INTERFACIAL POLYMERIZATION

Introduction

High molecular weight, synthetic condensation polymers of known composition

were prepared by Carothers and his co-workers in 1929 (1). The processes re-
quired high temperature and frequently high pressure or vacuum. The high tem-
perature procedure for polyamides led to the commercial production of the first
fully synthetic fiber, nylon-6,6. The technique is still the basic meltcondensation
process used for many polyamides. In the following years, melt processes were
applied successfully to a variety of condensation polymers, such as aliphatic
aromatic polyesters. However, simpler, faster procedures were required for lab-
oratory use and processes for polymers that cannot be melted or are thermally
unstable.
Between 1944 and 1960, techniques were gradually developed for the prepa-
ration of condensation polymers at low temperatures (2) (see Table 1). The inter-
facial process employs water and an organic liquid, whereas the solution method
uses a single liquid medium. These processes provide the required speed, need
only simple equipment, and are widely used (2,16,17).
Low temperature methods employ reactions that proceed at high rates and
are capable of giving nearly quantitative yields at room temperature. Best known
is the reaction of an organic acid chloride with a compound containing an active
hydrogen in the functional group, such as an amine, phenol, or thiol.
Condensation polymers are formed if the complementary intermediates are
bifunctional.

O O O O
NaOH
H2N R HN2 + Cl C R C Cl ( HN R NH C R C) + 2 NaCl
n

O O O O

Na+ O R O Na+
+ Cl C R C Cl (O R O C R C) + 2 NaCl
n

In interfacial polycondensation, the two fast-reacting intermediates are dis-

solved in a pair of immiscible liquids, one of which is preferably water. The wa-
ter phase contains the diamine or diol and usually an inorganic base to acti-
vate any diol and neutralize the by-product acid. The other phase consists of the
diacid chloride and an organic liquid such as dichloromethane, toluene, or hexane.
1
Encyclopedia of Polymer Science and Technology. Copyright

c 2011 John Wiley & Sons, Inc. All rights reserved.
2 INTERFACIAL POLYMERIZATION

Table 1. Interfacial Condensation Polymerizations

Polymer Date Refs.
urethanes 194445 3
urethanes 195455 4
amides, urethanes 1952 5
amides 1953 6
carbonatesa 1954 7,8
amides 1955 9
urethanes 1956 10
aromatic estersa 1957 11
aromatic sulfonates 1960 12
amides and others 1958 13
aromatic amides 1959 14
nylon-rope experiment 1959 15
aEarly use of phase-transfer agents.

Table 2. Interfacial Polycondensation Processes

Conditions
time 5 min to several hours
temperature 0 to 100 C
pressure 101.3 kPa (1 atm)
equipment simple; often open but may be closed for gaseous reactants
stirring low-to-high speed
Polymer characteristics
structure wide range possible
molecular weight low to high
copolymers some limitations
Product recovery
polymer isolation may need nonsolvent precipitant
filtration, washing, and drying
polymer yield low to high
by-products and solvents recovery or disposal required

Polymer formation takes place at or near the liquidliquid interface when the two
solutions are brought in contact or stirred together. By this process and its vari-
ations, thousands of polymers have been synthesized. Some of its features are
shown in Table 2.
The process is affected by many variables. Some of those relating to high
molecular weight and yield are given below:

high purity of intermediates nature and purity of the solvents

reaction rate volume ratio of the phases
freedom from competing side reactions concentration of reactants
adequate mixing addition of salts and bases
polymer swelling or solubility phase-transfer agents for some systems

The procedures are discussed here primarily in terms of AABB polymers pre-
pared from diacid chlorides. However, interfacial polycondensation can be used
 INTERFACIAL POLYMERIZATION 3

with many other reactants, for example, bis(trichloromethyl) esters (18), mixed
anhydrides of the diesters of orthophosphoric acid and dicarboxylic acid (6),
reactive alkylene dihalides (19), and epichlorohydrins (20). Addition reactions
also can be used, as in the reaction of diamines with diisocyanates (21,22),
isocyanatechloroformates (see also POLYAMIDES; ISOCYANATE-DERIVED POLYMERS;
POLYURETHANES) (23), or carbon suboxide (24). AB intermediates have been
employed with some success (25).

Polycondensation without Stirring

If the two solutions for an interfacial polycondensation are brought together with-
out stirring and if the polymer is not soluble in the organic liquid, certain poly-
mers form as thin films at the interface. Under the right conditions, this film is
coherent and fairly strong. It has a high molecular weight and can be pulled from
the area of the interface as a continuous collapsed tube (Fig. 1). This experiment
is called the nylon rope trick (2,15).
Solutions for the preparation of nylon-6,10 are 1.5 mL of sebacyl chloride
in 50 mL of dichloromethane as the bottom layer, and 2.20 g of hexamethylene-
diamine and 4.0 g of sodium carbonate in 50 mL of water as the top layer. An
alternative solvent of low toxicity for the bottom layer is 1,1,1-trifluoro-2,2,2-
trichloroethane.

Collapsed film

Diamine in water

Polymer film
forming at
interface

Diacid chloride in
organic solvent

Fig. 1. A polyamide film forming at and being withdrawn from a liquid interface.
4 INTERFACIAL POLYMERIZATION

O O O O
Na2CO3
H2N(CH2)6NH2 + CIC(CH2)8CCI HN ( CH2)6 NH C ( CH2)8C + NaCl
n
nylon-6,10

