3

Prog. Polym. Sci.
27 (2002) 20212054
www.elsevier.com/locate/ppolysci
Synthesis and structure of poly(vinyl chloride)

Kiyoshi Endo*
Department of Applied Chemistry, Graduate School of Engineering, Osaka City University, Sugimoto, Sumiyoshi-ku,
Osaka 558-8585, Japan
Received 29 October 2001; revised 21 June 2002; accepted 27 June 2002
Abstract
This article deals with the synthesis and structure of poly(vinyl chloride) (PVC) by radical and other
polymerization mechanisms. The features of solution, bulk, suspension, and emulsion polymerization of VC are
described. Terminal structure and defect structures introduced in the chain during the polymerization are
discussed. Control of core shell structure provides one method to improve the thermal stability of PVC. Tacticity
and crystallinity of PVC play an important role regarding the use of PVC. Radical copolymerization of VC with
various vinyl monomers has been described to improve the thermal stability of PVC. Graft copolymerizations with
other vinyl monomers including use of labile chlorine atoms are useful methods to improve the physical and
thermal properties of PVC. Synthesis of block copolymers has also been described by mechano-chemical methods
and using terminal functional polymers. Controlled polymerization can be achieved with anionic polymerization
catalysts. Promising metallocene catalyst promoted polymerization of VC are also described. q 2002 Elsevier
Science Ltd. All rights reserved.
Keywords: Poly(vinyl chloride); Radical polymerization; Defect structure; Tacticity; Copolymerization; Anionic catalysts;
Metallocene catalysts
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2022
2. Radical polymerization reactivity of VC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2023
3. Radical polymerization methods of VC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2023
3.1. Solution polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2024
3.2. Bulk polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2026
3.3. Suspension polymerization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2027
3.4. Emulsion polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2028
4. Elemental reactions of radical polymerization of VC and polymer structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2029
4.1. Initiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2029
4.2. Propagation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2029
* Tel.: 81-6-6605-2697; fax: 81-6-605-2697.
E-mail address: endo@a-chem.eng.osaka-cu.ac.jp (K. Endo).
0079-6700/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 7 9 - 6 7 0 0 ( 0 2 ) 0 0 0 6 6 - 7
2022
K. Endo / Prog. Polym. Sci. 27 (2002) 20212054
4.3. Termination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2032

4.4. Chain transfer reaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2032
4.5. Defect structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2034
5. Characterization and properties of PVC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2035
5.1. Tacticity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2035
5.2. Crystallinity and amorphous state. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2036
5.3. Thermal stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2036
6. Radical copolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2038
6.1. Copolymerization with olefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2038
6.2. Copolymerization with conjugated vinyl monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2039
6.3. Copolymerization with non-conjugated vinyl monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2040
7. Synthesis of graft and block copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2041
7.1. Synthesis of graft copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2041
7.2. Synthesis of block copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2045
8. Polymerization of VC using anionic catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2047
9. Transition metal promoted polymerization of VC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2049
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2050
1. Introduction
Vinyl chloride (VC) was first discovered by Regnault in 1835, and the polymer was first observed in
1838 [1]. In 1872, Baumann reported the polymerization of a number of vinyl halides including VC
using sunlight to afford the white powder product recognized as PVC [2]. Since then, the technology for
the polymerization of VC has progressed significantly mainly in Germany and USA [3]. Commercial
production of PVC first started in German, in the early 1930s using emulsion polymerization. The first
breakthrough to overcome the processing and heat stability problems of PVC came in 1932 when Semon
discovered plasticizers for PVC [4]. The use of stabilizer was developed in the 1930s [4 6].
PVC is now one of the worlds major polymers and a large amount of PVC is produced worldwide for
its superior mechanical and physical properties. Fluid plasticity and thermal stability of PVC are,
however, inferior to those of other commodity plastics such as polyethylene and polystyrene [5]. PVC is
mainly produced by radical polymerization. The radical polymerization of VC, however, results in the
formation of molecules with a number of isomeric forms and structural defects. These factors are of vital
importance to the users of PVC, because they cause a color problem, thermal stability of the polymer, its
crystallinity, processing behavior, and the mechanical properties of the finished article. Studies of
defects also give an insight into the nature of the side reactions occurring during polymerization [6].
Much work on improvement of the inferior properties of PVC has been carried out besides the
addition of additives such as plasticizers, heat stabilizers, lubricants, fillers and other polymers [6].
Examples include copolymerization with other monomers and modification of the particle morphology
to improve processability. Graft copolymerization of PVC with acrylic monomers and vinyl acetate
(VAc), and blends with MBS and ABS has been examined to improve the impact strength.
Copolymerization of VC with imide monomers and chlorination of PVC was investigated to increase the
heat resistance of PVC. Synthesis of high molecular weight polymers and a partially crosslinked PVC
have been performed to increase the modulus. Synthesis of inner platicized PVC is one solution to the
problem of platicizers like dioctyl phthalate (DOP) migrating from inner to the surface of materials [7].
Thermal stability of PVC may be related to the presence of anomalous units in the chain, and it is thus
2023
of interest to be able to synthesize PVC consisting of an exclusively head-to-tail structure. Ionic

polymerization of VC is an excellent way of preparing PVC consisting of only regular units due to the
nature of ionic polymerization. This is a fascination synthetic method from the viewpoint of thermally
stable PVC. It is, however, difficult to obtain high molecular weight PVC using anionic catalysts, and
believed to have its origin in the catalyst reacting with VC. Nevertheless, some work on the
polymerization of VC with anionic catalysts has been carried out [8 10], and the structure of PVC
obtained using these catalysts will be described in this article.
The advance of transition metal alkyl catalysts has made it possible to prepare stereoregulated
polymers of 1-olefins, dienes and some conjugated monomers [11]. Recently, metallocene
polymerization has seen remarkable progress, and many new polymers have been synthesized with
metallocene catalysts [12,13]. Stereoregular PVC has not been synthesized with a transition metal
catalyst [14]. Nevertheless, several attempts have been made to prepare PVC with metallocene catalysts
[15]. Some work on the polymerization of VC employing transition metal catalysts will be described.
2. Radical polymerization reactivity of VC

It is important to know the polymerization reactivity of VC for synthesizing PVC. Among many vinyl
monomers, VC is classified as a non-conjugated weak electron-withdrawing vinyl monomer from the Qand e-values of VC (0.44 and 0.2, respectively) determined from radical polymerization [16]. This
indicates that the VC monomer has low reactivity, but its radical is highly reactive. It follows that the
propagating radical of VC tends to induce chain transfer reactions to all substances in the polymerization
system such as monomer, initiators, solvents, and the resulting polymer. As a consequence, radical
polymerization of VC results in the formation of various anomalous units in the chain during
polymerization, which is unfavorable for thermal stability and control of the main chain. The bond
dissociation energy of the chlorine atom bonded to the tertiary carbon and the chlorine at the allylic
position contaminated are weak as shown in Fig. 1 [17]. Taking these bonds dissociation energies into
consideration, it is reasonable that the decomposition of VC is easily initiated at these bonds. It is thus
important to prevent or suppress the formation of these structures during the polymerization to
synthesize thermally stable PVC.
3. Radical polymerization methods of VC

PVC resin is utilized in durable applications such as pipes, window profiles, house siding, wire cable
insulation and flooring. Most PVC is commercially produced by suspension polymerization [4]. Bulk
and emulsion processes are utilized to a lesser, and solution polymerization is seldom employed. In the
Fig. 1. Structure and bond dissociation energy of PVC.
2024
Table 1
Chain transfer constants in radical polymerization of VC (50 8C)
Substance
C5 104
Substance
C5 104
Butylchloride
Isopropylchloride
1,2-dichloroethane
2,4-dichloropentane
2,4,6-trichloroheptane
Chlorobenzene
Acetoaldehyde
7.4
7.0
4.5
5.0
5.0
7.4
110
Butylaldehyde
Tetrahydrofuran
Butyl acetate
Tetrachloromethane
Tetrabromomethane
Dimethyl aniline
Vinyl chloride
350
24
8.4
386
47 000
2700
12.3
radical polymerization of VC, the monomer itself has a relative large chain transfer constant
(Cm 1:23 1023 ; 60 8C), leading to the upper limitation of molecular weight of the resulting polymers
Pn , 2000: Partially crosslinking is a useful method for synthesizing the high molecular weight PVC.
On the other hand, reagents with a large chain transfer constant such as THF and butyl aldehyde (Table 1)
can be used as modifiers to regulate the molecular weight [16].
In radical polymerization of VC, many attempts have been made to improve the thermal
stability. For example, the polymerization of VC is generally not taken to high conversion in order
to prevent the formation of long chain branches. Long branches are formed by hydrogen abstraction
from the main chain methine group of the polymer and this is thus favored at the final stages of
polymerization [18]. Internal double bonds are formed as a result of hydrogen abstraction from
the polymer backbone during the polymerization. This may be prevented by carrying out the
polymerization in the presence of a compound having active hydrogen such as cyclohexene [19].
The reaction product is used as binder materials of tapes.
A comparison of the different radical polymerization methods for VC is shown in Table 2. Although bulk
polymerization appears to be most simple method for the preparation of PVC, suspension polymerization is
used preferentially industrially to avoid the risk of explosive associated with the bulk process [4].
3.1. Solution polymerization
Solution polymerization of VC proceeds with homogeneously when the polymer is soluble in the
Table 2
Comparison of radical polymerization methods of VC
Factor
Initiator solubility
Additive
Stirring
Temperature control
Isolation of PVC
Particle size of PVC (mm)
Polymerization method
Bulk
Solution
Emulsion
Suspension
Soluble in VC
None
Not necessary
Difficult
Recover of VC
60 300
Soluble in VC
Solvent
Not necessary
Possible
Removal of solvent
,0.1
Insoluble in VC
Water, emulsifier
Necessary
Easy
Removal of emulsifier
0.1
Soluble in VC
Water, dispersing agent
Necessary
Easy
Removal of dispersing agent
20 300
Table 3
Comparison of radical polymerization reactivity of VC and other vinyl monomers
Reactivity
Monomer
Reactivity towards methyl radical

