WO2001016226A1 - Stabilisation de la durete au moyen de mercaptopyridines - Google Patents

Stabilisation de la durete au moyen de mercaptopyridines Download PDF

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Publication number
WO2001016226A1
WO2001016226A1 PCT/EP2000/008490 EP0008490W WO0116226A1 WO 2001016226 A1 WO2001016226 A1 WO 2001016226A1 EP 0008490 W EP0008490 W EP 0008490W WO 0116226 A1 WO0116226 A1 WO 0116226A1
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WIPO (PCT)
Prior art keywords
rubber
sulfur
coagent
vulcanization
process according
Prior art date
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PCT/EP2000/008490
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English (en)
Inventor
Rabindra Nath Datta
Nicolaas Maria Huntink
Auke Gerardus Talma
Original Assignee
Flexsys B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Flexsys B.V. filed Critical Flexsys B.V.
Priority to AU75124/00A priority Critical patent/AU7512400A/en
Publication of WO2001016226A1 publication Critical patent/WO2001016226A1/fr

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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
    • C08K5/378—Thiols containing heterocyclic rings

Definitions

  • the invention relates to a sulfur vulcanization process comprising (a) a non-productive stage of mixing of a rubber composition comprising styrene- butadiene rubber, (b) a productive stage of mixing of a rubber composition further comprising sulfur and a vulcanization accelerator, and (c) vulcanization of said rubber composition. It further relates to rubber articles comprising the rubber vulcanizate obtained by said process.
  • Vulcanizing rubber compositions by heating a sulfur-vulcanizable rubber composition with sulfur and/or a sulfur donor and a vulcanization accelerator has been known for many years.
  • vulcanizates having acceptable physical properties including tensile strength, resilience, and fatigue resistance can be obtained, but such vulcanizates tend not to have good aging properties.
  • a typical aging phenomenon is hardening, which is explained below.
  • Uncured as well as cured rubbers are prone to aging effects.
  • the unsaturated groups in diene rubbers e.g. styrene-butadiene rubber (SBR) or a blend of SBR with natural rubber, butadiene rubber or with both, make it possible to cure with sulfur, but at the same time they exhibit a sensitivity toward oxygen, ozone, and other reactive substances causing changes such as hardening in the rubber.
  • SBR styrene-butadiene rubber
  • soft rubbers based on diene rubbers contain free double bonds, they remain sensitive to the above reactive substances even after vulcanization. Higher temperatures make these effects more noticeable.
  • unreacted double bonds are present in the rubber vulcanizate, there is the possibility of further reaction with sulfur causing hardening, i.e. additional crosslinking, of the vulcanizate.
  • the use of antioxidants will retard the oxygen-induced aging of the vulcanizate, but will not affect the increase in hardness due to sulfur-
  • vulcanizates from which, e.g., pneumatic tyres can be made, having improved properties can be obtained.
  • coagents have the effect of stabilizing the hardness properties of the rubber vulcanizate, e.g., during the service life of a pneumatic tyre, without bringing the flex and dynamic properties of the rubber such as torque and modulus to undesired levels, and are hereinafter also referred to as hardness stabilizing coagents.
  • the process according to the present invention is characterized in that in the non-productive or productive stage of mixing there is added 0.1 to 1 phr of a hardness stabilizing coagent according to any one of formulae l-IV:
  • R 1 , R 2 , and R 3 independently represent H or a C ⁇ Cs hydrocarbon group, optionally containing one or more oxygen, nitrogen or sulfur atoms,
  • R 1 and R 2 provided that R is in the 4-position, or R 2 and R 3 together with the carbon atoms to which they are attached may form a 5 or 6-membered ring, said ring optionally being substituted with a C r C 5 hydrocarbon group, said group optionally containing one or more oxygen, nitrogen or sulfur atoms, n is 1 to 4,
  • M is selected from Na, Zn, Mg, Al, Fe, and Te, and x is 1 to 4.
  • the abbreviation "phr” means the number of parts by weight per 100 parts by weight of rubber. In the case of a rubber blend, it is based on 100 parts by weight of total rubber.
