Polymer 61 (2015) 204e212

Contents lists available at ScienceDirect

Polymer
journal homepage: www.elsevier.com/locate/polymer

Polymer communication

Development of ketonic resin by polymerization reaction: A critical

review
U. Appala Naidu, Srikanta Dinda*
Dept. of Chem. Engg., BITSePilani Hyderabad Campus, Hyderabad 500078, India

a r t i c l e i n f o a b s t r a c t

Article history: Synthetic resins are used for various applications including in paint industry to improve the glossiness,
Received 4 November 2014 adhesiveness, hardness, and dryness of paints. Resins are essentially polymers, which are builds up from
Received in revised form simple molecules or monomers and can be prepared mainly by either addition polymerization or
8 January 2015
condensation polymerization. Ketones and aldehydes can be converted to resinous products by
Accepted 5 February 2015
Available online 13 February 2015
condensation reaction. The desired property of a synthetic resin greatly depends on its method of
preparation and its field of application. In this communication, the literature pertaining to the self
econdensation of ketones to yield dimer, trimer and tetramer products and also the condensation of
Keywords:
Ketonic resin
various ketone molecules with aldehydes to produce ketoneealdehyde resins are analyzed and a state
Condensation polymerization eofetheeart review is written. The present study provides an overview of: i) effect of various operating
Hydroxyl value parameters like reaction time, temperature, pressure, type of catalyst and its loading on a condensation
polymerization reaction; ii) various techniques and ideas to analyze the product properties and to
remove the catalyst from the reaction mass; iii) effect of phase transfer catalysts (PTCs) on the resin
product properties such as softening temperature, moisture content, gardener color number etc. In a
nutshell, an attempt has been made to get the aforementioned aspects together in a coherent manner so
that the information is available at a glance and is expected to be useful to the researchers and for in-
dustrial practices.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction applications like production of perfumes, treatment of bows for

instruments such as violins and cellos.
Resin is an organic substance which has wide range of appli- Synthetic resins are essentially polymers, which are built up
cations including consolidants, adhesives, coatings, casting, mold- from simple molecules or monomers. There are two general
ing, and storage materials. Resins play a vital role like excellent methods for the production of polymers, namely, addition poly-
chemical resistance, good adhesion properties, heat resistance, merization and condensation polymerization, and which method
oxidative stability, and excellent electrical properties in the field of to be employed depends on the type of monomer. Common syn-
plastic, textile, electrical and electronics, paper, paint, construction thetic resins are: alkyd resins, epoxy resins, polyamide resins,
etc. In coating technology, resins are mainly used to provide gloss polyurethane resins, vinyl resins, polystyrene resins, acrylic resins,
and elasticity, for suspension of pigments, to provide resistance to phenolic resins, and ketonic resins etc. Most of the natural and
water and chemical, besides acting as a dispersant [1]. synthetic resins are insoluble in water but soluble in organic sol-
Broadly, resins are classified as natural resins and synthetic vents like propanol, butanol, chloroform, chlorobenzene, cyclo-
resins based on their occurrence. Natural resins are obtained from pentanone, cyclohexanone, toluene etc. [2].
trees which exude a viscous liquid when the bark is damaged. In this review, we have focused mainly on the polymerization
Commonly available natural resins are Dammar, Mastic, Rosin, reaction and polymer products from ketones and/or aldehydes to
Shellac and Beeswax etc. Natural resins are used for a wide range of obtain a ketonic resin and its major applications. It is well known
that ketones, aldehydes or their mixtures can be converted to
resinous products in presence of a base or acid catalyst. Cyclohex-
* Corresponding author. Tel.: þ91 4066303586; fax: þ91 4066303998. anone and formaldehyde react to give hard resins which find use in
E-mail address: [email protected] (S. Dinda). the coating industry [3].

http://dx.doi.org/10.1016/j.polymer.2015.02.013
0032-3861/© 2015 Elsevier Ltd. All rights reserved.
U. Appala Naidu, S. Dinda / Polymer 61 (2015) 204e212 205

Most of the natural resins are quickly affected by caustic potash Table 1
or caustic soda. Many synthetic resins (e.g. phenoleformaldehyde Effect of reaction parameters on selfecondensation of cyclohexanone.

resin) are also affected by strong alkali. Ketonic resins (obtained Reactant/monomer Pressure, kg/cm2(g) Temp, C Time, hr Yielda, wt.%
from ketone monomer) have the ability to resist caustic alkali and A B C D
even on boiling the resin with alkali [4]. Ketonic resins can be used
Cyclohexanone 20390 200 0.5 5 <1 1 0
in combination with high molecular weight film formers (e.g. cel-
Cyclohexanone 20390 250 0.5 1 <1 1 12
lulose derivatives, chlorinated rubber, vinyl esters, vinyl ethers, Cyclohexanone 35690 200 0.5 7 <1 2 0
vinyl chloride, vinyl aromatics etc.) or chemically drying binders Cyclohexanone 35690 250 0.5 1 <1 1 34
(e.g. alkyd resins) for production of surface coatings and also for Cyclohexanone 45890 200 0.5 1 <1 2 10
Cyclohexanone 45890 250 0.5 1 <1 1 27
making adhesives, printing inks, toner, pigments, varnishes for
a
surface treatment of wood, metal etc. [5,6]. A ¼ 2e(1ecyclohexenyl) cyclohexanone; B ¼ 2ecyclohexylidene cyclohexa-
Cyclohexanone (C6H10O) consists of sixecarbon cyclic molecule none; C ¼ 2,6edicyclohexenyl cyclohexanone; D ¼ dodecahydrotriphenylene.

