Cognis EP Surfactants 2011jun

Cognis EP Surfactants
Matthew Guo / June 1st, 2011

Functional Products
Content
EP-Surfactants Product Range

Some basic Surfactants
Emulsion Polymerization
Application Tests
Some Concepts in EP
Disponil® NG Series
Backup slides
2 Cognis – is now part of BASF

EP-Surfactants Product Range
Overview Portfolio Range

EP Surfactants - Basic Definitions
Surfactants are a critical component of a waterborne polymer

latex. They control the size of the polymer particle during
production and ensure latex stability during and after
processing

Surfactant - Characteristics
The hydrophobe / hydrophilic balance in a surfactant

molecule is responsible for the incorporation between
oil and aqueous phases to remove barriers between
regularly non-miscible substances.



Product Manufacture / Oleo chemistry

Product Manufacture Oleo chemistry

Refinement Technolgies in EP Surfactant
Manufacture

Products and Solutions

Cognis EP Surfactant Portfolio by Chemistry

Recommendation Guideline EP- Surfactants

Recommendation Guideline EP- Surfactants

Some basic Surfactants

Fatty Alcohol Ethoxylates
EO O H
OH O
n
Reaction Refining
Fatty Alcohol
EO
M M
Ethoxylate

HLB Value (Hydrophile-lipophile balance)
HLB value can be calculated roughly from their structural group
(Griffin, 1954).
MW H
HLB Value = 20 X
MW H + MW L
For example, in the case of Lauryl alcohol 7EO.
CH3(CH2)10CH2(OCH2CH2)7OH
MW H
HLB Value = 20 X
MW H + MW L
339
= 20 X = 13.7
494

Product Properties Eumulgin® O 2 Eumulgin® O 5 Eumulgin® O 10 Eumulgin® ET 5 Eumulgin® ET 10

HD-Ocenol HD-Ocenol HD-Ocenol HD-Ocenol
HD-Ocenol
Chemical description 50/55 V + 5 50/55 V + 10 50/55 III V + 5 50/55 III V + 10
50/55 V + 2 EO
EO EO EO EO
clear to cloudy clear to cloudy
Appearance pasty cloudy liquid pasty
liquid liquid
Colour yellowish yellowish yellowish yellowish yellowish
Active substance [%] 99.7 - 100 99.5 - 100 99.5 - 100
Water content [%] < 0.3 <= 0.5 < 1.0 <= 0.5 <= 0.5
Hydroxyl value [kg
155 -165 115 - 125 79 - 84 110 - 120 75 - 81
KOH/g]
71 – 74 (10%
Turbidity Temp. [°C] 65 - 74 70.5 – 73.5 60 - 65
in BDG)
Cloud point [°C]
< 25 16 - 22 26 - 31 <= 30 < 30
Solidification point [°C]
pH value (1%) 6 – 7.5 6.5 – 7.5 6.5 – 7.5 6 – 7.5 6 – 7.5
Registration AICS/DSL/ ENCS/EU/INV/ KECI/PICCS/ TSCA
According to EU-
yes
Detergent Regulation
Biodegration readily biodegradable

Fatty Alcohol EO/PO Adducts
CH3
Principle Structure: CH3(CH2)nCH2(OCH2CH2)x(OCHCH2)yOH
Dehypon® LS 24 / LS 36 / LS 45 / LS 54 / LS 64
Performance Profile
low foaming at higher temperatures

sufficient antifoam capability
stable at acidic and moderate alkaline pH

Dehypon® Dehypon® Dehypon® Dehypon® Dehypon®

Product Properties Method
LS 24 LS 36 LS 45 LS 54 LS 64
FA
FA FA FA FA C12/14+6E
Chemical description C12/14+2E C12/14+3E C12/14+4E C12/14+5E O+4PO
O+4PO O+6PO O+5PO O+4PO
Physical Form liquid liquid liquid liquid liquid

