US20050199854A1 - Rubber composition containing cyclic polysulfide vulcanization agent - Google Patents
Rubber composition containing cyclic polysulfide vulcanization agent Download PDFInfo
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- US20050199854A1 US20050199854A1 US11/126,354 US12635405A US2005199854A1 US 20050199854 A1 US20050199854 A1 US 20050199854A1 US 12635405 A US12635405 A US 12635405A US 2005199854 A1 US2005199854 A1 US 2005199854A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/14—Polysulfides
- C08G75/16—Polysulfides by polycondensation of organic compounds with inorganic polysulfides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
Definitions
- the present invention relates to a cyclic polysulfide compound and a method of production thereof as well as a rubber vulcanization agent comprises the same and a rubber composition containing the same.
- a cross-linked rubber sulfur vulcanized with sulfur has polysulfide bonds, and therefore, is inferior in heat resistance and vulcanization reversion.
- a vulcanization agent such as tetrasulfide polymer or cyclic polysulfide is effective (Noboru Yamazaki et al.: Abstracts of 1981 Research Announcement Conference, p. 53, 2-17, Japanese Rubber Industry Association and Japanese Unexamined Patent Publication (Kokai) No. 10-120788).
- a cyclic polysulfide is preferable in terms of the cross-linking efficiency, but the methods of production of a cyclic polysulfide reported up to now are not practical due to problems such as the long production process or use of expensive materials (Japanese Unexamined Patent Publication (Kokai) No. 58-122944).
- Japanese Unexamined Patent Publication (Kokai) No. 58-122944 reports the following method of production of a cyclic polysulfide compound:
- an object of the present invention is to provide an inexpensive simple production of a cyclic polysulfide compound useful as a rubber vulcanization agent from a dihalogen compound and a metal polysulfide.
- a method for producing a cyclic polysulfide having the formula (I): wherein x is an integer of 2 to 6, n is an integer of 1 to 15, and R indicates a substituted or unsubstituted C 2 -C 18 alkylene group or a substituted or unsubstituted C 2 to C 18 alkylene group including an oxiyalkylene group comprising:
- a method for producing a cyclic polysulfide having the above formula (I) comprising: reacting by adding a dihalogen compound having the formula X—R—X, wherein X independently indicates, a halogen atom and R indicates a substituted or unsubstituted C 2 to C 18 alkylene group or a substituted or unsubstituted C 2 to C 18 alkylene group including an oxyalkylene group with a solution of an alkali metal polysulfide having the formula M 2 S x , wherein, M is an alkali metal and x is an integer of 2 to 6, by adding the dihalogen compound at a rate such that the dihalogen compound reacts with the alkali metal polysulfide at the interface thereof.
- a cyclic polysulfide wherein, in formula (I), R is CH 2 m , —CH 2 CH 2 OCH 2 OCH 2 CH 2 —, or —CH 2 CH 2 OCH 2 CH 2 —, x is an integer of 2 to 6, and n is an integer of 1 to 15.
- a rubber vulcanization agent comprised of said cyclic polysulfide.
- a rubber composition comprising 100 parts by weight of a diene-based rubber and 0.5 to 30 parts by weight, preferably 0.5 to 20 parts by weight, of the rubber vulcanization agent.
- FIG. 1 is a graph of the test results of a rheometer (160° C. ⁇ 60 minutes) of Comparative. Example 1 and Examples 5 and 7.
- the cyclic polysulfide having the above-mentioned formula (I) is produced by reacting a dihalogen compound having the formula X—R—X, wherein X independently represents a halogen atom including fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, and R represents a substituted or unsubstituted C 2 to C 18 alkylene group or a substituted or unsubstituted C 2 to C 18 alkylene group including an oxyalkylene group with an alkali metal polysulfide M 2 S x , wherein M is an alkali metal, for example, sodium, potassium and lithium and x is an integer of 2 to 6, in an incompatible mixed solvent of a hydrophilic and lypophilic solvent by a two-phase system or reacting them by adding X—R—X in a solution of M 2 S x , in which, as the solvent, it is possible to use water and a C 1 to C 4 ali
- a straight or branched chain alkylene group such as ethylene, propylene, butylene, pentylene, hexylene, octylene, nonylene, decylene, and 1,2-propylene may be exemplified.
- alkylene groups may be substituted with a substituent group such as a phenyl group or benzyl group.
- the group R may further include an alkylene group including an oxyalkylene group.
- Examples of such a group are an alkylene group including an oxyalkylene group with the group (CH 2 CH 2 O) p and the group (CH 2 ) q , wherein p is an integer of 1 to 5 and q is an integer of 0 to 2, bonded in any way.
