WO2014186571A1 - Matériaux à base de benzoxazole pour des applications d'accélérateur de vulcanisation - Google Patents

Matériaux à base de benzoxazole pour des applications d'accélérateur de vulcanisation Download PDF

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WO2014186571A1
WO2014186571A1 PCT/US2014/038191 US2014038191W WO2014186571A1 WO 2014186571 A1 WO2014186571 A1 WO 2014186571A1 US 2014038191 W US2014038191 W US 2014038191W WO 2014186571 A1 WO2014186571 A1 WO 2014186571A1
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rubber
alkyl groups
benzoxazole
sulfenamide
sulfur
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PCT/US2014/038191
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English (en)
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Yi Pang
Guangzhuo RONG
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The University Of Akron
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles

Definitions

  • One or more embodiments of the present invention relate to the use of benzoxazole sulfenamide compounds in rubber compositions such as cure systems for vulcanizing rubber and asphalt and polymer compositions.
  • Vulcanization is a chemical process that converts a soft and tacky rubber into harder and more durable materials with greatly improved resistance to wear and abrasion.
  • the economically most important method remains to be the sulfur vulcanization in the presence of various vulcanization accelerators.
  • Thiazoles such as mercaptobenzothiazole (MBT) and its sulfenamide derivatives are among the accelerators of highest economic importance.
  • MBT mercaptobenzothiazole
  • the crosslink density is increased to a certain level within the rubber species, which is accompanied with increasing mechanical properties.
  • the rubber system using MBT however, often exhibits weakness in terms of reversion stability, meaning that the crosslink density could decrease after passing the vulcanization optimum.
  • benzothiazole-based accelerators exhibit much lower accelerating power than and are much less active than current accelerators.
  • a first embodiment provides a method of vulcanizing rubber comprising:heating a rubber in the presence of sulfur compound and a benzoxazole sulfenamide defined by the formula:
  • Rl and R2 are each individually selected from hydrogen atoms, alkyl groups, substituted alkyl groups, and aromatic groups, or where Rl and R2 join to form an alkane or substituted alkane group.
  • a second embodiment provides a method as in the first embodiment, where the rubber is selected from the group consisting of natural rubber, polybutadiene rubbers (BR), styrene-butadiene rubbers (SBR), polyisoprene, isoprene rubbers (IR) and polychloroprene.
  • the rubber is selected from the group consisting of natural rubber, polybutadiene rubbers (BR), styrene-butadiene rubbers (SBR), polyisoprene, isoprene rubbers (IR) and polychloroprene.
  • a third embodiment provides a method as in the either the first or second embodiment, where the sulfur compound is elemental sulfur, an allotrope of sulfur, a sulfur donor, or a combination thereof.
  • a forth embodiment provides a method as in any of the first through third embodiments, where the sulfur donor is selected from the group consisting of tetramethylthiuram disulfide, tetraethylthiuram disulfide, and dithiodimorpholine.
  • a fifth embodiment provides a method as in any of the first through forth embodiments, where one of Rl or R2 is a hydrogen atom and the other may be selected from alkyl groups, substituted alkyl groups, and aromatic groups
  • a sixth embodiment provides a method as in any of the first through fifth embodiments, where the benzoxazole sulfenamide is selected from the group consisting of
  • a seventh embodiment provides a method as in any of the first through sixth embodiments, where the benzoxazole sulfenamide is defined by the formula
  • An eighth embodiment provides a method as in any of the first through seventh embodiments, where the method further comprises an activator.
  • a ninth embodiment provides a method as in any of the first through eighth embodiments, where the activator is selected from zinc compounds, steric acid, or combinations thereof.
  • a tenth embodiment provides a method as in any of the first through ninth embodiments, where the method further comprises an amine.
  • a eleventh embodiment provides a method as in any of the first through tenth embodiments, where the method further comprises a secondary accelerator.
  • An twelfth embodiment provides a method of vulcanizing rubber comprising:
  • Rl and R2 are each individually selected from hydrogen atoms, alkyl groups, substituted alkyl groups, and aromatic groups, or where Rl and R2 join to form an alkane or substituted alkane group;
  • a thirteen embodiment provides a method as in the twelfth embodiment, where the benzoxazole sulfenamide forms a complex with a zinc atom defined by the formula
  • each X is selected from an oxygen atom or a sulfur atom provided that at least one X is an oxygen atom
  • each Rl and R2 are individually selected from hydrogen atoms, alkyl groups, and subsitituted alkyl groups, or where an Rl and an R2 join to form an alkane or substituted alkane group.