Colour yellowish yellowish yellowish colourless colourless
Active substance [%] 99.5 - 100 99.5 - 100 99.5 - 100 99.5 - 100 99.5 - 100
DGF C-III
Water content [%] <0.5 <0.5 <0.5 <0.5 <0.5
13a
DGF C-V
Hydroxyl value [kg
17a/ 110 - 120 86 - 96 87 - 97 89 - 99 88 - 94
KOH/g]
Q-C 2058.0
Cloud Point H2O, 1% [°C] DIN 53 917 10 - 12 20 – 22 28 - 31 37 - 40
Cloud Point in BDG [°C] approx. 28 approx. 35 approx. 43
Turbidity Titration Value
17.3 – 18.5 approx. 18 approx. 21 approx. 26
[ml]
0.903 - 0.920 - 0.927 - 0.933 - 0.944 –
Density [g/cm³, 70 °C] DIN 51757
0.907 0.924 0.931 0.938 0.948
Storage <40°C, 2 years

Defoaming
Dehypon® LS 24 Dehypon® LS 36 Dehypon® LS 45 Dehypon® LS 54 Dehypon® LS 64
Hydrophilie/Cleaning

Manufacturing APG® surfactants
Cognis is a world leader

coconut, palm in APG production corn, potato, wheat
coconut oil
starch
trans-esterification
hydrogenation hydrolysis
distillation
fatty alcohol glucose

The Sulphation Process Technologies
SO3
OH OSO3H
CSA
Y O3SO


Emulsion Polymers – where are they to be
found ? Typical Applications

Emulsion Polymerization : polymerization
equipment in the laboratory

A typical latex formulation consists Water:

of:
Water is the continuous phase, so
– Monomers required for emulsification and as
heat transfer medium.
– Initiator
Polymerization behavior is strongly
– Buffer
influenced by water quality.
– Water
Preferred is the use of emineralized
– Emulsifier water.
High inorganic salt content, e.g. in
tap water, can inhibit the polymer
reaction and will cause coagulation.

Emulsion Polymerization Monomers

Emulsion Polymerization Monomers

Monomers – the reactive C=C – double bond:

Initiators:
– Oxidation catalysts
ammonium persulfate
potassium persulfate
sodium persulfate
– Redox catalysts
persulfates / sulfoxides (hydrogensulfite, thiosulfate) /
metal salts
– Organic catalysts*)
tertiary butyl- and cumene hydroperoxide
*) organic initiators are used as secondary catalysts
to increase the conversion rate

Buffers:
– bi-carbonate NaHCO3
– borax Na2B4O7 . 10 H2O
– soda Na2CO3
– sodium dihydrogenphosphate NaH2PO4 . H2O
The pH value during polymerization is primarily in
between pH 2 and 9. Monomers as vinyl acetate show
the tendency to hydrolysis at lower pH-values.
To prevent hydrolysis, use of buffers is recommended.


all acrylic formulation:
– the reactor charge is given into the reactor, preemulsion is
prepared by filling the water phase into the preemulsion flask and
adding the monomers under stirring
– the apparatus is flushed w/ nitrogen for at least 15 minutes
– the heating jacket is adjusted to approx. 93°C, mea nwhil e 20ml of
the preemulsion are added to the reactor
– 2 minutes after the polymerization start has been observed, the
continuous dosage of the preemulsion is started and has to be
finished in 80, +/- 5 minutes
– postpolymerization is placed for 1 hour, heating jacket temperature
is adjusted to 96°C while the post polymerization t akes p lace
– the emulsion is cooled to < 40°C and the neutraliza tion c harge is
added
– filter the emulsion through a 80 µm sieve

Reaction mechanism – what‘s happening in the reactor ?


the different phases of the polymerization process:


small dosage – big effect !