Only some polymers form cohesive films in interfacial polycondensation. The

strongest films are derived from aliphatic and aliphaticaromatic polyamides and
some polyurethanes. Film-formation rate may be enhanced by addition of trifunc-
tional intermediates. The requirements for cohesive film formation are not under-
stood. Some important factors are a high reaction rate, appreciable swelling by
the solvent (but not dissolution), and a combination of reactant concentration and
other factors that lead to high molecular weight.
Mechanism of Polymer Formation. Many water-insensitive polymers
seem to form at the interface or in the organic phase near the interface (2,22). The
aqueous phase acts as a reservoir for one type of intermediate and the acid accep-
tor, and extracts any by-product acid from the polymerization zone. In polyamide
preparation the diamine has an appreciable potential partition toward the or-
ganic phase. The first diamine entering the organic phase meets a high concen-
tration of acid chloride and is acylated at both ends. The following diamine finds
a layer of acid chloride-terminated oligomers and diacid chloride. Polymerization
proceeds with an irreversible coupling of oligomers and a deepening penetration
of the organic phase as the oligomers diffuse from the interface. At some point the
polymer may gel or precipitate and although chain growth may not cease, chain
extension is presumably much slower. As the primary polymer growth declines
and if unreacted intermediates remain, low molecular weight polymer forms both
within the film and on the side toward the organic phase. By-product hydrogen
chloride or its diamine salt diffuses to the interface and the aqueous phase.
Formation of polyesters from phenoxides and aromatic diacid chlorides is
confined more closely to the interface zone because of the low solubility of the phe-
noxide and its counterion in the organic phase. The film is formed in the organic
phase but thickens on the side at the solventwater interface. Phase-transfer
agents accelerate film formation.
Similar mechanisms apply to other systems, eg, acid halides with apprecia-
ble water solubility, hydrophilic polymers, and polymerizations without solvents.
In the gasliquid system for the reaction of oxalyl chloride vapor with aqueous
hexamethylenediamine, the polymerization takes place at the gasliquid inter-
face, and with the less reactive 1,4-phenylenediamine in the aqueous phase. Stud-
ies of the preparation of polyphosphonates and polyphosphates under different
conditions showed that in both liquidliquid and liquidvapor systems, the reac-
tion site may be at the interface or in the aqueous phase near the interface.
Applications. The unstirred polymerization system can be reduced in
scale to produce fine filaments, which are, however, not compact enough for good
strength without additional treatment (9). The film or rope of collapsed film can
be shredded with a blender or other device to yield fibrous particles (fibrids),
which form tough paper or that can be used to bind other chopped fibers into
paper (26). This film-forming process yields membranes with ion-exchange prop-
erties (27) and reverse osmosis properties (28). A film-spreading technique can
be used to prepare polyhexamethyleneisophthalamide (1) with high molecular
 INTERFACIAL POLYMERIZATION 5

weight and yield by dripping the acid chloride solution on an aqueous diamine
solution.

NH ( CH2 )6 NH C

C O
n
(1)

A process for coating wool to reduce fabric shrinkage was developed (29).
Interfacial polycondensation has been used to form cell-like capsules containing
enzymes and other materials for use in artificial kidneys, catalysis, and ion ex-
change (3032). It has been applied to the encapsulation of dyes (33,34), catalysts
(35), and insecticides (3537). The latter use has been applied commercially (38).

Polycondensation with Stirring

Polymerization with stirring offers more versatility. It may be applied to polymers

that precipitate rapidly or to those that form metastable or stable solutions; con-
ditions may be adjusted to the reaction. For rapid reactions with polymer precipi-
tation, a laboratory blender at high speed is effective for small-scale preparations.
Slower reactions with the polymer in solution may be stirred at moderate speeds.
Although fast polymerizations are completed in a few minutes or as soon as the
two phases have been thoroughly mixed, the process is also applied to reactions
that require up to several hours at elevated temperatures. Typical procedures are
given in Table 3.
Polymerization with Water-immiscible Solvents.
Mechanism. The mechanism of polymer formation in a stirred system
is the same as that for an unstirred system. When the polymer forms a
precipitate at the interface of a minute droplet, polymerization ceases as soon as
the intermediate in that droplet reacts. For larger droplets and interface zones,
the precipitate is torn from the interface or dispersed, and new interface areas
are exposed for polymerization. When polymer solutions are present, the droplets
are presumably sheared to form smaller droplets or merged and mixed to some
degree by continued stirring until polymerization is complete.
Variables. Many variables influence yields and molecular weights. The
preparation of polyamides is affected by the equilibrium solubility of the diamine
in the organic phase, and the concentration of the intermediates must be ad-
justed to achieve maximum average molecular weight. Stirring rate, concentra-
tion, polymer precipitation, and other factors contribute to the final result. The
effect of changes in variables on inherent viscosity (an indicator of molecular
weight) of poly(sebacyl piperazine) (2) is shown in Table 4.
 Table 3. Typical Interfacial Polycondensations with Stirring
Polymer Organic solvent phase Aqueous phase yield, % Viscosity, inh a, dL/g Refs.
amide
aliphatic 4.78 g sebacyl chloride 1.20 g ethylenediamine 80 1.2 in m-cresol 2,39
60 mL dichloromethane 1.60 g sodium hydroxide
200 mL water
aromaticaliphatic 3.95 mL sebacyl chloride 2.00 g m-phenylenediamine 84 0.85 40
100 mL acetophenone 1.48 g NaOH
182 mL water
urea 4.95 g phosgene 5.80 g hexamethylenediamine 70 0.93 in m-cresol 39
200 mL CCl4 4.00 g NaOH
70 mL water
urethane 9.35 g ethylene 5.8 g hexamethylenediamine 72 1.19 in m-cresol 41
bischloroformate
10.6 g sodium carbonate
125 mL benzene 1.5 g sodium lauryl sulfate
150 mL water

6
sulfonamide 6.88 g 1,3-benzenesulfonyl 3.02 g hexamethylenediamine 78 2.71 in H2 SO4 42
chloride
5.30 g sodium carbonate
2 g sodium lauryl sulfate
190 mL water
thio ester 2.3 g sebacyl chloride 2.46 g 4,4 -dimercaptobenzophenone 82.5 1.14b 43
50 mL benzene 0.8 g NaOH
50 mL hexane 50 mL water
aryl ester 2.03 g isophthaloyl chloride 3.18 g phenolphthalein 95 0.93c 44
30 mL 1,2-dichloroethane 0.80 g NaOH
100 mL water
carbonate 5.4 g phosgene 13.8 g 2,2-bis(4-hydroxyphenyl)propane 93 1.81 in chloroform 45
150 mL dichloromethane 120 mL water
0.2 mL tri-n-butylamined
a
inh = [2.3 log rel ]/c except where otherwise indicated.
b
red = sp /c in phenol/tetrachloroethane (1/3); higher values are obtained in the presence of a phase-transfer agent.
c In 40/60 (by wt) tetrachloroethane/phenol.
dAdded late in polymerization period.
 INTERFACIAL POLYMERIZATION 7