  • An fourteenth embodiment provides a benzoxazole sulfenamide complex defined by the formula
  • each X is selected from an oxygen atom or a sulfur atom provided that at least one X is an oxygen atom
  • each Rl and R2 are individually selected from hydrogen atoms, alkyl groups, and subsitituted alkyl groups, or where an Rl and an R2 join to form an alkane or substituted alkane group.
  • a fifteenth embodiment provides a method of preparing an asphalt and polymer composition comprising mixing asphalt, a rubber, a sulfur compound, an activator, and a bezoxazole sulfenamide defined by the formula:
  • Rl and R2 are each individually selected from hydrogen atoms, alkyl groups, substituted alkyl groups, and aromatic groups, or where Rl and R2 join to form an alkane or substituted alkane group.
  • a sixteeth embodiment provides a method as in the fifteenth embodiment, where the rubber is selected from polybutadiene, polyisoprene or polyisobutene rubber, polychloroprene, polybutadiene, styrene-butadiene copolymers
  • a seventeenth embodiment provides a method as in the either the fifteenth or sixteenth embodiment, where the bezoxazole sulfenamide is selected from the group consisting of
  • a eighteenth embodiment provides an asphalt and polymer composition comprising an asphalt, a rubber, a sulfur compound, an activator, and a bezoxazole sulfenamide defined by the formula:
  • Rl and R2 are each individually selected from hydrogen atoms, alkyl groups, substituted alkyl groups, and aromatic groups, or where Rl and R2 join to form an alkane or substituted alkane group.
  • An nineteenth embodiment provides an asphalt cement comprising:
  • Figure 1 provides a l H NMR spectrum of benzoxazole derivatives 7, 8 and 9 in CD 3 OD.
  • Figure 2 provides a crystal structure of zinc complex 9.
  • Figure 3 provides a chart of the cure characteristic curves of compound 7 at 140°C.
  • the sample composition is shown in Table 2.
  • NR natural rubber
  • sulfur sulfur
  • Figure 4 provides a chart of the cure characteristic curves of 7 at different temperatures.
  • Figure 5 provides a chart showing the effect of cure rate on rubber sample (natural rubber: 100 Phr; sulfur: 2.4 Phr; compound 7 :0.6 Phr) in the presence of different activators at 140°C.
  • Figure 6A provides the CPMAS C NMR of cured rubber by using benzoxazole 7 as the vulcanization accelerator (cure time: 90min). The inset shows the enlarged region for 35-70 ppm.
  • Figure 6B provides the CPMAS 13 C NMR of cured rubber by using TBBS as thevulcanization accelerator (cure time: 90min).
  • the inset shows the enlarged region for 35-70 ppm.
  • Figure 6C provides the reference for assigning the chemical shifts of natural rubber for figures 6 A and 6B.
  • Figure 7A provides a chart of the effect of zinc compound 8 on the cure rate of rubber compound (100 NR + 2.4 sulfur) at 140°C.
  • Figure 7B provides a chart of the effect of zinc compound 9 on the cure rate of rubber compound (100 NR + 2.4 sulfur) at 140°C.
  • Figure 8 provides a chart showing the comparison of cure characteristic curves by using different accelerators at 140°C (using the rubber composition in the Table 2).
  • the inset shows the structure of diphenylguanidine (DPG).
  • the amount of amine (diphenylguanidine, DPG) used was 0.4 Phr.
  • Embodiments include the use of benzoxazole sulfenamide as accelerators for sulfur vulcanization.
  • benzoxazole sulfenamide is used an accelerator, a volcanized polymer may be prepared with little to no reversion.
  • benzoxazole sulfenamide revealed similar "scorch time," a desirable "delayed vulcanization.”
  • a chart of torque vs. time for benzoxazole sulfenamide cure rubber exhibits a long plateau, indicating the less danger of over-vulcanization.
  • Benzoxazole sulfenamide may also be used in asphalt and polymer compositions.
  • Vulcanization is a chemical process that converts a soft and tacky rubber into a harder and more durable material. Methods of vulcanizing rubber are detailed in "Rubber Compounding: Chemistry and Applications; Taylor & Francis, 2004, which is incorporated by reference.