- Preferable groups R include:
- x is preferably an average of 3.0 to 5.0, more preferably 3.5 to 4.5.
- n is preferably 1 to 10, more preferably 1 to 5.
- the reaction between the dihalogen compound and the alkali metal polysulfide is an equivalent amount reaction.
- the two compounds are reacted in a ratio by equivalents of 0.95:1.0 to 1.0:0.95, preferably at a temperature of 50 to 120° C., more preferably 70 to 100° C.
- hydrophilic solvents and lypophilic solvents usable in the present invention are not particularly limited. In an actual reaction system, it is possible to use any solvents which are incompatible with each other and to form two phases. Specifically, as a hydrophilic solvent, in addition to water, alcohols such as methanol, ethanol, ethylenglycol, diethylene glycol may be exemplified. These solvents may also be used in any mixtures.
- an aromatic hydrocarbon such as toluene, xylene, and benzene
- an aliphatic hydrocarbon such as pentane and hexane
- an ether such as dioxane and dibutylether
- an ester such as ethyl acetate, etc.
- solvents may also be used in any mixtures.
- the reaction at the interface of the dihalogen compound and the alkali metal polysulfide is an equivalent amount reaction.
- the two compounds are reacted in an equivalent ratio of 0.95:1 to 1:0.95.
- the reaction temperature is preferably 50 to 120° C., more preferably 70 to 100° C.
- the rubber composition according to the present invention is comprised of 0.5 to 30 parts by weight, preferably 0.5 to 20 parts by weight, of a rubber vulcanization agent having the above formula (I), blended into 100 parts by weight of a diene-based rubber.
- the rubber vulcanization agent of the present invention can be used, together with a conventional sulfur or other vulcanization agent. If the amount of the rubber vulcanization agent of the present invention is too small, a desired vulcanization effect cannot be sufficiently obtained and the strength of the vulcanized rubber etc. are decreased and therefore, this is not preferable, while if it is too large, the vulcanized rubber impreferably becomes hard.
- the diene-based rubber blended into the rubber composition according to the present invention includes, for example, any diene-based rubber which can be used as a starting rubber for tires.
- Typical examples of such diene-based rubbers are natural rubber (NR), polyisoprene rubber (IR), various types of polybutadiene rubber (BR), various types of styrene-butadiene copolymer rubber (SBR), ethylene-propylene-diene terpolymer rubber (EPDM). These rubbers may be used alone or in any blends thereof.
- the rubber composition according to the present invention may contain, in addition to the above-mentioned essential ingredients, a filler such as carbon black or silica, a vulcanization accelerator, various oils, antioxidants, plasticizers, silane coupling agent, or other various additives generally blended for tire or other general rubber use.
- a filler such as carbon black or silica
- a vulcanization accelerator such as carbon black or silica
- various oils, antioxidants, plasticizers, silane coupling agent such as a vulcanization accelerator
- various oils, antioxidants, plasticizers, silane coupling agent such as a vulcanization accelerator
- silane coupling agent such as a vulcanization accelerator
- the formulation may be mixed into a composition by a general method and used for vulcanization.
- the amount of these additives blended may be made the general amounts blended in the past unless the object of the present invention is not impaired.
- the number average molecular weight of the cyclic polysulfide thus obtained was 500 and the NMR data was as follows:
- the number average molecular weight of the cyclic polysulfide thus obtained was 600 and the NMR data was as follows:
- the rubber composition of the formulation (parts by weight) shown in Table I was mixed by an 8-inch open roll, then the rubber was vulcanized under vulcanization conditions of 160° C. and 20 minutes.
- the results are shown in Table II.
- the rubber compositions of Examples 4 to 6 according to the present invention are observed to exhibit excellent rates of retention of the breaking strength (TB) and elongation at break (EB) and to be superior in heat stability even after accelerated thermal ageing at 100° C. ⁇ 3 days.
- Example 1 i.e., sulfur vulcanization
- Example 5 i.e., vulcanization by vulcanization agent 1
- Example 7 i.e., vulcanization by vulcanization agent 2
- the results are shown in FIG. 1 as a curve of the change of the torque over time. From the results of FIG. 1 , no vulcanization reversion was recognized in Examples 5 and 7 using the rubber vulcanization agents according to the present invention. The existing vulcanization state was exhibited.
- the present invention by reacting a dihalogen compound and an alkali metal polysulfide in an incompatible mixed solvent of a hydrophilic and lypophilic solvent by a two-phase system, it is possible to inexpensively and simply produce a cyclic polysulfide. Further, when the cyclic polysulfide of the present invention is used as a rubber vulcanization agent, it is possible to give an optimal vulcanization state without causing the vulcanization reversion or improve the heat stability of the vulcanized rubber compared with an ordinary sulfur vulcanization system.