(65 8C)
Reactivity towards phenyl radical
(60 8C)
Reactivity towards benzoyloxy radical
(75 8C)
Reactivity towards t-butoxy radical (30 8C)
Propagation rate constant (25 8C)
Termination rate constant 1026 (25 8C)
Rate constant to polystyryl
radical (60 8C)
Chain transfer constant to
toluene 105 (60 8C)
Chain transfer constant to
monomer 105 (60 8C)
37
826
1420
(0.23)
(1.0)
(1.8)
0.04
1.9
0.22
6200
1100
1.2 (25 8C)
(0.009)
1100
80
3.3
(1.0)
106
50.4
176
(0.058)
273
24.4
340
208.9
1.25
5.25
123
19.1
7.9
1.8
Conjugated monomer
Non-conjugated monomer
VC; Q 0:044; e 0:20 VAc; Q 0:026; e 20:22 St; Q 1:0; e 20:8 MMA; Q 0:74; e 0:4
The values in parenthesis indicate relative rate constants.
2025
2026
solvent employed. In this case, the usual rate equation for radical polymerizations of vinyl monomers is
applicable, but solution polymerization is usually not employed in industry. The chain transfer constant
to VC Cm ; propagation rate constant kp ; and chain termination constant kt are larger than those of
typical vinyl monomers such as styrene (St) and methyl methacrylate (MMA) as shown in Table 3. As
mentioned above, the molecular weight of the formed PVC has an upper limit in solution polymerization
due to the large value of Cm.
3.2. Bulk polymerization
Bulk polymerization of VC is a simple process for production of PVC, but the PVC formed is
insoluble in the VC phase [21]. In bulk polymerization, precipitation begins to occur at 0.1% conversion.
After that, the polymerization proceeds heterogeneously in both the monomer and the polymer phases
[21 27]. At the initial stage of polymerization, the rate of polymerization remains constant. Diffusion
control of termination and propagation become predominant at the final stage of the polymerization.
When the reaction temperature is below Tg of the resulting PVC, diffusion of monomer to the
propagating radical is extremely slow and the conversion has an upper limit. The limiting conversion
levels were estimated to be 96% at 55 8C, 93% at 30 8C and 90% at 210 8C [21]. It is noteworthy that
both the diffusion process of propagating chains and a multiphase polymerization play important roles in
determining the rate of monomer addition to the propagating radicals.
Many workers have proposed kinetics models for the bulk polymerization of VC. Talamini [28]
asserted that the polymerization of VC occurs both in the monomer and polymer phases. Ugelstadt et al.
[29] assumed that the propagating radical is able to move both in phases. Olaj [30] presumed that radical
in the monomer phase propagate into coil structure and it adsorbs in polymer phase. Hamielec and
coworkers [31] considered the change of initiator and volume as a function of conversion. It is necessary
to elucidate the composition of both the monomer and polymer phases to determine the rate equation for
the bulk polymerization of VC. According to the treatment of Hamielec, a two-phase model of VC/PVC
mixture as a function of reaction temperature can be depicted in Fig. 2. The bulk polymerization can be
divided in three stages. At the first stage (conversion: 0 0.1%), the polymerization proceeds
homogeneously, and the rate of polymerization obeys the rate equations for a normal homogeneous
system. In the second stage (conversion: 0.1 77%), the polymerization proceeds by free VC in the
system and the entrapped VC in the polymer particles. Moreover, the free VC in the polymerization
system disappeared at a critical conversion xc : The values of xc are 80, 77, and 72% at 30, 50, and
70 8C, respectively. At the third stage (conversion: .77%), the polymerization proceeds with VC in the
swollen polymer particles. According to this model, the following equation for the bulk polymerization
of VC was proposed
dx=dt kp2 =kt 1=2 fkd I1=2 exp{ 2 kdt }1=1 2 Bx1 p1 2 xc 2 1=xc x
The term 1 2 Bx is a coefficient of volume change with conversion. This equation has been applied to the
actual polymerization of VC initiated with AIBN, and the experimental results are in a good agreement
with this equation [31]. The two-phase model has recently reported for the bulk and suspension
polymerization [32,33]. The second stage of polymerization extending from the conversion at which the
dilute phase disappears up to the limiting conversion. In this stage the reaction occurs in a homogeneous
and more and more viscous environment.
2027
Fig. 2. Mixture of VC/PVC as a function of temperature. (Reprinted with permission from J Appl Polym Sci 1973;16:782.
q1973 John Wiley & Sons, Inc [31]).
3.3. Suspension polymerization

Suspension polymerization is the process that is normally employed in industrial production of PVC.
The polymerization reaction proceeds heterogeneously and the kinetics of the process are similar to what
is observed in the case of bulk polymerization [34 38]. In suspension polymerization of VC, both
stirring and the state of the system play an important role determining the morphology of the resulting
polymers. A scheme description of a PVC particle formed during the suspension polymerization of VC is
depicted in Fig. 3 [39]. This particle was formed in the followings [40]. When the polymerization of VC
is initiated, coiled macroradicals consisting of about 10 monomers are formed. Macroradicals with a
chain length of about 50 gather to form unstable microdomains, which subsequently gather to make up
primary particles consisting of approximately 1000 microdomain. This occurs at a conversion of about
1 2%, and the size of a primary nuclear particle is approximately 0.1 0.2 mm. As polymerization
proceeds, the particle grows to afford grain (130 mm) through primary particle (0.6 0.8 mm, 2 4%
Fig. 3. Polymer particle obtained from radical suspension polymerization. (Reprinted with permission from Pure Appl Chem
1981;53:449. q1981 IUPAC [39]).
2028
conversion) third particle (1 2 mm, 10 80% conversion) and subgrain (40 mm). This grain structure
strongly affects the physical and mechanical properties of PVC.
The effects of some polymerization conditions on PVC particles produced by suspension
polymerization have been studied on a laboratory scale [41]. The method of addition of initiator has
a great effect on the PVC particle uniformity as well as the size distribution. When H80 (poly(vinyl
alcohol) (PVA) with a degree of hydrolysis of 80% and a molecular weight of 259 000) stabilizer was
used, the rigidity of the PVC particles was weak [41]. Drop coalescence processes in suspension
polymerization of VC was detected by use of a tracer dye technique to elucidate the effect of turbulence
intensity, stirring time, and the type and concentration of the suspending agent such as partially
hydrolyzed poly(vinyl acetate) (PVAc) on the coalescence rate of VC droplets in an agitated liquid
liquid dispersion [42].
3.4. Emulsion polymerization
Emulsion polymerization of VC is vastly different from bulk and suspension polymerization [4]. In
emulsion polymerization of VC, the radical concentration in the micelle is lower than unity [43]. Chain
transfer reaction to monomer tends to reduce the propagating radical concentration in the micelle.
Taking this into consideration, Ugelstad et al. [43] proposed the following rate equation for an emulsion
polymerization of VC
1=2
Rp kp2 =kt 1=2 {Mp fkd I0 exp2kdt 1=2 N 1=6 =kdis
where [M]p is the monomer concentration in the polymer particles, N, the number of polymer particles
per liter, and kdis is the disproportionation rate constant of propagating radicals in the polymerization of
VC. This equation has been confirmed by agreement with experimental results [43,44].
It is noteworthy that the molecular weight of PVC obtained in emulsion polymerization is similar to
that obtained in bulk or suspension polymerization, indicating that chain transfer to monomer is the
predominant factor to determine the molecular weight regardless of polymerization method. However,
when an emulsifier having low critical micelle concentration was used in emulsion polymerization of
VC, high concentration of polymer particle was obtained. Thus, the rate of polymerization became faster
than that of other polymerization.
Seeded emulsion polymerization is one of the known particle-producing polymerization methods.
This method has been applied to the polymerization of VC. Improved colloidal stability of the polymer
latex by addition of an emulsifier to a seeded emulsion polymerization has been achieved. When the
emulsifier was added to the growing particles, without emulsifier excess in the water phase, the colloidal
stability of the polymer latex was excellent, indicating that formation of new fine particles (,0.1 mm)
was prevented. This was supported by the viscosity properties of plastisols consisting of PVC and DOP
as plasticizer [45]. Seeded polymerization has also been utilized to improve the thermal properties of
PVC. A copolymer consisting of VC and VAc was used as a seed, and the emulsion polymerizations of
MMA, St, methyl acrylate (MA), ethyl acrylate (EA), and n-butyl methacrylate (n-BMA) were
investigated. Polymer particles consisting of a core shell structure were synthesized, and they exhibited
improved thermal stability compared to normal PVC [46].
Seeded emulsion polymerizations in the presence of an adequate mixture of anionic and non-ionic
surfactants have been investigated in order to avoid micellar initiation. New kinetic parameters were
2029
defined as follows. The minimum surface area of polymer seed particles necessary to capture all ionoligoradicals generated in the aqueous phase at a given initiator concentration; the maximum critical
concentration of initiator per unit surface of polymer particle under which the formation of new polymer
particles is avoided. The polymer volume per active growing radical is required to be within the particle
for 1 s. The average number of propagating radicals per particle depended on the size of the polymer
particle, as a result of entry and exit and initiation and termination reactions. The practical consequences
of accurate control of the polymer particles during seeded emulsion polymerization of VC were
emphasized [47].
Peroxide crosslinking of plasticized PVC blended with trimethylolpropane trimethacrylate
(TMPTMA) has been studied by the following gel formation and changes in the mechanical properties
[48]. By applying the right preparation conditions and peroxide type, it was possible to avoid
crosslinking while dry-blending the materials. During compression molding, the gel yield was found to
increase with increasing peroxide and TMPTMA concentrations and with curing time and temperature.
The crosslinking process comprised two primary reactions; rapid polymerization of TMPTMA followed
by grafting of the TMPTMA onto the PVC backbone.
4. Elemental reactions of radical polymerization of VC and polymer structure

4.1. Initiation
In radical polymerization of vinyl monomers, the chain end structure of the polymers consists of
initiator fragments or saturated and unsaturated chain ends produced by disproportionation. In radical
polymerization of VC, however, chain transfer reactions take place readily to produce different chain
ends as compared with other conjugated vinyl monomers. When 2,20 -azobisisobutylnitrile (AIBN) or
benzoyl peroxide (BPO) is used as initiator for the polymerization of VC, the fraction of chain ends
derived from the initiators is usually 0.14 0.4 [20,49,50]. If termination was induced by combination or
disproportionation exclusively, the value would be 2.0 or 1.0, respectively. An IUPAC working party
has reported that the chain end structure of PVC derived from initiator is negligible, indicating that chain
transfer to monomer is predominant [20]. The recently developed living radical polymerization
techniques [51] may be applied to the polymerization of VC to prepare a polymer with well-defined
structure.
A new method for determination of initiator decomposition rate constants kd based on the use of
instantaneous polymerization rates for two similar experiments with different initiator concentrations
has been reported. To verify the validity of the method, PVC latexes were prepared by potassium
persulfate (K2S2O8) initiated polymerization of submicron-sized monomer droplets. The value of kd was
determined to be 2.5 1026 s21 at 51 8C, and the order of reaction with respect to the initiator
concentration was found to be 0.50 [52].
4.2. Propagation
The propagation reaction is an important elemental reaction to determine molecular weight and
structural defects. The CH2yCHCl can add onto the polymer chain in two ways: head-to-head or headto-tail; polymer characterization studies show that it grows mainly by head-to-tail addition. Besides
2030
Fig. 4. Defect structures of PVC.
addition of monomer units, side reactions such as isomerization of the propagating radical and chain
transfer to polymer can occur to introduce structural defects into the polymer chain affording C2, C4
branches and long-branches. Similar defects are also introduced into the chain by the incorporation of
impurities. The structural defects such as head-to-head, short and long branches, and internal olefin units
in the main chain induce thermal instability (Fig. 4) [53,54]. The contents of these structures can be
estimated by use of NMR spectroscopy [55,56], from the contents of unsaturated chain ends [57] and by
Table 4
Defect structure of PVC. (Reprinted with permission from Macromolecules 1986;19:1090. q1986 American Chemical Society
[60]).
Defect structure
Contenta
I
II
III
IV
V
VI VII VIII
IX
Xb
6.4 6.9
0.1 0.3 (0.23)
3.8 (4.0)
0.8 (0.79)
0.1 (0.09)
0.75 (0.99)
3.5 (1.22)
2.7 (1.1)
a
b
Numbers in parenthesis are simulation results.

