US20140128538A1 - Vulcanization composition for unsaturated polymers - Google Patents

Vulcanization composition for unsaturated polymers Download PDF

Info

Publication number
US20140128538A1
US20140128538A1 US14/123,614 US201214123614A US2014128538A1 US 20140128538 A1 US20140128538 A1 US 20140128538A1 US 201214123614 A US201214123614 A US 201214123614A US 2014128538 A1 US2014128538 A1 US 2014128538A1
Authority
US
United States
Prior art keywords
vulcanization
bis
organic base
unsaturated polymer
unsaturated
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US14/123,614
Other languages
English (en)
Inventor
Isabelle Yarzabel
Thierry Aubert
Pierre Lugez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MLPC International SA
Original Assignee
MLPC International SA
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 MLPC International SA filed Critical MLPC International SA
Assigned to MLPC INTERNATIONAL reassignment MLPC INTERNATIONAL ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LUGEZ, PIERRE, AUBERT, THIERRY, YARZABAL, ISABELLE
Publication of US20140128538A1 publication Critical patent/US20140128538A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2311/00—Characterised by the use of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C08L23/283—Halogenated homo- or copolymers of iso-olefins

Definitions

  • the present invention relates to the field of the vulcanization of unsaturated polymers, in particular unsaturated halogenated polymers, more particularly unsaturated chlorinated polymers, such as, for example, polychloroprene.
  • unsaturated polymers in particular unsaturated halogenated polymers, more particularly unsaturated chlorinated polymers, such as, for example, polychloroprene.
  • the present invention relates in particular to the vulcanization agents which are employed in these processes as vulcanization accelerators.
  • the accelerators used in the vulcanization of unsaturated polymers, polyolefins or rubbers, in particular halogenated rubbers, such as polychloroprene, are generally thiourea-based accelerators which today compose the crosslinking systems for rubbers having the best performance.
  • Ethylene thiourea is the reference thiourea used today for the vulcanization of chlorinated rubbers, in particular polychloroprene.
  • ETU is toxic in itself, classified in carcinogenic group 2, according to the classification of the European Union, the IARC (International Agency for Research on Cancer) and the EPA (Environmental Protection Agency).
  • Patent U.S. Pat. No. 4,288,576 describes the use of 2,5-dimercapto-1,3,4-thiadiazole for the vulcanization of saturated chlorinated polymers, in the presence of a basic compound chosen from amines, amine salts, quaternary ammonium salts, aromatic guanidines and the condensation products of aniline with an aldehyde.
  • Patent U.S. Pat. No. 5,391,621 describes the use of certain organopolysulphide compounds derived from 1,3,4-thiadiazole as agents for the vulcanization of chlorinated polymers.
  • Other polysulphides, poly[2,5-bis(polysulphano)-1,3,4-thiadiazoles] are described in
  • Patent U.S. Pat. No. 5,563,240 where they are of use as agents for the vulcanization of polychloroprene.
  • Patent Application EP 0 796 890 describes the vulcanization of halogenated acrylic rubbers in the presence of 2,5-dimercapto-1,3,4-thiadiazole or derivatives and of a metal dialkyldithiocarbamate.
  • Patent Application US 2003/153652 also presents compositions for vulcanizing chlorinated polymers, the said compositions resulting from the mixing of a zeolite compound with a vulcanization agent chosen from mercaptotriazines, thiadiazoles and thiurams.
  • a first objective of the present invention consists in providing an agent (or accelerator) for the vulcanization of unsaturated polymers, in particular of polyalkadienes, more particularly of unsaturated halogenated polymers, typically of unsaturated chlorinated polymers and in particular polychloroprene, the said agent or accelerator advantageously having to be nontoxic or only very slightly toxic and more environmentally friendly.
  • Another objective of the present invention consists in providing a vulcanization accelerator which is less toxic than ETU and in particular which does not release compounds of nitrosamine type.
  • Yet another objective consists in providing a vulcanization agent which confers, on the unsaturated polymers, in particular unsaturated halogenated polymers, for example unsaturated chlorinated polymers, in particular of polychloroprene type, mechanical properties equivalent to those obtained with systems employing toxic accelerators.
  • unsaturated polymers in particular unsaturated halogenated polymers, for example unsaturated chlorinated polymers, in particular of polychloroprene type, mechanical properties equivalent to those obtained with systems employing toxic accelerators.
  • the vulcanization agent provided can confer good ageing properties on the polymers.
  • an objective also consists in providing a vulcanization accelerator which makes it possible to increase the scorch time (or prevulcanization time).
  • Yet another objective consists in reducing the amount of inorganic vulcanization agents, generally metal oxides, in particular zinc and/or magnesium oxides, used in the vulcanization of unsaturated polymers, in particular unsaturated halogenated polymers, more specifically unsaturated chlorinated polymers, without affecting the mechanical, rheological and other properties thereof, thus making it possible to also reduce the amount of toxic effluents associated with the process, while also reducing the production costs.
  • inorganic vulcanization agents generally metal oxides, in particular zinc and/or magnesium oxides
  • FIG. 1 is a graph of the change in torque as a function of time for mixtures containing vulcanization formulations.
