Chlorinated Polyethylene. II. Mechanisms of Chlorination

Quenum, Bienvenu-Magloire; Berticat, Philippe; Vallet, Guy

doi:10.1295/polymj.7.287

Cited by 15 publications

(20 citation statements)

References 12 publications

(25 reference statements)

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“…5 Those chlorinated at saturation level (73-% Cl2): i.e., branched polyethylene samples (type Ila) and linear polyethylene samples (type Ila') photochlorinated at 20°C in carbon tetrachloride (CCl4) during 4-6-8 hr; 7 branched polyethylene samples (type lib) and linear polyethylene samples (type Ilb')photochlorinated during 4 hr at 20°C; 40°C; 60°C 8 …”

Section: Methodsmentioning

confidence: 99%

“…are responsible for almost the whole chlorine content value 5 and the thermal CPE samples still keep crystallinity. When the poly(vinyl chloride) (PVC) triads am ( -CH2-C!…”

Section: Melting Points and Second-order Transitionsmentioning

confidence: 99%

“…When the thermal chlorination proceeds, the crystallinity of the polyethylene samples (branched or linear) is rapidly destroyed (Table I); the numerous -CC12-units appearing during the first chlorination step 5 can be regarded as responsible for this. But in the photochlorination process, the CPE samples keep some crystallinity up to a high chlorine-content value by weight; the crystallites disappearance is completed only beyound the 67.5-% chlorine content value, as proved by dynamic mechanical properties studies; the 67.5-73-% photochlorinated CPE samples are amorphous ones, although they are hard and brittle owing to the presence of dichloro and trichloroethylene units.…”

Section: Melting Points and Second-order Transitionsmentioning

confidence: 99%

“…:!Cl-CH2-) and /3m ( -CHC1-C! !2-CHC1-) appear from the 24-% Cl2 value) the chlorination mechanism becomes a random one, 5 which destroys the crystallinity of the thermal CPE samples. The numerous -CC12-units along with the few Polymer J., Vol.…”

Section: Melting Points and Second-order Transitionsmentioning

confidence: 99%

“…The CPE samples used for the above studies were, generally, commercial ones supplied without the specific conditions of their preparation which are required 5 to correlate microstructure and properties. In addition, their microstructural characterizations have been made only with infrared analysis, which is not sufficient.…”

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Chlorinated Polyethylene. III. Relationships of Microstructure and Thermal Properties

Quenum

Berticat

Vallet

1975

Polym J

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ABSTRACT:The thermal properties (viz., second-order transitions, melting points, dynamic and isothermal heat behaviour) of chlorinated polyethylene (CPE) samples are studied here. Thermomechanical analysis (TMA), differential thermal analysis (DTA), and thermogravimetric analysis (TGA) results are listed together to correlate the thermal properties and the microstructure of CPE samples, of various chlorine contents by weight, produced from thermal chlorinated or photochlorinated linear and branched polyethylene samples. The dehydrochlorination rate of a CPE sample is shown to be strongly dependent on its microtacticity up to a 56-61-% chlorine content by weight value· Beyond this 56-61-%Cb interval the microtacticity influence is screened by the steric hindrance introduced by the err (-CHz-C!:!Cl-CCb-or -CHCl-C!:!Cl-CCb-), an -CHCl-C!:!Cl-CHCl-or -CHz-C!:!Cl-CHCl-), and [3n (-CHCl-C!:!z-CCb-) structures. At the saturation level (73-% Clz), the higher a CPE ratio, nb CHCllnb CHz, is, the lower is its maximum dehydrochlorination rate. When its ratio, nb 2 CHCllnb CHz, is less than 4, a saturated (73%) CPE sample has a unique global dehydrochlorination activation energy (Ea); when this ratio stands between 4 and 6, there are two global dehydrochlorination E.. The structures which could be regarded as responsible for these different global Ea and the second-order transitions are specified.KEY WORDS Chlorinated Polyethylene I Thermomechanical Analysis I Differential Thermal Analysis I Thermogravimetric Analysis I Second-Order Transitions I Maximum Dehydrochlorination Rate I Very few studies have been published about the thermal properties of CPE. The first one, made by Oswald and Kubu 1 dealt with glass-transition temperatures (Tg)· Era and Lindberg 2 showed the effect of heat treatment on crystallinity. Abu I sa 3 studied the dechlorination mechanism and the effect of added antimony oxide on the rate of dehydrochlorination. Saglio, et at., 4 studied the degradation of saturated (73 %) CPE and showed that fibers of saturated CPE can be used as a carbon fiber precursor.relate their microstructure and thermal properties in this paper.In carbon backbone high polymers secondary transitions can be detected besides the main second-order transition, i.e., the glass-transition temperature (T g), and the main first-order transition, i.e. the solid-liquid-transition or the melting temperature. They are:(1) The secondary second-order transitions occuring, generally, at temperatures less than Tg. They are related to the motion of short segments of the polymer's backbone (viz., branchings, substituants, "crankshaft" or "kink" mechanisms11'12) related to motions in the amorphous or crystalline phase.The CPE samples used for the above studies were, generally, commercial ones supplied without the specific conditions of their preparation which are required 5 to correlate microstructure and properties. In addition, their microstructural characterizations have been made only with infrared analysis, which is not sufficient.Since we have...