  • SU-A-960203 discloses a sulfur vulcanization process wherein a composition comprising an unsaturated rubber such as cis-polybutadiene, 0.5-3.0 phr of zinc oxide, and 0.5-1.5 phr of zinc 2-pyridylthiooxide (further referred to in this application as zinc 2-mercaptopyridine N-oxide) is vulcanized. It is mentioned that the rubber vulcanizates obtained by this process have an increased dynamic fatigue resistance. This document does not relate to the problem of sulfur-induced hardening which is the subject of the present invention and which is particularly relevant to rubber compositions comprising styrene-butadiene rubber.
  • JP-A-04068042 discloses a vulcanizable rubber composition
  • a vulcanizable rubber composition comprising 0.1 to 10, preferably 0.2 to 5 phr of a pyridine compound such as 2- mercaptopyridine, 2-mercaptopyridine-N-oxide, 2,2'-dithiodipyridine, and 2,2'-dithiobis(pyridine-N-oxide) and 0.1-8 phr of sulfur.
  • a pyridine compound such as 2- mercaptopyridine, 2-mercaptopyridine-N-oxide, 2,2'-dithiodipyridine, and 2,2'-dithiobis(pyridine-N-oxide) and 0.1-8 phr of sulfur.
  • the rubber is selected from natural rubber, styrene-butadiene rubber, polyisoprene rubber, nitrile rubber, chloroprene rubber, butyl rubber, and ethylene-propylene terpolymer.
  • styrene-butadiene rubber polyisoprene rubber
  • nitrile rubber nitrile rubber
  • chloroprene rubber butyl rubber
  • ethylene-propylene terpolymer ethylene-propylene terpolymer.
  • 1.5 phr of a pyridine compound is used in rubber compositions comprising natural rubber.
  • the hardness stabilizing coagents according to formulae l-IV can be prepared by synthetic methods that are known to a person skilled in the art and using conventional equipment.
  • the 5 or 6-membered ring may be saturated or unsaturated, preferably unsaturated.
  • R 1 , R 2 , and R 3 represent H.
  • R 1 represents a C r C 5 hydrocarbon group and R 2 and R 3 form a 5 or 6-membered ring.
  • the C r C 5 hydrocarbon group is a C C 5 alkyl group, most preferably a methyl group.
  • the hydrocarbon group or ring does not contain an oxygen, nitrogen or sulfur atom.
  • n is 2.
  • M is Zn.
  • x is 1 or 2.
  • Suitable hardness stabilizing coagents include 2,2'- dithiobispyridine (formula IV), 2,2'-dithiobis(pyhdine N-oxide) (Pyro-S2, formula III), zinc 2-mercaptopyridine (ZnDTPy, formula II), zinc 2- mercaptopyridine N-oxide (ZPNO, formula I), sodium 2-mercaptopyridine (formula II), sodium 2-mercaptopyridine N-oxide (formula I), 2,2'- thiobislepidine (MTIep, formula IV), 2,2'-dithiobislepidine (DTIep, formula IV), and zinc 2-mercaptolepidine (ZnDTIep, formula II).
  • the hardness stabilizing coagent in accordance with the present invention is a coagent according to formula IV, most preferably 2,2'- thiobislepidine or 2,2'-dithiobislepidine.
  • Either a single coagent of formula I, II, III or IV or a mixture of coagents may be used.
  • Either styrene-butadiene rubber (SBR) or a blend of SBR with one or more other rubbers can be used in the invention process.
  • SBR a blend of SBR with natural rubber (NR), a blend of SBR with polybutadiene rubber or butadiene rubber (BR), or a blend of SBR with NR and BR is used.
  • NR natural rubber
  • BR polybutadiene rubber
  • BR butadiene rubber
  • a blend of SBR with NR and BR is used.
  • a blend of SBR and BR is used in the process of the present invention.
  • hardening is significant when the rubber blend contains 20 parts by weight or more of SBR per 100 parts by weight of the total rubber blend.
  • the amount of hardness stabilizing coagent employed in the process of the present invention is 0.1 to 0.9, more preferably 0.1 to 0.75, most preferably 0.25 to 0.5 phr.
  • sulfur a sulfur donor or a mixture thereof is employed.
  • the amount of sulfur to be compounded with the rubber usually is 0.1 to 10, preferably 0.1 to 5, more preferably 0.5 to 3 phr. If a sulfur donor is used the amount thereof should be calculated in terms of the amount of sulfur.
  • Typical examples of sulfur donors that can be used in accordance with the process of the present invention include dithiodimorpholine, caprolactam disulfide, tetramethylthiuram disulfide, and dipentamethylenethiuram tetrasulfide.
  • the reader is referred to W. Hofmann, Rubber Technology Handbook, Hanser Publishers, Kunststoff 1989, in particular pages 231-233.
  • vulcanization accelerators that can be used in accordance with the present invention the reader is referred to W. Hofmann, Rubber Technology Handbook, Hanser Publishers, Kunststoff 1989.