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Abstract
A method of production of a cyclic polysulfide having the formula (I):
wherein x is an integer of 2 to 6, n is an integer of 1 to 15, and R indicates a substituted or unsubstituted C2 to C18 alkylene group or a substituted or unsubstituted C2 to C18 alkylene group including an oxyalkylene group comprising:
wherein x is an integer of 2 to 6, n is an integer of 1 to 15, and R indicates a substituted or unsubstituted C2 to C18 alkylene group or a substituted or unsubstituted C2 to C18 alkylene group including an oxyalkylene group comprising:
-
- reacting a dihalogen compound of the formula X—R—X wherein, X independently indicates a halogen atom, and R indicates a substituted or unsubstituted C2 to C18 alkylene group or a substituted or unsubstituted C2 to C18 alkylene group including an oxyalkylene group and an alkali metal polysulfide of the formula M2Sx wherein, M is an alkali metal and x is an integer of 2 to 6, by a two-phase system in an incompatible mixed solvent of a hydrophilic and lypophilic solvent.
Description
- 1. Field of the Invention
- The present invention relates to a cyclic polysulfide compound and a method of production thereof as well as a rubber vulcanization agent comprises the same and a rubber composition containing the same.
- 2. Description of the Related Art
- A cross-linked rubber sulfur vulcanized with sulfur has polysulfide bonds, and therefore, is inferior in heat resistance and vulcanization reversion. To solve the problems of heat resistance and vulcanization reversion, it is known that a vulcanization agent such as tetrasulfide polymer or cyclic polysulfide is effective (Noboru Yamazaki et al.: Abstracts of 1981 Research Announcement Conference, p. 53, 2-17, Japanese Rubber Industry Association and Japanese Unexamined Patent Publication (Kokai) No. 10-120788). In particular, a cyclic polysulfide is preferable in terms of the cross-linking efficiency, but the methods of production of a cyclic polysulfide reported up to now are not practical due to problems such as the long production process or use of expensive materials (Japanese Unexamined Patent Publication (Kokai) No. 58-122944).
-
- According to this production method, it is necessary to react an expensive material, i.e., dithiol, and 2 equivalents of an expensive chlorotrimethylsilane as a protecting group of dithiol. Chlorotrimethylsilane and the S—SiMe3 group are easily hydrolyzed by moisture, and therefore, as a reaction condition, it is necessary to dry or treat the reaction apparatus so as to remove the humidity or moisture. Further, it is necessary to separately synthesize S3Cl2. Furthermore, the yield is 70% or lower, and therefore, there is a problem in the purification of the desired product.
- Accordingly, an object of the present invention is to provide an inexpensive simple production of a cyclic polysulfide compound useful as a rubber vulcanization agent from a dihalogen compound and a metal polysulfide.
- In accordance with the present invention, there is provided a method for producing a cyclic polysulfide having the formula (I):
wherein x is an integer of 2 to 6, n is an integer of 1 to 15, and R indicates a substituted or unsubstituted C2-C18 alkylene group or a substituted or unsubstituted C2 to C18 alkylene group including an oxiyalkylene group comprising: -
- reacting a dihalogen compound having the formula X—R—X, wherein X independently indicates a halogen atom, and R indicates a substituted or unsubstituted C2 to C18 alkylene group or a substituted or unsubstituted C2 to C18 alkylene group including an oxyalkylene group and an alkali metal polysulfide have the formula M2Sx, wherein M is an alkali metal and x is an integer of 2 to 6, in an incompatible mixed solvent of a hydrophilic and lypophilic solvent, by a two-phase system.
- In accordance with the present invention, there is also provided a method for producing a cyclic polysulfide having the above formula (I) comprising: reacting by adding a dihalogen compound having the formula X—R—X, wherein X independently indicates, a halogen atom and R indicates a substituted or unsubstituted C2 to C18 alkylene group or a substituted or unsubstituted C2 to C18 alkylene group including an oxyalkylene group with a solution of an alkali metal polysulfide having the formula M2Sx, wherein, M is an alkali metal and x is an integer of 2 to 6, by adding the dihalogen compound at a rate such that the dihalogen compound reacts with the alkali metal polysulfide at the interface thereof.
-
- In accordance with the present invention, there is still further provided a rubber vulcanization agent comprised of said cyclic polysulfide.
- In accordance with the present invention, there is still further provided a rubber composition comprising 100 parts by weight of a diene-based rubber and 0.5 to 30 parts by weight, preferably 0.5 to 20 parts by weight, of the rubber vulcanization agent.