O O

N N C (CH2)8 C
n
(2)

As a consequence of changing solvents, a precipitate is formed, followed by

a metastable solution and a stable solution. The metastable solution gives the
highest dilute solution viscosity with high yield. A plot of the effect of phase-
concentration ratio for the chloroform system of Table 4 is shown in Figure 2.
The highest yields usually occur at the highest molecular weight, although frac-
tionation (qv) and other variables can affect the result. The variation in results
for a single polymer shows that there is no single best formula for interfacial poly-
merization; conditions must be carefully explored to obtain the highest molecular
weight and yield. Impurities, side reactions, low reaction rate, and low swelling
affect the course of the reaction.
Kinetics. Many reactions used in interfacial polycondensation have kinetic
rates estimated to be 102 106 L/(mols). Numerous attempts have been made to
determine reaction rates (4750), which are often limited by diffusion or transfer
of the intermediates to the reaction site. This transfer is greatly affected by the
solubility of the reactant species in the medium at the reaction site, polymer pre-
cipitations, viscosity of the forming polymer solution, oligomer mobility, polarity
of the medium, functional group complexes and counterions, and interfacial en-
ergy barriers. Even when kinetic rates are low, some of these factors may remain
dominant.
Polymerization in Water-miscible Solvents. Completely or partially
water-miscible solvents (2,14) can be used for polyamides (2,17,37,51), polyesters
(17,52), polyurethanes (17,53), polysulfonamides, and in particular for systems

Table 4. Interrelation of Solvent, Stirring, and Diamine Partition Coefcients in the

Preparation of Poly(sebacyl piperazine)
Optimum unstirred system Optimum stirred system

Reactant inh c , Reactant inh c ,

a
Solvent K ratiob dL/g Kd
ratiob dL/g
e
carbon tetrachloride 460 7 1.68 700 0.10.2 1.52
1,2-dichloroethanef 200 0.08 3.17
chloroformg 45 0.3 2.5
aK is the equilibrium partition coefficient (water/solvent) at 25 C for piperazine, 0.40 M, and NaOH,
0.80 M, in the water phase.
bThe reactant ratio = the initial ratio of the piperazine/sebacyl chloride concentrations in their re-

spective phases. Unstirred system: piperazine, 0.80 M; NaOH, 1.60 M; stirred system: piperazine,
0.10 M; NaOH, 0.20 M (2,46).
c In m-cresol.
dAs in a with piperazine, 0.10 M, and NaOH, 0.20 M.
e Produces polymer precipitate in 77% yield.
f Forms metastable solution of polymer; yield, 93%.
g Produces polymer solution; yield, 93%.
8 INTERFACIAL POLYMERIZATION

with a diacid chloride component of relatively high hydrolytic stability. Hydroly-

sis is reduced by use of weakly alkaline acid acceptors, eg, sodium carbonate.
Polymers that have been made in high molecular weight
include polyhexamethylenesebacamide, poly(terephthaloyl trans-
2,5-dimethyl-piperazine) (3), poly(m-phenyIeneisophthalamide) (4),
poly(1,4-phenylenedioxycarbonylpiperazine) (5), poly(hexamethylene-1,3-
phenylenesulfonamide) (6), poly(terephthaloyl oxalamidrazone) (7) (54,55),
and poly[2,2-bis(4-phenylene)propane terephthalate] (8) (52).

CH3 O O
O O
HN NH C C
N N C C
n
CH3 n
(3) (4)

O O

N N C O O C HN ( CH2)6 NH SO2
n
SO2
n
(5) (6)

NH NH O O CH3 O O

HN C C NH C C O C O C C
n
CH3 n
(7) (8)

Examples of useful solvents are given in Table 5. Water-miscibility is re-

duced by salts, bases, intermediates, and polymers resulting in two liquid phases.
Water-miscible solvents accelerate reaction rates, enhance polymer swelling, and
facilitate product recovery.
Solventwater ratio (Fig. 3), concentration of intermediates (Fig. 4), and
mixing are important. Addition of sodium and lithium chlorides reduces phase
miscibility and may change the partition of the aqueous reactant toward the or-
ganic phase (52,54,56). The process has also been called emulsion polycondensa-
tion (52,56) or dispersion polymerization (57).
VaporLiquid Interfacial Polycondensation. The gas or vaporliquid
process is useful when one of the intermediates is a vapor at ambient or slightly
higher temperatures. It is mostly employed in the preparation of the polycarbon-
ates with phosgene (8,58,59), but it is also useful for the preparation of polyureas
from phosgene and a diamine and for polyoxamides from oxalyl chloride (60).
The reactant vapor is introduced into the system in an inert gaseous diluent.
The liquid system can be the aqueous phase alone or may contain an immiscible
organic solvent. The latter method produces polymers in higher yield and with
higher molecular weights (61). Raising the temperature does not significantly in-
crease the rate of acid halide hydrolysis, because of an accompanying reduction
 INTERFACIAL POLYMERIZATION 9

2.4

100
inh, dL/g

Yied
1.8
A
80
B

1.2 60

40
0.6
0.03 0.1 1.0 5.0
Sebacyl chloride in chloroform, M

Fig. 2. Poly(sebacyl piperazine) in a stirred system. Product solution viscosity A and

yield B vs reactant concentrations with the polymer in solution. Diamine, 0.10 M; stirred
at full speed in a blender; total liquid volume, 400 mL (2,46).

