Infrared determination of carboxyl and hydroxyl contents of functionally terminated polybutadienes

Tompa, Albert S.

doi:10.1021/ac60311a057

Cited by 9 publications

(6 citation statements)

References 7 publications

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“…7,36 The characteristic peaks at 730, 912, and 965 cm −1 corresponded to the cis-1,4 structure (cis-1,4), the 1,2-vinyl structure (1,2-vinyl), and the trans-1,4 structure (trans-1,4), respectively. 37,38 The intensities of the characteristic peaks of cis-HTPB and BR-9000 at 730 cm −1 are much larger than those of I-HTPB, which indicates that cis-HTPB contains a higher content of the cis-1,4 structure. According to the Lambert−Beer law, the relative contents of the three microstructures can be quantified by the following equation 39 (2)…”

Section: Effect Of Oxidative Cracking Process On Thementioning

confidence: 97%

Preparation of Hydroxyl-Terminated Polybutadiene by the Pyrolysis Method and Its Application in Polyurethane

Meng,

Sang,

Chang

et al. 2024

ACS Appl. Polym. Mater.

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Hydroxyl-terminated polybutadiene with a high cis-1,4 content (cis-HTPB) was prepared by direct oxidative cracking of cis-polybutadiene rubber (BR-9000) with periodic acid (H 5 IO 6 ). The results showed that the cis-HTPB structure contained more than 95% of the cis-1,4 structure, and the glass transition temperature (T g ) was as low as −104.7 °C, exhibiting excellent low-temperature resistance. In addition, the optimal reaction conditions were determined by optimizing the preparation process to achieve efficient and controllable preparation of cis-HTPB. Finally, polyurethane elastomers were prepared based on cis-HTPB, and the mechanical properties of the elastomers were improved by optimizing the formulation design. The tensile strength of the elastomers was as high as 1.84 MPa and the elongation at break was 721%, which can meet the requirements of different applications. This study provides a simpler strategy for the oxidative degradation of cis-polybutadiene rubber to prepare high-value-added cis-HTPB and also provides experience for the functionalization of other types of polyolefin rubbers.

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Section: Effect Of Oxidative Cracking Process On Thementioning

confidence: 97%

Preparation of Hydroxyl-Terminated Polybutadiene by the Pyrolysis Method and Its Application in Polyurethane

Meng,

Sang,

Chang

et al. 2024

ACS Appl. Polym. Mater.

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“…In the presence of a catalytic amount of DMF, the quantitative conversion of polymer 1 to polymer 2 is achieved in minutes. The reaction progress is followed with FTIR spectroscopy 4,15 by monitoring the shift in the carbonyl C¼ ¼O peak from 1709 cm À1 (polymer 1) to 1800 cm À1 (polymer 2), (Fig. 2).…”

Section: Chemical Derivatizationmentioning

confidence: 99%

“…Carboxyl-terminated polybutadiene (CTPB, polymer 1) liquid polymers are widely used as elastomeric binders in nondetonable solid propellant formulations, [1][2][3][4] and as additives to epoxy resins to increase toughness. [5][6][7][8][9][10] The final mechanical properties of these systems are directly correlated to the carboxyl (ACO 2 H) concentration in the CTPB.…”

Section: Introductionmentioning

confidence: 99%

“…The procedure is very time consuming and tedious, 13 and involves eluent mixtures containing carbon tetrachloride; a solvent that has become expensive to purchase and creates highly undesirable waste streams. A number of variations of this method have also been reported 4,15 including a more recent example containing nuclear magnetic resonance (NMR) spectroscopic analysis. 11 The difficulty in direct detection of carboxyl groups in CTPB compelled us to explore new, more practical, approaches for assessing their abundance in high molecular weight polymers.…”

Section: Introductionmentioning

confidence: 99%

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Derivatization of carboxyl‐terminated polybutadiene for determining relative functionality distribution

Straessler¹,

Li²,

Parry³

et al. 2011

J of Applied Polymer Sci

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A new and highly efficient method for determining relative carboxyl group distribution in carboxyl-terminated polybutadiene has been developed using practical synthetic and analytical techniques. Using oxalyl chloride, samples of carboxyl-terminated polybutadiene were rapidly transformed to acid chlorides that were then chemically derivatized with benzyl alcohol, 4-nitrobenzyl alcohol, and 3,5-dinitrobenzyl alcohol. This provided quick and quantitative conversion to the corresponding benzyl ester derivatives. Each new derivative was fully characterized by nuclear magnetic resonance and Fourier transform infrared spectroscopy. The benzyl ester modified polymers were investigated in detail to determine their relative carboxyl group concentrations. To do this, gel permeation chromatography combined with ultra violet/refractive index dual detection was employed. The 4-nitrobenzyl ester, having the highest extinction factor at 270 nm provided the best UV data for analysis. The ultra violet/refractive index data of four separate polymer samples were plotted as a function of molecular weight. The data were compared with a theoretical plot (carboxyl group ¼ two for all molecular weights) to illustrate the relative carboxyl concentration over the entire molecular weight range. Supplemental characterization of the 4-nitrobenzyl modified polymer was carried out using matrix-assisted laser desorption ionization coupled with time of flight mass spectrometry.

