Notes on Demulsification- Theory and Application

Compiled by
Chandran Udumbasseri

Demulsifiers Theory and applications

Demulsifier is a chemical used to break emulsions and separate into two phases.
Water is separated from crude oil by dozing demulsifier and breaking the emulsion.
The emulsion of water in crude oil is thermodynamically unstable but kinetically very
stable. Natural surfactants, wax and solids (inorganic salts, zinc, iron, aluminum
sulfate, calcium carbonate, silica and iron sulfide) stabilize such emulsions.
Asphaltene compounds were found to be one of the contributing materials to the
stability of crude oil. Asphaltenes are condensed aromatic rings containing saturated
carbon chains and naphthenic rings as substituents along with hetero atoms and
metals. Asphaltenes are capable of cross linking at the water drop oil interface and
preventing water droplets from coalescence. They are surface active agents present in
the oil water interface.
Demulsifiers reduce surface tension at the water-oil interface. Demulsifiers are
polymers that act as surfactants and counteract the effect of asphaltenes. The
polymers have both hydrophilic and hydrophobic groups. The polymeric surfactant,
when added to the crude emulsion locates itself in the interface between water and oil
molecules. The hydrophilic groups orient themselves towards water while the
hydrophobic ones orient themselves towards the oil. At the interface the demulsifier
either replaces the emulsifying surfactant or it provides additional steric forces within
the film interface. In either case, this absorption causes a random film thickness
fluctuation. This random film thickness fluctuation results in an increase in the film
surface area and also results in a localized decrease in the absorbed stabilizing
emulsifier. Hence causing a local increase in interfacial surface tension and thinning
of the film.
The following process takes place during the absorption of the demulsifier at the
interface:
1. The demulsifier absorbs the stabilizing emulsifier at the water liquid interface and
decreases the film forming capability of the emulsifying additives.
2. The demulsifier may render the additives soluble in the water phase and hence less
surface active.
3. The demulsifier may mix with the emulsifying additive and reduce the interfacial
tension at the water oil interface, there by creating less stable water dispersion.
The demulsifiers used for water separation from crude oil are a combination of
compounds having demulsifying activity and compounds that assist demulsification
but without demulsifying activity.
1. Compounds with demulsifying activity.
1.1. Polyethylene imine alkoxylate.
1.2. Mono or oligo-amine alkoxylate.
1.3. Alkoxylated alkylphenol formaldehyde resin.
1.4. Alkoxylated amine modified alkyl phenol formaldehyde resin.
1.5. Co or ter polymers of alkoxylated acrylates or methacrylates with vinyl
compounds.
1.6. Condesates of mono- or oligo- amine alkoxylates, dicarboxylic acids and
alkylene oxide block polymers (may be quaternized at nitrogen).
1.7. Cros linked products of 1 to 6.

2. Compounds acting as demulsifying assistant.

2.1. Poly alkylene glycol ethers
2.1.1. General Formula, [R(OA1)a ..OH]n , R = C7 to C20 alkyl group, phenyl
group, alkyl phenyl group: A1,A2,A3 = 1,2 alkylene group with 2 to 4
carbon atoms, phenyl ethyl group ( there should be one 1,2 alkylene group
with 4 carbon atoms); a = 1 to 50; n = 1 to 10.
2.1.2. General Formula H-(OA1)b-(OA2) c-(OA3) d-OH (where b, c and d each has
value from 0 to 50 and b+c+d is >3).
Action of Demulsifier.
The demulsifier tend to act on the emulsion by:
? Flocculation of oil droplets.
? Dropping of water.
? Coalescence of the water droplets.
? The speed and efficiency at which this occurs can be improved by process
equipment design and operating condition (e.g.: Increasing the temperature,
separator design, etc.).
The components of the demulsifier formulation are characterized according to their
primary function. But components can provide multipurpose function in a particular
crude oil. Also inclusion of surface wetters can assist in the treating of emulsion
problem.
Function of different demulsifiers
Oxyalkylated Phenolic Resins
High molecular weight phenolic resin oxyalkylates have been found to be highly
effective as crude oil emulsion breakers. Resins are used on emulsions of the waterin-oil type and work by counteracting the stabilizing influence of naturally present
emulsifying agents.
They are classified as nonionic surface-active organic chemicals that will not interact
with ionic type chemicals.
Applications
phenolic resin oxyalkylates are generally used in dilute form in aromatic solvent or
blended with chemicals of different generic structures to give synergistic formulas
which may have greater efficiency.
Polyalkylene Glycols
Polyalkylene glycols are non-ionic in character. Polyols work by counteracting
naturally occurring emulsifiers. Polyols have been found to be particularly effective
when used in low salt water brine or in fresh water emulsions. In these cases, polyols
are often formulated with sulfonates or used as is.
Polyols are stable to hydrolysis. Polyols exhibit exceptional ability to lower interfacial
tension and, as a result, have a high degree of wetting activity. For this reason, polyols
can effectively disperse or deflocculate solids.

