JOURNAL OF POLYMER SCIENCE VOL.

XLVI, ISSUE 148 (1960)

NOTES
Telechelic Polymers

I. Introduction
The vulcanization of rubber is a complex process which produces a three-dimensional
network structure. A network structure produced by any of the conventional vul-
canization reactions may possess several types of flaws or imperfections. Among these
are free chain ends, two of which exist for every primary polymer molecule. Floryl
emphasized the importance of the free chain ends in elastomeric vulcanixates and
pointed out that the two free chain ends per polymer molecule in the vulcanizates con-
tribute little to the physical properties. A schematic representation of a vulcanizate
with the free ends emphasized is given in Figure la. An estimate of the fraction of
rubber existing as free chain ends is given by the simple relationship, 2 M c / M , where M ,
is the average molecular weight between erosslinkages and M is the molecular weight
of the primary molecules. In a normal SBR tread vulcanizate this fraction probably
amounts to over one-tenth of the polymer molecules. The incorporation of this fraction
of the molecules into the network structure should contribute significantly to the proper-
ties of the vulcanizates.2 This contribution is difficult t o estimate because a terminal
group-chain linkage is trifunctional whereas an internal crosslink is tetrafunctional.
The two types of linkages are illustrated in Figure lb.
I n order to study the endgroup problem a simple means is needed for preparing poly-
mers possessing different kinds of terminal reactive groups. Since polymers possessing
terminal reactive groups should be of considerable interest and value, a word has been
coined to avoid a cumbersome description of these types of polymers.
The term "telechelic" is proposed for polymer molecules possessing two functional
terminal groups. The functional group is identified as a radical according to standard
nomenclature practice and is used as a prefix. For example, acetyl-telechclic polybuta-

Fig. 1. Schematic representation of ( a ) a conventional network structure of a vulcani-

zate emphasizing free chain ends; ( b ) a network structure of a cured telechelic polymer
with chain ends incorporated into the structure.
535
536 JOURNAL OF POLYMER SCIENCE, VOL. XLVI, ISSUE 148 (1960)

diene is a butadiene polymer which possesses two acetyl terminal groups per polymer
molecule.
This communication describes two convenient methods of preparing telechelic poly-
mers. I n one method of preparation, diazothioethers (DTE) function as initiator-modi-
fiers in emulsion polymerization systems. For the second procedure, alkali metallorganic
compounds are initiators for solution polymerization systems.
11. Acetyl-Telechelic Polybutadiene
As an example of the initiator-modifier method of preparing a telechelic polymer, some
results with the diazothioether, 3-(3-acetylphenyldiazothio) acetylbenzene,
0 0
// //
MeC C-Me

are presented. The acetyl-DTE was readily prepared according to a synthesis pre-
viously described.3 The polymerization recipe employed and experimental data ob-
tained as the amount of D T E was varied are given in Tables I and 11.

TABLE I
Recipe for the Preparation of Acetyl-Telechelic Polybutadiene
Ingredients Parts
Butadiene 100
Water 180
Duponol M E 5
KH2PO4 0.5
Acetyl-DTE Variable
Temperature, "C. 50

A proposed mechanism for the polymerization reactions is as follows:

Generation of free radicals:
MeCOC6H4N=NSC6H4COMe
Initiation and propagation:
- MeCOC6H4-f MeCOC6H4S.4-N2

