 0'4 l
I

l Ę o,z
5

01234 stola8c tiDc. monthŚ

Slorulctnnc, morrhs Fir' 4. DependeĄce rl ftee t'olnnldehyde (Fol cantcttt i1 lJF
Fig. 2 . UF rcsir rclatbe pkcasitV ftl, ) deperulence on storage rcsin ak stofą4e tifiq|or sy|1tbols see Fis' 1
time; fot symbols see FiS. 1

DISCUSSION
As rell the viscosity of all UF resins sliShrly de
creased during the first month of stora8e (Fig. 2), but It is clear from the results prescntcd that the certajn
durin8 th€ next months of stola8e the viscosity, as well part of meihylol derivative of urea undergoes transfor-
a" pH-vrlue increascd. Sigr'/icani irrcrpdse in v scosir) mation in the UF resins solutions. Later process in ihe
after the whole siorage was observed in case of non- UF resins seems to undergo a pscudo-stabilizatjon pe
modified resin or the resins modified with ethanol or riod. This assumption can be confirmed by the stability
of viscosity that in fact did not change at this siage dur-
inB frsr 45 diys ot uF r6ins *orasc poiod (Fi8 2). givs i óanĆe lo rg8uble thcirslu.qualiii.s, ih!.lÓg'
cgbtion iimc .bilizś, bÓ, hlt only bclweel ] łnd 2 solidif iotion and iherhal Śabil jv
ńodh alrohol lntod It was lound urat thc nodrficd resins keeD rhcn
valuc and ris.osity Du!ng thc se.ond month rhe
^pParendy, physi.G.hcmi.al i nd i.cs n the pemjlhd llńlb;wmA
]

chaĘes of free formaldchyd€.onhnt in thc UF PsilB 4 ńonihs

nodified by al.oho]s c iŃcEśtińg. Fomaldchyd€ Ón on the base of ińc re.eived r*UlE thc l,si mod GB
tent dKrcascs d! I3 this Śb!ag. pc od fmm 0.3 of UF resińs on th. da8. of Polycondcnsiiion aPP.a!.d
045'l' lo 0.05 a]5'r,' Ircan bc cxp]ained by thc ńd lobe k.PrcpJnoland bubnoLis wclliŚ d n.hlphthr_
tl'atpH d.aeas* atthc fnst *a8c oI sbnse (up b30 lil. a pLiłkżel Thł E whv lhey .ould b! rcom
diyo wlr aĆaie5 rh. .onditn n5 lol .thcrili- nendcd for lh. synthesis of mÓdified UF rcsiN' whi.h
'alor.ble .dions Th rnnor alc usld in rh. pmdudiÓn ol vamishcs and painb, as
hk! Plł.c it PH = 77 3'r, but.i| oc.ur at PlJ = wcll as in rhc paper, woÓdwork ind
Th. $ond{h]P.nd Mvd.hbc' Plitśrc.r vcd on th.
Dlijng stoIłgc the Irce fÓmaldchyd. nads with al
.ohÓlŚ and jś.on.cnłatiÓn iń UF LowłoxiĆ becaus€ oI ih. lowcr f.ec fom;Hóydc oF
sidclably l]ut ihe łbśrn.!of ęcc tonnaldohyde in thc tcni wh is a very ińPo ant r6ult of th. wolk Thc
.onsune6 in rhe branch oi idhcsi
aM pirh.l d{omPÓsition of thc lowu nole.ular dc. slłntl]' looking 1or th. soluiio| oI dre Prcbl; of lre
.vativ.s Fre fornrJldchyd..onĆ.Ńatjo. Gc. Fig .t) fońaldchvd. cnissioB lo the eńv
ina.ases lÓrashon timqbutthcpl.viousvi]uesarenÓt Th!opt ńJlsoluhonoj thsPfub cm i]]L mpńvclh.
N tornaldchvdcon c.oloA- ltlJhon o h.e
lnLJFrcsilBsonsca!.o|]yo'r j 3l';.óńlr'm
jday I
90' 'mnmci
ńon Fodlficd r.sitr thc frcc folmJldĆllydc .ontcnl

is the EŚuIt of thc

so, !'ork donc it b..ame
Pcsiblo rr 'cs.ai.h
obbnr thc mw srad.s
ation h.s been nadc 2. val€ c' P, Tły]d W c: "Anin
thc*aEc of slnthesisoIlow ńolc.ularrethył' and
n'ethylenc dcrnnuv.s .I !(i during ihe pro.e$ or UF 3' FńnhoBl H : & JJoil 1955' ł5' 2D
This lcr obrain thc uF rcsim ł' ldoloIUł Mrx;c03 G l2lr20993)
3rad.5 nodili.d hy thc noholG ola mÓdliclbuj]d iI 5 WiĘŹJ z" BrŻżński'
'l.215m, ],,^mjj]o
inlo t]trtr nruJu|! ! thout thc lhi |ss n fh! procś MosÓwr97],p'4ó+7,uq219
Thesr rc'ns sholv sońc sPccjlic proPc i* The d-
.reasld ontcnt of r6idlal ncc fomatdehvd.sivcs thc
poŚibiliN to r.du.r lhe to\iciiy ]sc "olbnł,, Kalush r9$,P 25
ft vcd Un thctr bi5e Mudłtr
'on
'.l.Ę'.fo'".lń.t
d ors.nicsolvcnb. '^rr

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