Applications
Polyalkylene glycols can be used with effectiveness in synergistic blends with
oxyalkylated phenolic resins or with sulfonic acid salts, or in blends of all three, to
break crude oil emulsions of the water in oil type.
Polymeric Elastomers
Polymeric elastomers are used in a variety of geographical locations in standard
emulsion breakers. Rapid penetration through the oil phase to finely emulsified water
droplets has made them indispensable in many areas. This penetration is vividly
demonstrated by the rapid blackening of cream colored emulsions and the quick
brightening of water-hazed emulsions. Being extremely oil soluble in nature,
polymeric elastomers exhibit great tenacity for finishing the dehydration of crudes
where more water-soluble compounds can wash out with the water phase of a
partially resolved emulsion.
Applications
Polymeric elastomers may require blending with other emulsion breaker intermediates
to achieve complete treatment of water-in-oil emulsion. Polymeric elastomers can be
formulated in toluene, xylene, or heavy aromatic solvent, and are compatible with
other emulsion breaker intermediates. If necessary, alcohols can be used as
brightening or stabilizing agents in these field strength blends.
Polymerized Polyols
Polymerized polyol intermediates are used in a variety of geographical locations in
standard emulsion breakers. Rapid penetration through the oil phase to finely
emulsified water droplets has made them indispensable in many areas. This
penetration is vividly demonstrated by the rapid blackening of cream-colored
emulsions and the quick brightening of water-hazed emulsions.
They are extremely oil soluble in nature and exhibit great tenacity for finishing the
dehydration of crudes where more water-soluble compounds can wash out with the
water phase of a partially resolved emulsion.
Applications
Polymerized polyols typically require blending with other emulsion breaker
intermediates to achieve complete treatment of water-in-oil emulsion. Polymerized
polyols can be formulated in toluene, xylene, or heavy aromatic solvent, and are
compatible with other emulsion breaker intermediates. If necessary, alcohols can be
used as brightening or stabilizing agents in these field strength blends.
Polyol Esters
Polyol esters are a reaction product of a polyalkylene oxide block polymer and a
polyfunctional organic acid. Polyol esters are particularly effective on fresh-water
emulsions and tend not to cause emulsion inversion or oil-in-water emulsions. Polyol
esters act, as do most emulsion breakers, by counteracting the effect of naturally
occurring emulsifiers.
Applications
Polyol esters are an effective emulsion breaker when used separately or in blends with
oxyalkylated phenolic resins. This high molecular weight chemical is non-ionic in
character.