Contents per 1000 monomer units.
Saturated monochloro chain end.
2031
Fig. 5. Head-to-tail and head-to-head addition of VC.
using the reactions of Br or Cl addition to double bonds [58,59], and by simulation [60]. Typical contents
of defect structures are shown in Table 4. The anomalous structures, except the chloromethyl group, are
believed to cause thermal instability. PVC contains a great number of anomalous units along the chain
than conjugated vinyl polymers such as poly(St) and poly(MMA).
Head-to-head (h h) linkages are formed with competitive addition reaction of head-to-tail (h t)
addition in the propagating step along with the coupling reaction between two propagating radicals as
shown in Fig. 5 [61,62]. However, the value of the chain transfer constant to VC is so large that the
former is predominant. Table 5 shows the contents of h h linkage under various polymerization
conditions. Since VC is a non-conjugated vinyl monomer, h h addition occurs in addition to h t
addition giving h h bonds in the chain. The propagating radicals produced by head-to-head addition
induce 1,2-chloro atoms migration followed by addition of VC, leading to the formation of chloromethyl
branches (C1) as shown in Fig. 6. This C1 branch is not a thermally unstable structure in PVC, because
there are no chlorine atoms bonded to the tertiary carbon. In addition to the formation of C1 branches,
elimination of chlorine atoms followed by addition of VC leading to the formation of terminated 1,2dichloro units and inner double bonds and allylic chlorine also occurs (Fig. 7).
Branch structures produced during the polymerization can be classified into two types, i.e. short
branches produced by isomerization of the propagating radical [63] and long branches formed by chain
transfer to polymer [64]. The C4 and C2 branches are produced by the backbiting of the propagating
radicals as shown in Fig. 8 [65].
The extents of formation of short branches derived from migration of hydrogen or chlorine of the
propagating radicals are independent of the monomer conversion. The content of long branches
increases with an increase in conversion, since hydrogen abstraction from the polymer chain is
intermolecular reaction. Unsaturated polymer chain ends are also produced by disproportionation. The
chlorine radical generated from chlorine atoms bonded to the tertiary carbons and the chlorine atom at
the allylic position are very active yielding anomalous units in the chains. The contents of labile
Table 5
Head-to-head content in the chain of PVC
Initiator
Temperature (8C)
Pw
h h linkagea
AIBN
Peroxide
BEt3/O2
BEt3/O2
60
50
40
0
800
450
790
15
6.4
5.7
2.5
Number of h h units per 1000 monomer units.
2032
Fig. 6. Formation of C1 branch in the polymerization of VC.
chlorines has been estimated by substitution reaction with phenol or 1H NMR spectroscopy. The
contents of labile chlorine reported are shown in Table 6 [55,56].
In radical polymerization of VC, the propagation rate constant kp can be expressed by the following
equation [6]
kp 3:3 106 exp{2 3700=RT}
Since VC is classified as a non-conjugated vinyl monomer, 1 3% head-to-head addition takes place

yielding head-to-head linkages in the chain as well as head-to-tail linkages. The activation energy for h
h addition is 1.5 kcal/mol higher than that for h t addition [61].
4.3. Termination
Termination occurs by combination and disproportionation in solution polymerization of VC. In bulk
and suspension polymerization, unimolecular termination may also contribute. Since the rate constant of
chain transfer to VC is large, propagating radicals do not occlude. The rate constant of termination can
be expressed in the following [6]:
kt 1:3 1012 exp24200=RT
It is difficult to determine the ratio of combination and disproportionation because of the large chain
transfer constant to VC. Combination is believed to be predominant termination mechanism, and it has
been pointed out that the primary radical termination also contributes [49].
4.4. Chain transfer reaction
As mentioned above, the chain transfer constant to monomer Cm in the polymerization of VC has
been determined to be 1.23 1023 (60 8C), which is about 68 times larger than for MMA [16]. Thus, the
Fig. 7. Formation of allylic chloride at chain end in the polymerization of VC.
2033
Fig. 8. Formation of C4 and C2 branches.
chain transfer to monomer plays an important role in determining the molecular weight and chain end
structure of PVC. The relation between Cm and reaction temperature can be expressed by the following
equation, i.e. Etrm 2 Ep is estimated to be 7.3 kcal/mol
Cm ktrm =kp 125 exp27300=RT
Table 6
Content of total labile chlorine atoms in PVC
Sample no.
Phenol method
NMR method
SOCl2 method
1
2
3
4
5
1.44
0.95
1.9
1.2
1.67
2.45
2.4
4.4
1.6
1.6
Number of labile chlorine atoms per 1000 monomer units.
2034
Fig. 9. Chain transfer reaction to VC in the polymerization of VC.
Since the value of Cm is small in the radical polymerization of conjugated vinyl monomers such as St and
MMA, the molecular weights of the polymers decreased with raising reaction temperature. This is
contrast to radical polymerization of VC. When the polymerization of VC was carried out at lower
reaction temperature, the molecular weight of PVC decreases due to a large Cm [66].
Since the reactivity of propagating radical in polymerization of VC is high, chain transfer reaction to
VC takes place to yield a monomer radical. The monomer radical generated is able to initiate the
polymerization to yield a new polymer chain. In the polymerization of VC, it is difficult to estimate what
reactions are the main reinitiation reactions. Taking the activation energies of the reactions into
consideration, the third reaction scheme in Fig. 9 would be the main reinitiation reaction.
Chain transfer constants to various solvents are shown in Table 1. The values are large as compared with
other vinyl monomers due to the high reactivity of the propagating VC radical. Chain transfer reactions to
polymer result in long chain branches were in the following [64]. The chain transfer to PVC takes place at
polymer chain ends and repeating units in the main chain. The chain transfer constant to PVC has been
estimated using model compounds such as isopropyl chloride and 2,4-dichloropentane [18]. The
concentration of long branches using isopropyl chloride was estimated to be 10 per 1000 monomer units,
which is larger than which has been found from polymerization experiments. This discrepancy may have its
origin in the inherent differences between small molecules and a polymeric system.
4.5. Defect structure
As described in Section 4.2, radical polymerization of VC results in the formation of macromolecules
containing a number of different isomeric forms and structural defects. These factors are of practical
importance, since they affect the color, thermal stability, crystallinity, processing and mechanical
properties of the finished materials.
Typical PVC molecules contain approximately 1000 vinyl chloride monomer units, joined in
predominantly head-to-tail fashion. Other structural arrangements are considered to be defects. The types
and concentrations of the defects have been summarized as shown in Fig. 8, and the effect of preparing PVC
samples under different conditions on these structural defect have been reported [5660].
Several kinds of short branches are also observed in the main chain in addition to the long branches.
The C1, C2 and C4 branches classified as short branches are introduced in the chain by intramolecular
2035
backbiting reactions. Thus, the degree of short branching is independent of the conversion in contrast to
that of long branching which increase with increasing conversion. The mechanism of formation of C2
(2-chloroethyl) and C4 (2,4-dichloroethyl) is the same as for polyethylene produced under high pressure,
but that of C1 (chloromethyl) is only observed in the radical polymerization of VC.
During the preparation of PVC under low monomer pressures, intramolecular hydrogen transfer
(backbites) lead to the formation of small amounts of 1,3-bis(2-chloroethyl) branch (DEB) structures,
as well as allylic chloride segments resulting from 1,6 shifts. The presence of these structural defects has
been established by 13C NMR of dechlorinated PVC specimens made by R3SnH reduction. At 55 80 8C,
the two backbites leading to DEB groups differ substantially in relative rate; the backbiting: addition rate
ratio is larger for the second backbite by a factor of 15 16, irrespective of temperature. No convincing
evidence has been obtained for the presence of a chlorinated 2-ethyl-n-hexyl branch (EHB) segments
resulting from double backbiting [67].
The content of short-chain branches in PVC and ethylene/VC copolymers has been estimated by
pyrolysis-hydrogenation gas chromatography [68]. The branch contents were determined from the
relative peak intensities of characteristic key isoalkanes on the C10 and C11 fragment region in the
observed pyrograms by comparing the data of reference model ethylene-co-olefin copolymers with
known contents of methyl, ethyl, and butyl branches. The results obtained by this method were in
reasonably good agreement with those obtained by 13C NMR spectroscopy.
Differences in the molecular mobility of PVC have been characterized by 13C NMR spectroscopy, and
these are related to the polymerization process. The arrangement of the chain sequences affects the NMR
parameters. This influence can be interpreted as a configurational sequence distribution in the
macromolecular structure [69].
5. Characterization and properties of PVC

5.1. Tacticity
The tacticity of PVC strongly affects both physical properties and the thermal stability. Although 1H
Table 7
Tacticity of PVC obtained by radical polymerization
Tacticity
Content (%)
Chemical shift (ppm, TMS)
Triad: methine resonance

rr
mr
mm
29.1
52.0
18.8
57.15, 57.06
56.29, 56.13
55.42, 55.29, 55.16
Tetrad: methylene resonance