in gas solubility. Phase ratios, temperature, stirring rate, polymer precipitation,

and addition rate of the reactant vapor are important variables. For polycarbon-
ate synthesis, the procedure has been modified in many ways to control molec-
ular weights, conserve phosgene, reduce color, produce uniform copolymers, and
facilitate polymer isolation. Usually, solvent, water, alkali, and bisphenols are
combined. Reducing agents to preserve color, monophenols to provide chain ter-
mination, and surface active agents may be present. Phase-transfer agents are
added at the beginning or, preferably, late in the polymerization to reduce hy-
drolysis of phosgene and chloroformate end groups. Phosgene is added with or

Table 5. Water Miscibility of Organic Liquids Used in the Preparation of Polyamides

Solubility limit, g/100 mL at 20 C

Organic solvent Solvent in water Water in solvent

carbon tetrachloride 0.08 0.0134
benzene 0.18 0.044
chloroform 0.82 0.15
cyclohexanone 2.43 8.62
2.4-dimethyltetramethylene sulfone 24.0 15.0
methyl ethyl ketone 26.7 12.1
1,2-propylene oxide 33(30 C) 12.8
tetramethylene sulfone
acetone
tetrahydrofuran
isopropyl alcohol
10 INTERFACIAL POLYMERIZATION

3.0

inh, dL/g
2.0

1.0

0.5 1.0 1.5 2.0 2.5 3.0

Ratio of tetrahydrofuran to water (vol/vol)

Fig. 3. Inherent viscosity vs the ratio of tetrahydrofuran to water in the prepara-

tion of poly(terephthaloyl trans-2,5-dimethylpiperazine). Total liquid volume, 200 mL;
0.02 mol of sodium carbonate; stirred for 5 min. Yields 8490%. Inherent viscosity in
tetrachloroethanephenol (4060 by wt) (17).

3.5

3.0
inh, dL/g

2.5

2.0

1.5
0 1.0 2.0 3.0 4.0 5.0
Mole concentration of diamine
in H2O and acid chloride in THF

Fig. 4. Inherent viscosity vs mole concentration of trans-2,5-dimethylpiperazine

and terephthaloyl chloride in the preparation of poly(terephthaloyl trans-2,5-
dimethylpiperazine); 100 mL of tetrahydrofuran and water; 2 mol of sodium carbon-
ate for each mol of diamine; stirred 5 min. Yields 8694%. Inherent viscosity in
tetrachloroethanephenol (4060 by wt) (17).

without an inert carrier gas. In one procedure, enough phosgene is introduced to

convert the bisphenols to bischloroformate oligomers. The phase-transfer agent is
added, and polymerization is completed by controlled hydrolysis combined with
reaction of other chloroformyl and phenolate groups.
 INTERFACIAL POLYMERIZATION 11

Copolymerization. The formation of completely random copolymers in

interfacial processes is difficult because conditions interfere with the uniform
introduction of two or more similar intermediates into the growing polymer
chains. There are differences in reaction rates of monomers and oligomers, par-
tition of aqueous reactants into the organic phase, solubility or precipitation of
oligomers, differing hydrolytic sensitivity of acid chlorides, transfer effects of
phase-transfer agents, etc. The same conditions interfere with monofunctional
chain terminators. The most uniform copolymers are obtained when pairs of
intermediates are much alike and the product polymers remain in solution. A
single-phase solution system gives better results. In addition to studies on ran-
dom copolymers, ordered copolymers such as alternating copolycarbonates (2,58),
alternating copolyamides (62), polyamide esters, and block copolymers (63) have
been described.
Water-insoluble Reactants. Occasionally a reactant, which would nor-
mally be placed in the aqueous phase, has little or no water solubility. In this case,
for example, the diamine bis(4-aminocyclohexyl)methane is dissolved in a por-
tion of the organic solvent added to the aqueous phase (39). Bisphenols, such as
9,9-bis(4-hydroxyphenyl)fluorene, which do not dissolve in equivalents of sodium
hydroxide, may be more soluble as the potassium phenolate or may be dissolved
in excess alkali (64).
Polycondensation in Two-phase Nonaqueous Systems. Nylon-6,
10 film can be prepared in xyleneethylene glycol (9). Other polyamides are pre-
pared in stirred systems with glycol, glycerol, and a cyclic sulfone instead of water
(46). Several nonaqueous, two-phase media have been evaluated for preparation
of organometallic polymers (qv) (65). Aromatic polyesters have been prepared in
immiscible pairs of solvents with triethylamine as the acid acceptor. Molecular
weights and yields are good.
Polycondensation without Organic Solvents. When the diacid chlo-
ride or the analogous reactant is a vapor or a liquid, the polymer can be prepared
at an aqueous interface. Thus, polycarbonates are prepared from phosgene va-
por and aqueous alkaline solutions of bisphenols (8,58). Other examples include
the polyamide from piperazine and liquid sebacyl chloride (points at right axis in
Fig. 2) (46), polyhexamethylenemalonamide from the diamine and gaseous car-
bon suboxide (24), polyureas from diamines and phosgene (22,66), and polyoxam-
ides from oxalyl chloride vapor (61,62,67). Yields and molecular weight are lower
than those obtained in the presence of a solvent. Using aerosols of diacid chlo-
rides and aqueous diamine solutions gives polyamides of high molecular weights
in high yields. Polysulfides have been prepared from aliphatic dithiols and di-
halides without solvents by heating the system above the melting point of the
polysulfide (68).
Phase-transfer Agents. Phase-transfer agents (PTA), also called cata-
lysts or accelerators (2,8), are used in the synthesis of small molecules (69,70).
Their addition to a two-phase system composed of a water-immiscible solvent
and water promotes a chemical reaction by enhancing the transfer of the aque-
ous intermediate across the interfacial boundary into the presence of the com-
plementary intermediate (Table 6). The effect is analogous to an increase in the
partition coefficient of a phenolate, dithiolate, or similar intermediate in favor
12 INTERFACIAL POLYMERIZATION