  • Typical vulcanization accelerators include thiazole- and benzothiazole- based accelerators, for example 2-mercaptobenzothiazole and bis(2- benzothiazolyl) disulfide (MBTS), benzothiazole-2-sulfenamide-based accelerators, such as N-cyclohexyl-benzothiazole-2-sulfenamide, N-tert- butyl-benzothiazole-2-sulfenamide (TBBS), N,N-dicyclohexyl- benzothiazole-2-sulfenamide, and 2-(morpholinothio)benzothiazole, thiophosphohc acid derivatives, thiurams, dithiOcarbamates, diphenylguanidine (DPG), diorthotolyl guanidine, dithiocarbamyl sulfenamides, xanthates, and mixtures of one or more of these accelerators.
  • MBTS 2-mercaptobenzothi
  • the vulcanization accelerator comprises a benzothiazole-2-sulfenamide.
  • Mixtures of one or more benzothiazole-2-sulfenamide-based vulcanization accelerators with diphenylguanidine are preferred, for example a combination of MBTS, TBBS, and DPG.
  • the vulcanization accelerator usually is employed in an amount of 0.1 to 5, preferably 0.3 to 3, most preferably 0.5 to 2.5 phr.
  • a typical sulfur-vulcanizable rubber composition to be used in the process in accordance with the present invention comprises SBR, preferably a blend of SBR and BR, 0.1 to 10 phr of sulfur and/or a sulfur donor, 0.1 to 5 phr of a vulcanization accelerator, preferably comprising a benzothiazole-2- sulfenamide, and 0.1 to 1 phr of a hardness stabilizing coagent according to any one of formulae l-IV.
  • the composition comprises 0.1 to 5 phr of sulfur and/or sulfur donor, 0.3 to 3 phr of a vulcanization accelerator, and 0.1 to 0.9 phr of a hardness stabilizing coagent according to any one of formulae l-IV.
  • Conventional rubber additives may also be included in the sulfur- vulcanizable rubber composition in accordance with the present invention.
  • examples include reinforcing agents such as carbon black, silica, clay, whiting and other mineral fillers, processing oils, tackifiers, waxes, (phenolic) antioxidants, (phenylenediamine) antidegradants, antiozonants, pigments, e.g. titanium dioxide, resins, plasticizers, factices, and vulcanization activators, such as stearic acid and zinc oxide.
  • reinforcing agents such as carbon black, silica, clay, whiting and other mineral fillers, processing oils, tackifiers, waxes, (phenolic) antioxidants, (phenylenediamine) antidegradants, antiozonants, pigments, e.g. titanium dioxide, resins, plasticizers, factices, and vulcanization activators, such as stearic acid and zinc oxide.
  • These conventional rubber additives may be added in amounts
  • vulcanization inhibitors i.e. scorch retarders, such as cyclohexyl- thiophthalimide, phthalic anhydride, pyromellitic anhydride, benzene hexacarboxylic trianhydride, 4-methylphthalic anhydride, trimellitic anhydride, 4-chlorophthalic anhydride, salicylic acid, benzoic acid, maieic anhydride, citraconic anhydride, itaconic anhydride, and N- nitrosodiphenylamine may be included in conventional, known amounts.
  • scorch retarders such as cyclohexyl- thiophthalimide, phthalic anhydride, pyromellitic anhydride, benzene hexacarboxylic trianhydride, 4-methylphthalic anhydride, trimellitic anhydride, 4-chlorophthalic anhydride, salicylic acid, benzoic acid, maieic anhydride, citraconic anhydride, it
  • steel-cord adhesion promoters such as cobalt salts and dithiosulfates in conventional, known quantities.
  • the sulfur vulcanization process of the present invention can be carried out using means and equipment that are well-known to a person skilled in the art. Suitable vulcanization procedures are described in W. Hofmann, Rubber Technology Handbook, Hanser Publishers, Kunststoff 1989.
  • a typical method comprises preparing a masterbatch comprising SBR, carbon black, a vulcanization activator, and a processing oil, in an internal mixer such as a Banbury mixer or a Werner & Pfleiderer mixer, i.e., the non-productive stage of mixing, and subsequently adding a vulcanization system comprising sulfur and a vulcanization accelerator, and the hardness stabilizing coagent in accordance with the present invention to the masterbatch on a two-roll mill, i.e. the productive stage of mixing.
  • the uncured rubber composition is then vulcanized by heating, e.g., by compression moulding.
  • the hardness stabilizing coagent may be added in the non-productive or productive stage of mixing.
  • the coagent is added in the productive stage of mixing, certainly in the case of a hardness stabilizing coagent according to formula III and IV with x is 3 or 4.
  • the invention vulcanization process typically is carried out at a temperature of 110-200, preferably 120-190, more preferably 140-180°C for a period of time of up to 12, preferably up to 6, more preferably up to 3 hours.