with a ketone functional group. Majority of cyclohexanone is

consumed for production of precursors for Nylone6,6 and Nylone6 temperature range of 80e110 C. The reported conversion of
polymer. Cyclohexanone is not carcinogenic in nature but moder- cyclohexanone is around 30% with a yield of around 95% of
ately toxic, with a threshold limit value (TLV) of 25 ppm for vapor. 2e(1ecyclohexenyl) cyclohexanone. However the scope of the
Ketonic compound itself offers as an excellent candidate for process disclosed in the patent is limited to the preparation of
manufacture of synthetic resin, and has the potential of replacing dimer products only and is silent about the polymerization prod-
more hazardous materials like phenolic and aldehyde compounds. ucts of cyclohexanone.
Muzart [9] in 1982 studied the selfecondensation reaction of
2. Literature review on cyclohexanone polymerization ketones (cyclopentanone and cyclohexanone) catalyzed by basic
reaction aluminium oxide (Al2O3) at room temperature. The reaction yielded
2ecyclopentylidene cyclopentanone from cyclopentanone, and
2.1. Studies on dimer and trimer formation reaction cyclohexanone yielded 2e(1ecyclohexenyl)cyclohexanone.
Walter et al. [10] in 1984 disclosed a process on aldol conden-
The most probable dimer products obtained from base catalyzed sation of acetone and other carbonylecontaining compounds using
aldol condensation of cyclohexanone are shown in Fig. 1. a synthetic clay mineral as catalyst. The general formula of the
Tsutomu et al. [7] in 1974 studied the selfecondensation of anionic clay mineral catalyst is: MmNn(OH)(2mþ2n)$Aa$bH2O, where,
cyclohexanone and its methyl substituted derivatives (e.g. ‘M’ is a divalent metal cation (e.g. Mgþ2), ‘N’ is a trivalent metal
2emethyl cyclohexanone, 2,6edimethyl cyclohexanone) at a cation (e.g. Alþ3), ‘A’ is a mono, di, or trivalent anion (e.g. CO2
3 ), ‘m’
pressure range of 20400e51000 kg/cm2(g) and temperature range and ‘n’ are numerical values which vary between 1 and 6, a ¼ n,
of 160e300 C in the absence of catalyst. Mixtures of dimer, trimer when ‘A’ is monovalent anion & a ¼ (1/2)n, when ‘A’ is divalent
and tetramer products were identified during the course of reac- anion, and ‘b’ is an integer having the values of 1e10. In the work,
tion. IR, NMR and mass spectroscope instruments were used to cyclohexanone was passed through a tubular reactor filled with
identify the products. They identified various products such as inehouse developed catalyst (M6N2(OH)16$A$4H2O) at a tempera-
2e(1ecyclohexenyl) cyclohexanone, 2ecyclohexylidene cyclohex- ture of 300 C. Gas chromatography technique was used to identify
anone, 2,6edicyclohexenyl cyclohexanone, and dodecahydro- the product compounds. Around 42% conversion of cyclohexanone
triphenylene as a result of selfecondensation of cyclohexanone. was identified. The product mixture contained around 13% of
The reported values of selfecondensation of cyclohexanone under 2e(1ecyclohexenyl) cyclohexanone and 24% of 2ecyclohexylidene
various reaction conditions are summarized in Table 1. cyclohexanone.
The work also reports that the selfecondensation of Jose et al. [11] in 1993 studied kinetics of selfecondensation of
2emethylcyclohexanone produces around 20 wt.% yield of cyclohexanone in presence of Amberlyste15 resin catalyst at a
2,2emethyle(2emethylcyclohexenyl) cyclohexanone at 20390 kg/ temperature range of 70e110 C. The experiments were conducted
cm2 pressure and 200 C temperature for a reaction time of 1 h. in a glass reactor equipped with a mechanical stirrer and reflux
From the results, it can be said that during selfecondensation of condenser with a DeaneStark apparatus for removal of the
cyclohexanone under high pressures and temperatures, initially condensate water. A mixture of dimer and trimer products such as
dimer products are formed and then it leads to the formation of 2(1ecyclohexenyl) cyclohexanone, 2ecyclohexylidene cyclohexa-
trimer, tetramer and polymer products with sufficient reaction none, 2,6edicyclohexylidene cyclohexanone were obtained during
time. However, the operations of high pressure process may not be the course of reaction. The concentration of cyclohexanone was
a viable route most of the time and enhanced safety features need measured by gas chromatography (GC) and the moisture content
to be incorporated in the process. was measured by KarleFischer analysis. In the work, the conversion
Joseph et al. [8] in 1976 patented a process for preparation of of cyclohexanone was studied at various temperatures and at
2e(1ecyclohexenyl) cyclohexanone by selfecondensation of different catalyst concentrations. The important findings of their
cyclohexanone in presence of Amberlitee200 resin catalyst at a study are summarized in Table 2.

