Maney Publishing

The Chemistry of Ketone Resins and the Synthesis of a Derivative with Increased Stability
and Flexibility
Author(s): E. René de la Rie and Alexander M. Shedrinsky
Source: Studies in Conservation, Vol. 34, No. 1 (Feb., 1989), pp. 9-19
Published by: Maney Publishing on behalf of the International Institute for Conservation of
Historic and Artistic Works
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THE CHEMISTRY OF KETONE RESINS AND THE SYNTHESIS
OF A DERIVATIVE WITH INCREASED STABILITY AND
FLEXIBILITY*
E. Renede la Rie and AlexanderM. Shedrinsky

Abstract-The chemistryof ketoneresins(poly- are considered to be too brittle foruse as the

cyclohexanone andthestability
resins) andflexibilitysingle ingredient of industrial clear coatings.
of varnishes
basedon ketoneresinsand reduced Brittleness is also one of theirshortcomings
ketone resinsarediscussed.Subsequently, thesyn- whenusedas a varnish:
thesisof a product withincreased picture at leastonesup-
stability and of artists'materials adds castor oil to the
isdescribed.
flexibility plier
varnish as a plasticizer.
In spiteofthefactthatketoneresins aremuch
morepronetoautoxidation thansynthetic clear
1 Introduction coatingsbasedon polymers, suchas poly(vinyl
acetate)or polymethacrylates, theyare used
Condensationproducts of methylcyclo- widely forthepurposeofvarnishing Old Master
hexanonesand/orcyclohexanone, generallypaintings.The reason for this lies in the
knownas ketoneresinsor polycyclohexanone difference betweenthe opticalproperties of
resins,have been used widelyin picturevar- ketoneresinsand thoseof polymeric coatings.
nishessincethe1950s[2].Suchresinshavebeen Ketoneresinshavebeenusedas replacements
availablein thepastfromBASF in WestGer- forsuchtraditional varnish materials as dammar
manyunderthetradenamesAW2and Ketone resinand gummastic,whichare stillhighly
ResinN. Thecompany currentlysellsa product valuedfortheir aestheticproperties. Ketoneand
underthenameLaropalK 80. Ketoneresins naturalresinshavein commonlow molecular
werealso producedin EnglandbyHowardsof weightand a relatively highrefractive index,
IlfordandlaterbyLaporteIndustries underthe bothof whichare requirements fora varnish
tradenameMS2t. Reducedketoneresinshave withgoodopticalqualities.LaropalK 80 has a
beenavailablein thepast fromHowardsand number-average molecular weight in the
Laporteunderthe namesMS2A and MS2B. 400-500rangeanda refractive indexof1.529[3].
Limitedamountsof MS2A have recently Sinceketoneresinsdo notyellowas muchas
becomeavailableagainfromLaporte.Ketone naturalresinsit has probably beenassumedby
resinsarealso manufactured in theUSA bythe manyusersthattheyareconsiderably moresta-
KrumbhaarResin Divisionof LawterInter- ble thanthenaturalresins.Ketoneresins, how-
national.Theirproducts,however,have not ever,autoxidize rapidlyas maybecomeevident
beenusedbypaintings conservators to thebest fromsomeoftheinformation presented in this
knowledge oftheauthors. paper.One oftheresults ofthisautoxidation is
Althoughketoneresinshave neverbeen a rapidchangeinthesolubility oftheresin, caus-
intended foruseas thesingleorchiefingredientsingan agedfilmto be solubleonlyin relatively
of clear coatings,picturevarnishes based on polar solvents[4-6]. Crackingor hazingmay
ketone resins
often consistofa simplesolution of occuras well,and a commondefectof older
theresininmineral spirits
(whitespirit).In com- ketoneresinvarnishes is the development of
mercialapplications theproducts are generally
usedas additivesforpaintsandlacquers, incon- *Thesynthetic work describedinthispaperforms the
centrationsvarying from5 to 50%, to improve basisfora chapter ofthePhDdissertation ofoneof
propertiessuchas glossandhardness. Theresins theauthors [1].
tHowardsofIlfordwasacquired
byLaporte
Indus-
Received19 January1988 tries
intheearly1960s.
Studiesin Conservation
34 (1989) 9-19 9

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 E. Rene de la Rie and AlexanderM. Shedrinsky

mattareas due to microscopic

Reducedketoneresins,
wrinkling[7].
suchas MS2A,aremore Ir 4
MAX=100.00 T

stable,but also morebrittle thantheirparent

products.
The chemistry of ketoneresinsand thesta-
and
bility flexibility basedonketone
ofvarnishes
resinsandreduced arediscussed
ketoneresins in
thispaper;subsequently, ofa deriv-
thesynthesis
ativeof LaropalK 80 withincreased stability
is described.
and flexibility SMIN=0.00 T
4000 3500 3000 2500 2000 1500 CM-1 1000