- In this specification and in the claims which follow, the singular forms “a,” “an” and “the” include plural referents unless context clearly dictates otherwise.
- The present invention will be better understood from the description set forth below with reference to the accompanying drawing, in which:
-
FIG. 1 is a graph of the test results of a rheometer (160° C.×60 minutes) of Comparative. Example 1 and Examples 5 and 7. - According to the present invention, the cyclic polysulfide having the above-mentioned formula (I) is produced by reacting a dihalogen compound having the formula X—R—X, wherein X independently represents a halogen atom including fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, and R represents a substituted or unsubstituted C2 to C18 alkylene group or a substituted or unsubstituted C2 to C18 alkylene group including an oxyalkylene group with an alkali metal polysulfide M2Sx, wherein M is an alkali metal, for example, sodium, potassium and lithium and x is an integer of 2 to 6, in an incompatible mixed solvent of a hydrophilic and lypophilic solvent by a two-phase system or reacting them by adding X—R—X in a solution of M2Sx, in which, as the solvent, it is possible to use water and a C1 to C4 aliphatic alcohol, preferably water, at a rate such that M2Sx and X—R—X react at the interface thereof. Note that, in the latter method, if the addition rate of the X—R—X is too fast, the concentration of X—R—X becomes higher, a reaction occurs outside the interface, and a reaction between the molecules is preferably occurs to form a chain, which is not desirable. Therefore, it is preferable for obtaining a cyclic polysulfide that the M2Sx and X-M-X are reacted in as a nonuniform or heterogeneous system as possible only at the interface.
- As the group R of the formula X—R—X and the formula (I), for example, a straight or branched chain alkylene group such as ethylene, propylene, butylene, pentylene, hexylene, octylene, nonylene, decylene, and 1,2-propylene may be exemplified. These alkylene groups may be substituted with a substituent group such as a phenyl group or benzyl group. The group R may further include an alkylene group including an oxyalkylene group. Examples of such a group are an alkylene group including an oxyalkylene group with the group (CH2CH2O)p and the group (CH2)q, wherein p is an integer of 1 to 5 and q is an integer of 0 to 2, bonded in any way. Preferable groups R include:
-
- —CH2CH2OCH2CH2—, —(CH2CH2O)2CH2CH2— —(CH2CH2O)2CH—CH2—, —(CH2CH2O)4CH2CH2—, —(CH2CH2O)5CH2CH2—, —(CH2CH2O)2CH2—, —CH2CH2OCH2OCH2CH2—
- In particular, x is preferably an average of 3.0 to 5.0, more preferably 3.5 to 4.5. n is preferably 1 to 10, more preferably 1 to 5.
- The reaction between the dihalogen compound and the alkali metal polysulfide is an equivalent amount reaction. In practice, the two compounds are reacted in a ratio by equivalents of 0.95:1.0 to 1.0:0.95, preferably at a temperature of 50 to 120° C., more preferably 70 to 100° C.
- The hydrophilic solvents and lypophilic solvents usable in the present invention are not particularly limited. In an actual reaction system, it is possible to use any solvents which are incompatible with each other and to form two phases. Specifically, as a hydrophilic solvent, in addition to water, alcohols such as methanol, ethanol, ethylenglycol, diethylene glycol may be exemplified. These solvents may also be used in any mixtures. Further, as the lyophilic solvent, an aromatic hydrocarbon such as toluene, xylene, and benzene, an aliphatic hydrocarbon such as pentane and hexane, an ether such as dioxane and dibutylether, an ester such as ethyl acetate, etc. may be exemplified. These solvents may also be used in any mixtures.
- The reaction at the interface of the dihalogen compound and the alkali metal polysulfide is an equivalent amount reaction. In practice, the two compounds are reacted in an equivalent ratio of 0.95:1 to 1:0.95. The reaction temperature is preferably 50 to 120° C., more preferably 70 to 100° C.
- In the above reaction, no catalyst is required, but sometimes it is possible to use, for example, a quaternary ammonium salt, phosphonium salt, crown ether, etc. as a catalyst. For example, (CH3)4N+Cl−, (CH3)4N+Br−, (C4H9)4N+Cl−, (C4H9)4N+Br−, C12H25N+(CH3)3Br−, (C4H9)4P+Br−, CH3P+(C6H5)3I−, C16H33P+(C4H9)3Br−, 15-crown-5,18-crown-6, Benzo-18-crown-6, etc. may be exemplified.