Fig. 1. Reaction scheme of base catalyzed aldol condensation of cyclohexanone. I¼ 2e(1ecyclohexenyl) cyclohexanone, II¼ 2ecyclohexylidene cyclohexanone.
206 U. Appala Naidu, S. Dinda / Polymer 61 (2015) 204e212

Table 2 to describe the dimerization reaction of cyclohexanone. The study

Effect of temperature and catalyst concentration on cyclohexanone conversion. says, accumulation of condensed water within the reacting system
Temp, C Catalyst Pressure, With water Estimated has negative effect on the reaction rate. The activation energies of
loading, g/L kg/cm2 (g) elimination, conversion, % forward and backward reactions (shown in Fig. 1) are 177.1 and
yes/no 51.8 kJ/mol respectively.
70 1 0.126 yes 2 YingeLing et al. [15] in 2012 patented a process for producing
80 1 0.126 yes 6 2e(1ecyclohexenyl) cyclohexanone by selfecondensation of
80 5 0.126 yes 33
cyclohexanone in presence of solid acidic (AlxSyOz) catalyst at a
80 10 0.126 yes 56
100 1 1 no 10 temperature range of 130e150 C using a stainless steel reactor
100 5 1 no 20 equipped with a stirrer. The catalyst was prepared by soaking
100 10 1 no 26 Al(OH)3 in sulfuric acid solution for 1 h followed by calcination at
100 10 0.126 yes 63
450 C. The samples were analyzed by GC to find the conversion
110 1 1 no 12
110 5 1 no 26
and selectivity. When the reaction was carried at 150 C for 6 h
110 10 1 no 31 duration with catalyst concentration of 4 wt.%, the conversion of
cyclohexanone is around 95% with a selectivity of 83% towards
2e(1ecyclohexenyl) cyclohexanone. The effect of temperature and
The data shows that the conversion increases with the increase catalyst loading on cyclohexanone conversion and selectivity to-
of reaction temperature and catalyst loading and it is more signif- wards 2e(1ecyclohexenyl) cyclohexanone is shown in Table 4.
icant when the condensed water is removed from the reaction The data says that rate of reaction increases with increase in
mixture. reaction temperature and catalyst loading. However, there is no
Shah et al. [12] in 1994 studied the liquidephase aldol information available in the article regarding the comparative
condensation of cyclohexanone to yield 2e(1ecyclohexenyl) study between the inehouse developed catalyst and the conven-
cyclohexanone in presence of Amberlyste15 and acidetreated clay tional alkali catalysts such as NaOH, KOH. Moreover, the scope of
as catalysts at a temperature range of 100e160 C. study was limited to dimerization reaction only.
Yogesh et al. [13] in 2008 have studied the selfecondensation of David et al. [16] in 2013 have studied the kinetics of dimer for-
cyclohexanone to yield mainly dimer, trimer and tetramer products mation reaction in the process of selfecondensation of cyclohexa-
in the presence of various types of acidic ion exchange resin cata- none in presence of sodium hydroxide catalyst. The liquidephase
lysts, such as, Amberlyste15, Amberlyste45, Te63, Te66, ZSMe5 reaction was conducted at a temperature range of 127e149 C in a
and Zeolite b. The experiments were conducted in a mechanically batch reactor equipped with thermostat glycerin bath in order to
agitated glass reactor equipped with constant temperature bath at maintain a constant temperature. The authors have studied the
a temperature range of 80e100 C under atmospheric pressure. The effect of reaction temperature and catalyst concentration on
effects of various parameters such as temperature, catalyst loading, condensation reaction. Nitrogen gas was used to maintain the
and reusability of catalyst on cyclohexanone conversion were reactor pressure. The samples were analyzed by using GC. Dimer,
investigated. Gas chromatography technique was used to identify trimer and tetramer products were identified and quantified by gas
the product compositions. Some important results obtained from chromatographyemass spectroscopy (GCeMS). Based on GCeMS
selfecondensation of cyclohexanone are summarized in Table 3. analysis, the calculated concentration of trimer and tetramer
From the table it can be said that the conversion of cyclohexa- products combindly was less than 5%. Some of the reported infor-
none increases with increase in both temperature and catalyst mation relevant to the present review is summarized in Table 5.
loading but the extent of increment is very small. With respect to The data shows that dimer concentration increased with the
monomer conversion, Amberlyste45 looks somewhat better than increase of both temperature and catalyst loading. Around 80%
Amberlyste15 catalyst. However, the monomer conversions are conversion of cyclohexanone was achieved in the study. ‘Lumped
comparable to both Te63 and Amberlyste45 catalysts under Model’ method was used to develop the kinetic rate expression of
identical conditions. the studied reaction. The estimated activation energy of cyclohex-
Yeqiang et al. [14] in 2011 have studied the kinetics of the anone selfecondensation reaction is 132.6 kJ/mol. The article
reversible dimerization reaction of cyclohexanone in presence of mainly deals with the formation of dimer and trimer products and
gealumina catalyst over the temperature range of 110e130 C. The no special attention was given on the formation of higher polymer
reactions were performed in a glass reactor equipped with a reflux compounds.
condenser and a mechanical stirrer. The product samples were
analyzed by GC. The water content was measured by KarleFischer 2.2. Studies on ketoneealdehyde resins
instrument. The LangmuireHinshelwood kinetic model was used
Huxham [4] in 1924 patented a process to prepare ketone-
ealdehyde resins. The objective of the study was to develop an
Table 3 infusible resin that can be used as binder in the manufacture of
Effect of temperature, type of catalyst and catalyst loading on cyclohexanone
conversion.
plastic articles or molded objects intended for insulating purposes,
heat resistance, acid and alkali resistance. The reaction was
Temp, C Catalyst type Catalyst loading, wt. % Estimated conversion, %

