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Improving Resin Colors

Article · September 2012

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 Improving resin colors

Dr. Dieter Guhl

TIB Chemicals AG, Germany

POLYCONDENSATION resins,
like of conjugated double bonds
alkyd- and polyester resins, require high unsaponifiable components and othe
— polymerizsation reactions. r
reaction temperatures during the man impurities. If this is not done properly
u- ,a
facturing process. Temperatures usua high final resin color will be the resu
lly lt.
significantly above 200°C are nece Quality of the raw materials Quality control and careful choice of
ssary the
for well known reasons: they help supplier here is the key for success.
to As long as mainly petrochemical raw
drive out the reaction water, to achi
eve materials are used in the resin recipe,
thedesired molecularweightandto the
lower color development is somewhat limi Proper control of the cooking
the Overall reaction time. Further an ted,
in but the more natural based raw material
the Gase of alkyd resins high tempera- s process
tures induce some polymerization are used, the higher the color incr
reac- ease The presence of Oxygen in the reactor
tions, which influence the viscosit can be.
y of is one of the main reasons for colo
the resin positively. r
Resin raw materials based an natural formation during the cooking proc
ess.
resources are available in a number Inertisation is usually a "must" duri
But there are not only positive effects of ng
qualities and from numerous sour resin production. Minimum requirem
for the application of high reaction tem ces. ent
- is a "blanketing" of the resin kettle with
peratures. Besides the energy cost nitrogen or another inert gas. If the
s the Although their composition and spec reac-
color of the resin is influenced. Not i- tion is run under vacuum, proper seal
very fication look identical, when used ing
surprisingly resin manufacturers note in the of the resin kettle and closing of all
,that resin cook the color development leaks
with high temperatures and Jong may are essential, but this is not easy to achi
reac- be totally different under the Same eve
tion times the color values of the pro- as experiences teil. After finishing
resins cessing conditions. The effect can the
increase. Resin customers prefer bind be resin cook, the vacuum in the reac
- clearly seen by an example usin tor
ers as lightly colored as possible g two should be broken with inert gase
to different grades of oleic acid in a s at
achieve full flexibility for the colo simple higher temperatures or with air, but
ristic ester. The resulting color number in
options in the finished paint. s of the this Gase preferably alter cooling dow
ester show a remarkable differen n
ce al- the resin. The last Option is only reas
The thermally induced color devel- though all other conditions were on-
kept ably viable at low viscosities of the resi
opment of the condensation resi the saure. n,
ns is because otherwise the dilution with
dependent an several factors: sol-
At 200°C 2-Ethylhexanol was este vents to the necessary solids content
ri- is
— quality of the raw material, especial fied under a nitrogen blanket with mechanically difficult and requires more
ly two
of the nature-based oils and fatty different grades of oleic acid. Cata time than usual.
ac- lyst
ids, was TIB KAT 188 at 0.05 % concentr
— proper control of the cooking proc a- Another source for color formation
ess tion in both Gases. The table 1 shows
— the catalyst the are the heat
results of the raw ester alter the ing coils inside the reaction
— use of antioxidants saure kettle. Limiting
reaction time. the maximum tempera-
ture of the heat transfer fluid is essential.
The color formation is chemical The bio based raw materials nee Ittakes itstime until a resin kettle reaches
ly d the desired reac
caused by different reactions as for purification and refining, before they tion temperature. For
ex- can obvious reas
ample: be used in a resin cook. The refi ons the heating time should
ning be as shor
— dehydration reaction process removes phospholipids, gum t as possible, tempting the
s, Operators to put the cont
— Oxidation reaction rols an maxi-
— formation of olefins, aldehyds Table 1: Colo mum va ues.
or r development of different olei
ethers, c acid types alter
esterification at 200°C
— elimination reactions with formatio Overheating
n Oleic Acid Acid Value [mg KOH/gr] the coils leads to
Gardner Color Number
decomposition
Querfes and Responses: Type 1 0,14 reactions of the
5,7
author.paintindia@gmail.com Type 2 0,66 raw materials an
1,4
the surface of the

paintindia O SEPTEMBER 201

2 O 65 ■
 color development, in combination with
Table 2: Catalysts for resins an effective antioxidant may be in the
RESIN Type Lithium Salts Organo Tin Other Metal salts end the more cost effective solution for
Catalysts the resin manufacturer.