rrr
rmmr
rrm
mmr mrm
mmm
16.1
14.6
28.2
32.0
9.2
47.47
47.35
47.01
46.33
45.59
2036
NMR spectroscopy has been used to determine the tacticity of PVC [70], 13C NMR spectroscopy has
been established as the method of preference to measure the tacticity of PVC [71,72]. These studies have
enabled the statistics of the addition of monomer units to the chain to be determined. The mode of
monomer addition to the growing chain is not affected by the stereochemistry of the chain end. The
tacticity of PVC is shown in Table 7. The activation energy for isotactic addition is higher than that for
syndiotactic addition by approximately 500 600 cal/mol. Thus, the content of syndiotacticity of the
PVC obtained from radical polymerization decreases with increasing reaction temperature, and
Bernoullian statistic applied for the polymerization [72].
5.2. Crystallinity and amorphous state
Crystallinity is associated with syndiotactic sequences. Although the syndiotactic sequences obtained
from radical polymerization are usually short, there are strong attractive forces between chains
associated with the C Cl dipoles that provide strong attractive forces to induce crystallinity [73]. The
theoretical melting point of a perfectly syndiotactic PVC is estimated to be about 400 8C [74], but such a
polymer has not been synthesized. The melting points of PVC synthesized by radical polymerization are
102 210 8C due to small size and imperfections in the ordered structure [75]. The gelation of PVC is
related to the crystallinity [76]. Most estimates for commercial polymers are of 7 20% crystallinity [77,
78]. When the polymerization was carried out at lower reaction temperature, the crystallinity of PVC
increases [79]. The ability of PVC to form a wide range of compositions with plasticizers is very
important for practical applications. The crystallites act as physical crosslinks in the practical materials
[80]. The unit cell dimension for syndiotactic PVC has been determined to be an orthorhombic unit cell
with a-, b-, and c-dimensions of 1.06, 0.54, and 0.51 nm, respectively [81].
Since most of the PVC is in the amorphous state, the Tg depends on the molecular structure. The
effects of Mn and the tacticity can be separated. The Tg of PVC is usually 70 80 8C. The addition of
plasticizers lowers the Tg to below room temperature [3].
5.3. Thermal stability
The susceptibility of PVC synthesized by radical polymerization toward thermal degradation is well
known and has been attributed to the presence of structural defects such as head-to-head units, tertiary
chlorines at branched carbons and chlorine atoms adjacent to internal double bonds. Heating PVC above
100 8C causes the polymer to degrade [82]. The polymer emits HCl that catalyzes the elimination of HCl
from the next monomer unit, resulting in the rapid unzipping of further acid to give polyene sequences.
The polyenes undergo secondary reactions such as scission and crosslinking, leading to the formation of
aromatic compounds such as benzene and toluene [83 85], affecting polymer properties. This results in
coloring, the solubility of the polymer decreases and the electrical and mechanical properties deteriorate.
The dechlorination is strongly catalyzed by HCl. The limited length of the polyene sequence could be
due to resonance stabilization or to the presence of blocking groups such as chain branches [86,87].
The instability of PVC is related to its structure. Impurities are unlikely to be a cause of degradation,
because the stability does not increase after reprecipitation. The chain end groups of PVC are quite
stable. Chloromethyl groups are stable because C1 has not bonded to carbon having tertiary chlorine
atom in the main chain. The two groups believed to be the cause of instability are the chlorines adjacent
to internal double bonds and the tertiary chlorines of branch carbons. The instability of the two groups is
2037
Table 8
Monomer reactivity ratios for copolymerization of VC (M1) with vinyl monomers (M2)
M2 monomer
r1
r2
Temperature (8C)
Reference
Ethylenea
Ethyleneb
Ethylene
Propylene
Isobutene
1,3-Butadienec
Styrene
Allyl chloride
Vinylidene chloride
Vinylidene chlorided
Allyl acetate
Diallyl phthalatef
Isobutyl vinyl ether
Phenyl vinyl ether
Triethoxy vinyl silane
Vinyl acetate
Vinyl acetate
Vinyl benzoate
Vinyl stealate
Acrylonitrile
Acrylonitrile
Methacrylnitrile
Acrylic acid
2-Ethylhexyl acrylate
Methyl acrylate
n-Butyl acrylate
Acrylamide
Methacrylic acid
Methyl methacrylate
Glycidyl methacrylate
n-Butyl methacrylate
Diethyl itaconate
Diethyl maleate
Maleic anhydride
N-Methyl maleimide
Diethyl fumalate
N-Vinyl pyrolidone
3.6
2.0
2
2.27
2.05
0.035
0.04
0.63
0.20
0.16
1.16
1.68
2.0
1.06
0.90
2.45
2
1.8
0.745
0.052
0.5
0.237
0.025
0.16
0.12
0.07
0
0.027
0.07
0.41
0.025
0.06
0.77
0.296
0.01
0.12
0.53
0.24
0.8
0.3
0.3
0.08
8.8
20
0.56
1.8
4.5
0
0.38
0.02
0.16
0
0.3
0.28
0.3
0.29
3.6
3.0
4.0
6.4
4.15
4.4
4.4
19.6
36
16.1
8.84
30.5
5.65
0.009
0.008
3.12
0.47
0.38
90
65
60
60
60
50
60
50
70
50
40
60
50
60
50
60
60
60
60
50
30
60
50
63
50
45
40
50
45
50
80
50
60
60
60
50
50
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
a
b
c
d
e
Ethylene 1000 atm.

Ethylene 300 atm.
Emulsion polymerization.
Suspension polymerization.
Cyclization polymerization.
2038
similar, but the concentration of tertiary chlorine is greater, and thus its effect is believed to be more
significant. Although conjugated systems are known to be unstable, the effect is unlikely to be significant
because of the low concentration. The main contribution of different VC defect structures to
dehydrochlorination is tertiary chlorine, (70 80%) [4,83].
6. Radical copolymerization
Copolymerization of VC with various monomers has been performed to improve physical and
mechanical properties of PVC [88,89]. Since VC is classified as a non-conjugated electron-withdrawing
monomer as mentioned above, it is not easy to copolymerize with conjugated monomers such as styrene
and methyl methacrylate to high molecular weight copolymers. However, VC copolymerizes readily
with non-conjugated monomers. One major aim of the copolymerizations of VC with other vinyl
monomers is the synthesis of inner plasticizer copolymers. The monomer reactivity ratios for the
copolymerization of VC with various vinyl monomers are shown in Table 8 [90 125].
Copolymerization of VC is also a method to suppress the content of anomalous units present in the
homopolymer. Since such units are formed by the isomerization of the propagating radical during the
homopolymerization of VC. If the crosspropagation step is faster than the isomerization of
the propagating radical, the formation of anomalous structures may be suppressed by such
copolymerization systems.
6.1. Copolymerization with olefins
The copolymerization of ethylene and VC has been investigated in order to obtain an inner plasticized
PVC using AIBN or BPO as initiator [90,91]. A random sequence distribution was confirmed by analysis
of the resulting copolymers. R3B is an effective initiator for the copolymerization of VC and ethylene at
lower reaction temperatures [92]. The copolymerization rate has been improved using R3B giving a
more thermally stable copolymer than PVC. When Et3B/O2 was used as an initiator, a rubber like
copolymer was obtained.
Branched structures of PVC and VC and ethylene copolymers obtained from suspension
copolymerization has been studied by use of NMR spectroscopy [126]. The 1H NMR spectra of the
copolymers showed no correlation between the contents of the anomalous structures and the
heterotacticity in vinyl chloride sequence and ethylene contents in the copolymers. The branched
structure in the ethylene vinyl chloride copolymer determined from 13C NMR spectra of the polymers
after dechlorination with tri-n-butyltin hydride at the part of vinyl chloride units is not so different from
that in PVC prepared with ordinary radical polymerization. The content of C1 branches was higher than
any other branched structure. The contents of branched structures decreased in the following order: C1
branch . C4 branch . C2 branch. The number of these branches increased with increasing
incorporation of ethylene units in the copolymers. Ethylene participates in the formation of the
branched structures that are produced by h h addition and back biting in the copolymerization of VC
with ethylene.
Copolymerization of VC and propylene has been performed. It is difficult to synthesize high
molecular weight copolymers consisting of VC and propylene by radical copolymerization because of
2039
Fig. 10. Copolymer synthesis from PVC using Friedel Crafts reaction.
degradative chain transfer of propylene. Moreover, the copolymer rich in propylene units is also difficult
to synthesize by radical polymerization [93].
6.2. Copolymerization with conjugated vinyl monomers
VC is reluctant to copolymerize with St even in the presence of only a small amount of St in the feed.
Since copolymers rich in VC units is difficult to synthesize from direct copolymerization of VC and St,
such copolymers have been successfully synthesized by means of a Friedel Crafts reaction from PVC as
shown in Fig. 10 [127]. Investigation of the copolymerization of VC and butadiene (Bd) has revealed
that the copolymerization hardly proceeds, since Bd is classified as a conjugated vinyl monomer as well
as St [95].
The copolymerization ability of VC with acrylic acid esters is not good either, since these are also
conjugated vinyl monomers [113]. To make matters worse, dechlorination of these copolymers takes
place readily. The copolymerizability of methacrylic acid esters with VC is considerable lower than that
of acrylic acid esters [116].
The crosstermination constant in the copolymerization of VC/N-phenylmaleimide (PMI) has been
estimated to be 8.3 by using non-linear least square fitting. This indicates that crosstermination is
significant. Using the calculated modeling parameters, the effects of temperature and initiator
concentration on the copolymerization rate were predicted, and the rate agreed with the experimental
data [128]. N-Phenylmaleimide has been copolymerized with VC in order to improve the heat resistance
of PVC. The variations of instantaneous and integral copolymer compositions with conversion for the
VC/PMI copolymerization system were investigated quantitatively. The copolymer composition could
be controlled and optimized by adjusting the content of a third monomer. For VC/PMI suspension
copolymerization, acrylonitrile and MMA are preferably selected to improve copolymer composition
homogeneity and heat resistance [129].
Diisopropyl fumarate (DiPF) was successfully copolymerized with VC employing a radical initiator
at 60 8C r1 0:488; r2 0:292: The polymer yield retained approximately constant for
copolymerizations containing less than 5 mol% DiPF. Introduction of DiPF units to poly-VC results
in no change in Tg when the content was less than 10 mol%. The thermal decomposition temperatures of
the copolymers decreased with increasing DiPF content [130].
The compatibility of poly(a-methyl styrene methyl acrylate) (PMSMA) and poly(a-methyl
styrene ethyl acrylate) (PMSEA) with PVC has been estimated by the solubility parameter method
and scanning electron microscopy. The mechanical properties, rheological behavior and morphology of
these blends show that these copolymers can be used as a processing aid for PVC [131].
2040
6.3. Copolymerization with non-conjugated vinyl monomers