80 Te63 3 33
90 Te63 3 38 Table 4
100 Te63 3 41 Effect of temperature and catalyst loading on conversion and selectivity.
90 Te63 5 41
Temp, C Catalyst loading, wt.% Approx. conversion, % Selectivity, %
90 Te63 7 43
100 Te66 3 29 130 4 38 100
100 Amberlyste15 3 36 140 4 86 92
100 Amberlyste45 3 41 150 4 95 83
100 ZSMe5 3 Negligible 140 8 89 80
100 Zeolite b 3 Negligible 140 12 96 66
U. Appala Naidu, S. Dinda / Polymer 61 (2015) 204e212 207

Table 5 Table 6
Effect of temperature and catalyst concentration on dimer formation. Effect of various operating parameters on physicoechemical properties of ketone-
ealdehyde resins.
Temp, C Pressure, Catalyst concentration, Dimer concentration,
kg/cm2(g) mmol/kg mmol/kg Raw materials Catalyst Temp, Time, Physicoechemical

C hr properties of resin
127 0.51 1.6 0.06
12.5 0.65 Methyl acetone NaOH 50e70 e d Soluble in acetone
30 1.10 and formalin d Fusible in nature
138 0.71 1.6 0.09 d Softening point <100 C
12.5 1.35 Methyl acetone NaOH 105 15 d Insoluble in acetone
30 2.50 and formalin d Slightly fusible in nature
149 0.81 1.6 0.11 Acetone and paraform NaOH 50e70 e d High viscous liquid
12.5 2.50 d Fusible in nature
30 3.35 Acetone and paraform NaOH 100 12 d Infusible in nature
d Opaque hard resin

performed in a mechanically agitated jacketed vessel with cooling

and heating arrangements. The patent says that when methyl
acetone was condensed with formalin (37% formaldehyde solution) Hurst et al. [18] in 1951 disclosed a process for synthesis of
in the presence of caustic soda at a temperature of about 65 C, a ketoneealdehyde resins by reacting the cyclohexanone and/or
brown colored viscous product was obtained. Once the viscous methyl cyclohexanone with formaldehyde in presence of NaOH as
material was formed, the reaction was stopped by adding dilute catalyst. The objective of the study was to develop a resin which
sulfuric acid to the reacting mixture to obtain a specific polymer could be used for coating application. In the process, aldehy-
product. Then the reaction mass was washed with hot and cold deetoeketone molar ratio was maintained in the range of 0.6e0.73
water successively to get the final resin product. The product was and the catalyst concentration varied in the range of 0.25e1.0 wt.%.
soluble in acetone, fusible in nature and its softening point was Initially the temperature of the reaction mixture was maintained at
below 100 C. The resin was further heated at 105 C for about 15 h around 60 C and then the temperature was raised to around 100 C
and then analyzed its physicoechemical properties. The product and maintained at this level until the reaction was substantially
was slightly infusible in nature and was insoluble in most of the complete. The pH of the reaction mixture was controlled within the
solvents such as acetone, alcohols and monochlorobenzol etc. In range of 6.5e7.5. In order to get a clear light colored resin, the re-
another set of experiments, acetone and paraform (crystalline action mass was dissolved in toluene to reduce the resin viscosity
polymer of formaldehyde) were used as raw materials to produce and separated the catalyst from resin solution by filtration. The
ketoneealdehyde resins. Some important observations of the in- effects of various operating parameters on product quality are
vention are summarized in Table 6. summarized in Table 8.
The patent also says that the developed resins can be used in The data shows that the melting point of the resin increased
molded articles in the range of 20e30 wt.% to reduce the cost of with the increase of reaction severity. However, the patent is silent
articles. Ketonic resins may be incorporated with other resins, such about the average molecular weight, hydroxyl content, iodine
as, natural resins or with synthetic resins like phe- value, and solubility of developed ketoneealdehyde resins.
noleformaldehyde resin, to change the properties. Rainer et al. [19] in 1980 disclosed a process to produce a
Harold et al. [17] in 1949 patented a process to prepare a highly ketoneealdehyde polymer of higher softening point. To achieve the
hydroxylated ketoneealdehyde resin by condensing ketones with required specification, polymerization reactions were carried out
aldehyde (formaldehyde) at a temperature range of 40e100 C. The under atmospheric pressure in presence of NaOH along with
reactions were carried out in presence of calcium oxide (CaO) various phase transfer catalyst (PTC). In the process, organic sol-
catalyst with catalyst concentration range of 0.25e0.75 mol per vents such as methanol, isobutanol etc. were used as mobile phase.
mole of ketone. The condensation reactions were performed in a The reaction was performed in a reactor with reflux facility. The
glass vessel equipped with an agitator and a reflux condenser. In reaction conditions and corresponding product properties are
the work, acetone was condensed with formaldehyde at a tem- mentioned in Table 9.
perature of 50 C for 2 h. After 2 h the reaction mass was cooled and From the reported data, it can be said that the presence of PTC
treated with dilute sulfuric acid followed by oxalic acid solution to greatly influenced the reaction yield. The yield of resins and also the
precipitate the catalyst in the form of calcium oxalate and calcium softening point of resins increased in the presence of PTC. In
sulfate. After removing the precipitate by filtration, the filtrate was presence of TCMAC and TCMPJ, the products softening points were
stirred for several hours in presence of basic ioneexchange resin. increased to about 30 C and 60 C respectively. The inventor claims
The resin was then removed by filtration, and subjected to treat that the developed resins can be used in various applications, such
with charcoal in order to remove color imparted by the resin. To as, making paints, adhesives, binders etc.
remove the moisture, the resin was dissolved in alcohol and treated Fischer et al. [5] in 1987 patented a process for the preparation
with watereimmiscible solvent, such as, benzene, followed by of stable aqueous dispersions of a ketonic resin or ketoneealdehyde
distillation. The inventor also performed the condensations using resin. According to the invention, ketonic resin from cyclohexanone
methyl ethyl ketone, cyclopentanone, diacetyl and mesityl oxide
with formaldehyde to produce different types of ketoneealdehyde Table 7
resins. The technical details of their invention are summarized in Effect of various parameters on hydroxyl content of a synthetic resin.
Table 7.
Raw materials Catalyst Temp, C Time, hr Hydroxyl content, %
The work exhibits that the hydroxyl content decreases with
Acetone and formalin CaO 50 2 27.3
increase in temperature. However, the scope of the study disclosed
Acetone and formalin CaO 90 2 13.7
in the patent is limited to the preparation of ketoneealdehyde Cyclopentanone and CaO 60 0.5 27.4
resins. It is silent about the physicoechemical properties, such as, paraformaldehyde
average molecular weight, solubility, viscosity, softening point, Diacetyl and formalin CaO 55 1 20
iodine value etc. and the applications of developed ketone- Mesityl oxide and CaO 45 2 24
paraformaldehyde
ealdehyde resin products.
208 U. Appala Naidu, S. Dinda / Polymer 61 (2015) 204e212