Application Tests

Determination of the viscosity

Determination of the solid content

Determination of the particle size

Determination of the electrolyte stability





Determination of the shear stability

Determination of the foaming behavior
purpose of the method: The thermostated dispersion is pumped in circulation for
10 min., with a flow
Through this method a statement on foam properties of
polymerdispersions of 3 l/min. ! The dispersion or test liquid is taken from the
bottom of the
and aqueous emulsifier solutions and the defoamer
efficiency cylinder and re-filled at the 2000ml mark. During this
procedure foam
to this kind of systems can be given.
formation takes place.
application:
After foam formation to a maximum volume, the flow
Aqueous and solvent based, filmbuilding latices for inducer is stopped and
adhesive-, paint-, textileand
the foam decomposition will be messured as ml foam
coating applications. volume after 1, 2, 3, 5,
Application range 10, 15, 20 and 30min!
Foam behavior at temperatures between 10 to 90°C Only for dispersions!
description: After 30 min. the dispersion will be foamed for another 5
50g of the latex will be diluted in 450g deionised water and min. to the
quantitative maximum volume and then 0,1 % (or less) defoamer are
charged into the foam apparatus. The foam apparatus is added on the foam
designed as surface. Here the foam formation will be measured after 10
graduated cylinder with double layer for thermostating and min., when the
a flow inducer. defoamer has been added to the polymer dispersion.
Usual the mesurement will execute at 20°C. (For emul sif result:
ier testing 1%
The result will be summarized in a diagramm. The
surfactant (active substance) in 500 g aq. solution is used.) diagramm shows the max.
of foam volume versus time. The result of the defoamer
test will be evaluated

Determination of the freeze / thaw stability
purpose of the method: This method describes the determination of the

freeze-thaw stability of polymer dispersions.
application: Aqueous and solvent based, film building latices for adhesive-,
paint-, textile- and coating applications.
description: 50g of the dispersion will be filled in a 75ml closeable bottle. The
bottle will be placed in a thermostated room and cooled down to –5 °C within
16h. Subsequently it is warmed to 23 °C within 8 h again. When the 23 °C
are reached, the dispersion is checked about its stability (1 cycle). Is it stable
the cycle will be repeated until it is instable, but for max. 4 times again. (five
cycles at all) Dispersions which are stable after the five cycles will be
replaced by a new sample wich is cooled the same way for five cycles again,
but this time to a temperature which is 5 °C below the minimum temperature
during the last cycles, but at most until –25 °C.
result: The result is the number of cycles, at which the dispersion becomes
instable. Note the temperature next to the value.
literature: ISO 1147

Determination of the water absorption
purpose of the method: This method describes the determination of the water
absorption of polymer films.
application: Aqueous and solvent based, film building latices for adhesive-,
paint-, textile-, and coating applications.
description: For the determination of the water absorption three films of each
dispersion (shape 75 * 35 * 0,5 mm) will be tested. Those films can be
prepared in especially designed PTFE-forms and dried for 48h at 50°C. The
dried films will be taken out of the form and its weight will be measured on a
scale (precision: 0,1 mg). Then the films will be placed in deionised water at
room temperature for 24, 48 or x hours. After that the weight of the wet film
will be measured. First the film will be slightly touched with a tissue to
remove water droplets from the film surface
result: As result the mass of the absorbed water in relation to the mass of the
dry film is calculated in percent. It is calculated on the mean value of the
three films. The single values have to be within 0,5 % deviation. %W =
percent water absorption
mN = mass wet film mT = mass dry film
literature: DIN EN 1024

Determination of the water / alkali resistance

Some Concepts in EP
Emulsification
Surfactants and foam
Gelling phase
Critical micelle concentration

Emulsification
Surfactant structure of different anionics.

Emulsification

Surfactant and foam
Foams are colloidal systems in

which the dispersed phase is a
gas and the continuous phase is
a liquid. The foam bubbles are
made possible by the presence of
surfactants at the gas-liquid
interface area, but they are
thermodynamically instable due
their interfacial free energy.
However, some foams can
persist for a long time in the
absence of external disturbance,
while others break down rapidly,
this depending on the stability of
the liquid film formed.