VC copolymerizes well with vinyl ester and vinyl ether monomers, because these vinyl monomers are
classified as non-conjugated vinyl monomers. Vinyl esters copolymerize with VC, but the resulting
copolymers have lower thermal stability than PVC. Among many non-conjugated vinyl monomers,
copolymerization of VC with VAc has been investigated in some detail [105,106]. The copolymers
obtained have solubility and fluid characteristic superior to PVC. Analysis of the tacticity of the
copolymer consisting of VC/VAc copolymers has revealed that the number of syndiotactic sequences of
VC decreased with increasing VAc content in the feed [132].
A thermally stable, high molecular weight copolymer of VC and trimethylolpropane monoallylether
(PVC-co-TMPME) has been synthesized by suspension polymerization [133]. The glass transition
temperature of the TMPME copolymer is similar to that of the homopolymer, and to that of a 5% vinyl
acetate (PVC-co-VA) copolymer. Dynamic mechanical analysis shows that both PVC-co-TMPME and
PVC-co-VA have lower modulus than the corresponding homopolymer. PVC-co-TMPME would be
expected to exhibit similar process and end-use property characteristics and thermal stability as
conventional PVC copolymers.
A model of the gel fraction of polymer based on a general model of the sol/gel partition has been
proposed, where the kinetic factors such as a two-phase polymerization mechanism, distinction of the
gel and sol radicals, and the effects of the gel on the kinetics are taken into account. The model was
applied to the VC/diallyl phthalate (DAP) suspension copolymerization, and successfully predicted the
development of the gel fraction with conversion. The crosslinks prove to be non-randomly distributed in
the VC/DAP suspension copolymerization [134].
The reactivity ratios of VC DAP suspension copolymerization system performed in a 5-l autoclave
and 200-ml stainless steel vessel at 45 8C were calculated as rVC 0:77 and rDAP 0:37: The
copolymer contained no gel when the feed concentration of DAP fDAP was lower than a critical
concentration fcr ; within the range of 0.4660.493 mmol/mol VC at 80 85% conversion. The degree
of polymerization (DP) increased with increasing fDAP and conversion. The VC DAP copolymer is
composed of a gel and a sol fraction when fDAP is larger than fcr. The DP of the sol fraction decreased
with increasing fDAP, but the gel content and the crosslinking density of gel increased. The gel content
increased with conversion [135]. The effects of the reactivity ratios and the concentration of the divinyl
monomer, the temperature and the conversion on the gel fraction, DP of the sol fraction and the
crosslinking density of the gel of crosslinked PVC (C-PVC) have been investigated. The crosslinking
efficiency of DAM was higher than that of DAP and ethyl glycol dimethyl acrylate (EGDMA). The
crosslinking efficiency of EGDMA was very low due to its high probability of homopolymerization. The
gel fraction and crosslinking density increased as the concentration of DAP was increased, and
decreased with increasing temperature. The DP of the sol fraction decreased with increasing
concentration of DAP. The crosslinking density of the gel increased gradually with increasing the gel
fraction at the lower gel fraction stage, and increased rapidly at the higher gel fraction stage [136].
Chemically, C-PVC was synthesized by VC suspension polymerization in the presence of DAP and
plasticized to prepare PVC thermoplastic elastomer (TPE) materials. The gel fraction and the
crosslinking density of the gel increased as the feed concentration of DAP was increased. C-PVC
prepared by VC/DAP copolymerization was lightly crosslinked as compared with irradiation C-PVC.
Physical entanglements would greatly influence the crosslinking density of the gel when the gel fraction
was high. Chemical crosslinking had little influence on the recrystallization behavior of PVC. Both
2041
chemical and physical crosslinking influence the processability and mechanical properties of chemically
C-PVC-TPE [137].
7. Synthesis of graft and block copolymers

7.1. Synthesis of graft copolymers
Graft copolymers containing VC chains have been synthesized by graft copolymerization with other
monomers in the presence of PVC or copolymerization of VC in the presence of other polymers. In this
article, only the former cases will be described. Several synthetic methods for graft copolymers
containing PVC sequences have been reported including: (1) radical chain transfer reaction, (2)
polymerization from labile chlorine in PVC (3) polymerization by polyozonide or polyperoxy radical,
(4) mechanochemical reaction, and (5) ionic copolymerization.
Among the many methods for synthesis of graft copolymers containing PVC sequences in the main
chain, the use of chain transfer to or from PVC first reported in 1950 [138 141] is the most basic and
widely adopted approach. Ravve and Khamis [141] synthesized graft copolymer consisting of PVC-gpoly(GMA) by radical polymerization initiated with BPO in MEK at 80 8C. The graft copolymerization
of MMA and PVC with BPO in cyclohexane at 70 8C has been performed. The graft efficiency increased
with increasing PVC concentration in the feed [142]. Graft copolymerization of St with partially
dehydrochlorinated PVC (degree of dehydrochlorination, 3.6%; number of conjugated double bond, 7.0;
total double bonds, 1.20%) used as a parent polymer has also been investigated using BPO [143]. The
graft efficiency increased with a decreasing St content in the feed and with decreasing temperature. Graft
copolymer rich in St units was revealed to be more thermally stable than PVC. Butyl acrylate has also
been used for graft copolymers synthesis by chain transfer reactions [144].
The chlorine in the anomalous units of PVC prepared from radical polymerization is labile. If such
chlorine is utilized as an initiation point of graft copolymerization, the contents of the chlorine should
decrease as a result of graft copolymerization, leading to improvement of the thermal and physical
properties. Kennedy [145] synthesized graft copolymer of VC and isobutylene (IB) from the
Fig. 11. Synthesis of graft copolymer of PVC and poly(IB).
2042
Fig. 12. Synthesis of VC/2CP-g-poly(IB).
polymerization of IB with Et2AlCl in CH2Cl2. The labile chlorines such as tertiary chlorine bound to the
main chain carbon or the allylic chlorine bond to the inner double bond in PVC can act as effective
initiation sites to give graft copolymer with high efficiency (Fig. 11). Accordingly, the amount of
dehydrochlorination of the graft copolymer was lower than that of PVC. Recently, it has been found that
the active chlorine in PVC can be replaced with allyl groups by allyltrimethylsilane in the presence of
Friedel Crafts acids. The thermal stability of allylated PVC was significantly superior to that of the
starting PVC [146].
The effect of PVC on low-polar isobutylene polymerization in the presence of BCl3 VC/2chloropropene (2CP) copolymer as an initiator has been examined. The low-polar polymerization of IB
in the presence of BCl3 was carried out in CH2Cl2 ([IB] 7 mol/l) at 2 78, 220 and 20 8C in the
presence of VC/2CP copolymer, representing PVC resin enriched in structures with chlorine atoms
bonded to the tertiary carbons. The polymerization products consist of mixtures of polyisobutylenes
(PIE) and grafted VC/2CP-g-PIB copolymer as shown in Fig. 12. The rate of polymerization of IB
decreases with increasing temperature, but the grafting efficiency increases. The VC/2CP copolymer
induces strong grafting compared with PVC, and it might therefore be assumed that the C Cl bonds with
chlorine atoms bound to tertiary carbons directly initiate the polymerization of IB [147].
Polymer radicals can be produced by g-irradiation under high vacuum or nitrogen atmosphere as
shown in Fig. 13. The generated PVC radicals can be used for graft copolymerization. By use of this
method, graft copolymers of St [148], MMA [149], and acrylic acid [150] have been synthesized.
PVC reacts with ozone to yield a polyperoxide, that can be used as a macroinitiator, to synthesize graft
copolymer [151]. The graft copolymers consisting of VC and seven kinds of vinyl monomers including
St have been synthesized by this method.
The chlorine in PVC can react with sodium salts at the chain end of polymers, leading to formation of
Fig. 13. Formation of polymer radical by g-irradiation.
2043
graft copolymer. This technique has been applied to the synthesis of amphiphilic graft-copolymers,
composed of PVC backbones and poly(ethylene oxide) side chains. The synthesis of graft copolymer
was performed by the reaction of the chlorine in PVC and the sodium salt of poly(ethylene glycol) (PEG)
having molecular weights of 200 and 600. The molecular weights of PEG were found to influence the
rate of the grafting reaction and the final degree of conversion. The maximum grafting percentage of the
resulting polymers after purification was ca. 34%, regardless of the molecular weight of PEG. No gel
was observed in the PVC-g-PEOs, in spite of the average numbers of grafting chains being as high as 32
[152].
Living radical polymerization is a fascinating approach to polymer design, and has been achieved via
several routes; polymerizations in the presence of nitroxides such as 2,2,6,6-tetramethyl-4piperidionoxy [153,154], atom transfer radical polymerization (ATRP) [155] including transition
metals mediated radical polymerization [156], a reversible addition fragmentation chain transfer
(RAFT) [157], iniferter polymerization [158], and cyclic disulfide mediated radical polymerization
[159]. The method that employs a transition metal compound [Mt] in combination with an organic halide
(RX) is advantageous as it is comparable with a wide range of monomers and at low temperature. ATRP
has been used to synthesize graft copolymers of PVC with St and (meth)acrylates. PVC containing a
small amount of pendent chloroacetate units was used as a macroinitiator for this type of graft
copolymerization (Fig. 14). Increased incorporation of butyl acrylate resulted in an increase in molecular
weight. From the measurement of thermal properties of the resulting polymers, one Tg was observed for
all copolymers, and the value of Tg decreased with increasing n-butyl acrylate content [160].
The chlorine in PVC can react with the sodium or potassium salt of dithiocarbamate or xanthate as
shown in Fig. 15 [161,162]. Such polymers can be used as macroinitiators for the synthesis of graft
copolymers containing PVC.
PVC n-propyl xanthate (PVC n PX) macroinitiators with 3 14 bonded xanthate groups per
molecule were synthesized using PVC and potassium n-propyl xanthate. The reaction took place rapidly
between 30 and 45 8C. The PVCn PX macroinitiators were grafted by MMA under ultraviolet (UV)
irradiation producing graft copolymers (Fig. 16). The molecular weights increased linearly with
increasing conversion, which is consistent with a living radical polymerization process. The active
species in the polymerizations are macroradicals and xanthyl radicals [163].
Fig. 14. Synthesis of graft copolymer of PVC containing St or MMA segment.
2044
Fig. 15. Reaction of PVC with sodium salt of dithiocarbamate and xanthate.
PVC with pendent N,N-diethyldithiocarbamate groups (PVC SR) has been prepared through the
reaction of PVC with sodium N,N-diethyldithiocarbamate (NaSR) in butanone, and used as a
photoinitiator for the grafting polymerization of St, MMA, and acrylamide (Am). The effects of UV
irradiation time, PVC SR amount, and the monomer amount on grafting and grafting efficiency were
investigated. The PVC SR could initiate the polymerization of three vinyl monomers effectively and
crosslinked copolymers were obtained. The grafting and grafting efficiency of St and MMA were higher
Fig. 16. Graft copolymerization of MMA using PVC-n PX macroinitiator.
2045
Fig. 17. Reaction of PVC SR under UV irradiation.
than those of Am. By analyzing the UV spectrum of PVC SR with a different irradiation time, PVC SR
was confirmed to be dissociated mainly into the macromolecular sulfur radical PVC-S and the small
molecular carbon radical as shown in Fig. 17 [164].
Mechanochemical degradation and mechanochemical reaction in heterogeneous systems of solid
poly(VC) PVA aqueous solutions have been studied by ultrasonic irradiation at 30 8C. The rate of
decrease in the viscosity-average degree of polymerization of the degraded PVC was much higher than
that of the degraded PVA. Mechanochemical reaction occurred by free-radicals produced from the chain
scissions of both polymers by ultrasonic waves to give the copolymer [165].
In the grafting of acrylamide (AAm) onto PVC films using g-radiation, the effects of radiation dose,
monomer concentration, solvent composition, types of inhibitors and acidity of the medium on the graft
yield have been investigated. The presence of sulfuric acid in the reaction medium has an adverse affect
on the graft yield to a greater extent than acetic acid. The effects of the multifunctional monomers N,N0 methylene allyl amide (MAAm) and 2,4,6-triallyloxy-1,3,5-triazine (TARA) on the graft yield have also
been studied. The presence of MAAm in the reaction medium markedly increases the graft yield, while
TARA has practically no effect on the grafting process. Grafted films have been characterized and
evidence of grafting has been obtained using thermal and spectroscopic analysis together with swelling
measurements in water [166]. Graft copolymer prepared by radical graft polymerization of butyl
methacrylate (BuMA) onto PVC, and PVC itself were effective permselective membrane materials for
the selective separation of benzene from benzene/cyclohexane mixture over the whole feed composition
range. The permeation rate was enhanced by the introduction of poly(BuMA) onto PVC membrane
[167].
7.2. Synthesis of block copolymers
Block copolymers can be good compatibilizers in polymer blends if tailored carefully. However, they
are produced by anionic polymerization which is not a versatile technique and, moreover, is expensive.
The following methods are available for synthesizing block copolymer containing PVC segment: (1)
mechanochemical reaction, (2) combination of polycondensation and radical polymerization, and (3)
polyaddition.
During mechanochemical polymerization, chain scission results in PVC radical can initiate
polymerization of other monomers, yielding block copolymers. Block copolymers consisting of PVC
with MMA or St segment has been synthesized by this method [168,169].
Polycondensation followed by radical polymerization is one of the synthetic methods for block
copolymers containing PVC segments using macroinitiators containing azo groups (ACVC). Azo group
containing PEG was synthesized by condensation polymerization of 4,40 -azobis-4-cyanovaleric acid
chloride with PEG. Block copolymer was synthesized by copolymerization of VC with ACVC as shown
in Fig. 18 [170,171].
2046
Fig. 18. Synthesis of PVC PEG block copolymer.
Similarly, block copolymers consisting of PVC-b-polyurethane-b-PVC having high impact strength