Table 8 Table 10
Effect of temperature, reflux time and aldehydeetoeketone ratio on product quality. Filmeforming properties: minimum filmeforming temperature and film hardness
for dispersions containing various filmeforming assistants.
Raw materials Aldehydeeto Temp, Reflux Product properties
eketone molar C time, hr Filmeforming Dispersion/filmeforming Minimum Efflux Film
ratio assistant assistant ratio, vol/vol filmeforming time, hardness
temp, C sec (by Konig
Cyclohexanone, 1.4 95 1 d Colorless resin
method), sec
cyclohexanol and d Melting point 90 C
formalin Ethyleneglycol 9:1 19 84 108
Methylcyclohexanone 1.6 90 1.2 d Colorless resin acetate
and formalin d Melting point 78 C Ethyleneglycol 4:1 16 108 69
Cyclohexanone 1.6 95 1 d Colorless resin acetate
and formalin d Melting point 87 C Xylene 9:1 20 127 69
Cyclohexanone 1.4 75 0.5 d Crystaleclear resin Xylene 4:1 16 206 58
and formalin d Melting point 79 C Mineral sprit 9:1 13 120 78

having a softening point of about 80 C was dissolved in isobutanol groups to hydroxyl groups and subsequent esterification of some of
at 80 C. Then a mixture of 15% aqueous solution of the hydroxyl groups. Laropal K80 (ketonic resin developed by BASF,
Nevinylepyrrolidone and vinyl propionate in the ratio of 2:1, and Germany) was used as the starting material for their study. The
oxyethylated tallow fatty alcohol as emulsifying agent were added reduction of Laropal K80 was studied by using LiAlH4 and NaBH4
to the resin solution at around 70 C and stirred it for 20 min. Then separately. PerkineElmer 599B grating infrared spectrophotometer
the required amount of water was added dropewise to the solution was used to analyze the samples. Based on IR analysis, the authors
during 90 min at 65 C and stirred continuously. The mixture was concluded that reduction of ketone groups into hydroxyl groups
then cooled to room temperature to obtain stable resin dispersion was achieved completely. The esterification reaction was per-
with solids content of 52.5%. The developed resin dispersion formed by using different acylating agents with various concen-
formed a film at around 70 C. Further the film formation was tration and it was found that sample with lower degree of
improved by adding different filmeforming assistants. The esterification is relatively more brittle in nature than the sample
filmeforming properties of the dispersions with respect to various with higher degree of esterification. Various properties such as
filmeforming assistants are summarized in Table 10. glass transition temperature, hardness, and flexibility of the
The data shows that the viscosity (efflux time) of products de- reduced resins were measured and compared with commercially
creases with the increase of dispersion concentration. The reason available resin MS2A. The measured values of physicoemechanical
for this inverse trend is not very clear from the disclosure but it is properties are given in Table 11.
quite possible if the viscosity of the dispersion resin is less Based on the data it can be said that the reduced ketonic resins
compared to the filmeforming assistants. However, the film hard- are more stable and flexible over nonereduced ketonic resins.
ness increases with the increase of dispersion concentration and Niklewicz et al. [21] in 1992 have patented a process for prep-
also with the polarity of the filmeforming assistant. The patent is aration of cyclohexanoneeformaldehyde resin in presence of NaOH
silent about the average molecular weight, hydroxyl content, and catalyst at a temperature of 260 C. According to the invention, the
iodine value of the developed ketoneealdehyde resins. developed resin was soluble in aliphatic solvents such as heptane,
Rie and Shedrinsky [20] in 1989 have published an article on the hexane etc.
synthesis of a ketonic resin that can be used as additive for paints Martina et al. [22] in 1998 have disclosed a process for the
and lacquers applications. Brittleness property is one of the draw- preparation of ketoneealdehyde resins through condensation re-
backs of a ketonic resin particularly for picture varnish applications. action of ketone (cyclohexanone, 4etertebutyl cyclohexanone,
Sometimes plasticizers are added to the ketonic resin to overcome methyl ethyl ketone, acetophenone etc.) with an aldehyde, espe-
the brittleness. In the article, the authors mainly focused on the cially formaldehyde in presence of NaOH. The inventors have
synthesis of a stable and flexible resin by reduction of ketonic studied the solubility and compatibility tests of the inehouse
developed resins with various solvents and resins. In the work, the
calculated amount of ketones and formalin was taken as initial
Table 9 charge and heated to 60 C. Then the required amount of 50%
Effect of various reaction parameters on product properties. aqueous NaOH solution was added dropewise and the mixture was
Raw materials PTCa Temp, C Reflux Product properties heated to 80 C. Subsequently the remaining quantity of formalin
time, hr was added dropewise over the course of 90 min and the mixture
Methyl ethyl ketone, e 80 2 d Hard resin was refluxed at 85 C for 4 h. After 4 h, the reaction was stopped by
acetone and formalin d Yield of 68% adding glacial acetic acid to the reaction mass. Then the reaction
d Softening point mass was washed with water to obtain a neutral resin. The solu-
of 88 C bility tests were performed in various solvents such as butanol,
Methyl ethyl ketone, TCMAC 80 2 d Hard resin
acetone and formalin d Yield of 79%
methyl ethyl ketone (MEK), xylene etc., and the same was
d Softening point compared with two commercially available
of 118 C
Cyclohexanone and e 90 1 d Hard resin
formalin d Yield of 69% Table 11
d Softening point Physical and mechanical properties of the ketonic resins.
of 88 C
Resin Glass transition Pendulum Flexibility,
Cyclohexanone and TCMPJ 90 1 d Hard resin
temp, C hardness, sec mm
formalin d Yield of 75%
d Softening point Laropal K80 43 130 149
of 148 C Reduced Laropal K80 58 185 199
a MS2A 57 214 189
TCMAC ¼ tricaprylmethylammonium chloride; TCMPJ ¼ tricaprylmethyl-
Acetic ester e 101 131
phosphoniumjodid.
U. Appala Naidu, S. Dinda / Polymer 61 (2015) 204e212 209