  • the components used to vulcanize rubber, including the rubber itself, may be referred to as a cure system.
  • the cure system may include a rubber, a sulfur compound, and a benzoxazole sulfenamide accelerator.
  • the cure system may optionally have other components such as activators, retarders, and secondary accelerators.
  • the vulcanized rubber may be prepared by mixing the ingredients of the cure system and then heating the cure system.
  • the sulfur compound and the benzoxazole sulfonamide accelerator are the final components cure system to be add.
  • a cure system may be prepared by mixing rubber for 1 to 5 minutes, adding an activator under continued mixing for 1 to 5 minutes, and then finally added the sulfur compound and the benzoxazole sulfonamide accelerator.
  • Rubbers suitable for vulcanization with a benzoxazole sulfenamide accelerator include those rubbers with unsaturated carbon-carbon bonds. Suitable rubbers include natural rubber or synthetic rubbers. Examples of synthetic rubbers include, but are not limited to, polybutadiene rubbers (BR), polystyrene-butadiene rubbers (SBR), polyisoprene, isoprene rubbers (IR) and polychloroprene.
  • BR polybutadiene rubbers
  • SBR polystyrene-butadiene rubbers
  • IR isoprene rubbers
  • polychloroprene polychloroprene
  • Benzoxazole sulfenamide accelerators include those compounds that include a benzoxazole group connected through a sulfur atom to an amine group. Those skilled in the art will understand that a benzoxazole may be defined by the formula:
  • R1 and R ⁇ are each individually selected from hydrogen atoms, alkyl groups, substituted alkyl groups, and aromatic groups, or where R1 and R ⁇ join to form an alkane or substituted alkane group.
  • alkyl groups may include linear or branched hydrocarbons with a carbon chain length of 1 to 6 carbons.
  • alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, n-butyl, sec -butyl, isopentyl, tertpentyl, n-pentyl, sec-pentyl, tert-hexyl, n-hexyl, isohexyl, and sec-hexyl.
  • Substituted alkyl groups include groups where a hydrogen atom has been replaced with a substituent. Suitable substituents include a halogen atom (e.g. F, CI, Br), a hydroxy 1 group, an alkoxy group, or an amino group.
  • halogen atom e.g. F, CI, Br
  • the benzoxazole sulfenamide accelerator may be defined by the formula:
  • R1 and are each individually selected from hydrogen atoms, alkyl groups, substituted alkyl groups, and aromatic groups, or where R.1 and R ⁇ join to form an alkane or substituted alkane group.
  • the amine may be a tertiary amine, and both R1 and R ⁇ are each individually selected from alkyl groups, substituted alkyl groups, and aromatic groups, or where R1 and R ⁇ join to form an alkane or substituted alkane group.
  • the amine may be a secondary amine, and one of R1 or R ⁇ may be a hydrogen atom and the other may be selected from alkyl groups, substituted alkyl groups, and aromatic groups.
  • benzoxazole sulfenamide accelerator may be defined by the follow formulas
  • the amount of the benzoxazole sulfenamide accelerator used to cure rubber may be stated in Phr (parts per hundred parts rubber).
  • the cure system may include at least 0.1, in other embodiments at least 0.3, and in still other embodiments at least 0.5 Phr of a benzoxazole sulfenamide accelerator.
  • the cure system may include at most 10, in other embodiments at most 7, and in still other embodiments at most 5 Phr of a benzoxazole sulfenamide accelerator.
  • the cure system may include at about 0.1 to 10, in other embodiments about 0.3 to 7, and in still other embodiments about 0.5 to 5 Phr of a benzoxazole sulfonamide accelerator.
  • Sulfur compounds may be used to crosslink active sites, typically unsaturated carbon-carbon bonds in on the rubber.
  • Sulfur compounds suitable for vulcanization with a benzoxazole sulfonamide accelerator include elemental sulfur, an allotrope of sulfur, a sulfur donor, or a combination thereof. Examples of sulfur donors include, but are not limited to, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and dithiodimorpholine.