MeCOC6H4. + nM MeCOC6H4(M),,
Chain transfer :
MeCOC6H4(M)n. + MeCOCsH4N=NSC6H4COMe
~~~~~CGH~(M),SC
-
f~MeCOC6H4.
H~CO~f L .Nz
~~
acetyl-telechelic polymer
Termination :
MeCOC6H4(M ) n . 4- MeCOC6H4S. M~COC~H~(M),SC~HICOM~
acetyl-telechelic polymer
Although these mechanisms were not directly established in our investigations, the
analyses, characterizations, curing experiments, and published studies by others of some
of these steps3 support the proposed reactions. Other complicating reactions such as
disproportionation, branching, crosslinking, other transfer reactions, etc.probably
occur to a minor extent in the systems studied.
 NOTES 537

TABLE I1
Experimental Data
Polymerization
Mooney
-4cetyl-DTE, Time, Conversion, Inherent Gel, viscosity,
parts hr . % viscosity % ML-4
0.4 20 80 1.82 15 141
0.8 20 69 2.45 0 57
1.2 21 67 1.39 0 22
4.0 40 73 0.96 0 Too soft
4.0 32 42 0.42 0 Too soft

Proof of the existence of acetyl groups in a telechrlic polJmer prepared in accordance

with the preceding recipe was established by (1) physical and (2) chemical means and
(3) by physical properties of compounded stocks.
(1) Infrared examination of a liquid acetyl-telechelic polybntadiene showed absorp-
tion a t 5.88, 9.25, and 1 2 . 7 5 ~consistent with that for meta-substituted acetophenone4
and showed all the bands for polybutadirne, u hereas a standard emulsion polybutadiene
exhibited only the polybutadiene bands.5 Reaction of the liquid acetyl-telechelic poly-
polybutadiene with hydroxylamine gave a product that absorbed infrared in the 6 and
3 p regions consistent with that expected from an oxime group,4and some absorption a t
5.88 p indicated the keto groups were not completely removed.
(2) Besides the reaction with hydroxylamine, evidence of reaction with semicarbazide,
hydrazides, n-butyllithium, and thiosemicarbazide \yere also obtained. Quantitative
analyses of an acetyl-telechelic polybutadiene with an inherent viscosity of 0.79 for sulfur,
oxygen, and hydroxyl content of a reduced polymer were 0.2,0.4, and 0.26%, respectively.
These values are considered reasonable for these types of measurements.
(3) An acetyl-telechelic butadiene-styrene copolymer of 47 Mooney viscosity was com-
pounded in a tread type formulation which also included three parts of 9- and 10-
mercaptostearohydrazide mixture. Some of the physical properties of this experimental
system are compared with those for the acetyl-telechelic copolymer control and with
SBR 1000 in the presence and absence of mercaptostearohydrazide in Table 111.

TABLE I11
Physical Propcrties for an Acetyl-Telechelic Butadiene-Styrene Copolymer and Controls
in the Presence and Absence of Mercaptostearohydrazide
30-min. cure
Cross- Com-
linking, pression 300% Resili-
MSH, nioles/cc. set, .Modulus, Tensile, AT, ence,
Polymer parts& x 104 % psi psi "F. %
Acetyl-telechelic - 1.09 20 1100 2400 70 58
copolymer
Acetyl-telechelic 3 1.31 19 1500 2800 61 64
copolymer
SBR 1000 - 1.25 20 1250 2890 68 57
SBR 1000 3 1.16 16 1250 2900 '73 56
a 9- and 10-mercaptostearohydrazide
538 JOURNAL OF POLYMER SCIENCE, VOL. XLVI, ISSUE 148 (1960)

The increase in crosslinking content, the increase in modulus, and an improved heat
build-up and resilience relationship in comparison to the controls is indicative of favor-
able reactions occurring in the experimental system. These reactions are believed to
occur between the acetyl group and the hydrazide and between the polymer chain and
the mercapto group. The resultant of these reactions should be the incorporation of the
polymer endgroups into the vulcanizate network structure.

111. Carboxy-Telechelic Polybutadiene

In the second procedure, bis( alkali metallorgano) compounds were used as initiators
for the polymerization of butadiene in solution. The polymerization solutions con-
tained alkali metal-telechelic polymers which oil carbonation yielded carboxy-tclechelic