2 Thechemistry ofketoneresins Wavenumber(cm-')

1spectrumofLaropal K 80.
The basicmethodof synthesis of ketoneresins Figure Infrared
is a polycondensation reactionof methyl
cyclohexanones and/orcyclohexanone in the structure of theresins.Patentsconcerning the
presenceof methanolic alkali.The industrialsynthesis ofketoneresins, whichstartedappear-
manufacture of AW2 was accomplished in a ingin the1930s,do notcontainanystructural
nickel-lined autoclaveat approximately 120'C information. The two mostimportant papers
and2-5atmospheres [8].Bychanging theratioof containing structuralinformation appearedin
methylcyclohexanones and cyclohexanone,theearly1950s[11,12].Itshouldbekeptinmind
productswith different meltingpoints are thatthosepapersreferto laboratory experi-
obtained.If onlycyclohexanone is usedas the mentsratherthanto theanalysisof industrial
startingmaterial a melting pointof 115-120'C products.
occurs.This can be loweredby additionof According toa fewstudies, stepinthe
thefirst
methyl cyclohexanones [8]. synthesisof ketoneresinfromcyclohexanone
AW2andMS2 werecondensation products of is condensationto 1-cyclohexanol-2-cyclo-
cyclohexanone and methylcyclohexanones, hexanone, i.e. a ketol[13-20].Thisstructure
is
whileKetoneResinN waslikely tobe theprod- easily dehydratedby heating to 2-cyclo-
uct of condensation of cyclohexanone only. hexenyl-cyclohexanone (followingHoffman's
Consequently, infrared spectraof AW2 and rule):
MS2 showa bandat 1380cm-',wheremethyl
groupsabsorb,whereas thisbandismuchdimin-
ishedinintensity inthespectraofKetoneResin
N andLaropalK 80[9].LaropalK 80,theprod- 1
uctcurrently availablefromBASF, is identical
to Ketone Resin N accordingto its manu- Further condensation maythenoccuras follows
facturer;theonlydifference appearsto be that
thelatterproduct wasmanufactured ina discon- [11]:
tinuousprocess, whileLaropalK 80 appearsto
beproduced ina continuous one[10].Ourobser-
vationsindicate
lar: theinfrared
identical
also thattheproducts
spectrum LaropalK 80 is
of
aresimi-
to thatof KetoneResinN; gas chro-
1 /
matography ofthefraction oftheresinswhich
allows for such analysisyieldsan identical
fingerprint ofthesetworesins. 2
Ketoneresinsareoligomers rather thanpoly-
mers, containingonly a few repeatingunits. Compound 2 hasbeenisolatedandidentifiedby
Infraredspectrademonstratethe presenceof a Mleziva.
large numberof carbonyland hydroxygroups It has,however, beenclaimedthatmethanol
(Figure 1). Littlehas been publishedabout the producesformaldehyde underthe conditions
10 34 (1989) 9-19
Studiesin Conservation

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 of ketoneresinsand thesynthesis
The chemistry of a derivative
withincreasedstabilityandflexibility

generallyused duringthe industrialprocess trometry inketoneresins,suchas LaropalK 80,

[11,21]: Ketone ResinN and AW2,whichis indisagree-
CHOH ---- CH2O + H2 ment with the above schemes.One explanation
+
CH3OH 02 - CH20 + H20 for theabsence of doublebonds is thereducing
thusformed in the environment during thereaction
supplied bythe
Formaldehyde participates the of and the
condensation reactionsyielding derivativesof high pressure, presence hydrogen
nickel-platedsurfaceof theautoclave in which
methylol: theindustrialprocesstakesplace.
H H The condensationof cyclohexanone with
CH2OH
formaldehyde understrongly basic conditions
------... wasstudied byTilichenko andZikova[12].They
reported thatwater-soluble
products areformed
2 G3 whenCH20 is present in excess.Someearlier
studieshad alreadydescribedtheseproducts
[22,23].Thereaction mechanismcan bethought
Of coursethe secondhydrogen atom in the of as a successive methylolation of the
a
position to theketone group couldreactwith a-hydrogen atoms:
formaldehyde as well. Anotherpossibility is
reductionoftheketonegroupbyreaction with

SoA
formaldehyde. Furthermore, stepssuchas the rCH2OH
followingcan be imagined easily:
A
CHOH CH2 CH2OCH5 0
4 molesCH2O HOCH2, L CHOH
HOCH,
'oCH20H
OH
S4 OCCH, 5 HOCH ) CH,OH
C
IndeedMlezivafoundevidencethata substan-
tialnumber existinthereaction WhenCH20 is inexcess,thecarbonyl
ofetherlinkages groupis
reducedto a hydroxy
group.Consequently,this
products. is in with
accordance theknown Tollens
An alternative process
pathwaywas proposedby scheme If
Tilichenko
and Zikova[12]: isinexcess,water-
[24]. cyclohexanone
insolublecyclohexanone-formaldehyde
resinis
formed.Tilichenkoand Zikova proposedthe
followingreaction
scheme:

C
BasOCH
+ CHO+
IQ
+ CH1O
Vi Q
0 Michael
add.
-r
R' R"
O 0 0

CH2

In theaboveformulathefragments
R' andR"
couldbe anycombinationofcyclohexanoneand CHnI

itsdimerand trimer. authorswere Thismechanism

The present is rathersimilarto thatofthe
numberof vinyl condensation
unableto detecta significant ofphenoland formaldehyde and
protonswithnuclearmagnetic resonancespec- can be rationalized
as follows:
34 (1989) 9-19
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 E. Renede la RieandAlexander
M. Shedrinsky

Q+0
CH2O-QCH0~CHH
H
0 0
+
3 Stability

The degradation
andflexibility
ketoneresins
reduced
ofketoneresinsand

of ketoneresinvarnishes is
causedbyautoxidation reactions. Someof the
Q CH Q etc. moreimportant reactions involved in theauto-
+ ' xidation ofvarnishes havealreadybeen
o o o
process
mentioned elsewhere [25,26]. Ketonegroups,
The molecular weightofthedifferent fractions ethergroupsand tertiary carbonatomspresent
(determined cryoscopically) was reported to be in the molecular structures of components of
betweenabout 400 and 900amu.Analysisof ketoneresinsare thesitesmostvulnerable to
OH- and CH2OH-groupsshowed hydroxy autoxidation. Carbon-carbon doublebonds,if
groupstobepresent exclusively as CH2OH.This present in theresin,wouldbe vulnerable sites
prompted theauthorsto proposethefollowing as well. Hydrogenatomsattachedto tertiary
structures forthethreedifferent fractionsrecov- carbonatomsarerelatively easilyabstracted to
eredbythem: producealkylradicals, whichsubsequently react
withoxygen toproduceperoxy radicals.Ketone
FractionI groups, however, probably weakest
are the parts