Surfactant and foam
Foam in EP occurs in various positions. mostly during removal of not

reacted monomer Stripping process or during filling the tank.
Foam measurement: pictures of a new nonionic with good foam decay
Foam creation under repetitious, measureable conditions by using SITA
Foam Tester

Surfactant and foam
Foam measurement: pictures of a new nonionic with good foam decay

Surfactant and foam

Gelling phase
Nothing is better than a convenient handling of surfactant in special if

the customers dilute his
raw materials for his emulsion polymerization process.

Gelling Phase
Below is a typical phase diagramm for surfactant, as a function of

concentration (in water) and Temperature.

Micelle Size and Viscosity
At higher concentration, surfactant can also form elongated columns

that pack into hexagonal Arrays. The columns are separated form
one another by water. At this point the viscosity is high. Or in other
words gelling occurs.

Gelling Phase
Phase diagram, this gives information about the solubility of the

surfactant with water. Surfactants are liquid below 30% actice or >/=
70-80% active. Between a gel phase or Liquid-crystalline phase
occurs. The new nonionic avoid those gel phases.

Critical micelle concentration, cmc


Inside of a micelle the polymerization takes place. The micelles are also called „mini reactors“.
Due to low concentration of surfactant the shape of the micelle is more or less spherical.
During the polymerization the micelle swells.

The amount is an important key factor !
To run an EP you need surfactant
To run a stable EP you need enough surfactant, that means >/= cmc value
To achieve a long term stable Polymer disperion (latex) during storage time and a stable latex
during handling like mixing the latex into an paint-emulsion, the performance of the used surfactant
should be sufficient.
BUT
the amount and kind of surfactant affects: particle size; polymer film properties; application
performance
and very important: process stability of customers EP system

The new generation of gel-free non-ionic

surfactants

Benefits of Disponil® NG Series
Sustainability Aspects
– APEO-free
– FDA approved
– Derived from renewable raw materials
– Energy saving through easier and faster handling
Performance Highlights
– Excellent phase behavior – No Gel
– Fast foam decay in the surfactant solution and in the
polymerization process
– Low pour point
– High and constant quality
– Low coagulum and high mechanical stability in the final latex

Disponil® NG Surfactants are modified ethoxylated C12/C14 fatty

alcohols

Disponil® NG Series - Test Results
Disponil® NG Series shows outstanding results in the
following parameters:
Excellent Phase Behaviour

When diluted with water, Disponil® NG presents no
gel phases over the whole concentration range
Low Foaming
Fast decay of foam in both, the surfactant solution and
the polymer latex
Low Pour Points
Disponil® NG 3050 LP shows an extremely low pour
point below -15°C

Test Method – Phase Behaviour
1. The Active matter material in Disponil® NG Surfactants was

diluted with water to obtain samples with various concentrations
2. Each sample was placed in a temperature bath until thermal
equilibrium was attained
3. Temperature was lowered stepwise by 1°C until the sample
solidified

Disponil® NG Series – Phase Behaviour
Disponil® NG presents no gel phases over the whole concentration range
50
40
30
Temperature °C
20
Disponil NG 3070
10 Standard surfactant
iso-Tridecyl-OH 30EO
0
-10
-20
-30
0 10 20 30 40 50 60 70 80 90 100
Active Substance %

Disponil® NG Series – Phase Behaviour
Disponil® NG presents no gel phases over the whole concentration range
50
40
30
20
Temperature °C
Disponil NG 1080
Disponil NG 2080
10
Disponil NG 3070
Disponil NG 4060
-10
-20
-30
0 10 20 30 40 50 60 70 80 90 100
Active Substance %

Test Method – Foam Behaviour
1. Disponil® NG Surfactants were diluted with demineralized water containing

NaCl (1 % Active matter, 0.05 % NaCl)
2. Surfactant solutions were examined in a SITA Foam Tester ("R-2000") at:
Temperature T = 20°C
Stirring Speed R = 1100 r.p.m.
Stirring Interval τ = 3 x 10 sec
Measurement t = 20 min
Measurement Interval θ = 10 sec
3. Determination of height of foam column by measurement of electrical

conductivity

Disponil® NG Series – Foam Behaviour
Disponil® NG show fast decay of foam in both, the surfactant solution and
the polymer latex
1% surfactant solution
400
350
300
250
Foam Column [mm]
Disponil NG 1080
Disponil NG 2080
200 Disponil NG 3070
Disponil NG 4060
iso-Tridecyl-OH 30EO
150
100
50
0
00:00 02:24 04:48 07:12 09:36 12:00 14:24 16:48 19:12 21:36
Time [min:sec]