[172], and PVC-b-polytetramethylene glycol-b-PVC have been synthesized [173].
Block copolymer containing PVC segments was also synthesized using polyaddition reaction
between diisocyanate and glycol [174]. Block copolymer can be synthesized by the reaction of hydroxy
terminated PVC, obtained by reduction of ozonided PVC by LiAlH4 in THF, with diisocyanate as shown
in Fig. 19.
Block graft copolymers can be prepared by radical grafting from readily available block copolymers,
in particular from St-b-Bd. The efficiency of two block graft copolymers, St-b-Bd-g-CHMA (CHMA,
Fig. 19. Synthesis of block copolymer using polyaddition reaction of diisocyanate and glycol.
2047
cyclohexyl methacrylate) and St-b-Bd-g-MMA as compatibilizers in PSt/PVC blends of polystyrene

(PSt) and PVC has been investigated by electron microscopy. Both copolymers greatly refined the coarse
morphologies of the PSt/PVC blends, covering the interfaces between the phase domains of PSt and
PVC with monolayers. This is in accord with the commonly assumed model of the compatibilizer effect
of block copolymers. However, the phase structures were even finer than predicted by the model;
perfectly compatibilized phase domains were torn apart during mixing in the kneader [175].
8. Polymerization of VC using anionic catalysts

It was not until 1956 that Szwarc and his coworkers conclusively demonstrated the lack of
termination in anionic polymerization of vinyl monomers in the absence of impurities. They
proposed the term living polymer for those macromolecules that may spontaneously resume their
growth whenever fresh monomer is supplied to the system. Since then, living polymerization has
been studied extensively, and block copolymers have been synthesized successfully by means of
living polymerization processes. It is well known that anionic polymerizations of many unsaturated
monomers including isoprene and styrene with alkyllithium (RLi) proceed via a living mechanism
[176]. The molecular weight of the resulting polymer can be controlled and the polymers have a
narrow molecular weight distribution. However, these processes were limited to conjugated
monomers, and polymerization of non-conjugated and polar monomers such as VC with anionic
catalyst have not been successful owing to deactivation reactions between the catalyst and the
halide in VC as shown in Fig. 20. In anionic polymerization, polymers consisting of only head-totail structure should be obtained on account of the influence of polarity. If VC could be
polymerized with anionic catalysts, it would be expected that polymer having a linear structure
without anomalous structures, and consequently of thermal stability, could be prepared.
Recently, much effort has been focused on controlled polymerizations of many vinyl monomers
with various kinds of polymerization mechanisms. Among them, living anionic polymerization is an
excellent process for the synthesis of polymers having a well-defined structure [176]. Although
Kolinsky and coworkers [9,177 179] have reported that polymerization of VC with RLis proceeds
to give polymer, the structures of the resulting polymers were not well defined. The structure of the
polymer obtained from polymerization of VC with butyllithium (BuLi) in n-hexane was reported to
consist of only regular head-to-tail units by use of NMR spectroscopy [10]. Although Kolinsky [9]
observed that the Mn of the polymers determined by viscometric measurement increased with
reaction times, controlled polymerization of VC has not been achieved. Since the polymerization
was carried out at 40 8C, side reactions may have been induced. Thus, lower reaction temperatures
may result in less the side reactions, leading to controlled polymerization. The bulk polymerization
of VC with t-BuLi proceeded at 2 30 8C to give high polymers. The Mn of the polymers and
Fig. 20. Metalation reaction of VC and RLi.
2048
Fig. 21. Relationships of Mn and Mw/Mn upon the polymer yields in the polymerization of VC with the tert-BuLi in bulk at
2 30 8C; [tert-BuLi] 0.165 mol/l (W) and 0.033 mol/l (X). (Reprinted from Polymer 1999;40:6883. q1999 with permission
from Elsevier Science [180]).
polymer yields increased as a function of the reaction time, although the initiator efficiency was
low due to side reactions between VC and the catalysts as depicted in Fig. 21. Linear dependence
of Mn and polymer yields was observed, but the Mw/Mn did not change significantly during the
polymerization. The Mw/Mn of the polymer was not narrow, which may be due to the heterogeneity
of the reaction media [180]. However, the stereoregularity of the resulting PVC mm 17%;
mr 49%; rr 34% is not so different from that obtained from radical polymerization
mm 12%; mr 49%; rr 39% [181]. The PVC obtained from RLi was not observed to
contain branches structures, as confirmed by 13C NMR of the PVC reduced with n-Bu3SnH [182].
Guyot and Tho [183] investigated the polymerization of VC with tertiary-butylmagnesium at 25 8C
for 37 h in THF in the absence of oxygen and light. The initiation reaction was reported to be very fast to
give polymer in high yield. However, the molecular weights of the resulting PVC were lower than 6300.
The polymerization of VC with t-BuMgCl was also investigated, and high polymers have been
synthesized [184,185]. However, the polymerization mechanism seems to be complex [186].
Polymerization of VC initiated by di-t-alkylmagnesium has been reported by Starnes and coworkers
[187], and new structural and mechanistic chemistry of VC polymerization were proposed. Bulk
polymerization of vinyl chloride initiated by di-t-butyl- or t-butyl-t-pentyl magnesium etherate gave
PVC specimens containing considerable amounts of cyclopropyl, trans-2-t-butylcyclopropyl, and
ZCHClCHyCH2 chain ends, which could not be formed by conventional free-radical methods. The
formation of the unusual end groups was rationalized in terms of reactions of various polymeric
intermediates having Mg C bonds. Ethylene formed in situ has been shown to be involved in the
2049
process that produces the cyclopropyl chain end. When the polymerization temperature is raised in
stages from 220 to 40 8C, the unusual chain ends are gradually replaced by structures that are known to
result from reactions of free macroradicals.
9. Transition metal promoted polymerization of VC

The advance of metal alkyl catalysts and Ziegler Natta catalysts made it possible to prepare many
stereoregular polymers of 1-olefins, dienes, cyclic olefins and some conjugated unsaturated monomers
[11,13]. When polar monomers including VC are polymerized with Ziegler Natta catalysts, special
conditions are required to obtain polymer by avoiding side reactions between monomer and catalysts. To
obtain the polymer, several ideas have been proposed [11]. In the polymerization of VC, typical Ziegler
catalysts were not effective for the polymerization of VC unless a nucleophilic reagent was added.
The polymerization of VC with a variety of modified Ziegler type catalysts has been investigated for the
synthesis of stereoregular PVC [11,188,189]. The modified catalysts were selected according to the
criteria of the ligands being less electrondrawing group than halogens. Ti(O-n-Bu)4 AlEtCl2 catalyst
produced high molecular weight PVC in good yields [189], and THF and triethylamine were found to be
effective for additives [190]. The stereoregularity of the polymer was also identical with commercial
polymers. Copolymerization of VC and ethylene with Ziegler type catalysts has also been investigated.
The rate of copolymerization was accelerated with Ti(OBu)4/Et2AlCl catalyst in the presence of THF or
Et3N, and an anionic polymerization mechanism was presumed to be in operation [191]. The VO(OEt)3/
EtxAlCl32x catalysts can initiate the copolymerization of VC and ethylene to give copolymer, although
the polymerization mechanism is not clear [192]. Copolymerizations of VC and propylene with Ziegler
type catalysts such as Et2AlOET EtAl(OEt)Br [193], Ti(O-n-Bu)4/alkylaluminums [190] have also
been performed. Although copolymer of VC with propylene was obtained, the polymerization
mechanism appears to be complex.
Taking the features and capability of metallocene catalysts into consideration, they should be
Fig. 22. Reaction scheme in the polymerization.
2050
applicable to the polymerization of VC, and thus giving polymers without the anomalous units that are
introduced into the polymer chain during radical polymerization. However, only limited research has
been carried out in this area [194,195].
In the polymerization of VC with modified Ziegler catalysts, Ti(O-n-Bu)4 in combination with
Et2AlCl has been reported to be able to polymerize VC [190]. The ligand of the titanium compound was
selected to be less electron withdrawing than halogens. A cocatalyst less reactive than alkylaluminum
toward chlorinated compounds was chosen. Taking this into consideration, the polymerization of VC
was investigated with the CppTiX3 (X Cl or OCH3) MAO catalysts [15].
The CppTiClX3 MAO (X: Cl and OCH3) catalysts were found to initiate the polymerization of VC,
although the polymerization rate was very low. The CppTi(OCH3)3 MAO catalyst in CH2Cl2 gave high
molecular weight polymer in good yields. Elemental analysis and 1H NMR revealed that the
CppTi(OCH3)3 MAO catalyst resulted in polymers consisting of repeating regular CH2 CHCl units
in contrast to that the CppTiCl3 MAO catalyst did not give polymer consisting of only regular structure.
Polymerization in CH2Cl2 as solvent gave higher polymer yields and molecular weights than in toluene.
This is consistent with previously reported results for the polymerization of St and propylene with
metallocene catalysts, in which a transition from a contact pair metallocene/MAO in toluene to free
separated species in CH2Cl2 has been suggested [196].
Recently, the polymerization of VC with rac-(EBI)ZrMe2/MAO (EBI: 1,2-bisindenylethylene)
catalyst was reported [197]. However, only low molecular weight polypropylene was obtained. The key
route for the reaction mechanism is shown in Fig. 22. In this polymerization, VC monomer is first
inserted into the Zr Me bond. However, further insertion of VC into the complex did not occur. Instead,
a complex containing the Zr Cl bond and propylene are formed. Since rac-(EBI)ZrMe2/MAO is able to
rapidly polymerize propylene, the propylene formed from the complex and VC homopolymerizes to
give atactic poly(propylene) with a low molecular weight of about 500.
I believe that stereoregular PVC will be synthesized in the near feature from transition metal
promoted polymerization or some other polymerization method. This achievement greatly reduce the
environmental problems associated with PVC synthesized by conventional means, and would bring
about drastic changes in the industrial production of PVC.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
Regnault HV. Liebigs Ann 1835;14:22.