4
oftheketoneresinmolecules: theyareproneto
CH,OH scissionreactions leadingto freeradicalswhen
o 0
oMW= 9 exposedto ultraviolet light(Norrish TypeI and
II reactions).Moreover,hydrogen atoms in
a-positions to ketone groups (as well as to
Fraction2 carbon-carbondouble bonds) are easily

4-Q3
abstracted to producealkylradicals.
-LCH4 CH,
Both types of Norrishreaction can occurin
MW=628haveboth
ketone resins: structures 1, 2 and 3 in section2
favours Norrish
a-substitution (which
typeI) anda y-hydrogen (whichfavours Norrish
Fraction3 typeII cleavage).It hasbeenarguedbefore that
thedegradation ofpicture varnishes is predom-
inantly initiated photochemically [26,27];Nor-
CH ;6
rish Type I and II scission reactions ofcarbonyl
CHI MW3
groupsare, therefore, likelyto be important
and processes in thedegradation ofketoneresins.
Eliminationof ketone groups,therefore,
greatly improves thestability of ketoneresins.
CHI CH1 MS2A is a ketone resin in which all carbonyl
CH2OH 0
cHOH MW=37s
groups have been reduced to hydroxy groups
withsodiumborohydride. It wasfirst produced
Fraction3 wasan approximately 50/50mixture byreduction ofMS2 byHowardsofIlfordinthe
oftheabovetwocompounds. Theauthorscon- late1950sat thesuggestion ofGarryThomson,
cluded that the resin consisted of a mixture of Scientific Adviser at the National Galleryin
of
products oligomers very of similarcompo- London [9, 28, 29]. As mentioned above, it has
sition.Thisconclusion was basedprimarily on recently becomeavailableagaininlimited quan-
themelting pointsofthedifferent fractions:the titiesfromLaporte.Theproduct is considerably
interval between initialsoftening and complete morestablethannon-reduced ketoneresins [27];
melting was verysmalland aboutthesamefor however, a majorshortcoming is its increased
the individualfractions.The meltingpointsof brittleness.
withincreasing
thefractionsincreasedregularly of ketoneresinscan be attrib-
The brittleness
molecular weight, suggestinga homologous utedlargelyto hydrogen bonding[30].Fellerhas
series. linkedthebrittleness of resinsto theirviscosity
12 Studiesin Conservation
34 (1989) 9-19

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The chemistry
of ketoneresinsand thesynthesis
of a derivative
withincreasedstabilityandflexibility

grades:polymers of highviscosity grade(i.e. 4 Results

withhighmolecular weight) arelessbrittlethan
resinsof low viscosity grade(low molecular 4.1 Reduction
weight)[2,p.127;31].The numberof hydroxyLaropalK 80 (BASF) was usedas thestarting
groupsin ketoneresins,however, has a great material forall ourexperiments. Initialexperi-
influence on theflexibilityof theresins:elimi- ments wereperformed withLiAlH4,whichfacil-
nation of all hydroxygroupsleads to an itatestotalreduction in 15-20minutes. Theuse
extremely soft,semi-liquidproduct(see section of LiA1H4 as the reducingagent,however,
4.2).Reducedketoneresins areevenmorebrittle provedtobe problematic. Thereaction involves
thantheirparentproducts due to an increased theproduction of largequantities ofhydrogen
numberof hydroxygroups,which causes gasandconsiderable heat.Moreover, inorderto
increased hydrogen bonding. keepthepolarreaction in
product solution, the
WhenHowardschangedthemanufacturing reactionhad to be carriedout in an ether-
processofMS2 in 1963,itreplacedMS2A with tetrahydrofuran (THF) mixture. Thepresence of
a productcalledMS2B,whichwas obtainedby THF makesthework-up procedure veryincon-
reduction oftheBASF product AW2.Theprod- venient becauseofthehighsolubility ofTHF in
uctionofthisresinceasedwhenBASF replaced water.Toluenehadtobeaddedduring thework-
AW2withKetoneResinN in 1967[9,28, 29]. up procedure to keeptheproductin solution.
The switchfromMS2 to AW2 as thestarting Reduction withNaBH4,although muchslower
material forthereducedresin,and thediscon- (thereaction typically required an entire night),
tinuation oftheproduction ofMS2BwhenAW2 turned outtobemorecontrollable. Thereaction
wasreplacedbyKetoneResinN, wereinitiated was carriedoutin a mixture ofabsolutemeth-
by chemicaldifferences betweenthe starting anol and toluene.Completereduction of the
materials: MS2 producedafter1963as wellas ketone groupsintohydroxy groups wasachieved
KetoneResinN reportedly gaveuselessly brittle (Figures1 and 2).
products afterreduction. Thisdifferencewasin
all likelihoodcausedbythefactthat'new'MS2 MAX= 100.00 T
and KetoneResinN werecondensation prod-
uctsof cyclohexanone only,ratherthanof a
mixture of cyclohexanoneand methyl-
cyclohexanones [9,28].
Thepresence ofmethyl groupsinthereduced
product, as was thecase in reducedversions of E
'old' MS2 (MS2A) and AW2 (MS2B), appar-
ently provides forsomeinternal of
plasticization
theresin.Nevertheless, reducedketoneresins,
even those containingmethylgroups,are MIN = 0.00 T