  • the invention relates to the use, as agent for the vulcanization of unsaturated polymers, in particular unsaturated halogenated polymers, more particularly unsaturated chlorinated polymers, of at least one mixture comprising bis(2,5-dimercapto-1,3,4-thiadiazole), denoted bis-DMTD in the continuation of the present description, and at least one organic base.
  • unsaturated polymers in particular unsaturated halogenated polymers, more particularly unsaturated chlorinated polymers, of at least one mixture comprising bis(2,5-dimercapto-1,3,4-thiadiazole), denoted bis-DMTD in the continuation of the present description, and at least one organic base.
  • bis-DMTD corresponds to one of the two following structures, depending on the tautomeric forms selected:
  • bis-DMTD is today mainly used in lubricant compositions but is used to a very slight extent in compositions comprising natural, artificial or synthetic rubbers, where it generally acts as preservative and has never been described as such as an additive for the vulcanization of unsaturated polymers. bis-DMTD does not generate nitrosamines.
  • the organic base used in combination (mixture) with the bis-DMTD can be of any type known to a person skilled in the art. However, preference is given to nitrogenous organic bases and more particularly guanidines, which are optionally substituted, with which an entirely unexpected effect of improving the kinetics of vulcanization and the scorch time has been observed, when they are used in combination with bis-DMTD.
  • guanidines substituted by one or more aryl groups, preferably by one or two aryl groups, preferably by two aryl groups.
  • An organic base which is altogether preferred in the context of the present invention is diphenylguanidine.
  • the bis-DMTD/organic amine molar ratio is between 1:99 and 99:1, preferably between 25:75 and 75:25, for example approximately 50:50.
  • a vulcanization composition in which the bis-DMTD/organic amine molar ratio is between 40:60 and 99:1, preferably between 50:50 and 99:1, more preferably between 60:40 and 99:1, entirely preferably between 70:30 and 99:1.
  • the polymers which can advantageously be vulcanized by virtue of the abovementioned mixture are unsaturated polymers, in particular unsaturated halogenated polymers, more particularly unsaturated chlorinated polymers. More specifically, the polymers targeted in the present invention are all the polymers and copolymers comprising at least one ethylenic unsaturation, among which may be mentioned, as nonlimiting examples, natural, artificial or synthetic rubbers, poly(butadienes), styrene and butadiene copolymers (SBRs), acrylonitrile and butadiene copolymers (NBRs), ethylene/propylene/diene copolymers (EPDMs), butyl rubbers, SBSs, halogenated polyalkadienes, in particular chlorinated polyalkadienes, and others, as well as the mixtures of these homopolymers and copolymers in all proportions.
  • unsaturated polymers in particular unsaturated halogenated polymers, more particularly unsaturated chlorinated
  • the chlorinated polyalkadienes comprise more than 1% by weight of chlorine, preferably more than 2% by weight of chlorine and more preferably approximately 5% by weight of chlorine.
  • the chlorine content can reach up to 40% by weight of chlorine, with respect to the total weight of the polymer.
  • chlorinated polyalkadienes without implied limitation, of chloroprene rubbers or polychloroprenes, chlorinated natural rubbers, chlorinated polyolefins, chlorinated butyl rubbers and others.
  • Such mixtures can comprise from 10% by weight to 90% by weight of each of the polymers, preferably from 25% by weight to 75% by weight, with respect to the total weight of the polymers in the mixtures.
  • the chlorinated polymers which can be used in the context of the present invention are chlorinated polymers comprising one or more ethylenic unsaturations and, entirely preferably, the chlorinated polymers targeted in the present invention are polychloroprenes, alone or as blends with other homopolymers and/or copolymers, as indicated above.
  • the bis-DMTD in combination with an organic base, in particular a nitrogenous organic base, more particularly a guanidine, acts synergistically in the vulcanization of the unsaturated polymers.
  • bis-DMTD appears to be a good sulphur donor, which makes it a good vulcanization agent.
  • the amine bases promote, on the one hand, the release of the sulphur present in the bis-DMTD, which improves the properties of the vulcanisate, and, on the other hand, they improve the kinetics of vulcanization, while maintaining a certain scorch safety.
  • sulphur can be added to the vulcanization process employing the vulcanizing composition according to the present invention. This is because it has been discovered that the addition of a small amount of sulphur to the bis-DMTD can catalyse the reaction and thus increase the bridging density. This makes it possible to obtain a very high degree of crosslinking, which confers excellent compression set properties and also very slight swellings in oil of the vulcanized polymer thus obtained.
  • the bis-DMTD can additionally be employed on an elastomer support, in order to promote the dispersion thereof and thus to reduce the mixing times.
  • bis-DMTD in combination with at least one organic base, for example a guanidine
  • at least one organic base for example a guanidine
  • vulcanization accelerator has proved to be entirely effective during the vulcanization of polychloroprene.
  • the kinetics of vulcanization employing a bis-DMTD/organic base mixture have proven to be comparable, indeed even superior, to the kinetics of vulcanization observed in the presence of ETU.
  • the use of the bis-DMTD/organic base mixture in place of ETU as vulcanization agent makes it possible to confer, on the unsaturated polymers, in particular unsaturated halogenated polymers, a good tear strength and a good tensile strength, and also good resistance to ageing.
  • the scorch time of the unsaturated polymers vulcanized by the bis-DMTD/organic base mixture can be effectively controlled by means of retardants appropriate to this novel vulcanization system (for example MBTS and/or CTPI in polychloroprene).