Resin Esters
Resin ester intermediates are reaction products of an oxyalkylated phenolic resin and
an organic carboxylic acid. Resin esters are unusually effective when used as a
detergent or as a wetting agent in emulsion breaker formulations.
Applications
Despite resin esters high detergency, they do not cause inversion to oil-in-water
emulsion. Resin esters have also been used in limited applications as a desalting
chemical and in treating slop oils.
Sulfonates
Sulfonates have outstanding characteristics that include low cost and a resistance to
burning or overtreating when used in formulations to treat crude oil emulsions of
the water-in oil type. Sulfonates aid in emulsion breaking by counteracting naturally
occurring emulsifiers and are extremely effective in resolving loose water emulsions
stabilized by solids. Sulfonates are often used in treating refinery slop emulsions as
well as tank bottoms.
Applications
Sulfonate intermediates are generally used in conjunction with oxyalkylated phenolic
resins and with polyglycols. The solubility characteristics of sulfonates enable them to
work at the oil/water interface where they are extremely effective in resolving loose
water emulsion stabilized by solids.
Classification
Water droppers
Water droppers coalesce water droplets in the crude oil and release free water.
Predominant type is based on alkyl phenol formaldehyde resins with low levels of
addition of ethylene oxide or propylene oxide. These demulsifiers also show excellent
desalting properties.
Treaters
The primary function of these compounds is to flocculate the large number of submicron water droplets dispersed in the crude oil. Water droplets are thus concentrated
at the base of the oil column prior to coalescence and the crude is dehydrated above
the settling level of the flocs. This can be noticed by the brightening of the top oil in
contrast to its dull appearance when the water dispersion existed.
The predominant type is based on high molecular poly propylene glycol molecules
with hydrophilic tipswhich solvate into the water droplets and facilitate gathering.
Hybrids
These compounds incorporate a balance of molecular design features such that both
droppingand treatingcharacteristics are exhibited. Hybrids are more cost effective
than blends of droppers and treaters.

Desalters
The emulsions coming along the crude to the desalting stage have low amounts of
water and are less stable. Some of the naturally occurring emulsion stabilizers have
been removed at the 1st stage demulsification process. The droplet size is not very
small. High potential electric field applied coalesce these polar salt water droplets. A
good desalter demulsifier would achieve rapid water separation at low level addition
rates.
Products from Uniqema (Datas are from website)
Most of the Uniqema resin alkoxylates (alkylphenol formaldehyde resin alkoxylates)
are good water droppers and desalters. Some of them are hybrids of dropping and
treating(flocculating water droplets and breaking emulsion).
Abbreviations: D: water dropper; S: Desalter; H: hybrid of water dropper and
desalter; T: Treater
Resin Alkoxylates
Product- Kemelix
3501X
3535X
3570X
3575X
3627X
D303
D304
D308
D309
D310
D311
D313
D322

RSN
15
19
7
17
12
23
24
17
29
20
18
21
14

Function
D
D
D
H
D,S
H
D,S
D,S
D,S
D
H,S
D
D,S

The polyimine derivatives from Uniqema are mostly treaters (flocculants of water
droplets)
Poly imine derivatives
Product- Kemelix
3216X
3422X
3515X
3549X
3551X
D510
D513

RSN
9
8
9
9
10
11
8

Function
H
T,S
T
T
T
T,S
T

The polyols from Uniqema show mixed primary functions and modified polyols
function as treaters and hybrids.
Polyol
Product- Kemelix
D501
D502
D503
D511
Synperonic T701
Synperonic PEL 64
Synperonic PEL 101

RSN
22
13
19
12
16
22
12

Function
D
T
H
T
H,S
D
H

Modified Polyol
Product- Kemelix
3503X
3504X
3566X
3584X
D317
D400
D401

RSN
8
16
7
10
9
6
7

Function
T
H
H
T
T
H
H

RSN
16

Function
D, unusual base, can
be used anywhere
Excellent resin blnds
withDP318
and
DP215
D,
better
water
dropper than DP280
Works better with
DP318 and DP188
Similar to DP479
Specific for Arabian
gulf and north Africa

Products from Majorchem

Resin alkoxylates
Product
DP 196
DP280

16

DP 292

17

DP 479

DP493
DP510

9
8

Polymer initiated Block Polymers

Product
RSN
DP188
16
DP314

DP318

EO/PO Co-Block Polymers

Product
DP215

RSN
13

DP216

22

DP285

15

DP336

20

Function
Hydrophilic version of
DP318
More
hydrophobic
than DP318
Good
emulsion
breaker Blends well
with Block polymers
and resin bases

Function
Main base for water
soluble formulations
Very
hydrophilic;
chief use is low
percentage component
to improve water drop
and interface.
Spectacular at water
dropping but tend to
leave B.S.
Instant and complete
treatment on some
crude, but higher
dosage than normal

Formulation
Product
DP193

RSN
N/A

Function
Unusual base

Diepoxides
Product
DP751

RSN
6

Function
Mostly for Arabian
gulf and particularly
useful when DP-188
and DP318 are not
good enough on any
specific crude

