Cognis EP Surfactants 2011Jun - carytrad.com.t EP Surfactants... · 4 Cognis – is now part of...

Cognis EP Surfactants

Matthew Guo / June 1st, 2011

Functional Products

2 Cognis – is now part of BASF

Content

� EP-Surfactants Product Range

� Some basic Surfactants

� Emulsion Polymerization

� Application Tests

� Some Concepts in EP

� Disponil® NG Series

� Backup slides


EP-Surfactants Product Range

Overview Portfolio Range


EP Surfactants - Basic Definitions

Surfactants are a critical component of a waterborn e polymer latex. They control the size of the polymer particl e during production and ensure latex stability during and af ter processing


Surfactant - Characteristics

The hydrophobe / hydrophilic balance in a surfactant molecule is responsible for the incorporation betwe en 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


Some basic Surfactants


Fatty Alcohol Ethoxylates

M M

Reaction Refining

Fatty Alcohol

EO

Ethoxylate

EOOH O

OH

n


Fatty Alcohol EthoxylatesHLB Value (Hydrophile-lipophile balance)

HLB Value = 20 XMW H

MW H + MW L

� HLB value can be calculated roughly from their stru ctural group(Griffin, 1954).

CH3(CH2)10CH2(OCH2CH2)7OH

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

HLB Value = 20 XMW H

MW H + MW L

= 20 X = 13.7339

494


Fatty Alcohol Ethoxylates

< 30<= 3026 - 3116 - 22< 25Cloud point [°C]

Solidification point [°C]

<= 0.5<= 0.5< 1.0<= 0.5< 0.3Water content [%]

6 – 7.56 – 7.56.5 – 7.56.5 – 7.56 – 7.5pH value (1%)

AICS/DSL/ ENCS/EU/INV/ KECI/PICCS/ TSCARegistration

yesAccording to EU-Detergent Regulation

readily biodegradable

155 -165

99.7 - 100

yellowish

clear to cloudy liquid

HD-Ocenol50/55 V + 2 EO

Eumulgin® O 2

HD-Ocenol50/55 III V + 10

EO

HD-Ocenol50/55 III V + 5

EO

HD-Ocenol50/55 V + 10

EO

HD-Ocenol50/55 V + 5

EOChemical description

Biodegration

60 - 6570.5 – 73.565 - 7471 – 74 (10%

in BDG)Turbidity Temp. [°C]

75 - 81110 - 12079 - 84115 - 125Hydroxyl value [kg KOH/g]

99.5 - 10099.5 - 100Active substance [%]

yellowishyellowishyellowishyellowishColour

pastycloudy liquidpastyclear to cloudy

liquidAppearance

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


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

CH3(CH2)nCH2(OCH2CH2)x(OCHCH2)yOH

CH3

Performance Profile

� low foaming at higher temperatures

� sufficient antifoam capability

� stable at acidic and moderate alkaline pH

Principle Structure:

Fatty Alcohol EO/PO Adducts


0.933 -0.938

approx. 26

approx. 43

28 - 31

89 - 99

<0.5

99.5 - 100

colourless

liquid

FA C12/14+5E

O+4PO

Dehypon®

LS 54

0.944 –0.948

0.927 -0.931

0.920 -0.924

0.903 -0.907

DIN 51757Density [g/cm³, 70 °C]

<40°C, 2 yearsStorage

FA C12/14+6E

O+4PO

FA C12/14+4E

O+5PO

FA C12/14+3E

O+6PO

FA C12/14+2E

O+4POChemical description

approx. 21approx. 1817.3 – 18.5Turbidity Titration Value [ml]

approx. 35approx. 28Cloud Point in BDG [°C]

37 - 4020 – 2210 - 12DIN 53 917Cloud Point H2O, 1% [°C]

88 - 9487 - 9786 - 96110 - 120DGF C-V

17a/ Q-C 2058.0

Hydroxyl value [kg KOH/g]

<0.5<0.5<0.5<0.5DGF C-III

13aWater content [%]

99.5 - 10099.5 - 10099.5 - 10099.5 - 100Active substance [%]

colourlessyellowishyellowishyellowishColour

liquidliquidliquidliquidPhysical Form

Dehypon®

LS 64Dehypon®

LS 45Dehypon®

LS 36Dehypon®

LS 24MethodProduct Properties



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

Defoaming

Hydrophilie/Cleaning



fatty alcohol glucose

coconut, palm

trans-esterificationhydrogenationdistillation

coconut oil

corn, potato, wheat

hydrolysis

starch

Cognis is a world leaderin APG production

Manufacturing APG® surfactants


O3SOY

OSO3HOHSO3

CSA

The Sulphation Process Technologies


Emulsion Polymerization


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


Emulsion Polymerization : polymerization equipment in the laboratory



A typical latex formulation consists of:

– Monomers

– Initiator

– Buffer

– Water

– Emulsifier

Water:

Water is the continuous phase, so required for emulsification and as heat transfer medium.