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Section: Methodsmentioning

confidence: 99%

“…are responsible for almost the whole chlorine content value 5 and the thermal CPE samples still keep crystallinity. When the poly(vinyl chloride) (PVC) triads am ( -CH2-C!…”

Section: Melting Points and Second-order Transitionsmentioning

confidence: 99%

Section: Melting Points and Second-order Transitionsmentioning

confidence: 99%

Section: Melting Points and Second-order Transitionsmentioning

confidence: 99%

mentioning

confidence: 99%

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Chlorinated Polyethylene. III. Relationships of Microstructure and Thermal Properties

Quenum

Berticat

Vallet

1975

Polym J

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Kinetics of the Solid-State Chlorination of High-Density Polyethylene

Stoeva¹,

Vlaev

2002

Macromol. Chem. Phys.

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Chlorocarboxylation of polyethylene. I. Preparation and structure of chlorocarboxylated polyethylene

Joshi

Natu

1986

Angew. Makromol. Chem.

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Chlorocarboxylated polyethylene (CCPE) is produced by simultaneous reaction of chlorine and maleic anhydride (MA) with polyethylene (PE). Low concentrations of the carboxyl groups in CCPE have been quantitatively estimated by dye interaction method and non-aqueous titration procedure. IR spectroscopic data are presented for the structural characterization of CCPE. During chlorocarboxylation, maleic anhydride can be anchored to the backbone chlorinated PE (CPE) chain as a chlorinated single monomeric unit without forming any graft copolymer of short branches. ZUSAMMENFASSUNG:Chlorcarboxyliertes Polyethylen (CCPE) wird durch simultane Reaktion von Chlor und Maleinsiiureanhydrid mit Polyethylen hergestellt. Niedrige Konzentrationen der Carboxylgruppen in CCPE sind quantitativ mit Hilfe der Farbstoffwechselwirkungsmethode und nichtwwriger Titrationen bestimmt worden. IR-spektroskopische Daten sind ftkr die Strukturcharakterisierung angegeben. Bei der Chlorcarboxylierung kann Maleinsilureanhydrid als eine einfache Monomereinheit ohne Entstehung von Pfropfcopolymeren an die Kette aus chloriertem PE (CPE) addiert werden.

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Chlorinated Polyethylene. II. Mechanisms of Chlorination

Cited by 15 publications

References 12 publications

Chlorinated Polyethylene. III. Relationships of Microstructure and Thermal Properties

Chlorinated Polyethylene. III. Relationships of Microstructure and Thermal Properties

Kinetics of the Solid-State Chlorination of High-Density Polyethylene

Chlorocarboxylation of polyethylene. I. Preparation and structure of chlorocarboxylated polyethylene

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