Table 12
Solubility of ketoneealdehyde resin in various solvents.

Resin sample Solvent

Butanol MEK Butyl acetate Xylene Mineral oil

a
4etertebutylecyclohexanone and formalin resin S S S S S
4etertebutylecyclohexanone, methyl ethyl ketone and formalin resin S S S S S
4etertebutylecyclohexanone, cyclohexanone, 3,3,5etrimethyl cyclohexanone, and formalin resin S S S S S
AFS resin S S S S PSb
CA resin S S S S PS
a
S ¼ completely soluble.
b
PS ¼ partly soluble.

cyclohexanoneeformaldehyde resins such AFS resin from Bayer AG among nonehydrogenated resins. The inventor claims that the
and CA resin from Huls AG. A summary of the solubility test are developed resins could be used in various fields, such as, making
tabulated in Table 12. coating materials, printing dyes, inks and polishes. However, in the
The synthesized resins were also compatible with various patent, there is no information available regarding the hydroxyl
binders and resins such as polymethacrylate resin, epoxy resin, value, iodine value and acid value of the developed resin.
polyamide resin, linseed oil and with two commercially available Gloeckner et al. [24] in 2006 patented a process to produce low
AFS resin and CA resin. According to the disclosure, the synthetic water content, high thermal stability ketoneealdehyde resins by
resins were brittle in nature, the average molecular weights of the condensing cyclohexanone with formaldehyde in presence of
ketoneealdehyde resins were in the range of 500e1000 g/mol, and NaOH along with benzyltributylammonium chloride as phase
softening point was in the range of 80e90 C. transfer catalyst (PTC). Methanol was used in the condensation
Dorffel [23] in 1988 patented a process to produce an alkyl aryl reaction as auxiliary solvent. The reaction was performed in a
ketoneeformaldehyde resin of high softening points in presence of threeeneck flask with stirrer and reflux condenser at a temperature
alkali metal hydroxides such as NaOH, KOH etc. To enhance the of about 60 C and at atmospheric pressure. The reaction reflux
condensation reaction, phase transfer catalysts (PTCs) such as time was maintained for 4 h. Acetic acid was added to the product
quaternary ammonium or phosphonium salts were used in the for neutralization and was washed with water for several times.
process. The organic solvents such as methanol, isopropanol were Finally the product was subjected to vacuum distillation at 165 C
used in the process as coesolvents. The condensation reaction was for removal of solvents. The inventor claims that the developed
performed in an agitated flask with reflux provision. The reaction resin can be used in various applications including in coatings,
temperature was maintained in the range of 70e100 C with a printing inks, pigment pastes, tinting pastes, ballpoint pastes, pol-
reflux time of 2 h. The reaction was carried out under atmospheric ishes, adhesives, sealants and insulating materials. Some relevant
pressure. The aqueous phase from the reaction mass was separated properties of the developed resin are mentioned in Table 14. The
by gravity decantation. The residue was dissolved in methylene author compared the properties of the developed resins (in pres-
chloride and the organic phase was washed with deeionized water. ence of PTC) with similar kind of resins prepared in absence of PTC
Excess solvent from the product was evaporated at a vacuum of by various research groups. It is reported that a variety of
0.004 kg/cm2 and a temperature of 160 C. The softening points and
molecular weights of the resins were determined by capillary
Table 14
method and vapor pressure osmometry respectively. The reported
Physicoechemical properties of the developed ketoneealdehyde resin.
reaction conditions and product properties are summarized in
Table 13. The inventors also studied the catalytic hydrogenation Physicoechemical properties Reported values