  • the present invention also pertains to articles of manufacture, such as pneumatic tyres, e.g., for passenger cars and trucks, and industrial rubber goods, which comprise the rubber vulcanizate obtained by the invention process.
  • articles of manufacture such as pneumatic tyres, e.g., for passenger cars and trucks, and industrial rubber goods, which comprise the rubber vulcanizate obtained by the invention process.
  • the invention is illustrated by the following examples.
  • a masterbatch of rubber, carbon black, stearic acid, zinc oxide, processing oil, and antidegradant was made in an internal mixer.
  • the sulfur, accelerators, and hardness stabilizing coagent were mixed on a two-roll mill at approx. 50-70°C.
  • Rubber compounds were vulcanized by compression moulding at 145°C for a period of time equal to 1.7xt go . After cooling the vulcanized rubber sheets for 24 h, test pieces were cut and analyzed.
  • Scorch time (t s 2) is the time to increase the torque 2 dNm above the minimum torque (M L ).
  • Optimum vulcanization time (t 90 ) is the time at 90% of the maximum torque (M H ).
  • T end is the time at the rheometer and is set at 1 h.
  • Delta torque (Delta S) is the difference between the minimum and the maximum torque.
  • the slope of a rheogram between M L and M H is a measure of the cure rate (RH).
  • Hysteresis is the percentage of energy lost per cycle of deformation.
  • the ratio of loss modulus to storage modulus is defined as mechanical loss and this corresponds to tangent delta (tan d).
  • the rubber test pieces were aged in a hot air circulation oven for 3 days (72 h) at 100°C to simulate hardening during use, for example, as a tyre.
  • the hardness stabilization characteristics were determined by calculating the so-called modulus stabilization (MS).
  • the modulus stabilization is the ratio of the modulus at elongation 200% (Mod200) of the aged and the unaged rubber test pieces and is expressed as a percentage by multiplying this ratio by 100%.
  • the lower the ratio Mod200 aged /Mod200 unaged the better the modulus retention or hardness stabilization.
  • the Mod200 was obtained from tensile stress-strain tests which were performed in accordance with ISO 37-1994 (dumb-bell type 2).
  • the coagents were compounded into a rubber composition comprising SBR as shown in Tables 1 and 4.
  • the rheological properties are shown in Tables 2 and 5, and the modulus stabilization, an indication of the hardness stabilizing effect of a coagent, is shown in Tables 3 and 6.
  • MS Mod200 aged /Mod200 u ⁇ aged x 100%
  • Tables 3 and 6 shows that the use of a low amount of a hardness stabilizing coagent in accordance with the present invention leads to the formation of rubber vulcanizates showing improved modulus stabilization (MS), i.e. hardness stabilization, as compared to the control.
  • MS modulus stabilization
  • Examples 1-4 indicate that a two-fold increase in the amount of the hardness stabilizing coagent does not improve modulus stabilization much further.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé de vulcanisation sulfurique comprenant (a) une étape non productive de mélange d'une composition de caoutchouc contenant un caoutchouc de styrène-butadiène, (b) une étape productive de mélange d'une composition de caoutchouc contenant en outre du sulfure et un accélérateur de vulcanisation, et (c) une vulcanisation de cette composition. L'invention se caractérise en ce qu'elle fait intervenir entre 0,1 et 1 phr d'un coagent de stabilisation de dureté au cours de l'étape productive ou non productive conformément aux formules (I) à (IV), dans lesquelles R?1, R2 et R3¿ représentent indépendamment H ou un groupe hydrocarbure C¿1?-C5 contenant éventuellement un ou plusieurs atomes d'oxygène, d'azote ou de soufre, R?1 et R2¿, à condition que R1 se trouve en position 4, ou R2 et R3, conjointement avec les atomes de carbone auxquels ils sont fixés, peuvent former un cycle à 5 ou 6 éléments, ledit cycle étant éventuellement substitué par un groupe hydrocarbure C¿1?-C5, ledit groupe contenant éventuellement un ou plusieurs atomes d'oxygène, d'azote ou de soufre, n vaut entre 1 et 4, M est choisi dans le groupe constitué par Na, Zn, Mg, Al, Fe et Te, et x vaut entre 1 et 4. L'invention concerne également un article de fabrication, tel qu'un pneumatique, constitué par le vulcanisat de caoutchouc obtenu selon ce procédé.
PCT/EP2000/008490 1999-08-31 2000-08-29 Stabilisation de la durete au moyen de mercaptopyridines WO2001016226A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU75124/00A AU7512400A (en) 1999-08-31 2000-08-29 Hardness stabilization by mercaptopyridines