extremely A waytoreducethebrittleness 4000 3500 3000 2500 2000

brittle. 1500 CM- 1000

of reducedketoneresinswould be partial Wavenumber(cm-1)

esterificationof thehydroxy groupspresent in Figure2 Infrared spectrum ofreduced LaropalK 80

theresin.Somepreliminary experiments along (NaBH4).
theselineswereperformed byMillswithMS2A
intheearlysixties. Theproducts were,however, Thereduced product provedverybrittle, sup-
neverfullytested[32]. portingtheassumption thatLaropalK 80 is
The present authorsdecidedto examinefur- similarto KetoneResinN and 'new'MS2, in
therthepossibility ofimproving thestabilityand thatit is lowin methyl groups.The productis
flexibilityof ketone resinsby reduction of the insolublein mineral spirits.
ketonegroupsto hydroxy groups,and sub-
sequentesterification
ofa portionofthehydroxy 4.2 Esterification
groups. The resultsof these experimentsare Preliminaryexperimentswereperformed with
describedin theremainderofthisarticle.Experi- variousacylatingagents,rangingfromstearic
mentaldetailsare presentedin the Appendix. chlorideto valerylchloride.Esterification
of
Studiesin Conservation
34 (1989) 9-19 13

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 E. Renede la RieandAlexander
M. Shedrinsky

evena smallportionof thehydroxy groupswith transitiontemperatures of MS2A and reduced

theselong-chainchloridesresultedin verysoft Laropal K 80 are considerablyhigherthanthat
products.Otherproblemsoccurredas well,such ofunmodified Laropal K 80. The glasstransition
as discolorationof theproducts,possiblydue to temperatures of the propionicestersare lower
theuse of dimethylaminopyridine (DMAP) as a than that of Laropal K 80 and decrease with
catalyst.The use of a catalystwas necessaryin increasingdegreeof esterification
(Table 1).
order to obtain esterificationof the hydroxy
groups,manyofwhichare likelyto be sterically Table1 Glasstransition
temperatures
(?C)
hindered:

CH LaropalK 80 43
OH ReducedLaropalK 80
MS2A
58
57
Propionicester#1* 37
Propionicester#2* 34
Propionicester#3* 19
Therefore,as an alternative,esterificationPropionic ester#4* 20
withshort-chain anhydrideswas chosen,which
does not requirea catalyst.Experimentswith *Propionic esters#1,#2,#3and#4refer toproducts
propionicand aceticanhydridewerecarriedout, with increasingdegreeofesterification.
bothof whichled to usefulproducts.The hard-
ness of the end productcould be tailoredby Furthercomparativetests were performed
varyingthe degreeof esterification
(Figure 3). with an acetic esterof intermediate hardness.
=100.00
MAX T
Pendulumhardnesstestswere carriedout with
Laropal K 80,reducedLaropal K 80,MS2A and
the acetic ester.The resultsappear in Table 2.
Again, the effectof reductionand subsequent
esterificationon the hardnessof thecoatingsis
obvious. MS2A and reduced Laropal K 80
E give high hardness values, Laropal K 80 is
intermediate, and theaceticesterhas thelowest
hardnessvalue.
MIN= 0.00T Table2 Pendulum values
hardness
4000 3500 3000 2500 2000 1500 CM-1 1000
Wavenumber(cm-')
K 80 130
Figure3 Infrared spectrum ofreducedandesterifiedLaropal
acetic Reduced Laropal K 80 185
LaropalK 80 (1-5ml anhydride). MS2A 214
Aceticester 101
Four different samples of the propionicester
were prepared with differentdegrees of
usingthesame amountof reduced Flexibilities
esterification wereroughlydetermined by ben-
Laropal K 80 (1.65g) but differentquantitiesof dingof metallicplateson whichcoatingsof the
propionic anhydride (lml, 1.5ml, 2ml and different resinswere applied. Despite the fact
2.5ml). The sample with the lowest degree of thatthe experiments wererathercrude,a clear
esterification(iml) was still relativelybrittle differencebetweenthesampleswas found*.The
while the sample with the highestdegree of acetic esteris the most flexiblecoating,while
(2.5ml) was verysoft.
esterification reducedLaropal K 80 and MS2A have theleast
(Table 3).
flexibility
4.3 Physicaland mechanicalproperties
Glass transitiontemperatures were determined *Standardized testssuchas ASTM D 522
flexibility
forthefourpropionicestersof different degree areunsuitable, oftheresins
sincetheflexibilities under
of modification, as well as for Laropal K 80, consideration are outsidetherangeforwhichthese
reduced Laropal K 80 and MS2A. The glass testsaredesigned.
14 34 (1989)9-19
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 of ketoneresinsand thesynthesis
The chemistry of a derivative
withincreasedstabilityandflexibility

Table 3 Flexibilities* =100o00

MAX T

LaropalK 80 149
ReducedLaropalK 80 199
MS2A 189
Aceticester 131
*Valuesaretheradii(in mm)ofthecircleswhichfit 2
thebendat whichcrackingstartsto occur.
Acetic esters of intermediatehardness are
soluble in hydrocarbonsolventmixtureswhich 200 250 300 350 400 450 500
MIN 0.00 T
550 600
are about 40% aromatic.Theytherefore require (nm)
Wavelenght

a somewhathigheraromaticitythan Laropal
K 80. Figure4 UV-VIS spectraof a filmof Laropal K 80,
aging(1), afterfadeometeragingfor 71 hours
The refractiveindexat 20'C of theproductis before
(2), and 418 hours(3).
1-515,slightlylowerthanthatof Laropal K 80
(1-529). 0.4-A