polymers. The sequence of reactions representing the preparation of carboxy-telechelic

-
polymers is essentially as follows:
(a) Initiation and propagation:
(Plle)zR +2dI (Me)M,RM,(Me)
alkali metal-telechelic polymer

-
where (Me) represents an alkali metal atom.
(b) Carbonation:
(Me)M,RMn(Plle) + 2C02 (Mc)OrCM.RM.COt(Me)
metal carboxylate-tclechelic polymer
(c) Acidification:

(Plle)O,CRI.RR.I.COz(Me) + 2H + - 2(Mcf) + H02CM,RM,C02H

carboxy-telechelic polymer

Liquid carboxy-telechelic polymers have been characterized by the methods described

in Section 11. Liquid polymers prepared by the procedure outlined above %-erefound
to be over OOyo telechelic (actual per crnt rarboxyl content/thcorctical per cent car-
boxyl content). Coupling of alkali metal-telcchclic polymers by active coupling agents
has resulted in five- to eightfold increases of inherent viscosities over that of the un-
coupled control.
Encouraging progress has been made in curing liquid telechelic polymers. In screen-
ing tests the ingredients can be mixed in a beaker with a spatula. In larger scale test-
ing, the ingredients after being mixed in a container can be precured under mild con-
ditions, and the partially cured stock can then be milled further prior to final curing.
An example of the latter procedure used in curing a pigmented carboxy-telechelic poly-
butadiene is given in Table IV.

TABLE IV
Cure of a Liquid Carboxy-Telechelic Polybutadiene Pigmented Formulation
Recipe Parts
Carboxy-telechelic polybutadienen 100
HAF carbon black 50
Polyaziridinyl curing agentb Variable
Precure, time and temperature 30 min., 110°C.
Final cure, time and temperature 60 min., 113OC.
~~

a Carboxyl content, 1.14-1.03y0, inherent viscosity 0.35.6

Hexa-2-methyl aziridinyl triphosphatriazine obtained from Interchemical Corp.
 NOTES 539

TABLE V
Physical Properties
Poly aziridinyl
curing agent,
% of Tensile, Elongation, Resilience, Shore
stoichiometric" VTb psi % AT, O F . yo hardness

150 0.364 1300 160 80 52 68

160 0.377 1350 160 71 60 75
200 0.373 1400 170 76 60 67
a Aziridinyl units equivalent to carboxyl units.
b Volume fraction of cured polymer in n-heptane swollen gel.

The properties for the cured carboxy-telechelic polybutadiene (Table V) are far su-
perior to any that have been obtainrd for liquid non-telechelic polybutadiene cured by
any known formulation. However, much reeearch work remains to be done on the
curing of liquid telechelic polymers.
Preparations and evaliiations of telechelic polymrrs by different procedures arc being
actively explored by others in this laboratory.

The authors wish to acknowledge their appreciation to W.W.Crouch and J. K.Short

of Phillips Petroleum Company for their encouragement, ideas, and judgment which
contributed to the effectiveness of this research and to G. Kraus under whose direction
the polymer evaluations wcre performed.

References
1. Flory, P. J., Znd. Eny. Chern., 38, 417 (1946).
2 . Pierson, R. M., A. J. Costanza, and A. H. Weinstein, J . PoIyuer Sci., 17, 221
(1955); A. J. Costanza, R. J. Coleman, R. M. Pierson, C. S. Marvel, and C. King, ibid.,
17, 319 (1955).
3. Reynolds, \V. B., and E. W. Cotton, Znd. Eng. Chern., 42, 1905 (1950).
4. Bellamy, L. J., The Infrared Spectra of Complex Ilfolecules, hlethuen, London,
1958.
5. Short, J. N., V. Thornton and G. Kraus, Rubber and Plastics B g e , 38, 880 (1957).
6. Cragg, L. H., J . Colloid Sci., 1, 261 (1946).
C. A. URANECK
H. L. HSIEH
0. G. BUCK
Phillips Petroleum Company
Research and Development
Bartlesville, Oklahoma
Received September 6, 1960

Stereospecijk Polymerization of Styrene and Methyl Methacrylate

Catalyzed b y Metallic S o d i u m

Stereospecific polymerization of vinyl monomers such as styrene or methyl methac-

rylate has been hitherto achieved only by using some Ziegler-type catalysts, Alfin-type
catalysts, or organo-metallic compounds, but not by such a simple component system as