- The rubber composition according to the present invention is comprised of 0.5 to 30 parts by weight, preferably 0.5 to 20 parts by weight, of a rubber vulcanization agent having the above formula (I), blended into 100 parts by weight of a diene-based rubber. The rubber vulcanization agent of the present invention can be used, together with a conventional sulfur or other vulcanization agent. If the amount of the rubber vulcanization agent of the present invention is too small, a desired vulcanization effect cannot be sufficiently obtained and the strength of the vulcanized rubber etc. are decreased and therefore, this is not preferable, while if it is too large, the vulcanized rubber impreferably becomes hard.
- The diene-based rubber blended into the rubber composition according to the present invention includes, for example, any diene-based rubber which can be used as a starting rubber for tires. Typical examples of such diene-based rubbers are natural rubber (NR), polyisoprene rubber (IR), various types of polybutadiene rubber (BR), various types of styrene-butadiene copolymer rubber (SBR), ethylene-propylene-diene terpolymer rubber (EPDM). These rubbers may be used alone or in any blends thereof.
- The rubber composition according to the present invention may contain, in addition to the above-mentioned essential ingredients, a filler such as carbon black or silica, a vulcanization accelerator, various oils, antioxidants, plasticizers, silane coupling agent, or other various additives generally blended for tire or other general rubber use. The formulation may be mixed into a composition by a general method and used for vulcanization. The amount of these additives blended may be made the general amounts blended in the past unless the object of the present invention is not impaired.
- The present invention will now be explained further by using Examples, but the scope of the present invention is of course not limited to these Examples.
- 28.1 g (0.15 mole) of 1,2-bis(2-chloroethoxy)ethane and 89.76 g (0.155 mole) of an aqueous 30% by weight sodium polysulfide (Na2S4) solution were reacted in an incompatible mixed solvent of 150 g of water and 100 g of toluene at 90° C. for 5 hours. After the end of the reaction, the organic phase was separated and condensed in vacuo at 90° C. to obtain 34.3 g (yield 94%) of a cyclic polysulfide (i.e., vulcanization agent 1) of the formula (I) wherein R=(CH2)2O(CH2)2O(CH2)2, x (average)=4, and n=1 to 5. The number average molecular weight of the cyclic polysulfide thus obtained was 500 and the NMR data was as follows:
- 1H-NMR (chloroform-d1) δ: 2.9 to 3.2 (4H, CH2Sx), 3.7 to 4.0 (8H, CH2O)
- A solution of 28.1 g (0.15 mole) of 1,2-bis(2-chloroethoxy)ethane dissolved in 30 g of toluene was dropwise added to a mixed solvent of 89.76 g (0.155 mole) of an aqueous 30% by weight sodium polysulfide (Na2S4) solution, 150 g of ethanol, and 100 g of toluene at 90° C. for 2 hours and the mixture allowed to react for a further 3 hours. After the end of the reaction, the organic phase was separated and condensed in vacuo at 90° C. to obtain 35.0 g (yield 96%) of a cyclic polysulfide of the formula (I), wherein R=(CH2)2O(CH2)2O(CH2)2, X (average)=4, and n=1 to 2. The number average molecular weight of the cyclic polysulfide thus obtained was 300 and the NMR data was as follows:
- 1H-NMR (chloroform-d1) δ: 2.9 to 3.2 (4H, CH2Sx), 3.7 to 4.0 (8H, CH2O)
- 23.3 g (0.15 mole) of 1,6-dichlorohexane and 89.76 g (0.155 mole) of an aqueous 30% by weight sodium polysulfide (Na2S4) solution were allowed to react in a mixed solvent of 120 g of ethanol and 100 g of toluene at 90° C. for 5 hours. After the end of the reaction, the organic phase was separated and condensed in vacuo at 90° C. to obtain 31.2 g (yield: 98%) of a cyclic polysulfide of the formula (I) wherein R=(CH2)6, x (mean)=4, and n=1 to 5. The number average molecular weight of the cyclic polysulfide thus obtained was 500 and the NMR data was as follows:
- 1H-NMR (chloroform-d1) δ: 1.4 to 1.9 (4H, CH2Sx), 3.7 to 4.0 (8H, CH2)
- 89.8 g (0.15 mole) of an aqueous 30% by weight sodium tetrafluoride solution was diluted by adding 100 g of water, then 25.9 g (0.15 mole) of 1,2-bis(2-chloroethoxy)methane was dropwise added thereto at 90° C. over 2 hours and the mixture was allowed to further react at that temperature for 3 hours. After the end of the reaction, the water insolubles were washed with water, then dried in vacuo at 100° C. for 2 hours to obtain 33.2 g (yield: 96%) of cyclic polysulfide (i.e., vulcanization agent 3) of the formula (I), wherein R=—CH2CH2OCH2OCH2CH2—, x (average)=4, and n=1 to 5. The number average molecular weight of the cyclic polysulfide thus obtained was 600 and the NMR data was as follows:
- 1H-NMR (chloroform-d1) δ: 2.9 to 3.3 (4H, CH2S), 3.7 to 4.0 (4H, CH2O), 4.8 (2H, OCH2O)
- The following tests were carried out for evaluating the blended physical properties of the rubber vulcanization agent of the present invention.