4.4 Acceleratedagingtests A
The stabilityof the acetic esterwas compared 0.3 LAROPALK 80

withthatof theunmodified product(Laropal K

80), reducedLaropal K 80, and MS2A. Acceler- 0.2-
ated agingwas carriedout in a xenonarc fade- A MS2A
ometer.*Changes in filmsof the resins were
determinedby ultraviolet-visible light trans- 1 ELAR. K 80

mission(UV-VIS) spectrophotometry and solu- *

ACET.ESTER
bilitytests.
Althoughfilmsof Laropal K 80 do notyellow
0.0 I I I
0 500 1000 1500

extensively, theyrapidlydevelopUV-absorbing AGINGTIME (HOURS)

chromophores duringagingunderlightin much Figure5 AA(300)as a functionofagingtimeduring

the same way as filmsof dammar resin [26] fadeometeragingforfilmsof LaropalK 80, reduced
(Figure 4). It is thereforeagain convenientto LaropalK 80, MS2A, and reducedand esterified
follow the change in absorbance at 300nm: LaropalK 80.
AA(300) = A(300,t) - A(300,0), in which
expressionA(300,t) representsthe absorbance than Laropal K 80. The acetic ester,however,
at 300nmand at timet. PlotsofAA(300) against
performseven betterthanthe formertwo.
agingtimeforthedifferent resinsappear in Fig-
The solubilityof unmodifiedLaropal K 80
ure5. The positiveeffectofreductioncan be seen
changes rapidlyduringfadeometeraging due
clearly: MS2A and reduced Laropal K 80 to the occurrenceof polar oxidationproducts.
develop chromophoresat a much slower rate It changes in about 300 hours froman initial
solubilityin 100% cyclohexaneto solubility
*In thecase of ketoneresinsand derivatives,heat in a 25:75 acetone: toluenemixture.Thereafter
agingappearstobeevenlessuseful thaninthecaseof further
changeoccurs,althoughat a slowerrate
dammarresin[26].According to themanufacturer,
(Figure 6). Reduced Laropal K 80 requires
LaropalK 80 partiallydecomposes at temperatures
100% toluenebeforeaging.Littlechangeoccurs
above80'C. Heatingof filmsof theresinat 100?C
leadstoa verystrongyellowingwhich doesnot in the solubilityof thisproductduringthefirst
clearly
reflect sinceitiswellknownthat 2000 hoursof aging.MS2A performs
realagingproperties, somewhat
ketoneresinsdo notyellowextensivelyduringnatural better than Laropal K 80, although the
aging.The mostlikelyexplanationforyellowing difference is not dramatic.The solubilityof the
duringheatagingis theoccurrence of unsaturationacetic ester changes at a considerablyslower
dueto dehydration reactions[1]. ratethanthatof Laropal K 80 and MS2A: it is
Studiesin Conservation
34 (1989) 9-19 15

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 E. Rene de la Rie and AlexanderM. Shedrinsky

soluble in 100% toluene after2000 hours of sequent partial esterification with short-chain
fadeometeraging. anhydrideof Laropal K 80 lead to a product
Acet/Tol with improved stabilityand flexibility.The
50o50 workability and aestheticproperties ofvarnishes
preparedfromthisproductwerefoundto be at
K 80 MS2A
LAR.

least equivalentto those of ketone resinvar-

RED.
LAR.
K80
2575
nishes duringtests on paintings.There is no
doubt thattheresincan be further stabilizedby
ACET.ESTER
Chex/Tol
0100 theadditionofadditivessuchas hinderedamine
lightstabilizers[25]. The stabilityof theresinis
5050 comparedwithothercommercially availableres-
ins whichhave potentialforpicturevarnishing
purposes.It willdependon theoutcomeofthese
0 500 1000 1500 2000 2500 experimentswhether manufacturerswill be
AGINGTIME(HOURS) approachedabout thepossibilityof production
oftheresin.Duringpreliminary discussionswith
Figure 6 Change insolubilityduringfadeometer aging BASF, a
offilmsofthesameproducts as inFigure5. willingness expressedto undertake
was
the modificationof Laropal K 80 on a pilot
plantscale to make theproductavailableto the
4.5 Testsonpaintings conservationcommunity.
Batchesof about 200g of the acetic esterwere
preparedin orderto testtheproductforwork- Acknowledgements
abilityand opticalproperties duringapplication
as a temporary varnishon paintings.A solvent The authorswishto thankJohnM. Brealey, Chair-
mixture suitableforbrushapplicationwas found manofthePaintings Conservation Department ofthe
in a mixtureofmineralspirits150-ECand TS-28 Metropolitan MuseumofArt,formakingthiswork
solvent(Shell). The lattersolventhas an aro- possibleand forhisenthusiasm fortheproject, and
maticcontentof 76% and an evaporationrate Prof.Stephen R. WilsonofNewYorkUniversity for
to that of mineral spirits valuable suggestionsduring thecourse ofthe synthetic
approximatelyequal work.The authorsare indebted to Christopher W.
[33].A 50:50mixtureofthetwosolventsgivesan who carried out the accelerated
aromaticcontentof about 40%. Agingexperi- McGlinchey aging
andmechanical testsandto MichaelSchilling at the
mentswithfilmsof the productpreparedfrom
GettyConservation Instituteforcarrying out the
solutionsin thismixturegave resultswhichdevi- glass transitiontemperature measurements. The
ated onlyslightly fromthosewithfilmsprepared authors furtherwishtothankProf.JanW.Verhoeven
fromsolutionsin reagentgrade toluene.(Some oftheUniversity ofAmsterdam forhiscomments on
solventremainstrappedin thevarnishfilmsfor the manuscript and GeorgeBisacca and Michael
extendedperiods of time; solventswhich are Heidelberg fortheirhelpduringtheeditingof this
prone to autoxidation reactions, such as oil of paper.
turpentine, maytherefore reducethestabilityof
varnishes.) Appendix:experimental methods
Varnishesconsistingof solutions of about
40% (weightby weight)of the productwere Reduction ofLaropalK 80 withLiAJH4
applied on various paintingsby conservators of Fiftygrams ofLaropalK 80 dissolved in 300mlofa
the MetropolitanMuseum of Art. The general 50:50mixture of drytetrahydrofuran and etherwere
that the work- added dropwise under stirringthrough an addition
opinionof theconservatorswas funneltoa solution of20gofLiAIH4in200mlofthe
abilityand aestheticappearanceof thevarnishes samesolventmixture. The reactionproceeded very
are at least equivalentto thoseof ketoneresin and neededcoolingin an ice bath.The
vigorously
varnishes. additionwas completed in 25-30minutes. Afterthe
reaction mixture had cooleddown,somewaterwas
5 Conclusions addedslowlyto decompose remaining LiAIH4.Sub-
sequently,300mloftoluene wereadded.Thesolution
Reductionwithsodium borohydrideand sub- was washedtwicewith10% HCI, twicewith5%
16 Studiesin Conservation
34 (1989) 9-19

