Polybutadiene Vulcanization. Chemical Structures from Sulfur-Donor Vulcanization of an Accurate Model

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Abstract
Only 1,5-polyenes with three or more double bonds crosslinked in a curing recipe with 2-benzothiazolyl-N-morpholyl disulfide (BMD) or bis(dimethylthiocarbamyl) disulfide (TMTD) as the crosslinking agents. A suitable chemical model for 1,4-polybutadiene (PB) is cycIohexadeca-1,5,9,13-tetraene (CHT). The preparation of CHT is described. The crosslink density of a CHT vulcanizate agreed well with the chemical crosslink density of cis- 1,4-polybutadiene rubber, similarly cured. The crosslink density of the CHT vulcanizate was measured by isolating, identifying, and weighing the various crosslink structures. The non-crosslink structures of the network and the extranetwork structures were also identified and quantified. Various amounts of curative fragments attach to the PB network structure, as exemplified by the amount of curative fragments attached to CHT. About 16% of the lauric acid attached to the network structure. The curing agent, BMD, divided into three fragments: 2-thiobenzothiazole, morpholyl, and thio groups. About 67% of the thio groups, 25% of the 2-thiobenzothiazole groups, and about 6% of the morpholyl groups attached to the network structure. About 57% of the thio groups formed crosslinks. The main crosslink structure was 85% bis(allylic) monosulfide and 15% bis(allylic) disulfide. The length of the disulfide crosslink was only 60 pm greater than the length of the monosulfide crosslink. This compares with the 0.2 nm length of a sulfur atom. Very little cis-trans isomerization occurred in the unreacted CHT as a result of vulcanization. This indicated almost no cis-trans isomerization of unreacted segments of PB in PB vulcanizates. However, extensive cis-trans isomerization occurred in the CHT that crosslinked, which indicates that cis-trans isomerization in PB vulcanizates is confined to the reaction sites of the PB molecules. The configurational isomerism was essentially exclusively cis-to-trans. No trans-to-cis isomerism was observed. The insoluble solid in the vulcanizate was a mixture of cadmium bis(2-thiobenzothiazole), cadmium sulfide, and morpholinium sulfate. Material balances of the reaction products with the curatives showed that 90% by weight of the reaction products of the vulcanization of CHT were identified. The hydrogen transfer balance showed that CHT is the main hydrogen donor during crosslink formation. The morpholyl group from BMD was the main hydrogen acceptor and formed morpholine and morpholinium sulfate. Escape of volatile substances during vulcanization of PB resulted in much reduced crosslinking. For this reason, a hydraulic reactor for vulcanization of liquids, such as CHT, without loss of volatile substances was described.

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