Table 6. Polymerizations Aided by Phase-Transfer Agents

Phase-
transfer
Polymer Intermediates Processa agentb Refs.
carbonates bisphenolphosgene dichloromethane TEN; BTEAC 8
water
bisphenol dichloromethane BTPPCc 71
bischloroformate water
bischloroformate 1,2-dichloroethane TEAC 72
water
esters bisphenoldiacid trichloroethanewater TEAC; 44,73
chloride BTEAC
sulfonates bisphenoldisulfonyl dichloromethane BTEAC 12,74
chloride water
ethers bisphenoldihalide toluenewater TeBuNHSO4 19
bisphenol dioxanewater BTEAC 20
epichlorohydrin
bisphenol acetonepotassium 18-crown-6 75
hexafluorobenzene carbonate
sulfides dithioldihalide chloroformwaterd DC-18- 68
crown-6
dihalideNa2 S dihalidewater CTMAC 76
hydrocarbon dihalide anisoiewater BTEAC 77
phenylacetonitrile
aMost procedures require an acid acceptor.
bTEN, triethylamine; BTEAC, benzyltriethylammonium chloride; BTPPC, benzyltriphenylphospho-
nium chloride; TEAC, tetraethylammonium chloride; TeBuNHSO4 , tetrabutylammonium hydrogen
sulfate; 18-crown-6, cyclic ether with six ethyleneoxy units; DC-18-crown-6, cyclic ether with four
ethyleneoxy and two 1,2-cyclohexyleneoxy units; CTMAC, cetyltrimethylammonium chloride.
c See Table 7.
dAliphatic intermediates were polymerized without solvents.

of the organic phase. Addition of phase-transfer agents increases the rate of

polymer formation and results in higher molecular weight and yield. Polyethy-
lene glycols, tertiary aliphatic amines, quaternary ammonium, phosphonium,
arsonium, and sulfonium compounds, crown ethers (78) and similar substances
act as phase transfer agents.
Addition of tertiary amines and quaternary ammonium salts facilitates the
syntheses of diphenyl carbonate (79) and polycarbonates (7,8,59) from phosgene
and phenols. Onium compounds assist in the synthesis of polycarbonates, aro-
matic polyesters, and polysulfonates (Table 7) (11,71).
Mechanism. Phase-transfer agents are effective in an aqueous two-phase
system when one intermediate is an ionic species such as a phenolate, which re-
quires base. Ionic phase-transfer agents provide alternative cations which form
ion pairs with the phenolate ions with increased solubility in the organic phase.
A complex-forming PTA associates with inorganic cations and likewise yields ion
pairs with increased solubility in the organic phase. After the phenolate has
reacted in the condensation step, the PTA ion or ion-bearing complex diffuses
to the aqueous phase with the by-product anion; thus the PTA is continuously
 INTERFACIAL POLYMERIZATION 13

Table 7. Effect of Quaternary Phase-transfer Agents (PTA) in the Preparation of

Polycarbonate from 2,2-Bis(4-hydroxyphenyl)propane and its Bischloroformatea
[], dL/gb

PTA, 0.05%c PTA, 2.0%c

Phase-transfer agent 5 mind 30 min 5 min 30 min

triethylbenzylammonium chloride 0.26 0.10 0.70
methyltriphenylarsonium iodide 0.68 0.96 1.65
methyltriphenylphosphonium iodide 0.40 0.80 0.90 1.24
benzyltriphenylphosphonium chloride 0.41 0.90 0.90 1.36
p-xylylene-, -bis(dihydroxyethyl)sulfonium 0.28 0.38 0.76
bromide
aPolymerization in waterdichloromethane with NaOH as acid acceptor (2,71).
bVariation of the intrinsic viscosity of the product with the PTA concentration and reaction time; []
measured in sym-tetrachloroethane at 25 C.
c By weight based on the theoretical weight of polymer.
dCounted from time of complete addition of acid chloride.

cycled. Polymerization time is reduced with increasing amount of PTA. However,

an excessive amount may result in a low molecular weight (2,4) due to impurities,
increased hydrolysis of acid chloride, rapid introduction of the aqueous reactant,
or interference in the removal of the by-product salt.
Some agents may cause ion-pair separation, which could accelerate the
condensation reaction. Onium compounds with long-chain alkyl substituents,
eg, cetyltriethylammonium chloride, may act both as surface-active agents and
phase-transfer agents. In the preparation of polycarbonate, tertiary amines were
particularly effective in increasing the rate of hydrolysis of chloroformate end
groups (79). Tetraethylammonium chloride can also be used for this reaction (80).
The hydrolysis step is important in polycarbonate synthesis to increase molecular
weight if most of the oligomer ends have been converted to chloroformate groups.
Among the systems shown in Table 6, two depart from the usual process.
In one, solid potassium carbonate is solubilized to promote the preparation of a
polyether from hexafluorobenzene and a bisphenol.

F F
CH3 CH3
K2CO3
HO C OH + C6F6 O C O
CH3 CH3
F F n

In the other, sodium sulfide is solubilized to participate in a condensation

with a dihalide

ClCH2 CH CH CH2Cl + Na2S ( CH2 CH CH CH2S )n

(see also POLYSULFIDE POLYMERS).

14 INTERFACIAL POLYMERIZATION

Reactions on Polymers. Phase-transfer agents have been associated with

polymers in reactions other than condensation polymerization. Polymeric sub-
strates such as polychloromethylstyrene, poly(vinyl chloride), poly(vinyl chloro-
formate), and cellulose or its derivatives react with various nucleophilic or hy-
drolytic reagents in the presence of phase-transfer agents (78,81,82). In other
systems, polymeric phase-transfer agents are synthesized containing crown ether
units or quaternary ammonium or phosphonium groups, which are used to pro-
mote condensation reactions between small molecules (78,83,84). These proce-
dures are carried out in liquidliquid, solidliquid, and even triphase systems.
The mechanisms are the same as that of interfacial polycondensation.
Applications. Interfacial polycondensation with stirring is widely ap-
plied in research on polymer synthesis. Special applications are the use of
organophosphorus (85) and silicon halides, ferrocene intermediates (88), and
group IVA, IVB, and VA metallic intermediates (65). Polycarbonates (qv) are
manufactured by interfacial polycondensation in the United States, Europe, and
Japan.
Interfacial polycondensation in water-miscible solvents is particularly use-
ful in the preparation of many aromatic polyamides, which are frequently ob-
tained with low molecular weight when water-immiscible solvents are used
(87,88). This is, however, not true for the polyamide from 2,5-pyridine diacid chlo-
ride and p-phenylenediamine (88).