  • the cure system may include at least 0.1 , in other embodiments at least0.3, and in still other embodiments at least 0.5 Phr of a sulfur compound. In these other embodiments, the cure system may include at most 40, in other embodiments at most 20, and in still other embodiments at most 10 Phr of a sulfur compound. In these other embodiments, the cure system may include at about 0.1 to about 10, in other embodiments about 0.5 to about 7, and in still other embodiments about 1 to about 5 Phr of a sulfur compound.
  • An activator may be used to improve acceleration and allow the cure system to reach its full crosslinking potential.
  • Activators suitable for vulcanization with a benzoxazole sulfonamide accelerator include zinc compounds, steric acid, or combinations thereof. Examples zinc compounds include, but are not limited to, zinc oxide (ZnO) and Zn-soap.
  • the amount of activator used to cure rubber may be stated in Phr.
  • the cure system may include at least 0.1, in other embodiments at least 0.5, and in still other embodiments at least 1 Phr of an activator.
  • the cure system may include at most 20, in other embodiments at most 10, and in still other embodiments at most 6 Phr of an activator.
  • the cure system may include at about 0.1 to about 20, in other embodiments about 0.5 to about 10, and in still other embodiments about 1 to about 6 Phr of an activator.
  • a retarder may be used to reduce the tendency of a rubber compound to vulcanize prematurely by increasing scorch delay.
  • Retarders suitable for vulcanization with a benzoxazole sulfenamide accelerator include N-(cyclohexylthio) phthalimide and stearic acid.
  • the amount of activator used to cure rubber may be stated in Phr.
  • the cure system may include at least 0.01, in other embodiments at least0.05, and in still other embodiments at least 0.1 Phr of a retarder. In these other embodiments, the cure system may include at most 5, in other embodiments at most 3, and in still other embodiments at most 2 Phr of a retarder.
  • the cure system may include at about 0.01 to about 5, in other embodiments about 0.05 to about 3, and in still other embodiments about 0.1 to about 2 Phr of a retarder.
  • the cure system may optionally include a secondary accelerator in addition to the benzoxazole sulfenamide accelerator.
  • a secondary accelerator may be used to control vulcanization speed.
  • suitable secondary accelerators include N-cyclohexyl-2-benzothiazolesulfenamide, N- (cyclohexylthio)phthalimide, N,N'-dibutylthiourea,N,N-dicyclohexyl-2- benzothiazolesulfenamide ⁇ , ⁇ '-Diethythiourea, di-o-tolylguanidine, diphenylguanidine, dipentamethylenethiuram hexasulfide, dithiodimorpholine, ethylenethiourea, 2- (morpholinothio)benzothiazolesulfenamide, 2-mercaptobenzothiazole, benzothiazyl disulfide, N-nitrosodiphenylamine, polyethylene glycol, N-t-Butyl-2- benzothiazolesulfenamide, tellurium diethyldithiocarbamate, tetraethylthiuram disulfide, polymerized 2,2,
  • the amount of the secondary accelerator used to cure rubber may be stated in Phr.
  • the cure system may include at least 0.1, in other embodiments at least0.5, and in still other embodiments at least 1.0 Phr of a secondary accelerator.
  • the cure system may include at most 10, in other embodiments at most 6, and in still other embodiments at most 4 Phr of a secondary accelerator.
  • the cure system may include at about 0.1 to 8, in other embodiments about 0.5 to 6, and in still other embodiments about 1 to 4 Phr of a secondary accelerator.
  • the amount of the secondary accelerator used to cure rubber may also be stated in as a ratio between the benzoxazole sulfonamide accelerator and the secondary accelerator.
  • the cure system may include a ratio of benzoxazole sulfenamide accelerator to secondary accelerator of about 1 to 50, in other embodiments about 5 to 25, and in still other embodiments about 10 to 15.
  • an amine compound may be included in the cure system. It has been found that when a cure system includes a benzoxazole sulfenamide accelerator and an amine show increased accelerator activity.
  • suitable amine compounds include diphenylquanidine, butyraldehydeanine, hexamethylenetetramine, di(P-naphthyl)-p-phenyldiamine, a dialkylamine such as dibutyl amine or cyclohexylethylamine, trimethylthiourea, 1,3-dibutylthiourea.
  • the amount of the amine used to cure rubber may be stated in Phr.