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 of ketoneresinsand thesynthesis
The chemistry of a derivative
withincreasedstabilityandflexibility

NaHCO3andtwicewithwater.Theorganic layerwas Infraredspectra

driedover Na2SO4 and subsequently evaporated, Infraredspectraof the various productswere
yielding46gofcolourless porousmaterial. obtained bycasting filmsonsaltplatesusingsolutions
in toluene.The filmsweredriedundera heatlamp
Reductionof Laropal K 80 withNaBH4 beforespectra wererunon a Perkin-Elmer 599Bgra-
A solution of30gofNaBH4in500mlofmethanol was tinginfrared spectrophotometer. Nevertheless, some
addedtoa solution of 100gofLaropalK 80 in 500ml absorption bandsdue to the solventtoluenemay
oftoluene undercoolingwithice.Themixture turned appearin thespectra.
noticeably yellow;however, afteritwas leftto stand
overnight it was colourless. The work-up procedure Refractive indices,UV-VIS spectra,solubility testsand
consistedof washingthe solutiontwicewith10% acceleratedagingmethods
HC1,oncewith5% NaHCO3 and twicewithwater. Theprocedures havebeendescribed elsewhere [3,26].
The organiclayerwas driedoverNa2SO4 and the
solventwas subsequently removedundervacuum, Glass transition temperatures
yielding93gofwhiteporousmaterial. Glass transition temperatures weredetermined by
MichaelSchilling atTheGetty Conservation Institute
Esterificationwithlong-chain acid chlorides on a Mettler DSC 30equippedwitha liquidnitrogen
FivemgofDMAP and500mgofC17H35COC1 were reservoir and a TC10A controller. The differential
addeddropwise undernitrogen through a syringeto scanningcalorimeter was calibratedon the fusion
a solutionof 1-65gofreducedLaropalK 80 in 10ml temperatures of indium,lead and tin.Samplesof
CH2C12 in a 25mltwo-neck flask.The reaction was about10mgweresubjected totwoheating cyclesfrom
completed intwohours.After thisthesolution hada - 100to 100oCata rateof10OC/min. Glasstransition
markedly yellowcolourwhichcouldnotbe removed temperatures wereobtained fromthesecondheating.
during thework-up procedure. Theorganic layerwas Since glass transition temperatures determined by
washedtwicewith5% NaHCO3,oncewithHCI and DSC maydependon variousfactors suchas sample
twicewithwater.After drying withNa2SO4thesol- size,heatingrate,thermal history, etc.,thedata in
vent was removed under vacuum. Despite TableI shouldbeconsidered as relativerather thanas
esterificationofonlya smallportionofthehydroxy absolute.
groups, theproduct wassoftandsticky. Itwasalmost
impossible toremove unreacted chloride
without mul- Pendulumhardnesstests
tiplewashings withNaOH,whichisundesirable since K6nigpendulum hardness valuesweredetermined on
it leadsto decomposition oftheester. a Byk-Chemie pendulum hardness testeraccording to
SimilarresultswereobtainedafteresterificationASTM methodD 4366.The apparatusconsists ofa
withpalmityl, lauryland caprylchlorides. A some- pendulum attached to a cross-bar, whichrestson the
whatharderproduct wasobtainedwithvaleryl chlo- coatingsurface through twoball-bearings. Theoscil-
ride;however, ithad a veryunpleasant smell. lationsofthependulum aredampened morebysofter
coatings thanbyharder coatings. Thehardness values
Esterificationwithshort-chain anhydrides in Table 2 are thenumber of oscillations occurring
Onehundred andtwenty mlofdrypyridine and50ml beforetheswingamplitude decreases to 30 froman
of aceticanhydride wereaddedundernitrogen and initialvalueof 120.Filmsoftheresinswereprepared
during stirringtoa solution of93gofreduced Laropal on microscope slidesfromsolutions in tolueneand
K 80 in 500mlofCH2Cl2.Thereaction mixture was allowedto dryforoneweek.Subsequently thefilms
leftfor22 hours.The mixturewas subsequentlywereheatedat 80'C for 30 minutesto driveoff
washedfourtimes witha saturated solution ofCuSO4 residualsolvent. Thefilmswerethenconditioned to
andthree timeswithwater.Duringthelaststepa very thelaboratory environment forat least24hours.The
stableemulsion formed, whichwas destroyed witha datainTable2 aretheaverages ofsixmeasurements
saturatedNaCl solution. Theorganiclayerwasdried persampleand twosamplesperresin.
overnight overNa2SO4,yielding 112gof an almost
colourlessproductafterevaporation ofthesolvent. Flexibilitytests
Thepropionic acidesterwasobtainedbya similar Flexibility testsweredone by bendingaluminium
procedure. plateson whichcoatingsof approximately equal
thickness wereapplied.Thecoatings wereallowedto
NMR spectra dryforoneweek,thenheatedat 800Cfor30minutes
Protonmagnetic resonance (1H NMR) spectrawere to drive off residual solvent (toluene), and sub-
obtained usinga Nicolet/Oxford NT-300NMR spec- sequently allowedtocondition tothelaboratory envi-
trometer. Chemicalshifts weremeasured relativeto ronment for24 hours.Theplateswerebentbyhand
tetramethylsilane as an internal standard. untilcracksstarted to appear.Theshapeofthebent
Studiesin Conservation
34 (1989) 9-19 17