O O

HN NHC C
N n

The procedure has been used on a large scale to prepare aromatic

polyamides and aromatic polyesters for plastics (56,89). The preparation of
poly(terephthaloyl oxalamidrazone) (7) has been studied extensively (55) (see also
POLYAMIDES, AROMATIC; POLYESTERS).
Health and Safety Factors. Interfacial polycondensations are no more
hazardous than most simple laboratory procedures. The usual care should be
observed in the storage, handling, and disposal of solvents and reagents. Of par-
ticular concern is phosgene, which is highly toxic and volatile; reactions must
be carried out with good shielding in high-draft hoods. Effluent gases should be
passed through an alkaline scrubber. Warning signs should be displayed on doors
and hood-exhaust areas.
All polymerizations and isolation procedures should be carried out in fume
hoods. Flammable solvents should not be handled in the presence of flames, hot
surfaces, or unprotected electrical motors or switches. For example, motors on
blenders or similar stirring devices should be enclosed and blanketed with a flow
of nitrogen (2).
Some solvents and reagents are known carcinogens or mutagens. Informa-
tion on such hazards can be obtained from up-to-date toxicity sources. In working
with low boiling solvents and scaled-up operations, the uncontrolled development
of heat from the reaction and prolonged stirring must be considered and counter-
acted by adequate cooling.
 INTERFACIAL POLYMERIZATION 15

Table 8. Properties of Intermediates

Boiling point

Molecular Melting

Intermediate weight C kPaa point, C
diacid chloride
phosgene 98.92 8.2 101 126
oxalyl 126.93 61.1 99 10
adipyl 183.04 125128 1.47
sebacyl 239.14 109110 0.130.26 7 to 5
isophthaloyl 203.03 143144 1.76 4344
terephthaloyl 203.03 141 2.16 8384
ethylene bischloroformate 186.98 72 0.29
2,2-bis(4-chlorocarbonyloxy 353.20 183187 0.027 9698
phenyl)propane
1,3-benzenedisulfonyl 275.13 6262.5
diamine
ethylene- 60.10 117.2 8.5
hexamethylene- 116.20 9092 1.87 42
piperazine 86.14 145.5 99 108
trans-2,5-dimethylpiperazine 114.19 161.9 99 117118
1,3-phenylene- 108.14 285.5 62.8
1,4-phenylene- 108.14 267.0 140
bis(4-aminophenyl) ether 200.23 186187
bisphenol
hydroquinone 110.11 170.3
2,2-bis(4-hydroxyphenyl)propane 228.29 156157
2,2-bis (4-hydroxy-3, 366.09 133134
5-dichlorophenyl)propane
phenolphthalein 318.31 261262
aTo convert kPa to mm Hg, multiply by 7.5.

Intermediates. Properties of intermediates used in interfacial polycon-

densation are given in Table 8. Additional data on these and other intermediates
are given in Ref. 2, Appendix C, and in Refs. 90 and 91.

BIBLIOGRAPHY

Interfacial Polymerization in EPSE 2nd ed., Vol. 8, pp. 221237, by Paul W. Morgan,
Consultant.

CITED PUBLICATIONS

1. H. Mark and G. S. Whitby, eds., Collected Papers of Wallace Hume Carothers on High
Polymeric Substances, Wiley-Interscience, New York, 1940.
2. P. W. Morgan, Condensation Polymers by Interfacial and Solution Methods, Wiley-
Interscience, New York, 1965.
16 INTERFACIAL POLYMERIZATION