  • the bis-DMTD/organic base mixture is advantageously used as accelerating agent for the vulcanization of chlorinated polymers, in combination with one or more inorganic vulcanization agents well known to a person skilled in the art.
  • the inorganic vulcanization agents are chosen from metal oxides and in particular from zinc oxide (ZnO), magnesium oxide (MgO) and others, and also the mixtures of two or more of them in all proportions.
  • the present invention relates to the process for the vulcanization of an unsaturated polymer, the said process comprising at least the following stages:
  • the mixing of the unsaturated polymer with the bis-DMTD/organic base combination can be carried out according to any technique known per se, for example as a masterbatch (with regard to molten polymer, solid polymer, as granules, as chips, and others) or in paste form (for example with regard to wax or with a high oil content).
  • the bis-DMTD and the organic base can be added simultaneously or separately.
  • the bis-DMTD can be introduced in the supported form, for example supported on an olefin, in order to reduce the mixing time of the said bis-DMTD with the polymer to be vulcanized.
  • sulphur can be added simultaneously or before or subsequently to the bis-DMTD/organic base mixture and simultaneously or before or subsequently to the inorganic agents (in particular metal oxides).
  • inorganic agents in particular metal oxides.
  • the vulcanization is carried out according to any procedure known to a person skilled in the art, at a temperature, at a pressure and for a period of time which is appropriate according to the nature and the type of vulcanization carried out.
  • additives can be added during the vulcanization process according to the present invention.
  • additives are well known to a person skilled in the art and can be chosen, as nonlimiting examples, from lubricants, fillers, colourants, preservatives, antioxidants, heat stabilizers, UV stabilizers, vulcanization inhibitors or retardants, such as MBTS (mercaptobenzothiazole disulphide), CTPI (N-cyclohexylthiophthalimide), and others.
  • MBTS mercaptobenzothiazole disulphide
  • CTPI N-cyclohexylthiophthalimide
  • the vulcanization can be carried out by simultaneously adding a mixture of the vulcanization agents, in or not in combination with the covulcanization agents and other additives.
  • a mixture (“mixture for vulcanization”) can thus comprise one or more of the following ingredients, which will be premetered according to the nature of the chlorinated polymer and the degree of vulcanization thereof desired: sulphur, bis-DMTD, organic base, inorganic agents and additive(s).
  • the mercaptan-grade neoprene WRT is generally vulcanized in the presence of ETU, used as vulcanization accelerator, which confers the best results in terms of compression set (CS) and ageing.
  • ETU is a toxic product due to its chemical nature and exhibits risks when used: ETU is regarded as carcinogenic by ingestion, mutagenic or also as exhibiting risks of sterility by simple contact with the skin.
  • the mixtures are prepared so as to obtain a blank weighing approximately 600 g, corresponding to 2 plaques with a thickness of 2 mm, and the production of the CS graphs. Vulcanization is carried out to T 90 (vulcanization time for obtaining 90% of the maximum torque) at 170° C.
  • the mixtures M 1 to M 9 and M 0 are characterized mechanically (rheometric study).
  • the change in the torque as a function of time, at a temperature of 170° C., is shown in FIG. 1 . It is noticed that the mixtures M 2 to M 9 according to the invention exhibit a greater torque than that of the control mixture M 0 , where the vulcanization agent used is ETU.
  • the mixtures M 1 to M 9 are characterized mechanically and the data collected are used in the matrix of the experimental plan, which makes it possible to obtain a theoretical change in the properties of the mixtures vulcanized with bis-DMTD.
  • the experimental plan makes it possible to obtain a change in 3D of the properties.
  • DPG has a synergistic effect with the bis-DMTD, favouring the release of the sulphur atoms present in the bis-DMTD and thus improving the final properties of the material. It can also be deduced that the sulphur acts as catalyst of the reaction.
  • this bis-DMTD/organic base (in the example, DPG) mixture makes it possible to reduce the content of ZnO necessary, without affecting the properties of the final product.
  • reducing the metal oxides is one of the major ways of improving the environmental impact.
  • the coupling provided in the present invention due to the reduction in the content of ZnO, thus contributes to new environmental regulations.
  • SBR Styrene/Butadiene Rubber
  • Example 1 the mixing of components is carried out in a 2.5 l Repiquet internal mixer at 50 revolutions/min with a filling coefficient of 1.4.
  • the amine compounds act synergistically with the bis-DMTD: the DPG promotes the release of sulphur, which increases the bridging degree and improves the kinetics of vulcanization.
  • the mixing is carried out in a 2.5 l Repiquet internal mixer at 50 revolutions/min and a filling coefficient of 1.4.
  • the “EPDM base” used exhibits the following composition, in which the parts are expressed by weight:
  • E1 E2 E3 E4 EPDM base 282 282 282 282 Stearic acid 2 2 2 2 Ekaland ® ZBEC pd 1.4 1.4 1.4 1.4 Mixland ® + ZDTP 50 GA F500 3 3 3 3 Mixland ® + DPG 80 GA F140 0.5 0 0.5 0.5 bis-DMTD powder (MLPC Intl) 0 0.5 0.5 1 Mixland ® + SM300 80 GA F140 2 2 2 2 2 Rheometry on an MDR at 170° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
US14/123,614 2011-06-06 2012-06-05 Vulcanization composition for unsaturated polymers Abandoned US20140128538A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR1154904A FR2975996B1 (fr) 2011-06-06 2011-06-06 Composition de vulcanisation pour polymeres insatures
FR1154904 2011-06-06
PCT/FR2012/051249 WO2012168642A1 (fr) 2011-06-06 2012-06-05 Composition de vulcanisation pour polymères insaturés