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“…A linear calibration curve was plotted against butanol in a binary system: ethylacetate-CC1,. A solution of polybutadiene in carbon disulfide and a band a t 3615 cm-l were used [180]. LAW [42] found the content of HG in fractionated oligobutadienes from the peak height a t 3620cm-l in CCI,.…”

Section: ! -------------mentioning

confidence: 99%

Determination of hydroxyl groups in polymers. Review

Boiko¹,

Grischenko²

1985

Acta Polymerica

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The analysis of hydroxyl groups in polymers is reviewed. Recent achievements of chemical, physico-chemical and physical methods for the determination of hydroxyl groups and their differentiation by reactivity have been examined. Particularly, infrared spectroscopy and nuclear magnetic resonance used for this determination are considered. Die Bestimmung yon Hydroxylgruppen in Polymeren. FortschrittsberichtIn dem Bericht werden neuere Entwicklungen chemischer, physikalisch-chemischer und physikalischer Methoden zur Bestimmung von Hydroxylgruppen und ihrer Differenzierung hinsichtlich der Reaktivitat dargestellt. Insbesondere wird die Anwendung der Infrarotspektroskopie und der magnetischen Kernresonanz behandelt. Onpeaenenue zur3powuJabnwx zpynn 8 nom.wepax. O630p 0 6 3 0~ IIOCBfiQeH aHaJIH8y rHAPOKCHnbHhIX rpynn B IIOJIEiMepaX. PaCCMOTpeHbI IlOCJIeAHlle AOCTEiXeHllfi XHMH9eCKHX, @H3HHO-XHMH9eCHHX Ei @H3H4eCKHX MeTOAOB KOJIEi9eCTBeHHOrO OIIpeAeneHElH I' HApOKCHJIbHbIX I'pyIIII H HX AH@-@epeHqEi~EiEinOpeaKqHOHHOltCnOCO6HOCTH. ~C O 6 O~B H l l M~H H~~~~j I~H O H H @~~K~~C H O~C I I~K T~O C MarHHTHOMY pe30HaHCy. Chemical methods of analysisChemical methods a r e simple a n d accessible, t h e y do not require special equipment a n d expensive instruments. At t h e same t i m e t h e y a r e rather time-consuming a n d require considerable amounts of t h e substance t o be analyzed. These methods can mainly give quantitative information. If t h e differentiation of HG is necessary, they become much more time-consuming. Recently t h e effective methods of chemical analysis have appeared which enable HG t o b e determined rapidly a n d exactly enough. Acylation of HG is most widely used, its application for polymers is detailed in t h e handbooks o n polymer analysis. The classical acylation procedure [27, 281 uses acetic (AA) or phthalic anhydride (PA) in pyridine solution, t h e latter being t h e solvent and catalyst of t h e reaction. T h e use of propionic [29], succinic [30--321, nitrobenzoic [33], osulfobenzoic [34], nitrophthalic [35]anhydrides for t h e same purpose is described. As a rule, primary a n d secondary HG a r e fully acylated within 1 t o 2 h a t 100 t o 115°C. Pyromellitic dianhydride (PMDA) [36-381 is more effective. It has as high activity as AA a n d does not interact with aldehyde groups a n d phenolic HG which is characteristic of PA. Dimethylsulfoxide (DMSO) is especially recommended as a solvent [37].T o acylate HG, more active acyl chlorides can b e used. BOIKO and GRISHCHENKO:Deterinination of liydroryl groups in polymers. Review Acta Polymcrica 36 (1985) Nr. 9

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Infrared determination of carboxyl and hydroxyl contents of functionally terminated polybutadienes

Cited by 9 publications

References 7 publications

Preparation of Hydroxyl-Terminated Polybutadiene by the Pyrolysis Method and Its Application in Polyurethane

Preparation of Hydroxyl-Terminated Polybutadiene by the Pyrolysis Method and Its Application in Polyurethane

Derivatization of carboxyl‐terminated polybutadiene for determining relative functionality distribution

Determination of hydroxyl groups in polymers. Review

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