Special functions of Uniqema products

Low temperature demulsification
These products are designed to treat crude oil at ambient or low temperature with
greatest efficiency.
Polyimine alkoxylates-Kemelix
Product
RSN
D510
11
D513
8
3418X
14
3422X
8
3515X
9
3551X
10

Desalters from Uniqema

These products are good at desalting
Product -Kemelix
D308
D309
D310
D311
D510
D511
3501X
3575X
3678X

Chemical type
Resin ethoxylate
Resin ethoxylate
Resin alkoxylate
Resin alkoxylate
Polyimine alkoxylate
Polyol
Resin alkoxylate
Resin ethoxylate
Resin ethoxylate

RSN
17
29
20
18
11
12
15
17
21

Chemical type
Resin alkoxylate
Resin alkoxylate
Modified Polyol
Polyol
Imine
Polyol
Polyimine alkoxylate
Polyimine alkoxylate
Polyimine alkoxylate
Polyimine alkoxylate
Polyimine alkoxylate

RSN
20
16
6
19
11
12
8
14
8
9
10

Uniqema Dehazers
Product -Kemelix
D310
D311
D400
D503
D510
D511
D513
3418X
3422X
3515X
3551X

Heavy Oil demulsifiers from Uniqema

Product -Kemelix
D310
D311
D313
D322
D400
D401
D501
D510
Synperonic T701
3422X
3424X
3501X
3515X
3551X
3575X
3627X
3678X

Chemical type
Resin alkoxylate
Resin alkoxylate
Resin alkoxylate
Resin ethoxylate
Modified Polyol
Modified Polyol
Polyol
Polyimine alkoxylate
Polyol
Polyimine alkoxylate
Resin alkoxylate
Resin alkoxylate
Polyimine alkoxylate
Polyimine alkoxylate
Resin ethoxylate
Resin alkoxylate
Resin ethoxylate

RSN
20
18
21
14
6
7
22
11
16
8
20
15
9
10
17
11
21

Note
RSN is the Relative Solubility Number of the solvent stripped demulsifier. Products
with an RSN<13 are insoluble in water. Products with RSN 13 17 are dispersible
and products with RSN >17 are considered soluble in fresh water.

Preparation of demulsifier bases

The methods of preparation of demulsifiers are taken from various U.S. Patents that
were developed in their laboratories.
Initially the intermediate product, resin (alkyl phenol formaldehyde resin,
Polyalkylene poly imine resin, Polyalkylene resin, intermediate amine,
polyoxyalkylene glycol, polyoxyalkylene glycol-diglycidyl ether condensate,
polyamidoamine, vinyl polymers) is prepared. This product is then condensed with
ethylene oxide, propylene oxide or butylenes oxide or their mixture to make
oxyalkylate. As the number of molecules of alkylene oxide increases the solubility of
the resin in water increases. Depending on the requirement of degree of solubility in
oil/water the ratio of resin to alkylene oxide is varied.

Alkyl phenol formaldehyde resin ethoxylate/propoxylate

Phenol reacts with formaldehyde at ortho and para sites allowing 3 molecules of
formaldehyde to attach to the ring.
Further reaction takes place between mono, di ant tri hydroxymethyl phenol, phenol
and formaldehyde and eliminating water molecules and causing polymerization.

Resin ethoxylate/propoxylate
The free phenolic groups in the resin are reacted with ethylene oxide and propylene
oxide to form resin ethoxylate / propoxylate. More ethylene oxide undergoes
condensation reaction with more phenolic groups giving resin alkoxylates with higher
molecules of alkylene oxides. The hydrophilic nature of the resin increases as the
number of alkylene oxide molecules attached to the resin increases.