3. Fr. Pat. 892,361 (Apr. 5, 1944) and 895,395 (Jan. 23, 1945), (to I. G. Farbenindustrie
AG).
4. Ger. Pat. 904,471 (Feb. 18, 1954), 912,863 (June 3, 1954), 915,868 (July 29, 1954),
925,612 (Mar. 24, 1955), 929,214 (June 23, 1955), L. Orthner, P. Schlack, and co-
workers (to Farbwerke Hoechst AG).
5. U.S. Pat. 2,660,574-5 (Nov. 24, 1953) and Brit. Pat. 683,504 (Nov. 26, 1952), W. D. Jones
and S. B. McFarlane (to Celanese Corporation).
6. U.S. Pat. 2,625,536 (Jan. 13, 1953), J. E. Kirby (to I. E. du Pont de Nemours & Co.,
Inc.).
7. H. Schnell, Angew. Chem. 68, 633 (1956); Belg. Pat. 523,543 (1954), H. Schnell, L.
Bottenbruch, and H. Krimm (to Farbenfabriken Bayer AG).
8. H. Schnell, Chemistry and Physics of Polycarbonates, Wiley-Interscience, New York,
1964.
9. U.S. Pat. 2,708,617 (May 17, 1955), E. E. Magat and D. R. Strachan (to I. E. du Pont
de Nemours & Co., Inc.).
10. U.S. Pat. 2,731,445-6 (Jan. 17, 1956), E. L. Wittbecker (to I. E. du Pont de Nemours &
Co., Inc.).
11. A. Conix. Ind.Eng. Chem. 51, 147 (1959); Ind. Chim. Beige, 22, 1457 (1957); Belg.
Pat. 563,173 (Dec. 13, 1957), A. Conix (to Gevaert Photo-Producten N. V.).
12. A. Conix and U. L. Laridon, Angew. Chem. 72, 116 (1960); A. Conix, Angew. Chem. 72,
272 (1960)
13. E. L. Wittbecker and P. W. Morgan, J. Polym. Sci. 40, 289 (1959) and the following
papers presented in part at the 134th National ACS Meeting, Chicago, 1958.
14. Fr. Pat. 1,199,460 (Dec. 14, 1959) and U.S. Pat. 3,006,899 (Oct. 31, 1961), H. W. Hill, S.
L. Kwolek, and P. W. Morgan (to I. E. du Pont de Nemours & Co., Inc.).
15. P. W. Morgan and S. L. Kwolek, J. Chem. Ed. 36, 182, 530 (1959).
16. F. Millich and C. E. Carraher, Jr., eds., Interfacial Synthesis, Vols. 1 and 2, Marcel
Dekker, New York, 1977.
17. P. W. Morgan, J. Macromol. Sci., Chem. A15(5), 683 (1981).
18. U.S. Pat. 2,937,161 (May 17, 1960), E. K. Ellingboe (to I. E. du Pont de Nemours & Co.,
Inc.).
19. T. D. Nguyen and S. Boileau, Synthesis of Polyethers by Phase-Transfer Catalyzed
Polycondensation, in L. J. Mathias and C. E. Carraher, eds., Crown Ethers and Phase
Transfer Catalysis in Polymer Science, Vol. 2, Plenum Press, New York, 1984, p. 59;
V. Percec, T. D. Shaffer, and H. Nava, J. Polym. Sci., Polym. Lett. Ed. 22(12), 637
(1984).
20. A. K. Banthia, D. Lunsford, D. C. Webster, and J. E. McGrath, J. Macromol. Sci., Chem.
Al5(5), 943 (1981).
21. U.S. Pat. 2,852,494 (Sept. 16, 1958), W. Lehman and H. Rinke (to Farbenfabriken
Bayer AG); Ref. 2, pp. 223, 494.
22. K. C. Steuben and A. E. Barnebeo, Interfacial Preparation of Polyureas, in Ref. 16,
Vol. 2, pp. 269307.
23. K. Hayashi and Y. Iwakura, Makromol. Chem. 94, 132 (1966); Y. Iwakura, K. Hayashi,
and K. Imazaki, Makromol. Chem. 104, 56 (1967).
24. I. Daniewska, Polyamides from Carbon Suboxide, in Ref. 16, Vol. 2, pp. 125
156.
25. J. R. Schaefgen, F. H. Koontz, and R. F. Tietz, J. Polym. Sci. 40, 377 (1959).
26. U.S. Pat. 3,068,527 (Dec. 18, 1962), P. W. Morgan (to I. E. du Pont de Nemours & Co.,
Inc.).
27. V. Enkelmann and G. Wegner, J. Appl. Polym. Sci. 21(4), 997 (1977).
28. J. E. Cadotte, R. S. King, R. J. Majerle, and R. J. Petersen, J. Macromol. Sci., Chem.
A15(5), 727 (1981); J. E. Cadotte and R. J. Petersen in A. F. Turbak, ed., Synthetic
 INTERFACIAL POLYMERIZATION 17

Membranes, Vol. 1, ACS Symposium Series No. 153, American Chemical Society,
Washington, DC, 1981, pp. 305326.
29. R. E. Whitfield, L. A. Miller, and W. L. Wasley, Text. Res. J. 31(8), 704 (1961); J. Appl.
Polym. Sci. 8, 1607 (1964).
30. T. M. S. Chang, Chemtech, 5(2), 80 (1975).
31. E. Shchori and K. F. ODriscoll. Polymer 19(9), 1074 (1978).
32. W. Sliwka, Angew. Chem., Int. Ed. Eng. 14(8), 539 (1975).
33. H. W. Mackinney, SPE Trans. 3(1), 71 (1963).
34. Brit. Pat. 1,046,409 (Oct. 26, 1966) (to Moore Business Forms, Inc.).
35. U.S. Pat. 3,270,100 (Aug. 30, 1966), R. M. Jolkovski, A. C. Laws, and D. H. Powers (to
Delavan Manufacturing Company).
36. U.S. Pat. 3,577,515 (1963), J. E. Vandegaer (to Pennwalt Corporation).
37. Chem. Eng. News, 68 (June 5, 1972); 15 (July 29, 1974).
38. E. D. Oliver and Y.-C. Yen, Commercial Applications of Interfacial Synthesis, in Ref.
16, Vol. 2, pp. 126.
39. R. G. Beaman, P. W. Morgan, C. R. Roller, E. L. Wittbecker, and E. E. Magat, J. Polym.
Sci. 40, 329 (1959).
40. P. W. Morgan and S. L. Kwolek, Macromolecules 8, 104 (1975).
41. E. L. Wittbecker and M. Katz, J. Polym. Sci. 40, 379 (1959).
42. S. L. Kwolek and P. W. Morgan, Macromol. Synth. 4, 109 (1972).
43. W. Podkoscielny and A. Kultys, J. Polym. Sci., Chem. Ed. 22, 2265 (1984).
44. P. W. Morgan, J. Polym. Sci. A2, 437 (1964); Macromol. Synth. 4, 29 (1972).
45. U.S. Pat. 3,038,879 (June 12, 1962), T. M. Laakso and D. A. Buckley (to Eastman Kodak
Company).
46. P. W. Morgan and S. L. Kwolek, J. Polym. Sci. 62, 33 (1962).
47. J. H. Bradbury and P. J. Crawford, Kinetics and Mechanisms, in Ref. 16, Vol. 1, pp.
77102.
48. F. MacRitchie, Interface Effects and Chemical Reaction Rate, in Ref. 16, Vol. 1, pp.
102139.
49. V. Z. Nikonov and V. M. Savinov, Polyamides, in Ref. 16, Vol. 2, pp. 157207.
50. Z. K. Brzozowski, J. Petrus, and J. Dubczynski, J. Macromol. Sci., Chem. AI3(7), 887
(1979).
51. L. B. Sokolov and T. V. Kudim, Vysokomol. Soedin. 7(11), 1899 (1965).
52. U.S. Pat. 3,933,713 (Jan. 20, 1976), L. B. Sokolov and T. V. Kudim; T. V. Kudim and L.
B. Sokolov, Vysokomol. Soedin. 20A(8), 1802 (1978).
53. U.S. Pat. 2,658,886 (Nov. 10, 1953), J. Swerdloff and S. B. McFarlane (to the Celanese
Corporation).
54. Brit. Pat. 1,286,240 (Aug. 23, 1972), M. Wallrabenstein, A. Schopf, and D. Frank (to
Glanzstoff AG); M. Wallrabenstein, Macromol. Synth. 49, 8 (1982).
55. D. W. Van Krevelen, Angew. Makromol. Chem. 22, 133 (1972).
56. T. V. Kudim and L. B. Sokolov, Vysokomol. Soedin. 20A(8), 1802 (1978).
57. S. Foti, P. Maravigna, and G. Montaudo, Chim. Ind. (Milan) 65(5), 337 (1983).
58. H. Vernaleken, Polycarbonates, in Ref. 16, Vol. 2, pp. 65124.
59. L. Bottenbruch, Polycarbonates, in N. M. Bikales, ed. Encyclopedia of Polymer Sci-
ence and Technology, 1st ed., Wiley-Interscience, New York, 1969, pp. 710764.
60. L. B. Sokolov, Liquid-Vapor interfacial Polycondensation, in Ref. 16, Vol. 1, pp. 141
165.
61. T. C. Fletcher and P. W. Morgan, J. Polym. Sci., Chem.. Ed. 18, 643 (1980).
62. W. Deits, S. Grossman, and O. Vogl, J. Macromol. Sci., Chem. A 15(5), 1027
(1981).
63. P. T. Andolino-Brandt, D. C. Webster, and J. E. McGrath, Polym. Prepr., ACS Div.
Polym. Chem. 25(2), 91 (1984).
18 INTERFACIAL POLYMERIZATION