  • the cure system may include at least 0.1, in other embodiments at least0.2, and in still other embodiments at least 0.4 Phr of an amine. In these other embodiments, the cure system may include at most 10, in other embodiments at most 8, and in still other embodiments at most 5 Phr of an amine. In these other embodiments, the cure system may include at about 0.1 to 8, in other embodiments about 0.2 to 5, and in still other embodiments about 0.5 to 3 Phr of an amine.
  • the vulcanized rubber shows little or no reversion.
  • the vulcanized rubber systems show a non-appreciable amount of reversion.
  • the amount of reversion may be determined using a rheometer. In one or more embodiments, the amount of reversion may be less than 10%, in other embodiments, less than 5%, and in still other embodiments less than 2%.
  • the benzoxazole sulfenamide accelerator may form a complex with a zinc atom defined by the formula
  • each X is selected from an oxygen atom or a sulfur atom provided that at least one
  • X is an oxygen atom
  • each R1 and are individually selected from hydrogen atoms, alkyl groups, and subsitituted alkyl groups, or where an R1 and an R.2 join to form an alkane or substituted alkane group.
  • the complex is typically prepared from a cure system that includes a zinc compound activator, a zinc compound, and a secondary accelerator that includes a benzothiazole group.
  • an asphalt and polymer composition comprises an asphalt, a rubber, a sulfur compound, an activator, and a bezoxazole sulfonamide.
  • the asphalt and polymer composition may include a bezoxazole sulfonamide defined by the formula:
  • R.1 and are each individually selected from hydrogen atoms, alkyl groups, and substituted alkyl groups, or where R.1 and R ⁇ join to form an alkane or substituted alkane group.
  • the amount of the benzoxazole sulfenamide for use in an asphalt and polymer composition may be stated in percent weight of the total asphalt and polymer composition.
  • the asphalt and polymer composition may include at least 0.01%, in other embodiments at least 0.02 %, and in still other embodiments at least 0.05% benzoxazole sulfenamide.
  • the asphalt and polymer composition may include at most 0.1 %, in other embodiments at most 1%, and in still other embodiments at most 4 % benzoxazole sulfenamide.
  • the asphalt and polymer composition may include at about 0.01 % to about 4 %, in other embodiments about 0.02 % to 1 %, and in still other embodiments about 0.05 % to 0.1 % benzoxazole sulfonamide.
  • Asphalt which may also be referred to as bitumen, is a viscous liquid or semisolid form of petroleum.
  • the amount of the asphalt for use in an asphalt and polymer composition may be stated in percent weight of the total asphalt and polymer composition.
  • the combined weight of asphalt and rubber polymer may be considered as 100%.
  • the asphalt and polymer composition may include at least 85%, in other embodiments at least 90 %, and in still other embodiments at least 95% asphalt.
  • the asphalt and polymer composition may include at most 96 %, in other embodiments at most 98%, and in still other embodiments at most 99 % asphalt.
  • the asphalt and polymer composition may include at about 85 % to about 99 %, in other embodiments about 90 % to about 99 %, and in still other embodiments about 95 % to about 98 % asphalt.
  • Rubbers suitable for use in an asphalt and polymer composition include, but are not limited to, polybutadiene, polyisoprene or polyisobutene rubber, polychloroprene, polybutadiene, styrene-butadiene copolymers.
  • the amount of the rubber for use in an asphalt and polymer composition may be stated in percent weight of the total asphalt and polymer composition.
  • the asphalt and polymer composition may include at least 1%, in other embodiments at least2 %, and in still other embodiments at least 3% rubber.
  • the asphalt and polymer composition may include at most 6 %, in other embodiments at most 8%, and in still other embodiments at most 10 % rubber.
  • the asphalt and polymer composition may include at about 1 % to about 10 %, in other embodiments about 2 % to about 8 %, and in still other embodiments about 3 % to about 6 % rubber.
  • Activators suitable for use in an asphalt and polymer composition include, but are not limited to, zinc compounds, steric acid, or combinations thereof.
  • zinc compounds include, but are not limited to, zinc oxide (ZnO) and Zn-soap.
  • the amount of the activator for use in an asphalt and polymer composition may be stated in percent weight of the total asphalt and polymer composition.
  • the asphalt and polymer composition may include at least 0.01%, in other embodiments at least0.03 %, and in still other embodiments at least 0.05% activator.
  • the asphalt and polymer composition may include at most 0.1 %, in other embodiments at most 0.5%, and in still other embodiments at most 1 % activator.