Baumann E. Liebigs Ann 1872;163:308.
Smallwood PV. Encyclopedia of polymer science engineering, 2nd ed. New York: John Wiley & Sons; 1989. p. 295.
Semon WL, Stahl GA. History of polymer science and technology. New York: Marcel Dekker; 1982.
Stephensen RC, Smallwood PV. Encyclopedia of polymer science engineering, 2nd ed. New York: John Wiley & Sons;
1989. p. 843. Supplement.
Poly(vinyl chloride)basic and application. Nikkan Kogyo Shinbun; 1988.
Nass LI, Heiberger CA, Encyclopedia of PVC, vol. 1. New York: Marcel Dekker; 1985.
Elgert KF. Polym Bull 1983;10:244.
Kolinsky M. J Macromol Sci, Chem 1977;A11:1411.
Endo K, Kaneda T, Aoki S. Koubunshi Ronbunsyu 1998;54:900.
Boor Jr. J. Ziegler Natta catalysts and polymerizations. New York: Academic Press; 1979.
Kaminsky W, Arndt M. Adv Polym Sci 1996;127:143.
Fink G, Mulhaupt R, Brintzinger HH. Ziegler catalysts. Berlin: Springer; 1995.

[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
[53]
[54]
[55]
[56]
[57]
[58]
[59]
[60]
[61]
[62]
[63]
2051
Yamazaki N. Prog Polym Sci Jpn 1971;2:171.

Endo K, Saitoh M. Polym J 2000;32:300.
Brandrup J, Immergent EH. Polymer handbook, 2nd ed. New York: Wiley; 1974.
Isaacs NS. Physical organic chemistry. London: Longman; 1987. p. 36.
Schulz GV. J Polym Sci 1955;17:45.
Nakamura N, Saeki Y, Yamakawa M, Nakayama A, Nakano A. Polym Prepr Jpn 1996;45:46.
Ugelstadt J, Mork PC, Hansen FK, Kaggrrud KE, Ellingsen T. Pure Appl Chem 1981;53:323.
Langsam M. Hydrocarbon Process 1979;47.
Suresh AK, Chanda M. Eur Polym J 1982;18:607.
Weckkert G, Henschel G, Weissenborn KD. Angew Makromol Chem 1987;147:1.
Weckkert G, Henschel G, Weissenborn KD. Angew Makromol Chem 1987;147:19.
Willmouth FM, Rance DG, Henman KM. Polymer 1984;25:1185.
Tornell BE, Ustalu JM. Polymer 1986;27:250.
Nolzold G, Behrens H. Plast Kautsch 1981;316:377.
Talamini G. Makromol Chem 1968;117:140.
Ugelstadt J, Flogstad H, Hertzberg T, Sund E. Makromol Chem 1973;164:171.
Olaj OF. Angew Makromol Chem 1975;1:47.
Abdel-Alim AH, Hamielec AE. J Appl Polym Sci 1973;16:782.
Talamini G, Visentini A, Kerr J. Polymer 1998;39:1879.
Talamini G, Kerr J, Visentini A. Polymer 1998;39:4379.
Sanderson AK. Br Polym J 1980;12:186.
Lucas R, Paleckova V, Mrazer Z, Kolinsky M. Int Polym Sci Tech 1982;9:83.
Smallwood PV. Polymer 1986;27:1609.
Sladky P, Parma L, Zdrazil J. Polym Bull 1982;7:401.
Gaylord NG, Nagler M. Polym Bull 1982;8:395.
Allsopp MW. Pure Appl Chem 1981;53:449.
Ravey M, Waterman JA, Shorr LM, Kramer M. J Polym Sci, Polym Chem 1974;12:2821.
Zerfa M, Brooks BW. J Appl Polym Sci 1997;65:127.
Kiparissides C, Daskalakis G, Achilias DS, Sidiropoulou E. Ind Engng Chem Res 1997;36:1253.
Ugelstad J, Mork PC, Dahl P, Rangnes P. J Polym Sci 1969;C27:49.
Peggion E, Testa F, Talamini G. Makromol Chem 1964;71:173.
Suenaga Y, Akimoto A. Colloids Surf Phys Engng Aspects 1999;153:321.
Omi S, Shiyama E, Sakurai K, Yoshimoto H, Iso M, Nakano A, Nakamura M. Polym Int 1993;30:271.
Forcolin S, Marconi AM, Ghielmi A, Butte A, Storti G, Morbidelli M. Plast Rubber Compos 1999;28:109.
Saethre B, Gilbert M. Polymer 1996;37:3379.
Okieimen EF. Eur Polym J 1983;19:255.
Starnes Jr. WH. Macromolecules 1984;17:2507.
Matyjaszewski K, editor. Controlled radical polymerization, vol. 685. Washington, DC: American Chemical Society;
1997.
Saethre B. Polym Int 1998;45:222.
Braun D. Eur Polym J 1984;20:799.
Braun D. Eur Polym J 1986;22:299.
Hjertberg T, Sorvik EM. J Macromol Sci, Chem 1982;A17:983.
Hjertberg T, Sorvik EM. Polymer 1983;24:673.
Darricades NF. Macromol Sci, Chem 1986;A23:221.
Boissel J. J Appl Polym Sci 1977;21:855.
Hildebr P. J Macromol Sci, Chem 1982;A17:1093.
Guyot A. Macromolecules 1986;19:1090.
Shimizu A, Otsu T. Kogyo Kagaku Zasshi 1964;67:966.
Mitani K, Ogata T, Awaya H, Tomari Y. J Polym Sci, A-1 1975;13:2813.
Liebman SA, Ahistron DH, Starnes WH, Schilling FC. J Macromol Sci, Chem 1982;A17:935.
2052
[64]
[65]
[66]
[67]
[68]
[69]
[70]
[71]
[72]
[73]
[74]
[75]
[76]
[77]
[78]
[79]
[80]
[81]
[82]
[83]
[84]
[85]
[86]
[87]
[88]
[89]
[90]
[91]
[92]
[93]
[94]
[95]
[96]
[97]
[98]
[99]
[100]
[101]
[102]
[103]
[104]
[105]
[106]
[107]
[108]
[109]
[110]
[111]
[112]
[113]

Rigo A, Palma G, Talamini G. Makromol Chem 1972;153:219.
Willbourn AH. J Polym Sci 1969;34:569.
Talamini G, Vidotto G. Makromol Chem 1962;53:21.
Starnes WH, Zaikov VG, Chung HT, Wojciechowski BJ, Tran HV, Saylor K, Benedikt GM. Macromolecules 1998;31:
1508.
Mao SC, Ohtani H, Niwa H, Nagata M. Polym J 1999;31:79.
Tavares MIB. Polym Test 1997;16:271.
Mansa JA. J Polym Sci, A-1 1972;10:179.
Crowther MW, Szeverenyi NM, Levy GC. Macromolecules 1986;19:1333.
Pham G. Makromol Chem 1974;175:945.
Fordham JWL. J Polym Sci 1959;39:321.
Gouinlock G. J Polym Sci, Polym Chem Ed 1975;13:1533.
Illers KH. Makromol Chem 1969;127:1.
Summers JW. J Vinyl Technol 1981;3:107.
Gouinlock G. J Polym Sci, Polym Chem Ed 1975;13:961.
Ballard DGM, Burgess AN, DeKoninck JM, Robert EA. Polymer 1987;28:3.
Manson JA. J Polym Sci, A-1 1972;10:179.
Soni PL, Geil PH, Collins EA. J Macrmol Sci, Chem 1981;20:479.
Natta G, Corradini P. J Polym Sci 1956;20:215.
Owen D. Degradation and stabilization of poly(vinyl chloride). London: Elsevier; 1984. p. 21.
Grassie N. Development in polymer degradation-3. Barking: Applied Science Publishers; 1981. p. 101.
Scheirs J. Polymer recycling. Chichester: Wiley; 1998. chapter 14.
Minsker KS. J Macromol Sci, Rev 1981;C20:243.
Martinetz G. J Polym Sci 1978;A12:489.
Abbas KB. J Appl Polym Sci 1973;19:2991.
Samoilov SM. J Macromol Sci, Rev 1967;C20:333.
Takemoto K. Gousei Kobunshi I Asakura Syoten 1971;315.
Burkhart RD, Zutty NL. J Polym Sci 1963;A1:1137.
Otsu T, Rai C, Kinoshita Y, Nakamachi A, Imoto M. Kogyo Kagaku Kaishi 1968;71:904.
Misono A, Uchida Y, Yamada K. Bull Chem Soc Jpn 1966;39:2458.
Matsuoka K, Takemoto K, Imoto M. Kagaku Kaishi 1965;68:1941.
Lewis FM, Walling C, Cummings W, Briggs ER, Wenisch WJ. J Am Chem Soc 1948;70:1527.
Tkachenko GV, Khomikovskii PH, Abkin AD, Medvedev SS. Zh Fiz Khim 1959;31:342.
Nakata N, Otsu T, Imoto M. J Macromol Sci, Chem 1966;1:563.
Kagiya T, Takayama S, Fukui K. Kogyo Kagaku Kaishi 1968;71:745.
Yamasaki N, Kambara S. J Polym Sci, C 1968;22:75.
Yamashita Y, Ito K, Ishii H, Hoshino S, Kai M. Macromolecules 1968;1:529.
Moffett EW, Smith RE. US Patent 2,356,871; 1944.
Matsumoto A, Ise T, Oiwa M. Nippon Kagaku Kaishi 1972;209.
Chapin EC, Ham GE, Mills GL. J Polym Sci 1961;55:S-6.
Deryabina GL, Frolov YL. Kalabina Vysokomol Soedin 1971;3A:1162.
Thompson BR. J Polym Sci 1956;19:373.
Grassie N, NcNeill IC, McLaren IF. J Polym Sci, B 1965;3:897.
Hayashi K, Otsu T. Makromol Chem 1969;127:54.
Mravel CS, Depierri WG. J Polym Sci 1958;27:39.
Thompson RB, Raines RH. J Polym Sci 1959;41:265.
Ogata Y, Minoura Y. Kogyo Kagaku Zasshi 1963;66:1710.
Graillet C, Guillet J, Guyot A. J Macrmol Sci, Chem 1974;A8:1099.
Janovic Z, Marvel CS, Diamond MJ, Kertesz DJ, Fuller G. J Polym Sci, A-1 1971;9:2639.
Talamini G, Vidoto G, Garbugio C. Chem Ind Milan 1955;47:955.
Marvel CS, Schwen R. J Am Chem Soc 1957;79:6003.