- The formulations of the rubber (parts by weight) are as shown in Table I.
TABLE I Comp. Ex. 1 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Polyisoprene rubber*1 100 100 100 100 100 Carbon black*2 50 50 50 50 50 Zinc oxide 3 3 3 3 3 Stearic acid 1 1 1 1 1 Antioxidant*3 1 1 1 1 1 NS*4 0.8 0.8 0.8 0.8 0.8 Sulfur*5 1.5 0 0.75 0 0 Vulcanization agent 1*6— 3 1.5 — — Vulcanization agent 2*7— — — 3 — Vulcanization agent 3*8 — — — — 3
*1Nipole IR 2200 (available from Nippon Zeon)
*2Seast KH (available from Tokai Carbon)
*3Santoflex 6PPD (available from Flexis)
*4(N-t-butyl-2-benzothiazolylsulfenamide)
*5Insoluble sulfur (available from Akzo Kashima)
*6Vulcanization agent produced by Example 1
*7Vulcanization agent produced by Example 3
*8Vulcanization agent produced by Example 4
- The rubber composition of the formulation (parts by weight) shown in Table I was mixed by an 8-inch open roll, then the rubber was vulcanized under vulcanization conditions of 160° C. and 20 minutes. The results are shown in Table II. As is clear from the results shown in Table II, compared with the rubber composition of Comparative Example 1, the rubber compositions of Examples 4 to 6 according to the present invention are observed to exhibit excellent rates of retention of the breaking strength (TB) and elongation at break (EB) and to be superior in heat stability even after accelerated thermal ageing at 100° C.×3 days.
TABLE II Comp. Ex. 1 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Before thermal ageing 100% modulus (MPa) 2.76 3.0 3.42 3.13 3.09 300% modulus (MPa) 12.72 13.68 14.85 13.69 13.65 TB 30.17 33.43 32.66 32.24 33.21 EB (%) 556.2 566.8 545.5 556.2 565.3 After thermal ageing 100% modulus (MPa) 4.15 4.36 — — 4.07 300% modulus (MPa) 17.2 17.49 — — 16.86 TB 20.0 24.27 — — 25.82 EB (%) 332.1 395.1 — — 407.5 - Test Method
- 100% and 300% modulus: Measured according to JIS K6251 (dumbbell shape no. 3).
- Breaking strength (TB) and elongation at break (EB): Measured according to JIS K6251 (dumbbell shape no. 3).
- The rubber compositions of Comparative Example 1 (i.e., sulfur vulcanization), Example 5 (i.e., vulcanization by vulcanization agent 1), and Example 7 (i.e., vulcanization by vulcanization agent 2) were tested at 160° C. for 60 minutes using a rheometer (i.e., vulcanization tester). The results are shown in
FIG. 1 as a curve of the change of the torque over time. From the results ofFIG. 1 , no vulcanization reversion was recognized in Examples 5 and 7 using the rubber vulcanization agents according to the present invention. The existing vulcanization state was exhibited. - According to the present invention, as explained above, by reacting a dihalogen compound and an alkali metal polysulfide in an incompatible mixed solvent of a hydrophilic and lypophilic solvent by a two-phase system, it is possible to inexpensively and simply produce a cyclic polysulfide. Further, when the cyclic polysulfide of the present invention is used as a rubber vulcanization agent, it is possible to give an optimal vulcanization state without causing the vulcanization reversion or improve the heat stability of the vulcanized rubber compared with an ordinary sulfur vulcanization system.
Claims (10)
1. (canceled)
2. (canceled)
3. A method for producing a cyclic polysulfide having the formula (I):
wherein x is an integer of 2 to 6, n is an integar of 1 to 15, and R indicates a substituted or unsubstituted C2-C18 alkylene group or a substituted or unsubstituted C2 to C18 alkylene group containing an oxyalkylene group comprising:
reacting a dihalogen compound having the formula X—R—X, wherein X independently indicates a halogen atom and R indicates a substituted or unsubstituted C2 to C18 alkylene group or a substituted or unsubstituted C2-C18 alkylene group containing an alkynene group,
with a solution of an alkali metal polysulfide having the formula M2SX, wherein M indicates an alkali metal and x is an integer of 2 to 6, by adding the dihalogen compound at a rate such that the dihalogen compound reacts with the alkali metal polysulfide at the interface thereof.
