Thermal degradation of vinyl polymers I—Thermal degradation of polystyrene-poly(α-methylstyrene) mixtures

Richards, D. H.; Salter, David A.

doi:10.1016/0032-3861(67)90017-1

Cited by 58 publications

(17 citation statements)

References 29 publications

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“…where rJ, (a+bi) and (a-bi) are roots of the cubic expression in the denominator of the term on the right in eq (14), as found by Cardano's method, [28], I and the coefficients are:…”

Section: Dq =K3r(t)p(t)q(t) Dt V(t)mentioning

confidence: 99%

“…A recent major study [14,15,16] of the decomposition of polystyrene utilized poly (a-methylstyrene) [14] as catalyst for the polystyrene degradation, anionically '" prepared polystyrene with specifically formed thermolabile structures [15] and carbon 14 labeled polystyrene [16]. The results of this very extensive experimentation raise many points but the most interesting aspects are: (1) the confirmation of short zip lengths of approximately 3, (2) 1.2 intermolecular transfer steps per radical formed, (3) strong evidence for termination by combination with the possibility that the cage effect may tend to make termination kinetically first order.…”

Section: Introductionmentioning

confidence: 99%

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Pyrolysis of anionic and thermally prepared polystyrenes

Wall¹,

Straus²,

Florin³

et al. 1973

J. RES. NATL. BUR. STAN. SECT. A.

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The changes in molecular weights, their distributions, and initial rates have been measured, for a series of polystyrenes prepared by thermal and anionic procedures. The information obtained and previous results can be explained to a very large extent by a kinetic chain decomposition comprised of competing end and random initiation, depropagation, intra-and intermolecular transfer and termination by combination.Key words: Anioni c polysl yre ne; molec ular weight distributions; molecular weights; thermal poly· s t yre :1 e; polymer ; pc ! ys t y !"e~e de g!"2da t!op. ; pyrolys is; thermolys is.

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“…where rJ, (a+bi) and (a-bi) are roots of the cubic expression in the denominator of the term on the right in eq (14), as found by Cardano's method, [28], I and the coefficients are:…”

Section: Dq =K3r(t)p(t)q(t) Dt V(t)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Pyrolysis of anionic and thermally prepared polystyrenes

Wall¹,

Straus²,

Florin³

et al. 1973

J. RES. NATL. BUR. STAN. SECT. A.

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“…First order kinetics was used in this work because random scission was assumed to be negligible. [8,15,20,29,35,45,[50][51][52][53][54] as shown in Table 6 . • • [20] up to 180 min.…”

mentioning

confidence: 99%

Thermolysis of polystyrene

Simard

Kamal

Cooper

1995

J of Applied Polymer Sci

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Styrene was r EK:overed trom polystyrene (molecular weight of 138 OO~) by thermolysis in a nitrog,en atmosphem .at templ3ratures between 368°C and 407°C. The' results wc~n9 inaepElndent of thE~ initial weight of polystyrene which was varied between ~30 and 480 grar~s. Up to 70% of the polystyrene was converted to styrene. The styrene yield increased with temp€;'rature. At higher temperatures, the residue left il1 thE! reactor Gonsisted mainly of styrene monomer, dimer and trimer (MW of 190). The maximum rate constant of volatile production was found to fit a first order modal. The activation energy obtained was 166.5 kJ/mol, which is in accordanco with literature values .•

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“…Acco rding to th ese rate data, the hi ghe r molecul ar we ight polymers offer no feature not co ntained in eq (1) a nd its limitin g form eq (4) but the zip length is revised upward .…”

Section: Nowmentioning

confidence: 97%

“…considerably (table 1) [1][2][3][4][5][6]. I The availability of monodisperse poly-(alpha-methylstyre ne) of higher molecular weight up to five million, as well as deuterated analogs, led us to reinvestigate the kineti c relations in the hope of resolving disagreements.…”

Section: • Based On a Phd Thesis Submitted By Roestamsjah To Americmentioning

confidence: 99%

Pyrolysis of monodisperse poly-alpha-methylstyrene

Roestamsjah¹,

Wall

Florin

et al. 1978

J. RES. NATL. BUR. STAN.

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Pyrolysis of monodisperse poly-a-methylstyrene of wide molec ular weight range (M:25,000-5,OOO,OOO) was studied isothermally under vac uum in the tempe ra ture range 240-280 0c. Thermogravime tric a nal ysis was used for measuring the rate of degradation, and gel permeation chromatography for analyzing the molec ular weight and molec ular weight d istribution as a func tion of conve rsion.The initial rate of monodisperse poly-a -methylstyrenes, and the deuterated sampl es (poly-a-trid eut erometh yl-(3, (3-dide uterostyrene) inc reases with increasing molecular weight. At mol ec ular weight highe r than 1 X lOS , the initial rate continues to inc rease almost linearly instead of bei ng co nstant as concluded fro m earli e r work . The molec ular weight distribution ratio, MJMn, inc reases as a fu nction of conve rsion a nd approaches the most probable distribution . The results conform to a degradati on mechanism with random initia ti on.The c urves of initial rate as a fun ction of molecular weight lead to higher zip le ngths than previous estimates. Attempts at simultaneous estimation of zip le ngth and transfer constant from the rate and molecular weight data le d to inconsistent results. U the variation of te rmination ra te with molecular weight plays a role, thi s variation must be less than that de rived naively from melt viscosity. Bimodal molecular weight distributions were not found .

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Thermal degradation of vinyl polymers I—Thermal degradation of polystyrene-poly(α-methylstyrene) mixtures

Cited by 58 publications

References 29 publications

Pyrolysis of anionic and thermally prepared polystyrenes

Pyrolysis of anionic and thermally prepared polystyrenes

Thermolysis of polystyrene

Pyrolysis of monodisperse poly-alpha-methylstyrene

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