Example
Preparation of p-t-butyl phenol formaldehyde resin from p-t-butyl phenol and para
formaldehyde
A reactor was charged with 24.5 lbs. of para-tert-butyl phenol, 6 lbs. of para
formaldehyde and 57.25 lbs. of xylene. The above charge was heated to 50oC. and
0.213 lbs. of 50% aqueous sodium hydroxide was added. The product was now heated
to 90oC and held there for 0.5 hour, then heated to reflux. Reflux began at 135oC. and
gradually increased to 145oC under azeotropic conditions to remove 4.0 lbs. aqueous
layer and 2.25 lbs. solvent. Total time at reflux was 41/2 hours. After cooling to 50oC,
the product was dropped. Some solid stayed behind because it had caked out on the
coils. Analysis of the material so obtained indicated 77-80% yield of the desired
cyclic tetramer.
Preparation of Resin oxyalkylate
General procedure for the oxyalkylation of cyclic phenol-formaldehyde tetramers
Pure cyclic tetramer and 3 to 5% by weight of KOH, dissolved in an equal amount of
water, are heated together with two to four times their weight of xylene, under
azeotropic reflux, until catalyzation is complete and no more water can be removed.
This usually takes from 3 to 6 hours depending upon the batch size. Since the tetramer
is very poorly, if at all, soluble in the xylene, it is essential that efficient rapid stirring
is needed to keep the very finely dispersed solid homogeneously distributed
throughout the liquid. The mixture is then transferred to a pressure reactor or
autoclave equipped with a means of external (electric) heating, internal cooling and
efficient mechanical agitation. The resin is heated to 120oC -140oC and the
alkyleneoxide or mixture of oxides is charged into the reactor until the pressure is 2575 p.s.i. During the ensuing oxyalkylation reaction the original suspension gradually
clears up and after all the oxide has been added and the reaction has been completed,
which usually takes from 2 to 12 hours depending upon the nature of the reactants, the
resulting product solution, the oxyalkylated derivative of the cyclic tetramer, now
completely soluble in xylene, is cooled and ready to be applied for demulsifier use.

Polyethylene imine oxyalkylate

Polyethylene-imine
Polyalkylene-polyamines may be obtained from ethyleneimine and/or propyleneimine
by the conventional method. Preferably, ethyleneimine is used as the starting material.
The polyalkylenepolyamines have at least two recurring alkyleneimine units per
molecule. Polyethyleneimines comprising from 10 to 3,000 recurring ethyleneimine
units are used for oxyalkylate preparation.
n

CH2-CH2

? -[CH2-CH2- NH]n-

NH
Ethylene imine ? Polyethylene polyimine
Where n can have values from 10 to 3000

Polyethylene imine oxyalkylate

The oxyalkylation of polyethylene imine may be carried out with any common
alkylene oxide, e.g. ethylene oxide, 1, 2-propylene oxide, 1, 2- and 2,3-butylene
oxide, isobutylene oxide, styrene oxide or cyclohexene oxide, amongst which
propylene oxide and ethylene oxide should be singled out particularly.
- [CH2-CH2- NH] n- +

CH2-CH2 ?
O

Poly(ethylene imine)

Ethylene oxide

- [CH2-CH2- N] n CH2-CH2-O-H
Polyethylene imine oxyalkylate
.
The polyalkylenepolyamines can be reacted with the various alkylene oxides by using
these either individually or as a mixture and (in the latter case) the reaction can take
the form of a block copolymerization or a random copolymerization. If the reaction is
carried out in two steps, the alkylene oxide may, in the first step, again be used
individually using the same procedure.
Preferably, either propylene oxide alone is used, or propylene oxide and ethylene
oxide are used and are reacted by block copolymerization. In the latter case, 1, 2propylene oxide is introduced in the first step in order to form the corresponding
propanolamine, and thereafter further propylene oxide and, finally, ethylene oxide are

introduced, satisfactory results being obtained with a ratio of propylene oxide to