Disponil® NG Series – Pour Point
Disponil® NG 3050 LP* offers easy handling through its extremely low
pour point
Product name Active Matter Pour Point
Disponil NG 3050 LP* 50% <-15°C
Iso-C13 alcohol 70% 5°C
*Low pour point

Registration
EINECS (EU), EINCS (Japan), TSCA (USA), DSL (Canada),
KECI/ECL (Korea), IECSC (China), PICCS (Philippines),
AICS
(Australia), NZIoC (New Zealand)
FDA 21 CFR §§ 175.105, 176.170, 176.180, 181.30

Top Performance of Disponil® NG Series
Key characteristics
Excellent phase behaviour – No Gel
Fast foam decay in the surfactant solution and in the
polymerization process
Low pour point
Low foaming performance in final applications
FDA approved
suitable for all types of latexes

as in-process non-ionic surfactant
as post-stabilization surfactant

Cognis EP Surfactants 2011jun

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Cognis EP Surfactants

Matthew Guo / June 1st, 2011

EP-Surfactants Product Range

2 Cognis – is now part of BASF

Overview Portfolio Range

3 Cognis – is now part of BASF

Surfactants are a critical component of a waterborne polymer

4 Cognis – is now part of BASF

The hydrophobe / hydrophilic balance in a surfactant

5 Cognis – is now part of BASF

6 Cognis – is now part of BASF

7 Cognis – is now part of BASF

8 Cognis – is now part of BASF

9 Cognis – is now part of BASF

10 Cognis – is now part of BASF

11 Cognis – is now part of BASF

12 Cognis – is now part of BASF

13 Cognis – is now part of BASF

14 Cognis – is now part of BASF

15 Cognis – is now part of BASF

16 Cognis – is now part of BASF

For example, in the case of Lauryl alcohol 7EO.

17 Cognis – is now part of BASF

Product Properties Eumulgin® O 2 Eumulgin® O 5 Eumulgin® O 10 Eumulgin® ET 5 Eumulgin® ET 10

18 Cognis – is now part of BASF

low foaming at higher temperatures

19 Cognis – is now part of BASF

Dehypon® Dehypon® Dehypon® Dehypon® Dehypon®

Physical Form liquid liquid liquid liquid liquid

20 Cognis – is now part of BASF

Dehypon® LS 24 Dehypon® LS 36 Dehypon® LS 45 Dehypon® LS 54 Dehypon® LS 64

21 Cognis – is now part of BASF

Cognis is a world leader

fatty alcohol glucose

22 Cognis – is now part of BASF

23 Cognis – is now part of BASF

24 Cognis – is now part of BASF

25 Cognis – is now part of BASF

26 Cognis – is now part of BASF

A typical latex formulation consists Water:

27 Cognis – is now part of BASF

28 Cognis – is now part of BASF

29 Cognis – is now part of BASF

Monomers – the reactive C=C – double bond:

30 Cognis – is now part of BASF

31 Cognis – is now part of BASF

32 Cognis – is now part of BASF

33 Cognis – is now part of BASF

34 Cognis – is now part of BASF

Reaction mechanism – what‘s happening in the reactor ?

35 Cognis – is now part of BASF

36 Cognis – is now part of BASF

the different phases of the polymerization process:

37 Cognis – is now part of BASF

38 Cognis – is now part of BASF

small dosage – big effect !

39 Cognis – is now part of BASF

40 Cognis – is now part of BASF

41 Cognis – is now part of BASF

42 Cognis – is now part of BASF

43 Cognis – is now part of BASF

44 Cognis – is now part of BASF

45 Cognis – is now part of BASF