Short Oil Alkyd LiOH TIB KAT 248, Ca(OH)Z, Pb0 Very well known antioxidants are
TIB KAT 256 Zinkacetate
based an phosphor containing sub-
Medium Oil Alkyd LiOH, Lithium TIB KAT 248, Zinkacetate, PbO, stances. Triphenylphosphite is one of
Octoate TIB KAT 256 Calcium Octoate the well known additives. Choice of the
Long Oil Alkyd LiOH TIB KAT 248, Ca(OH)Z, Calcium antioxidant is somewhat critical for the
TIB KAT 256 Octoate, Pb0 cooking process, because the antioxi-
dant can lead to formation of turbidity,
Liquid Saturated - TIB KAT 256, -
Polyester Resins TIB KAT 250
which is difficult to remove at higher
resin viscosity. Additionally it can haue
an influence an the catalyst efficiency.
coils. It is well known, that for example In Table 3 it is shown the color devel- Most catalysts are Lewis Acids, which
certain resin catalysts are decomposing opment for an alkyd resin formulation react immediately with the phosphorous
an the coil leaving black layers or par- based an soy bean oil, glycerol, phthalic based Lewis Bases. The result is an in-
ticles an the surface. It can be so much anhydride under the Same reaction con- crease in reaction time.
in quantity that it can be visually seen ditions (Transesterification at 240°C,
alter emptying the reactor. Esterification at 220°C, TIB KAT 248 Table 4 shows results for a medium
concentration at 0.035 %, diluted with oil length alkyd resin testing different
Catalyst influence xylene to 60% solids) for different oil antioxidants.
length.
Use of a catalyst is the most preferred The result of this study is, that steri-
measure to shorten reaction time for cally hindered and hydrolytically stable
condensation resins. Expectation is that Use of antioxidants antioxidants give a good performance
shorter reaction times should result in The use of zntioxidants is the easiest together with TIB KAT 248, although a
lower color numbers for the final resin. measureforthe resin manu-
facturer to influence the
This is not always the case. Most resin color in his favor. Table 3: Color development in dependency of oil length
widely used catalysts are shown in the Although it adds additional Oil Length Catalyst Gardner Color Number
Table 2. cost to the resin, antioxi-
dants increase the flexibil- Short Oil TIB KAT 248 3.4
The catalysts promote the esterifica- ity in raw material selec- Medium Oil TIB KAT 248 5.3
tion and transesterification reaction dur- tion as in catalyst selec-
Long Oil TIB KAT 248 7.5
ing the resin cook. Besides this purpose tion. Using a low-cost oil,
the catalysts also catalyze or induce a which is unfavorable for Long Oil Lithium Hydroxide 5.5
number of side reaction, which increase
the color development. Table 4: Catalysd Antioxidant combinations and their effect an
reaction time and color
It is well known that acidic catalysts
are especially unfavorable in this respect. Catalyst Antioxidant Turbidity Reaction Gardner Color
TIB KAT 250 for example belongs to this Time Number
group of catalysts and Works only in
TIB KAT 248, - Clear 90 min. 5.5
saturated polyester resins without sig-
0.1
nificant color development. For alkyd
resins TIB KAT 250 is not suitable. TIB KAT 248, Tris(2,4 Di-Tert- Clear 120 min. 4.7
0.1 % Butylphenyl)phosphite,
Lead Oxide provides excellent resin 0.06
colors, but is not very well liked due to TIB KAT 248, Trisbutylphosphite, Hazy Not Not measurable
its unfavorable toxicological profile. 0.1 % 0.25 finished
Non acidic catalysts like TIB KAT 248 TIB KAT 248, Triethyleneglycol-bis Clear 145 min. 4.6
0.1 % (3-(5-tert.butyl-4-hydroxy-
work very wel I as accelerator of the reac-
m-tolyl)propionate,
tion with only moderate color develop-
0.06
ment. The lower the oil length of the
alkyd resin, the lower the color number TIB KAT 248, Pentaerythrit-tetra(3,5- Clear 140 min. 3.4
increase. For Jong oil alkyd it is more 0.1% di-tert.butyl-4-
favorable to use Lithium salts than TIB h yd roxyh yd roci n na m at),
0.06
KAT 248.

`~O paindia O SEPTEMBER 2012

 Table 5: resin composition for TIB AOA is favorably added alter
Table 6: Results for antioxidants the
TIB AOA study transesterification, because it offers
a
Antioxidant Gardner Color Number double function as "bleachin a ent"
Raw Material Weight g g as
well as a "suppressor" of color develop-
No Antioxidant added 7.5 ment. The product is water based, which
Soy Bean Oil 485,2 gr TIB AOA 5.0 needs some care when Teeding into the
Pentaerythritol 108,2 gr TIB AOA-2 5.4 reactor, but otherwise TIB AOA is easy
TIB KAT 220 0,4 gr TPP 6.3 to handle.
TIB AOA 0,2 gr
Maleic Anhydride 1,8 gr TIB AOA proves to be a highly effi-
The resin was formulated as listed in
Phthalic Anhydride cient antioxidant for improvement of
193,4 gr Table 5.
resin colors, which Works at extremely
Xylene 590,0 gr
low concentrations. It offers the resin
The Soy bean oil, catalyst and PE is
manufacturer new possibilities to im-
transesterified at 240°C under a nitro-
certain increase in reaction time cannot prove the quality of the resins even fur-
gen blanket in 1 hour reaction time.
be avoided. ther. Several resin manfucturers already
Aftercompletionofthetransesterification
trusttheabilitiesofthehighperformance
the mixture is cooled to 120°C and all
TIBChemicalstriedtoovercomethese AOA additive in their production. ■
other ingredients are added. The resin is
difficulties and has developed a new reheated to 230°C and cooked until the TIB Chemicals AG is represented in India
antioxidant TIB AOA for improving the by
acid value dropped below 1.0 mg KOH/ Shamrock, 320-321, KuberComplex, New pink
resin colors even further without increas- gr. The resin is cooled and diluted with Road, Andheri(w), Mumbai -400053. Tel: 022-
ing the reaction time. 26740631 Email: infoQshamrock.co.in
solvent to a 50% solution.
Distributor: Vimal Intertrade Pvt Ltd , C-310,
The following example shows clearly Shyamkamal, Agarwal Market, Vile Parle (E),
The results were obtained with differ- ~vtumbai - 400 05~, Tel: 022-42551 1 00,
the beneficial effect of this new additive. ent antioxidants are shown in Table 6. infoCa~vimalagencies.net.

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paintindia O SEPTEMBER 2012 O 67 ■

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