  • the asphalt and polymer composition may include at about 0.01 % to about 0.1 %, in other embodiments about 0.03 % to about 0.5 %, and in still other embodiments about 0.05 % to about 0.1 % activator.
  • Suitable sulfur for use in an asphalt and polymer composition include, but are not limited to, elemental sulfur, an allotrope of sulfur, a sulfur donor, or a combination thereof.
  • sulfur donors include, but are not limited to, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and dithiodimorpholine.
  • the amount of the sulfur compounds for use in an asphalt and polymer composition may be stated in percent weight of the total asphalt and polymer composition.
  • the asphalt and polymer composition may include at least 0.05%, in other embodiments at least0.07 %, and in still other embodiments at least 0.10% sulfur compound.
  • the asphalt and polymer composition may include at most 0.2 %, in other embodiments at most 0.5%, and in still other embodiments at most 1 % sulfur compound. In these other embodiments, the asphalt and polymer composition may include at about 0.05 % to about 1 %, in other embodiments about 0.07 % to about 0.5 %, and in still other embodiments about 0.10 % to about 0.2 % sulfur compound.
  • the asphalt and the rubber may be combined at a temperature of between 130° and 230° C, and mixed for 1 to 10 hours.
  • the rubber and asphalt may be aged or the sulfur compound, activator, and bezoxazole sulfonamide may be added immediately after mixing. After the addition of the sulfur compound, activator, and bezoxazole sulfonamide the composition may be mixed or agitated for 20 minutes to 10 hours.
  • an aggregate may be added to the asphalt and polymer composition.
  • An aggregate is generally rock, and it may be used with an asphalt and polymer composition for paving a road.
  • Compositions of that include asphalt and polymer compositions along with aggregate may be referred to as asphalt cement.
  • Suitable aggregates include but are not limited to, granite, basalt, and limestone.
  • the amount of the aggregate for use with an asphalt and polymer composition may be stated in percent weight of the total asphalt, polymer, and aggregate composition.
  • Natural rubber (SMR CV60) was purchased from Akrochem. sulfur (Harwich), zinc oxide (Akrochem), stearic acid (Harwick), TBBS (Flexsys America), 2-mercaptobenzoxazole (Fisher), zinc acetate dihydrate (Fisher), tert- butylamine (Aldrich) were used as received.
  • Zinc bis(benzoxazole-2-thiolate) 1.0 g, 2.73 mmol
  • tert-butylamine 4 ml, 38 mmol
  • the complex was partially dissociated during crystallization,
  • Natural rubber masterbatch was made by masticating natural rubber (SMR CV60) in a Brabender internal mixer (speed: 50 rpm; temperature 55°C; loading chute: manual + 5kg). If applicable, zinc oxide and/or stearic acid were also mixed with rubber in the mastication process. Natural rubber was mixed for 1.3 min, and the mixture was mixed for additional 2 min after addition of zinc oxide/stearic acid. Sulfur and/or accelerators were then mixed with the masterbatch on a two roll mill (roll speed: front 12 rpm, rear 10 rpm; temperature: 120°C).
  • Zinc complex 9 1.3 0.75 — — —
  • bt90 time when cure curve reaches 90 percent of full cure. t90 is generally the time when most physical properties of a vulcanizate reach optimal results.
  • cCure rate index 100 / (t90 - ts2).
  • the desirable benzoxazole-2-sulfenamide 7 was synthesized from benzoxazole-2 -thiol 2 and tert-butyl amine in high yield, by using a literature procedure for a similar compound.
  • the l H NMR spectrum of 7 detected four aromatic protons in anticipated two doublet and two triplet ( Figure 1), confirming its structure.
  • Bis(benzoxazole-2-ylthio)zinc 8 was also prepared from 2 by reaction with base followed by treatment with zinc acetate Zn(OAc)2.
  • the amine complex was conveniently prepared by reaction of 8 with tert- butylamine to give crystalline product.
  • the synthesis of the amine complexes 9 appeared to be simpler than its zinc benzothiazole-2-thiolate (6), where the corresponding zinc complex of i-butylamine was prepared by substitution from the ammonium complex of zinc benzothiazole-2-thiolate (Ar-S-Zn(NH 3 ) 2 -S-Ar ⁇ Ar-S-Zn( H 2 -Bu) 2 -S-Ar. 12
  • the amine complex 9 was found to partially dissociate, similarly as observed from its thiazole analogue 6.