4. A method for producing a cyclic polysulfide as claimed in claim 3 , wherein the reaction at the interface is carried out at a temperature of 50 to 120° C.
5. A rubber vulcanization agent comprising a compound having the formula (I) produced by the method according to claim 3 .
6. A rubber vulcanization agent comprising a cyclic polysulfide compound having the formula (II):
wherein x is an integer of 2 to 6, n is an integer of 1 to 15, and R indicates a substituted or unsubstituted C2 to C18 alkylene group or a substituted or unsubstituted C2 to C18 alkylene group containing an oxyalkylene group.
7. A rubber composition comprising 100 parts by weight of a diene-based rubber and 0.5 to 30 parts by weight of a rubber vulcanization agent comprising a cyclic polysulfide compound having the formula (I):
wherein x is an integer of 2 to 6, n is an integer of 1 to 15, and R indicates a substituted or unsubstituted C2 to C18 alkylene group or a substituted or unsubstituted C2 to C18 alkylene group containing an oxyalkylene group.
8. A rubber composition as claimed in claim 7 , wherein said cyclic polysulfide compound has the formula (I), wherein x is an average of 3.0 to 5.0, n is an integer of 1 to 10 and R indicates a straight or branched chain alkylene group selected from the group consisting of ethylene, propylene, butylene, pentylene, hexylene, octylene, nonylene, decylene and 1,2-propylene or an alkylene group selected from the group consisting of —CH2CH2OCH2CH2—, —(CH2CH2O)2CH2CH2—, —(CH2CH2O)2CH—CH2—, —(CH2CH2O)4CH2CH2—, —(CH2CH2O)5CH2CH2—, —(CH2CH2O)2CH2—, and —CH2CH2OCH2OCH2CH2—.
9. A rubber composition as claimed in claim 7 , wherein the amount of the rubber vulcanization agent is 0.5 to 20 parts by weight, based upon 100 parts by weight of the diene-based rubber.
10. A rubber composition as claimed in claim 7 , wherein said diene-based rubber is at least one member selected from the group consisting of NR, IR, BR, SBR and EPDM.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US11/126,354 US20050199854A1 (en) | 2000-12-08 | 2005-05-11 | Rubber composition containing cyclic polysulfide vulcanization agent |
Applications Claiming Priority (6)
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---|---|---|---|
JP2000-374924 | 2000-12-08 | ||
JP2000374924 | 2000-12-08 | ||
JP2001-17579 | 2001-01-25 | ||
JP2001017579 | 2001-01-25 | ||
US09/993,759 US6984711B2 (en) | 2000-12-08 | 2001-11-27 | Method for production of cyclic polysulfide compound and rubber composition containing the same |
US11/126,354 US20050199854A1 (en) | 2000-12-08 | 2005-05-11 | Rubber composition containing cyclic polysulfide vulcanization agent |
Related Parent Applications (1)
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US09/993,759 Division US6984711B2 (en) | 2000-12-08 | 2001-11-27 | Method for production of cyclic polysulfide compound and rubber composition containing the same |
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US20050199854A1 true US20050199854A1 (en) | 2005-09-15 |
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US09/993,759 Expired - Lifetime US6984711B2 (en) | 2000-12-08 | 2001-11-27 | Method for production of cyclic polysulfide compound and rubber composition containing the same |
US11/126,354 Abandoned US20050199854A1 (en) | 2000-12-08 | 2005-05-11 | Rubber composition containing cyclic polysulfide vulcanization agent |
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US09/993,759 Expired - Lifetime US6984711B2 (en) | 2000-12-08 | 2001-11-27 | Method for production of cyclic polysulfide compound and rubber composition containing the same |
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US (2) | US6984711B2 (en) |
DE (1) | DE10160184B4 (en) |
Cited By (1)
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US10472343B2 (en) | 2017-01-23 | 2019-11-12 | Mitsubishi Gas Chemical Company, Inc. | Method for producing 1,2,3,5,6-pentathiepane |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1761709A (en) * | 2003-10-14 | 2006-04-19 | 横滨橡胶株式会社 | Rubber composition containing cyclic polysulfide as vulcanizer and pneumatic tire made therefrom |
KR101006016B1 (en) * | 2003-10-14 | 2011-01-06 | 요코하마 고무 가부시키가이샤 | Rubber composition containing cyclic polysulfide as vulcanizer and pneumatic tire made therefrom |