ethylene oxide of up to 1:15. However, the converse procedure can also be used, i.e.
ethylene oxide can be introduced first, followed by propylene oxide, in which case the
ethylene oxide: propylene oxide ratio is advantageously from 20:1 to 1:20. Both
embodiments can be carried out in one step or in two steps.
Preparation (by the 2-step method) of component B, containing about 100 recurring
propylene oxide units per nitrogen valency
First Step: 172 g (2 mole equivalents) of a 50% strength aqueous solution of a
polyethyleneimine containing about 100 recurring ethyleneimine units are introduced
into a stirred autoclave and 116 g (2 moles) of propylene oxide are introduced in
portions at 90oC to 100oC Time: 3 hours; pressure: 6 atmospheres gauge; temperature;
90oC to100oC. The water is then removed by distillation at 100oC /15-20 mm Hg.
Second step: 15.6 g (0.15 mole) of the product from step 1 and 0.624 g (4 percent by
weight, based on 1.) of KOH powder are introduced into a stirred autoclave and
thereafter 687 g (11.85 moles) of propylene oxide are introduced in portions at 135oC
and 132 g (3 moles) of ethylene oxide are introduced in portions at 125oC.
Time: 6 hours (PrO); pressure: 6-8 atmospheres gauge; temperature: 135oC (PrO),
2 hours (EO); 125oC (EO).
The mixture is then stirred for 4 hours until the pressure remains constant.
The product obtained can be used directly. It consists of the polyethyleneimine which
now contains about 80 moles of propylene oxide and 20 moles of ethylene oxide as
adduct.

Amine Oxyalkylates:
Into a stainless steel autoclave with the usual devices for heating, heat control, stirrer,
inlet, outlet, etc., which is conventional in this type of apparatus was charged 500
grams of triethylene tetramine, 300 grams of xylene, and 15 grams of sodium
methylate. The autoclave was sealed, swept with nitrogen gas and stirring started
immediately and heat applied. The temperature was allowed to rise to approximately
145oC. At this particular time the addition of butylene oxide was started. The butylene
oxide employed was a mixture of the straight chain isomer substantially free from
isobutylene oxide. It was added continuously at such speed that it was absorbed by the
reaction as added. The amount added in this operation was 1500 grams. The time
required to add the butylene oxide was two hours. During this period the temperature
was maintained at 130 to 145oC. using cooling water through the inner coils when
necessary and otherwise applying heat if required. The maximum pressure during the
reaction was 50 pounds per square inch.
(NH2) 2CH-CH2-CH2-CH2-CH2-CH (NH2) 2 +

CH3CH-CH2 ?

O
Triethylene tetramine
Propylene oxide
(NH2) 2CH-CH2-CH2-CH2-CH2-(H2N) CH NH - (CH3)CH-CH2-OH
Triethylene tetramine mono propoxylate

Polyalkylene oxyalkylate Block polymers

1. Preparation of Low Molecular Weight Pentaerythritol Polyol with Propyleneoxy
and ethyleneoxy block polymers.
A 5-gallon pressure reactor equipped with mechanical stirrer was charged with 3 lb.
of pentaerythritol 24-molar propoxylate and 14 g KOH. Water was removed by
vacuum treatment at 100 to 100oC, followed by addition of 4 lb. propylene oxide at
115 to 120oC. This product had hydroxyl number of 88.2. Three pounds of this
material was charged to a 5-gallon pressure reactor and treated with 7 pounds
ethylene oxide at 115oC. The final product had a molecular weight of 8400, basis the
hydroxyl number and contained 70% ethylene oxide by weight.
C[CH2O-{CH(CH3)-CH2-O}6-H] 4 + (CH3)CH-CH 2 ? Polymer product
O
Pentaerythritol 24 propoxylate + CH2-CH2 ?
O
Polyalkylene propoxy ethoxylate
Block polymer
2. Preparation of High Molecular Weight Pentaerythritol Polyol with Propyleneoxy
and ethyeleneoxy block polymers
Four pounds of the product of Example I was charged to a 5-gallon pressure reactor,
contents purged with N.sub.2, and treated with 8 pounds ethylene oxide at 120oC. The
product had a molecular weight, basis the hydroxyl number of 18,900 and
containing 90% by weight ethylene oxide.
3. Preparation of Low Molecular Weight Sucrose Polyol with Propyleneoxy and
ethyeleneoxy block polymers
A 5-gallon pressure reactor equipped with mechanical stirrer was charged with 3
pounds sucrose 8-molar propoxylate and 8 g potassium hydroxide. The mixture was
vacuum stripped for one hour at 120oC, nitrogen purged and treated with 3 pounds
propylene oxide at 110 to 125oC, followed by treatment with 12 pounds ethylene
oxide at 125oC. The product had a molecular weight of 4,900, basis the hydroxyl
number and contained 66.7% ethylene oxide.
4. Preparation of Sucrose Polyol with Alternating Blocks of Propyleneoxy and
ethyeleneoxy block polymers
To 5 pounds of the product of Example 3 in a 5-gallon pressure reactor were added
successively at 125oC, 4 g KOH (H.sub.2 O subsequently removed in vacuum), 3
pounds propylene oxide, and 12 pounds ethylene oxide. To 5 pounds of this product
were added 1.5 pounds propylene oxide and then 6 pounds ethylene oxide at