  • test samples for Figure 3 were consisting of natural rubber, zinc oxide, sulfur and accelerator (see Table 2).
  • Other carbon-containing ingredients e.g. carbon black, oil, stearic acid, and anti-degradent
  • 13 C NMR was thus acquired from the cured samples by using benzoxazole 7 as vulcanization accelerator.
  • the major signals were detected at 134.7, 125.2, 31.9, 26.1, 23.0 ppm, attributing to the polymer backbone.
  • the inset in Figure 5 shows the minor signals arising from the crossing-linking reaction.
  • the characteristic signal at -56.8 ppm is detected as minor signal, indicating that the vulcanization is occurring at the indicated position in 11.
  • Two minor signals at 39.7 and 44.4 ppm were also detected, which indicates the presence of the structure 12 with mono sulfur bridge.
  • the crystal structure of amine complex 9 reveals that the benzoxazole-2- thiolate ligand is attached to Zn(II) in two different isomeric forms (i.e. thio- or thioketo- forms, see Figure 2).
  • the complex 9 is ruled out to be an effective active sulfurating species, since the additional ZnO is required for the complex 9 to exhibit the accelerator function.
  • the zinc complexes 14 and/or 15 are proposed to be potential sulfurating species in the rubber system (Scheme 4). It should be noted that 14 and 15 could be formed directly from "7 + ZnO," without necessarily going through the zinc compounds 8 and 9.
  • the proposed mechanism removes the concern that the amine complex 6 is synthesized by reaction of the ammonium complex 5 ⁇ ( ]3 ⁇ 4)2 with an amine (not 5 with amine).

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Abstract

L'invention concerne des accélérateurs de benzoxazole sulfénamide. Les accélérateurs de benzoxazole sulfénamide peuvent être utilisés dans un système de durcissement pour vulcaniser du caoutchouc. Les accélérateurs de benzoxazole sulfénamide peuvent également être utilisés dans des compositions d'asphalte et de polymère. De façon avantageuse, il a été découvert que lorsque le benzoxazole sulfénamide est utilisé comme accélérateur, un polymère vulcanisé peut être préparé avec peu voire pas de réversion.
PCT/US2014/038191 2013-05-15 2014-05-15 Matériaux à base de benzoxazole pour des applications d'accélérateur de vulcanisation WO2014186571A1 (fr)

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US10150600B2 (en) 2014-10-01 2018-12-11 Sonoco Development, Inc. Container structure with a built-in opening and reclosing feature
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US10138026B2 (en) 2015-04-01 2018-11-27 Sonoco Development, Inc. Resealable flexible package and method of using the same
US10026339B2 (en) 2015-05-21 2018-07-17 Sonoco Development, Inc. Flexible laminate for packaging with integrated peelable portion
US9928757B2 (en) 2015-05-21 2018-03-27 Sonoco Development, Inc. Flexible laminate for packaging with integrated peelable portion
US10733912B2 (en) 2015-05-21 2020-08-04 Sonoco Development, Inc. Flexible laminate for packaging with integrated peelable portion
US11203477B2 (en) 2015-10-30 2021-12-21 Sonoco Development, Inc. Integrated package opening feature
CN109071884A (zh) * 2016-04-15 2018-12-21 横滨橡胶株式会社 橡胶组合物、硫化橡胶制品以及硫化橡胶制品的制造方法
US11148851B2 (en) 2017-07-21 2021-10-19 Sonoco Development, Inc. Tamper evident hybrid resealable container
US11597559B2 (en) 2017-07-21 2023-03-07 Sonoco Development, Inc. Tamper evident hybrid resealable container
US10689151B2 (en) 2017-07-21 2020-06-23 Sonoco Development, Inc. Tamper evident hybrid resealable container
US11225355B2 (en) 2017-11-08 2022-01-18 Sonoco Development, Inc. Membrane lid with integrated peelable portion
KR20210149392A (ko) * 2020-06-02 2021-12-09 원광대학교산학협력단 설펜아마이드 화합물 및 이의 제조 방법
KR102396180B1 (ko) * 2020-06-02 2022-05-10 원광대학교산학협력단 설펜아마이드 화합물 및 이의 제조 방법

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