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP99202822 1999-08-31
EP99202822.5 1999-08-31
US19026600P 2000-03-17 2000-03-17
US60/190,266 2000-03-17

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001070870A2 (fr) * 2000-03-21 2001-09-27 Flexsys America L.P. Derives de pyrimidine comme stabilisants de durete
WO2003070820A1 (fr) * 2002-02-22 2003-08-28 Flexsys B.V. Accelerateurs promoteurs d'adhesion de cable d'acier
JP2009040898A (ja) * 2007-08-09 2009-02-26 Toyo Tire & Rubber Co Ltd タイヤ用ゴム組成物
JP2011074313A (ja) * 2009-10-01 2011-04-14 Yokohama Rubber Co Ltd:The ゴム組成物およびそれを用いた空気入りタイヤ

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4482663A (en) * 1982-07-12 1984-11-13 Phillips Petroleum Company Rubber compositions comprising a siliceous filler in combination with an organosulfur substituted pyridine promotor
JPH0468042A (ja) * 1990-07-10 1992-03-03 Bridgestone Corp ゴム組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4482663A (en) * 1982-07-12 1984-11-13 Phillips Petroleum Company Rubber compositions comprising a siliceous filler in combination with an organosulfur substituted pyridine promotor
JPH0468042A (ja) * 1990-07-10 1992-03-03 Bridgestone Corp ゴム組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 016, no. 273 (C - 0953) 18 June 1992 (1992-06-18) *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001070870A2 (fr) * 2000-03-21 2001-09-27 Flexsys America L.P. Derives de pyrimidine comme stabilisants de durete
WO2001070870A3 (fr) * 2000-03-21 2002-01-03 Flexsys America Lp Derives de pyrimidine comme stabilisants de durete
US6646029B1 (en) 2000-03-21 2003-11-11 Flexsys America L.P. Pyrimidine derivatives as hardness stabilizers
KR100706415B1 (ko) * 2000-03-21 2007-04-10 플렉시스 아메리카, 엘.피. 경도 안정화제로서의 피리미딘 유도체
WO2003070820A1 (fr) * 2002-02-22 2003-08-28 Flexsys B.V. Accelerateurs promoteurs d'adhesion de cable d'acier
JP2009040898A (ja) * 2007-08-09 2009-02-26 Toyo Tire & Rubber Co Ltd タイヤ用ゴム組成物
JP2011074313A (ja) * 2009-10-01 2011-04-14 Yokohama Rubber Co Ltd:The ゴム組成物およびそれを用いた空気入りタイヤ

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