Polymerization behavior is strongly influenced by water quality.

Preferred is the use of emineralizedwater.

High inorganic salt content, e.g. in tap water, can inhibit the polymer reaction and will cause coagulation.


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 catalys ts to increase the conversion rate



Buffers:

– bi-carbonate NaH CO3

– 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 recommende d.



all acrylic formulation:

– the reactor charge is given into the reactor, preem ulsion is

prepared by filling the water phase into the preemu lsion flask and

adding the monomers under stirring

– the apparatus is flushed w/ nitrogen for at least 1 5 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 o bserved, the

continuous dosage of the preemulsion is started and has to be

finished in 80, +/- 5 minutes

– postpolymerization is placed for 1 hour, heating jac ket 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:

Through this method a statement on foam properties of polymerdispersions

and aqueous emulsifier solutions and the defoamerefficiency

to this kind of systems can be given.

application:

Aqueous and solvent based, filmbuilding latices for adhesive-, paint-, textileand

coating applications.

Application range

Foam behavior at temperatures between 10 to 90°C

description:

50g of the latex will be diluted in 450g deionised water and quantitative

charged into the foam apparatus. The foam apparatus is designed as

graduated cylinder with double layer for thermostating and a flow inducer.

Usual the mesurement will execute at 20°C. (For emul sifier testing 1%

surfactant (active substance) in 500 g aq. solution is used.)

The thermostated dispersion is pumped in circulation for 10 min., with a flow

of 3 l/min. ! The dispersion or test liquid is taken from the bottom of the

cylinder and re-filled at the 2000ml mark. During this procedure foam

formation takes place.

After foam formation to a maximum volume, the flow inducer is stopped and

the foam decomposition will be messured as ml foam volume after 1, 2, 3, 5,

10, 15, 20 and 30min!

Only for dispersions!

After 30 min. the dispersion will be foamed for another 5 min. to the

maximum volume and then 0,1 % (or less) defoamer are added on the foam

surface. Here the foam formation will be measured after 10 min., when the

defoamer has been added to the polymer dispersion.

result:

The result will be summarized in a diagramm. The diagramm shows the max.

of foam volume versus time. The result of the defoamertest 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


Disponil® NG Series

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 t he polymerization process

– Low pour point

– High and constant quality

– Low coagulum and high mechanical stability in the f inal latex



Disponil® NG Surfactants are modified ethoxylated C12 /C14 fatty

alcohols


Disponil ® NG Series - Test ResultsDisponil ® 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


Disponil ® NG SeriesTest 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 concentrat ion range

-30

-20

-10

0

10

20

30

40

50

0 10 20 30 40 50 60 70 80 90 100

Active Substance %

Tem

pera

ture

°C

Disponil NG 3070

Standard surfactant

iso-Tridecyl-OH 30EO


Disponil ® NG Series – Phase Behaviour

Disponil ® NG presents no gel phases over the whole concentrat ion range

-30

-20

-10

0

10

20

30

40

50

0 10 20 30 40 50 60 70 80 90 100

Active Substance %

Tem

pera

ture

°C Disponil NG 1080

Disponil NG 2080

Disponil NG 3070

Disponil NG 4060


Disponil ® NG Series

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 andthe polymer latex

0

50

100

150

200

250

300

350

400

00:00 02:24 04:48 07:12 09:36 12:00 14:24 16:48 19:12 21:36

Time [min:sec]

Foa

m C

olum

n [m

m]

Disponil NG 1080

Disponil NG 2080

Disponil NG 3070

Disponil NG 4060

iso-Tridecyl-OH 30EO

1% surfactant solution


Disponil ® NG Series – Pour Point

Disponil ® NG 3050 LP* offers easy handling through its extrem ely low pour point

<-15°C50%Disponil NG 3050 LP*

5°C

Pour Point

70%

Active Matter

Iso-C13 alcohol

Product name

*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 t he 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 - carytrad.com.t EP Surfactants... · 4 Cognis – is now part of...

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Transcript of Cognis EP Surfactants 2011Jun - carytrad.com.t EP Surfactants... · 4 Cognis – is now part of...