64. P. W. Morgan, Macromolecules 3(5), 536 (1970).

65. C. E. Carraher, Jr., Organometallic Polymers, in Ref. 16, Vol. 2, pp. 367416.
66. U.S. Pat. 2,816,879 (Dec. 17, 1957), E. L. Wittbecker (to I. E. du Pont de Nemours &
Co., Inc.).
67. L. B. Sokolov, J. Polym. Sci. 58, 1253 (1962).
68. Y. Imai, A. Kato, M. Ii, and M. Ueda, J. Polym. Sci., Polym. Lett. Ed. 17(9), 579 (1979);
Y. Imai and M. Ueda, in Ref. 78, p. 121.
69. W. P. Weber and G. W. Gokel, Phase Transfer Catalysis in Organic Synthesis, Springer-
Verlag, New York, 1977.
70. C. M. Starks and C. Liotta, Phase Transfer Catalysis. Academic Press, New York, 1978.
71. Fr. Pat. 1,284,226 (Feb. 9, 1962) and Ger. Pat. 1,162,079 (Jan. 30, 1964), A. J. Conix (to
Gevaert Photo-Producten N. V.).
72. Ref. 2, p. 360.
73. U.S. Pat. 3,028,364 (Apr, 3, 1962), A. J. Conix and U. L. Laridon (to Gevaert Photo-
Producten, N. V.).
74. Fr. Pat. 1,277,208 (Nov. 24, 1961), A. J. Conix and U. L. Laridon (to Gevaert Photo-
Producten N. V.).
75. R. Kellman, D. Gerbi, R. F. Williams, and J. L. Morgan, Polym. Prepr., ACS Dw. Polym.
Chem. 21(2), 164 (1980); 23(1), 174 (1982).
76. M. Ueda, Y. Oishi, N. Sakai, and Y. Imai, Macromolecules, 15(2), 248 (1982).
77. Y. Imai, A. Kameyama, T.-Q. Nguyen, and M. Ueda, J. Polym. Sci., Polym, Chem. Ed.
19(11), 2997 (1981); Ref. 78, p. 121.
78. L. J. Mathias and C. E. Carraher, eds., Crown Ethers and Phase Transfer Catalysis in
Polymer Science, Plenum Press, New York, 1984.
79. Ref. 8, p. 93.
80. Fr. Pat. 1,332,408 (July 12, 1963), A. Conix and L. M. Dohmen (to Gevaert Photo-
Producten N. V.).
81. S. Boivin, A. Chettouf, P. Hemery, and S. Boileau, Polym. Bull. (Berlin) 9, 114120
(1983).
82. H. Kise and H. Ogata, J. Polym. Sci., Chem. Ed. 21(12), 3443 (1983).
83. L. J. Mathias and K. Al Jumah, J. Polym. Sci., Chem. Ed. 18(10), 2911 (1980).
84. M. Tomoi, Y. Hosokawa, and H. Kakiuchi, J. Polym. Sci., Chem. Ed. 22(6), 1243 (1984).
85. F. Millich, L. L. Lambing, and J. Teague, Polyphosphonates, Polyphosphates, and
Polyphosphites, in Ref. 16, Vol. 2, pp. 309350.
86. E. Neuse and H. Rosenberg, Metallocene Polymers, Marcel Dekker, New York, 1970.
87. Ref. 2, pp. 99101, 191192, 492493.
88. N. Ogata, K. Sanui, T. Onozaki, and S. Imanishi, ACS Div. Org. Coat. Plast. Chem.
Prepr. 42, 390 (1980).
89. L. B. Sokolov, Jpn. Plast, Age, 4749 (Nov./Dec. 1975).
90. J. K. Stille and T. W. Campbell, eds., Condensation Monomers, John Wiley & Sons, Inc.,
New York, 1972.
91. W. R. Sorenson and T. W. Campbell, Preparative Methods of Polymer Chemistry, 2nd
ed., Wiley-Interscience, New York, 1968.

GENERAL REFERENCES

Refs. 2, 8, 16, 58, 59, 69, 70, 78, 90, and 91 are good general references.

PAUL W. MORGAN
Consultant