135.degree. C. The final product had a molecular weight, basis the hydroxyl number
30,000 and contained 79% ethylene oxide.
5. Preparation of Hydrophobic Sorbitol Polyol with Propyleneoxy and ethyeleneoxy
block polymers
Using the alkoxylation methods described in Examples 1-4, sorbitol 174-molar
propoxylate was treated with 85 moles ethylene oxide to prepare a product of about
14,000 molecular weight hydroxyl number=24.5 having 26.6 weight percent ethylene
oxide content.

Polyoxyalkylene glycol-diglycidyl ether block polymers

Condensation Products prepared with diglycidyl ethers
CH2-CH-CH2-O-Polyoxyalkylene glycol-O-CH2-CH-CH2
O
Di glycidyl ether of polyoxyalkylene glycol

Polyoxyalkylene glycols to be used in condensates with diepoxides were prepared by

addition of the desired alkylene oxide or a mixture of two or more oxides to a suitable
monohydric or polyhydric compound. The reaction conditions vary somewhat
depending on the alkylene oxide used, but generally the temperature employed will be
within the range of about 90o-160oC. A small amount of alkaline catalyst is needed for
polyglycol formation. Preferred catalysts include potassium hydroxide, sodium
hydroxide and sodium hydride with a concentration of about 0.1 to 0.8 weight
percent, based on finished product. A non-exclusive list of suitable alcohols, phenols
and glycols includes normal and branched alcohols, phenols, propylene glycol,
ethylene glycol, butylene glycol, glycerin, pentaerythritol and the like.
(Refer Polyalkylene oxyalkylate block polymer)
Diepoxide condensates
Preparation of diepoxide condensates with polyoxyalkylene glycols is carried out
according to the following general procedure.
Reaction of polyoxyalkylene glycols with diglycidyl ethers take place at temperatures
from 70o -160oC, preferably between about 80o -120oC. Generally, the reaction is
carried out without solvent, although the reaction can also be carried out in the
presence of an inert organic solvent. Normally the molar ratio of polyoxyalkylene
glycol to diglycidyl ether is from about 1:0.5 to about 1:1. At the 1:1 ratio,
crosslinking may become pronounced and may result in insoluble lumpy material.
To minimize insolubles, the total amount of diglycidyl ether is preferably added in
two or three steps, rather than all at once. The reaction takes place in the presence of
alkaline catalysts. Usually, the catalyst that is present in the freshly prepared
polyoxyalkylene glycols is all that is needed to prepare the condensate with the
diglycidyl ether. The reaction can also be catalyzed by Lewis acid-type catalysts, such
as ZnCl2, BF3 -etherates and the like. In this case, the residual catalyst from the initial
oxyalkylation is first neutralized, followed by the subsequent addition of the Lewis

acid. The reaction time depends on the temperature and is generally stopped when the
epoxy number of the condensate has decreased to 2 or less.
Oxyalkylation
Polyoxyalkylene glycol/diepoxide condensates can be further oxyalkylated using a
procedure similar to that for the polyoxyalkylene glycol preparation