JP3761552B2 (en) * | 2004-03-01 | 2006-03-29 | 横浜ゴム株式会社 | Process for producing polysulfide compound and rubber composition containing the same |
JP4156022B2 (en) * | 2006-08-23 | 2008-09-24 | 横浜ゴム株式会社 | Rubber composition |
US8592506B2 (en) * | 2006-12-28 | 2013-11-26 | Continental Ag | Tire compositions and components containing blocked mercaptosilane coupling agent |
US7781606B2 (en) * | 2006-12-28 | 2010-08-24 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making and uses in rubber |
US7737202B2 (en) * | 2006-12-28 | 2010-06-15 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
US7968634B2 (en) * | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated core polysulfides |
US7687558B2 (en) * | 2006-12-28 | 2010-03-30 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
US7960460B2 (en) * | 2006-12-28 | 2011-06-14 | Momentive Performance Materials, Inc. | Free-flowing filler composition and rubber composition containing same |
US7968635B2 (en) * | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
US7968636B2 (en) * | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated cyclic core polysulfides |
US7696269B2 (en) * | 2006-12-28 | 2010-04-13 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
US7968633B2 (en) * | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
CN101796124B (en) * | 2007-09-05 | 2013-04-10 | 住友橡胶工业株式会社 | Rubber composition for studless tire and studless tire utilizing the same |
JP4915467B2 (en) * | 2010-06-04 | 2012-04-11 | 横浜ゴム株式会社 | Rubber composition for tire |
JP6724377B2 (en) * | 2016-01-19 | 2020-07-15 | 横浜ゴム株式会社 | Pneumatic tire |
WO2019122688A1 (en) | 2017-12-19 | 2019-06-27 | Compagnie Generale Des Etablissements Michelin | Composition comprising a polysulfide compound |
EP3727879A1 (en) * | 2017-12-19 | 2020-10-28 | Compagnie Generale Des Etablissements Michelin | Composition comprising a polysulfide compound |
US11919877B2 (en) | 2018-03-22 | 2024-03-05 | Mitsubishi Gas Chemical Company, Inc. | Production method for 1,2,3,5,6-pentathiepane |
FR3090634A3 (en) | 2018-12-21 | 2020-06-26 | Michelin & Cie | POLYSULFURATED COMPOUND |
WO2020128259A1 (en) | 2018-12-21 | 2020-06-25 | Compagnie Generale Des Etablissements Michelin | Polysulphide compound as a crosslinking agent |
WO2020128260A1 (en) | 2018-12-21 | 2020-06-25 | Compagnie Generale Des Etablissements Michelin | Rubber composition comprising a polysulfide compound |
FR3090647A3 (en) | 2018-12-21 | 2020-06-26 | Michelin & Cie | RUBBER COMPOSITION COMPRISING A POLYSULFURATED COMPOUND |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4339590A (en) * | 1980-05-21 | 1982-07-13 | Japan Synthetic Rubber Company, Limited | Cyclic sulfur compounds |
US6518367B1 (en) * | 1999-02-25 | 2003-02-11 | The Yokohama Rubber Co., Ltd. | Rubber composition |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56164181A (en) * | 1980-05-21 | 1981-12-17 | Japan Synthetic Rubber Co Ltd | Preparation of cyclic polysulfide |
JPS58122944A (en) * | 1982-01-18 | 1983-07-21 | Japan Synthetic Rubber Co Ltd | Organic vulcanizing agent for rubber |
EP1110972B1 (en) * | 1999-12-22 | 2005-01-26 | Rhein Chemie Rheinau GmbH | Use of dialkylpolysulphides for the mastication of natural and synthetic rubbers |
-
2001
- 2001-11-27 US US09/993,759 patent/US6984711B2/en not_active Expired - Lifetime
- 2001-12-07 DE DE10160184.0A patent/DE10160184B4/en not_active Expired - Lifetime
-
2005
- 2005-05-11 US US11/126,354 patent/US20050199854A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4339590A (en) * | 1980-05-21 | 1982-07-13 | Japan Synthetic Rubber Company, Limited | Cyclic sulfur compounds |
US6518367B1 (en) * | 1999-02-25 | 2003-02-11 | The Yokohama Rubber Co., Ltd. | Rubber composition |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10472343B2 (en) | 2017-01-23 | 2019-11-12 | Mitsubishi Gas Chemical Company, Inc. | Method for producing 1,2,3,5,6-pentathiepane |
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US20020107338A1 (en) | 2002-08-08 |
DE10160184B4 (en) | 2017-08-24 |
DE10160184A1 (en) | 2002-09-26 |
US6984711B2 (en) | 2006-01-10 |
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