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 E. Rene de la Rie and AlexanderM. Shedrinsky

platewas thendrawnon a sheetof paper.Sub- 10 BASF AKTIENGESELLSCHAFT,private commu-

sequentlytheradiusofthecirclefittingtheregionof nication.
bendoftheplatewasdetermined.
sharpest Thefigures 11 MLEZIVA,J., 'Cyclohexanoneresins',Collection
in Table 3 reflect
theaveragesof a fewsamples.It Czechoslov.Chem. Commun.,19 (1954)
shouldbekeptinmindthatflexibilities
aredependent 505-516.
on severalfactorssuchas adhesionto thesubstrate, 12 TILICHENKO, M. N., and ZIKOVA,P. V., 'Chem-
temperature andhumidity.ThedatainTable3 should ical structure
of cyclohexanone-formaldehyde
thereforebe regardedas crudeapproximationsonly. resins',J.AppliedChem.(USSR) 25 (1952) 64.
13 O., 'Ober Condensationsprodukte
WALLACH,
innerhalbder
KetoneundSynthesen
cyclischer
Suppliers Terpengruppe',Chemische Ber. 29 (1896)
2955-2966.
American SocietyforTestingand Materials,
Phila- 14 WALLACH, O., 'Zur Kenntnisseder Terpeneund
delphia,PA 19103,USA. der itherischenOele', Ann.Chem.329 (1903)
BASF Aktiengesellschaft,D-6700 Ludwigshafen, 82-133.
WestGermany. 15 WALLACH, O., 'Condensationproductsof cyclo-
Byk-Chemie USA, Wallingford,CT 06492,USA. hexanone',ChemischeBer. 40 (1907) 70-71.
LaporteIndustries
Ltd,Widnes,CheshireWA8OJU, 16 RAPSON, W. S., 'l-methoxy and 2-
England. methoxytriphenylene', J. Chem. Soc. (1941)
LawterInternational, IL 60062,
Inc., Northbrook, 15-18.
USA. 17 EVANS,L. K., and GILLAM,A. E., 'Effectof
Perkin-Elmer
Corp.,Norwalk, CT 06856,USA. molecularenvironmenton the absorption
ShellChemical
Co., Houston,TX 77251,USA. in solution.
spectraoforganiccompounds II.
ketones',J. Chem.Soc. (1941)
a, fl-unsaturated
815-820.
References 18 REESE,J., '2-cyclohexylidenecyclohexanone, an
isomerof 2-(1-cyclohexenyl)-cyclohexanone',
1 SHEDRINSKY, A. M., PhD dissertation,Depart- ChemischeBer. 75 (1942) 384.
mentof Chemistry, New York University19 KOHLER,E. P., and THOMPSON, D., 'Supposed
(1986)ChapterIII: 'Synthesisof a newsyn- enolizingpower of organicmagnesiumcom-
theticvarnishforthe purposeof paintings pounds', J. AmericanChem. Soc. 55 (1933)
conservation', 147-198. 3822-3823.
2 FELLER,R. L., STOLOW, N.,andJONES, E. H., On 20 STANEK,J., 'Condensationof cyclohexanonein
Picture Varnishesand theirSolvents,revised alkaline medium',J. Chem. Listy 46 (1952)
andenlarged NationalGallery
edition, ofArt, 110.
Washington DC (1985). 21 DOLGOV,B. N., and SAMSONOVA, I. N., 'Catalytic
3 DELARIE,E. R., 'Theinfluenceofvarnisheson of alcoholswithketones',Zh.
condensation
theappearance Studiesin Con-
of paintings', Obsch.Kh.22 (1952)632-637.
32 (1987)1-13.
servation 22 MANNICH, C., and BROSE,W., 'Synthesisof keto
4 FELLER,R. L., and BAILY,C. W., 'Solubilityof alcoholsand plurivalent
alcoholsfromcyclic
masticand
agedcoatingsbasedon dammar, ketonesandformaldehyde', Ber.56
Chemische
resinAW-2', Bulletinof theAmericanGroup- (1923)833-844.
IIC 12 (1972)72-81. 23 GAULT,H., and STECKL,E., 'Condensationof
5 FELLER,R. L., and CURRAN,M., 'Changes in acyclic aldehydeswith saturatedcyclic
solubility of varnishresins
and removability ketones. with
andacetaldehyde
Formaldehyde
withage', Bulletinof AIC 15 (1975) 17-26. cyclohexanone',Comptes Rend. 207 (1938)
6 FELLER,R. L., 'Studieson thephotochemical 475-477.
of thermoplastic
stability resins'in ICOM 24 MARCH,J., AdvancedOrganic Chemistry,
2nd
Committeefor Conservation,4th Triennial edn, McGraw-Hill Book Co., New York
Venice(1975)75/22/4.
Meeting, (1977)863& 1139.
7 THOMSON,G., 'Some picturevarnishes',Studies 25 DE LA RIE, E. R., 'Polymerstabilizers.A survey
in Conservation
3 (1957) 64-78. withreference to possibleapplications in the
8 HILL,A., 'Manufacture anduseofAW-2resin', conservationfield',Studiesin Conservation 33
ModernPlastics25 (Aug. 1948) 119-120. (1988)9-22.
9 MILLS,J.S., and WHITE,R., The OrganicChem- 26 DE LA RIE, E. R., 'Photochemical and thermal
istryof MuseumObjects,Butterworths, Lon- degradation offilms ofdammar resin',Studies
don(1987)118-120. in Conservation 33 (1988) 53-70.
18 Studiesin Conservation
34 (1989) 9-19