Polyamido oxyalkylate
Preparation of the polyamido component
918.4 g (7 moles) of dipropylenetriamine and 2,377.2 g (21 moles) of caprolactam
were heated at 180oC in a stream of nitrogen. The mixture was stirred for 17 hours at
180 oC , after which the temperature was increased to 190oC and the mixture was
stirred for a further 5 hours. 3246.6 g of a polyamidoamine of MP 110oC were
obtained.
The amine number was 7.27meq/g and the product contained about 11% of 6aminohexanoic acid.
Oxyalkylation
Example 1
947 g (16.32 moles) of propylene oxide were forced a little at a time, in the course of
6 hours, under 6-10 bar and at 135oC into a stirred stainless steel autoclave containing
72.5 g (0.154 moles) of the polyamido component prepared as described above and 1g
of KOH powder.
Stirring was then continued for a further 4 hours until the pressure remained constant.
The product can be used directly. As adduct of about 106 moles of propylene oxide
with one mole of the polyamidoamine was formed.
Example 2
1,128 g (19.4 moles) of propylene oxide and then 365 g (8.3 moles) of ethylene oxide
were forced a little at a time, in the course of 10 hours at 135oC and under 6-10 bar,
into a stirred stainless steel autoclave containing 84.7g (0.18 mole) of the polyamido
component and 1 g of KOH powder, and the mixture was then stirred for a further 4
hours until the pressure remained constant. The product can be used directly. An
adduct of about 108 moles of propylene oxide and 46 moles of ethylene oxide with
one mole of the polyamidoamine was formed.
Example 3
The procedure described in Example 2 was followed, and 108 g (0.23 mole) of the
polyamido component were reacted with 1,040 g (17.9 moles) of propylene oxide and
then with 304g (6.9 moles) of ethylene oxide.
The product can be used directly. An adduct of about 78 moles of propylene oxide
and 30 moles of ethylene oxide with one mole of the polyamidoamine was formed.

Example 4
197.5 g (0.03 moles) of the oxypropylate described in Example 1 and 1 g of KOH
powder were reacted with 53 g (1.2 moles) of ethylene oxide in a stirred stainless steel
autoclave in the course of 3 hours under a pressure of from 6 to 10 bars at 125oC.
The mixture was then stirred for a further 4 hours until the pressure remained
constant. Analysis showed that the resulting adduct contained about 106 moles of
propylene oxide and about 40 moles of ethylene oxide per mole of polyamidoamine.

Vinyl polymer alkoxylate

Vinyl polymer with a site capable of being alkoxylated should be used.
The vinyl polymer contains a hydrophobic monomer and a hydrophilic monomer.
The monomer may contain heteroatoms, like nitrogen, sulfur and phosphorous.
Percentage hetero atom (PHA) is calculated as follows.
E.g. A molecule of dimethyl aminoethyl acrylate has a formula C7H13O2N and an
estimated molecular weight of 143. The weight % attributable oxygen and nitrogen is,
Nitrogen: 14 and Oxygen: 32 (2molecules) and Total 14+ 32= 46. %PHA =
46x100/143 = 32.3% or 32.2.
Hydrogen bonding is also estimated like this
E.g. A molecule of Hydroxyethyl acrylate with formula C5H8O3 and Mol.wt = 116
has one hydroxyl group (OH = 17). So %PHB is 17x100/116 = 14.7
Hydrophobic monomers are which having PHA less than 27 and hydrophilic
monomers are those which have PHA > 27.
Hydrophobic monomers are butyl acrylate, styrene, decyl acrylate, lauryl acrylate, etc.
Hydrophobic monomers are compounds such as hydroxyethyl, hydroxypropyl,
methoxyethyl acrylate and methacyrlates, methyl methacrylate, acrylamide,
vinylpyrolidine, acrylic acid, maliec anhydride methacrylic acid, vinyl pyridine and
vinyl acetate.
Vinyl polymers
Butyl acrylate = BA
Hydroxyl ethyl acrylate = HEA
Methyl methacrylate = MMA
Hydroxy ethyl methacrylate = HEMA
Lauryl acrylate = LA
Decyl acrylate = DA
Polymers
BA/HEA copolymer
BA/HEA/MMA terpolymer
BA/HEMA copolymer
BA/HEMA/DA terpolymer
BA/HEMA/LA terpolymer
BA/HEA/LA terpolymer
The preferred polymer is placed in an autoclave with inhibitor and heating to -160oC.
The polymerized vinyl polymer is thereafter reacted with alkylene oxide.

Vinyl polymer alkoxylates with small % of alkylene oxides are good demulsifiers
than non-alkoxylated vinyl polymer.
BA/HEA copolymer with ratio 93:7 and ethylene oxide 4% or more are found better
demulsifiers than those having ethylene oxide 0-2%.
Prepared by
Chandran Udumbasseri