reaction of the developed alkyl aryl ketoneeformaldehyde resin. Physical appearance d Colorless, clear and brittle
The hydrogenation reaction was carried out in a longitudinal stroke Solubility, wt% d Around 10% soluble in ethanol,
MEK, acetone, ethyl acetate and xylene
autoclave in presence of copper catalyst activated with chromium
Softening temperature, C 106
at a temperature of 135 C and a pressure of 306 kg/cm2. The hy- Gardner color number, 0.5
drogenated resin was soluble in ethanol and its softening point was 50 wt.% in ethyl acetate
around 136 C. KarleFisher water content, wt.% 0.14
Based on the reported data, it may be said that the molecular Hydroxyl number, mg KOH/g resin 96
Glass transition temperature, C 71
weights and softening points of the resins increased in presence of Molecular weight, g/mol Mn ¼ 650; Mw ¼ 1200
PTCs and observed that molecular weights and softening temper- Volatiles content, wt.% d 1 h at 120 C ¼ 0.2
atures are independent of conversion of monomer. It is further d 1 h at 140 C ¼ 0.4
observed that hydrogenated resin offers higher softening points d 1 h at 160 C ¼ 0.5

Table 13
Effect of various reaction parameters on product properties.

Reactants PTCa PTC loading, wt.% Conversion, % Number average molecular weight, g/mol Softening point, C

Acetophenone and formalin TMBAC 1 >96 1060 98

Acetophenone and formalin TMBAC 0.5 >95 1100 94
Acetophenone and formalin TEBAC 0.5 >96 1210 98
Acetophenone and formalin BTPPC 0.5 >96 830 80
Acetophenone and formalinb e e >96 650 65
a
TMBAC ¼ trimethylbenzylammonium chloride; TEBAC ¼ triethylbenzylammonium chloride; BTPPC ¼ benzyltriphenylphosphonium chloride.
b
NaOH was washed with deionized water alone (without methylene chloride).
210 U. Appala Naidu, S. Dinda / Polymer 61 (2015) 204e212

Table 15 Table 17
Physicoechemical properties of the developed resin. Specifications of ketoneealdehyde resins.

Properties Reported values/Remark Resin properties Product specifications

Solubility d Soluble in ethanol and xylene KTRe100 KTRe118 KTRe123

Water content, wt.% <0.3
Appearance White prills White prills White prills
Thermal stability d Low tendency to undergo
Softening point, C 95e105 105e115 105e115
yellowing
Viscosity (50 wt.% solution in 75e95 100e120 110e140
Nonevolatile content at 160 C, wt.% 99.4
butyl acetate at 25 C), cP
Softening point, C 50e80
Moisture content, wt.% (max) 3.0 3.0 3.0
Hydroxyl number, mg KOH/g resin 5e200
Acid value, mg KOH/g resin, (max) 0.2 0.2 0.2
Number average molecular weight, g/mol 400e900
Hydroxyl value, mg KOH/g resin, (max) 170e200 180e210 200e230
Iodine value, g Iodine/100 g resin (max) 2.0 2.0 2.0

In the patent, the scope of the study was limited only to the
condensation reaction of cyclohexanone and formaldehyde
mixture, and it is silent about condensation of any other ketones
either as a single compound or their mixtures.
Gloeckner et al. [25] in 2010 patented a process to prepare a
ketoneealdehyde resin of broad solubility properties and low color
numbers. According to the invention, a ketone was condensed with
Fig. 2. Probable structure of cyclohexanoneeformaldehyde resin.
an aldehyde in presence of NaOH along with tribu-
tylbenzylammonium chloride (TBBAC) as phase transfer catalyst
(PTC). Low molecular weight organic alcohol (e.g. methanol,
cyclohexanoneeformaldehyde resins prepared in absence of PTC, ethanol) was used in the condensation reaction as an auxiliary
are available in the market with the softening point range of solvent. The reaction was carried out in a glass reactor at a tem-
75e120 C, hydroxyl number range of 80e260 mg KOH/g resin and perature of 85 C for 4 h under atmospheric pressure. The reaction
water content between 0.4 and 2.5 wt%. conditions and product properties are summarized in Table 16.
From the reported information, it is clear that the presence of According to the disclosure, the developed resins could be used for
PTC in the condensation reaction leads to obtain a low moisture making coating materials, printing inks, pigment pastes, and pol-
content and low Gardner color number ketoneealdehyde resin. ishes etc.
Werner et al. [3] in 2007 have disclosed a process for preparing The result shows that the addition of PTC into the condensation
ketoneeformaldehyde resin which possesses low water content, reaction significantly decreases the Gardiner color number without
high thermal stability and yellowing resistance. In coating industry, altering the solubility of the resins.
resins are often used to reduce the solvent fraction. However, high Suparna Chemicals [6], an Indian chemical company, manufac-
molecular weight resins are not favorable for coating applications tures synthetic resins by reacting cyclohexanone with formalde-
due to their limited solubility. The major drawbacks for aqueous hyde in a batch process. The resins are available in market by
alkali catalyzed condensation reaction of ketones with aldehyde different trade names such as KTRe100, KTRe118 and KTRe123
are: i) large amounts of methanol or ethanol have to be used as and used for various applications.
solvent since ketones have a limited solubility in water; ii) removal Ketonic Resins (KTR) dissolve readily in alcohols (e.g. propanol,
of catalyst from reaction mixture by simple washing is a time butanol, pentanol), ketones (methyl ethyl ketone, cyclohexanone),
consuming process. Therefore, considering all these facts, the in- ester, and in low chlorinated hydrocarbons. It is neutral, light in
ventors performed the condensation reaction by adding cyclohex- color and inert to saponification. Ketonic Resins have good pig-
anone and paraformaldehyde in a threeeneck flask equipped with mentewetting properties. This leads to brilliant gloss even at high
a water condenser in presence of tetraeethylammonium hydroxide pigmentation. In printing inks, KTR improves solid content, hard-
(TEAH) catalyst at a temperature range of 60e80 C. The reaction ness, adhesion and drying time. KTR also increases yield of coating
was continued for around 3 h and the condensed water was systems. The available specifications of ketoneealdehyde resins are
removed continuously. The pH of the reaction mixture was main- summarized in Table 17.
tained at around 8. After 3 h, the catalyst was removed from the
reaction mixture under vigorous stirring at a temperature of about
160 C and then the reaction mass was allowed to cool to room 2.3. Studies on ketonic resins
temperature. A light colored resin was obtained with a yield of 87%.
The physicoechemical properties of the product are summarized in Kocian et al. [26] in 1971 patented a process to prepare ketonic
Table 15 and the simplified structure of cyclo- resins by condensing the methylcyclohexanone with cyclohexa-
hexanoneeformaldehyde resin is shown in Fig. 2. none in a Ni reactor in presence of methanolic KOH catalyst.