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All use subject to JSTOR Terms and Conditions
 of ketoneresinsand thesynthesis
The chemistry of a derivative
withincreasedstabilityandflexibility

27 THOMSON,G., 'New picturevarnishes'in Recent 'Stablevarnishes

forold masterpaintings'.
Author's
Advancesin Conservation,ed. G. THOMSON, address:Metropolitan MuseumofArt,FifthAvenueat
London(1963)176-184.
Butterworths, 82nd Street,New York,NY 10028, USA.
28 PLESTERS,
J.,privatecommunication concerning
notesmadeby GarryThomsonin 1965on ALEXANDER M. SHEDRINSKY,born 1943.Graduated
AW2,MS2, MS2A and MS2B. fromtheChemistry Department of Leningrad State
29 HUTTON, D. A., LaporteIndustries Ltd,private Universityin 1965.Completed hispostgraduate study
communication. inPolymer Chemistryat thesameUniversity in 1970.
30 TOBOLSKY, A. V.,andSHEN, M. C., 'Theeffectof LecturerinOrganicandGeneralChemistry at Lenin-
hydrogen bondson theviscoelastic propertiesgradNorth-West Polytechnical FirstLenin-
Institute,
of amorphouspolymernetworks', J. Phys. gradMedicalInstitute andLeningrad Pharmaceutical
Chem.67 (1963)1886. College.In 1980heimmigrated totheUSA. MS 1983,
31 FELLER, R. L., 'New solvent-type varnishes'in PhD (Synthetic OrganicChemistry) 1986fromNew
Recent Advances in Conservation,ed. G. York University. 1984-1986Charlesand Frances
THOMSON, Butterworths,London (1963) Atkins Fellow at the PaintingsConservation
171-175. Department of the Metropolitan Museumof Art.
32 MILLS,J.S., privatecommunication (1984). 1986-1988 PostdoctoralFellowat Conservation Cen-
33 DE LARIE,E. R., 'Researchon picturevarnishes: teroftheInstitute of FineArts(NewYorkUniver-
statusof the projectat the Metropolitansity).Presently AndrewW. MellonFellowin the
MuseumofArt'in ICOM Committee for Con- ObjectsConservation Department of theMuseum,
8thTriennial
servation, Meeting,Sydney(1987) and AssistantProfessor, Chemistry Department,
791-796. Long Island University.Author'saddress:as forde la
Rie.
E.RENE DE LA RIE receivedhis degree in physical
chemistry fromtheUniversity of Amsterdam,after
Resumi--Apres avoir6tudi6la chimiedes r6sines
whichhecarried outa subsidizedresearchprojecton ainsique la
thefluorescence of paintand varnishlayersat the c6toniques (r'sinespolycyclohexanone)
et la flexibilit6
stabilit6 des vernisa base de r6sines
Central Research Laboratory,alsoinAmsterdam. He
thenjoinedthetraining forrestorers, c'toniquesetde r6sinesc6toniquesr6duites,on d'crit
program newly la d'unproduit etune
unestabilit6
setup undertheMinistry synth6se
ofCultureofTheNether- flexibilite poss6dant
accrues.
lands,to developandteachthescienceprogram and
to assistin thegeneraladministration oftheschool.
Since1982he has beenresponsible forestablishingZusammenfassung-Der BeitragbefaBtsichmitder
and supervising a researchlaboratoryforthePaint- Chemievon Ketonharzen (Polycyclohexanonharze).
ingsConservation Department of theMetropolitan Weiterhin wirddie Stabilititund Elastizititvon
MuseumofArtinNewYork.He teachesat theCon- Firnissenauf der Basis dieser und reduzierter
servation CenterofNewYorkUniversity. Mr de la Ketonharzediskutiert. AbschlieBend wirdauf die
Rie obtaineda doctoratefromthe University of Synthese einesProduktes miterh6hter und
Stabilitit
Amsterdam in 1988basedon a dissertationentitled Elastizitat
eingegangen.

Erratum:E. Ren6 de la Rie, 'Photochemicaland thermaldegradationof filmsof dammarresin',

Studies in Conservation 33 (1988), 53-71.

A few errors occurred in Figure 13. The bottom part of the figureshould read as follows:

Isomerization
ofisolated
double
bonds
intoconjugated
systems:

-,CH=CH-CH2-CH=CH ROO. -CH=CH-CH-CH=CH- -* -CH=CH-CH=CH-CH-~

"
ROOH

-,CH-CH=CH-CH=CH-
Studiesin Conservation
34 (1989) 9-19 19

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