[114]
[115]
[116]
[117]
[118]
[119]
[120]
[121]
[122]
[123]
[124]
[125]
[126]
[127]
[128]
[129]
[130]
[131]
[132]
[133]
[134]
[135]
[136]
[137]
[138]
[139]
[140]
[141]
[142]
[143]
[144]
[145]
[146]
[147]
[148]
[149]
[150]
[151]
[152]
[153]
[154]
[155]
[156]
[157]
[158]
[159]
[160]
[161]
[162]
[163]
[164]
2053
Tkachenko GV, Stupen LV, Kofman LP, Kargin VA. Vysokomol Soedin, A 1967;9:2503.
Matsuoka K, Takenmoto K, Imoto M. Kogyo Kagaku Zasshi 1966;69:134.
Gilbert H. J Am Chem Soc 1956;78:1669.
McNeil IC, Straito T. Eur Polym J 1977;13:17.
Imoto M, Shimizu S. Kobunshi Kagaku 1961;18:747.
Gadzhiev TA, Razaev ZM, Madedova SG. Azerb Khim Zh 1971;75:21146R.
Nagai S, Yoshida K. Kobunshi Kagaku 1960;17:77.
Lewis FM, Mayo FR. J Am Chem Soc 1948;70:1533.
de Wide MC, Smet G. J Polym Sci 1950;5:253.
Otsuka M, Matsuoka K, Takemoto K, Imoto M. Kogyo Kagaku Zasshi 1969;72:2505.
Braun D, Thallmaier M. J Polym Sci, C 1967;16:2351.
Breitenbach JW, Edelhauser H. Ric Sci 1969;25:242.
Niwa H, Nagata M. Kobunshi Ronbunshu 1995;52:718.
Teyssie PH, Smets G. J Polym Sci 1956;20:351.
Du M, Weng ZX, Shan GR, Huang ZM, Pan ZR. J Appl Polym Sci 1999;73:2649.
Du M, Weng ZX, Shan GR, Huang ZM, Pan ZR. Eur Polym J 2000;36:1455.
Koinuma Y, Murata Y, Otsu T, Takita Y. Kobunshi Ronbunshu 1997;54:69.
Gao JG, Yang LT, Li ZT, Ren L. J Appl Polym Sci 1996;59:1787.
Schlothauer K. Polym Bull 1981;5:299.
Parker A. J Appl Polym Sci 1997;66:1603.
Luo YW, Weng ZX, Huang ZM, Pan ZR. J Appl Polym Sci 1997;64(9):1681 90.
Bao YZ, Weng ZX, Huang ZM, Pan ZR. J Appl Polym Sci 2000;77:156.
Bao YZ, Weng ZX, Huang ZM, Pan ZR. Eur Polym 2000;36:981.
Bao YZ, Weng ZX, Huang ZM, Pan ZR. J Appl Polym Sci 2000;76:868.
Smets G, Claesen M. J Polym Sci 1952;8:289.
Hayes RA. J Polym Sci 1953;11:531.
Minoura Y, Hayashi Y, Imoto M. Kobunshi Kagaku 1958;15:260.
Ravve A, Khamis JT. J Polym Sci 1962;61:185.
Rao SP, Santappa M. J Polym Sci, A-1 1968;6:95.
Mukherjee AK, Gupta A. J Appl Polym Sci 1983;28:1283.
Walsh DJ, Sham CK. Polymer 1984;25:1023.
Kennedy JP, Davidson DL. J Appl Polym Sci, Appl Polym Symp 1977;30:13.
Zhengjie PI, Kennedy JP. J Polym Sci, Part A: Polym Chem 2001;39:307.
Toman L, Spevacek J, Holler P, Lukas R. Polymer 1996;36:557.
Chapiro A, Matsumoto A. J Polym Sci 1962;57:743.
Chapiro A, Palma G. Eur Polym J 1967;3:151.
Gasparrini G, Carenza M, Palma G. J Polym Sci, Polym Lett Ed 1980;18:29.
Landler Y. J Polym Sci 1960;48:477.
Feng Y, Zhao JR, Wang Q, Li M, Chen XF. J Appl Polym Sci 2000;75:475.
Goto A, Fukuda T. Macromolecules 1997;30:4272.
Georges MK, Veregin RPN, Kazmaier PM, Hamer GK. Macromolecules 1993;26:2987.
Wang JS, Matyjaszewski K. J Am Chem Soc 1995;117:5614.
Sawamoto M, Kato M, Kamigaito M, Higashimura T. Macromolecules 1995;29:1721.
Mayadunne RTA, Rizzardo E, Chiefari J, Krstina J, Moad G, Postma A, Thang SH. Macromolecules 2000;33:243.
Otsu T, Matsumoto A. Adv Polym Sci 1998;136:75.
Endo K, Shiroi T, Murata K. J Polym Sci, Part A: Polym Chem 2001;39:145.
Paik HJ, Gaynor SG, Matyjaszewski K. Macromol Rapid Commun 1998;19:47.
Nakai T, Kawaoka H, Okawara M. Bull Chem Soc Jpn 1969;42:508.
Nakagawa T, Hopfenberg HB, Stannett V. J Appl Polym Sci 1971;15:231.
Huskic M, Roha M, Harwood HJ, Sebenik A. Polym Int 1996;40:227.
Guan JJ, Yang WJ. J Appl Polym Sci 2000;77:2569.
2054
[165]
[166]
[167]
[168]
[169]
[170]
[171]
[172]
[173]
[174]
[175]
[176]
[177]
[178]
[179]
[180]
[181]
[182]
[183]
[184]
[185]
[186]
[187]
[188]
[189]
[190]
[191]
[192]
[193]
[194]
[195]
[196]
[197]

Fujiwara H, Ishida T, Taniguchi N, Wada S. Polymer 1999;42:197.
ElNesr EM, Dessouki AM, AbdelBary EM. Polym Int 1998;46:150.
Yoshikawa M, Tsubouchi K. J Membr Sci 1999;158:269.
Guyot A, Michel A. J Appl Polym Sci 1969;13:911.
Fujiwara H, Kimura K, Mori H, Goto K. Polym J 1981;13:927.
Laverty JJ, Gardlund ZG. J Polym Sci, Polym Chem Ed 1977;15:2001.
Kita Y, Ueda A, Harada T, Tanaka M, Nagai S. Chem Express 1986;1:543.
Furukawa J. Angew Makromol Chem 1967;1:92.
Laverty JJ, Gardlund ZG. ACS Polym Prepr 1974;15:306.
Laverty JJ, Gardlund ZG. J Appl Polym Sci 1981;26:3657.
Braun D, Fischer M, Hellmann GP. J Polym Sci 1996;37:3871.
Morton M. Anionic polymerization: principles and practice. New York: Academic Press; 1983.
Jisova V, Kolinsky M, Lim D. J Polym Sci, A1 1970;8:1525.
Jisova V, Kolinsky M, Lim D. J Polym Sci, Symp 1973;42:467.
Jisova V, Kolinsky M, Lim D. J Polym Sci, Symp 1973;42:657.
Endo K, Kaneda N, Waku H. Polymer 1999;40:6883.
Crowther MW, Szevernyi NM, Levy GC. Macromolecules 1986;19:1333.
Starnes Jr. WH, Schilling FC, Plitz IM, Cais RC, Freed DJ, Hartless RL, Bovey FA. Macromolecules 1983;16:790.
Guyot A, Tho PQ. Compt Rend 1963;265:165.
Minato H, Oku M, Higosaki N. Bull Chem Soc Jpn 1970;43:500.
Elgert KF, Henschel R, Kosfeld R. Polym Bull 1983;9:423.
Guyot A, Mordini J. J Polym Sci 1971;C33:65.
Benedikt GM, Cozens RJ, Goodall BL, Phodes L, Bell MN, Kemball AC, Starnes WH. Macromolecules 1997;30:10.
Yamazaki N, Sasaki K, Kambara S. J Polym Sci 1964;B2:487.
Yamazaki N, Sasaki K, Kambara S. Kogyo Kagaku Zasshi 1965;68:881.
Yamazaki N. Prog Polym Sci, Jpn 1971;2:171.
Misono A, Uchida Y, Yamada K, Saeki T. Bull Chem Soc Jpn 1968;41:2995.
Misono A, Uchida Y, Yamada K. Bull Chem Soc Jpn 1967;40:2366.
Ravuvaev GA. Dokl Akad Nauk 1965;160:1093.
Matsukawa T, Kiba R, Ikeda T. Japanese Patent 08,208,736; CA 1996;125:276,902.
Taeji K, Uozumi T, Soga K. Polym Prepr Jpn 1995;42:2.
Coevoet H, Cramail H, Deffieux A. Macromol Chem Phys 1996;197:855.
Stockland Jr. RA, Jordan RF. J Am Chem Soc 2001;122:6315.

3

Загружено:

Сведения о документе

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

3

Загружено:

Авторское право:

Доступные форматы

Prog. Polym. Sci.

Synthesis and structure of poly(vinyl chloride)

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

4.3. Termination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2032

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

of interest to be able to synthesize PVC consisting of an exclusively head-to-tail structure. Ionic

2. Radical polymerization reactivity of VC

3. Radical polymerization methods of VC

Fig. 1. Structure and bond dissociation energy of PVC.

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

Reactivity towards methyl radical

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

The values in parenthesis indicate relative rate constants.

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

3.3. Suspension polymerization

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

4. Elemental reactions of radical polymerization of VC and polymer structure

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

Fig. 4. Defect structures of PVC.

Numbers in parenthesis are simulation results.

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

Fig. 5. Head-to-tail and head-to-head addition of VC.

Number of h h units per 1000 monomer units.

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

Fig. 6. Formation of C1 branch in the polymerization of VC.

Since VC is classified as a non-conjugated vinyl monomer, 1 3% head-to-head addition takes place

Fig. 7. Formation of allylic chloride at chain end in the polymerization of VC.

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

Fig. 8. Formation of C4 and C2 branches.

Number of labile chlorine atoms per 1000 monomer units.

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

Fig. 9. Chain transfer reaction to VC in the polymerization of VC.

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

5. Characterization and properties of PVC

Chemical shift (ppm, TMS)

Triad: methine resonance

Tetrad: methylene resonance

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

Ethylene 1000 atm.

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

6.3. Copolymerization with non-conjugated vinyl monomers

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

7. Synthesis of graft and block copolymers

Fig. 11. Synthesis of graft copolymer of PVC and poly(IB).

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

Fig. 12. Synthesis of VC/2CP-g-poly(IB).

Fig. 13. Formation of polymer radical by g-irradiation.

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

Fig. 14. Synthesis of graft copolymer of PVC containing St or MMA segment.

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

Fig. 16. Graft copolymerization of MMA using PVC-n PX macroinitiator.

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

Fig. 17. Reaction of PVC SR under UV irradiation.

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

Fig. 18. Synthesis of PVC PEG block copolymer.

Similarly, block copolymers consisting of PVC-b-polyurethane-b-PVC having high impact strength

K. Endo / Prog. Polym. Sci. 27 (2002) 20212054

cyclohexyl methacrylate) and St-b-Bd-g-MMA as compatibilizers in PSt/PVC blends of polystyrene

8. Polymerization of VC using anionic catalysts