Table 16
Effect of various reaction conditions on product properties.

Raw materials Solvent PTC loading, wt.% Softening temp, C Gardner color number, Solubility, 10 wt.% in
50 wt.% in ethyl acetate white spirit/ethanol

Trimethylcyclohexanone, cyclohexanone and formalin Ethanol e 57 4.5 þþ/þþ

Trimethylcyclohexanone, cyclohexanone and formalin Ethanol e 59 3.9 þþ/þþ
Trimethylcyclohexanone, cyclohexanone and formalin Methanol 0.3 60 1.1 þþ/þþ
Trimethylcyclohexanone, cyclohexanone and formalin Methanol 0.3 56 0.8 þþ/þþ

þþ ¼ completely soluble.
U. Appala Naidu, S. Dinda / Polymer 61 (2015) 204e212 211

Initially the reactor was pretreated with 20% aqueous NaOH at a Table 18
temperature of 125 C and at around 2.5 kg/cm2 pressure. Once Physicoechemical properties of MS2A resin.

pretreatment step was complete, the aqueous NaOH was drained Resin properties Values
from the reactor and the reactants were charged into the reactor for Acid value, mg KOH/g resin Practically zero
condensation reaction. The obtained resin according to the inven- Hydroxyl value, mg KOH/g resin >190
tion was having a softening point of 90 C. Softening temperature, C 85e100
Vincent [27] in 2000 has published a report on history of Density, g/cc 1.08
Refractive index 1.505
development of various ketonic resins such as MS2, MS2A, AW2
Molecular weight, g/mol Mn ¼ 769, Mw ¼ 1776
and Ketone ResineN. The report says that synthetic resin from
methylcyclohexanone and cyclohexanone mixture was produced
commercially in1930's by the brand name AW2 (by BASF, Ger-
many). At the same time, a similar kind of ketonic resin was pro- authors have studied the effect of various operating parameters
duced commercially as MS2 (by Howards, UK) by condensation of like reaction time, reaction temperature and ketoneetoealkali
methylcyclohexanone. Both the resins were used mainly in paints ratio on the polymerization reaction. In the study, reaction time
and varnishes as lightefast additives to improve gloss and hard- varied in the range of 12e20 h and temperature varied in the range
ness. It is reported that these resins lose its yellowing resistance of 130e160 C. The reaction was performed in an autoclave under
and solubility over a time and that may be due to degradation of autogenously developed pressure. Various physico-chemical
ketonic groups and/or double bonds in presence of light. In 1959, properties like solubility, hydroxyl value, iodine value etc. of the
Howards with the support of Garry Thompson (the Scientific resin products were analyzed in the study. Based on the outcome
Advisor of London National Gallery) developed MS2A resin from of the study, it is concluded that the degree of polymerization
MS2 by reduction with sodium borohydride in presence of meth- increases with the decrease in ketoneetoealkali ratio, leads to
anol. The probable chemical structure of MS2A resin is shown in increase in hydroxyl value, softening point and decrease in
Fig. 3 and the physicoechemical properties of MS2A resin are solubility.
summarized in Table 18. In 1963 the BASF developed MS2B resin
from AW2 as an alternative source of ketonic resin. MS2B was 3. Conclusion/perspective
produced commercially for paintings conservators until 1967. In
1967 the BASF developed Ketone ResineN from cyclohexanone as a Resins are essentially polymers, which are built up from simple
replacement of AW2. The batch process for Ketone ResineN was molecules or monomers and can be prepared mainly by either
succeeded by a continuous process to produce Larapol K80. addition polymerization or condensation polymerization. Ketones
Dinda et al. [28] in 2014 have studied the selfepolymerization and aldehydes can be converted to resinous products by treatment
reaction of cyclohexanone to develop a synthetic ketonic resin. The with an alkali/acid through an aldol condensation reaction. The

Fig. 3. Probable structures of MS2A resin.

212 U. Appala Naidu, S. Dinda / Polymer 61 (2015) 204e212

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