Infrared Studies of 1,2- and <i>trans</i> 1,4-Structure of Polybutadiene and Butadiene--Styrene Copolymers Polymerized at Various Temperatures

Hart, Edwin J.; Meyer, A. W.

doi:10.1021/ja01174a023

Cited by 47 publications

(11 citation statements)

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“…It seems unlikely from the information available on the polymers investigated and from the results of infrared studies on similar polymers by Hart and Meyer [8] that any appreciable differences in heat of polymerization would arise from differences in the relative amounts of 1 …”

Section: Discussionmentioning

confidence: 99%

Heats of copolymerization of butadiene and styrene from measurements of heats of combustion

Nelson¹,

Jessup²,

Roberts³

1952

J. RES. NATL. BUR. STAN.

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The h eats of combustion of two sam ples of polybutadi ene and four cop olvm ers of butacli ene and styrene pr epared at 50° C (122° F ), and one sample of polybutadiene an d four copolym ers po lym eri ze d at 5° C (4 1 ° F ) were m eas ured in a bomb cal ori m eter. Th e stn ene contents in th e co polymers vari ed from approximate ly 8 to 55 weigh t percent.. A va lu e for t he heat of polymerization (or co polym eri zation) was calculated for each sample by comb ining th e exper im ent al valu e for t he h eat of combustion wi th other known t hermoch e.mical data. Th e m ean valu e obtai ned for th e h eat of polymerization (-tlI-J p 0) of polybutad lene IS 17.4 kcal per mono m er unit, and the values obtain ed for t he heat of copolym eri zation var ied fr om 17.1 to 17.7 kcal p er m onom er uni t . No app er ciab le differe nce was found betweep ti? e heats of copolym eri zation of t he 5° C and 50° C pol.vmers. Th e h eat of cop oly meri za t IOn can be repr ese n~ed a s a fun ction of styr ene conte nt of t he p olym er b.v a n equatIOn of a form den ved theor etICall y by Alfrey ancl Lewis, a lthough th e co ncli t ions und er whICh th e polym ers were form ed were su ch t hat som e of the as~u m pt i o n s und erl Yinp: t h e de ri vatio n of th e equation wer e not satisfi ed..

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Section: Discussionmentioning

confidence: 99%

Heats of copolymerization of butadiene and styrene from measurements of heats of combustion

Nelson¹,

Jessup²,

Roberts³

1952

J. RES. NATL. BUR. STAN.

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“…Treumann and Wall (238) have applied the infrared spectrometric method to the quantitative determination of the butadiene units which have undergone 1,2addition in polymers and copolymers of butadiene. Hart and Meyer (100) show that the infrared spectrometer is not only valuable in determining the 1,2-addition but can also measure the trans-1,4 structure of these polymers. Hampton (99) extended the work still further and was able to determine the quantity of cis-1,4 addition and also the amount of combined styrene in GR-S synthetic rubbers.…”

Section: Unvulcanized Rubbermentioning

confidence: 99%

Natural and Synthetic Rubbers

Bekkedahl¹

1950

Anal. Chem.

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“…Polymers may also be examined ' as thin films, molded in optically flat molds, or deposited from solution. In comparison with carbon disulfide solutions, the °Results reported by Hart and Meyer (6). % 1,2 and % trans based on octene standards; styrene estimated from refractive index.…”

Section: Materials Studiedmentioning

confidence: 99%

Infrared Analysis of Low Temperature Polymers

Hampton¹

1949

Anal. Chem.

135

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Because of the considerable interest in methods of polymer analysis by which the amount of each type of unsaturation can be determined, this paper gives a description of the method used in obtaining the data on 1,2 and trans-1,4 addition and an extension of the method that permits determination of cis-1,4 addition and combined styrene, and gives more accurate results for 1,2 and trans-1,4 addition. MOSTof the rubberlike polymers (both natural and synthetic) are diene addition polymers or copolymers. In diene polymerization, addition may take place in several ways. With butadiene, for example, cis-1,4, trans-1,4, and 1,2 addition are all possible (Figure 1). With substituted butadienes, such as isoprene, there is the additional possibility of 3,4 addition. (Resonance considerations, 5, indicate that addition will normally be "head to tail.") Natural rubber is polyisoprene, that is all, or nearly all, in the cis-1,4 configuration. Balata is inms-1,4polyisoprene. Synthetic polyisoprene, on the other hand, is a random mixture of at least three of the possible configurations and does not have the desirable physical properties of either rubber or balata. Ordinary GR-S contains a random mixture of styrene units and the three possible types of butadiene units. Recently Hart and Meyer have shown ( 6) that, when butadiene polymers are prepared at low temperatures, the addition of the butadiene units is preponderantly trans-1,4. Low temperature butadiene polymers have also been showrn to have significantly improved (15,19) physical properties.Accordingly, there has been considerable interest in methods of polymer analysis by which the amount of each type of unsaturation can be determined. The present paper describes the method used to obtain the data for 1,2 and trans-1,4 addition, as previously reported (ß), and an extension of that method which permits the determination of cis-1,4 addition and combined Table I.

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Infrared Studies of 1,2- and trans 1,4-Structure of Polybutadiene and Butadiene--Styrene Copolymers Polymerized at Various Temperatures

Cited by 47 publications

References 1 publication

Heats of copolymerization of butadiene and styrene from measurements of heats of combustion

Heats of copolymerization of butadiene and styrene from measurements of heats of combustion

Natural and Synthetic Rubbers

Infrared Analysis of Low Temperature Polymers

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