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/FR2012/051249 A-371-Of-International WO2012168642A1 (fr) 2011-06-06 2012-06-05 Composition de vulcanisation pour polymères insaturés

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/271,878 Continuation US10087308B2 (en) 2011-06-06 2016-09-21 Vulcanization composition for unsaturated polymers

Publications (1)

Publication Number Publication Date
US20140128538A1 true US20140128538A1 (en) 2014-05-08

Family

ID=46420427

Family Applications (3)

Application Number Title Priority Date Filing Date
US14/123,614 Abandoned US20140128538A1 (en) 2011-06-06 2012-06-05 Vulcanization composition for unsaturated polymers
US15/271,878 Expired - Fee Related US10087308B2 (en) 2011-06-06 2016-09-21 Vulcanization composition for unsaturated polymers
US16/133,160 Abandoned US20190194424A1 (en) 2011-06-06 2018-09-17 Vulcanization composition for unsaturated polymers

Family Applications After (2)

Application Number Title Priority Date Filing Date
US15/271,878 Expired - Fee Related US10087308B2 (en) 2011-06-06 2016-09-21 Vulcanization composition for unsaturated polymers
US16/133,160 Abandoned US20190194424A1 (en) 2011-06-06 2018-09-17 Vulcanization composition for unsaturated polymers

Country Status (7)

Country Link
US (3) US20140128538A1 (fr)
EP (1) EP2718360A1 (fr)
JP (1) JP5925882B2 (fr)
CN (1) CN103597022B (fr)
FR (1) FR2975996B1 (fr)
TW (1) TWI551629B (fr)
WO (1) WO2012168642A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190002605A1 (en) * 2015-12-23 2019-01-03 Arlanxeo Deutschland Gmbh Low temperature cross linkable polychloroprene compositions
US20190023821A1 (en) * 2015-12-23 2019-01-24 Arlanxeo Deutschland Gmbh Novel polychloroprene compositions

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2975996B1 (fr) * 2011-06-06 2013-05-24 Mlpc Internat Composition de vulcanisation pour polymeres insatures
WO2014119517A1 (fr) * 2013-01-30 2014-08-07 電気化学工業株式会社 Composition de caoutchouc chloroprène et article moulé vulcanisé
JP2014169378A (ja) * 2013-03-04 2014-09-18 Denki Kagaku Kogyo Kk ゴム組成物及び加硫発泡成形体

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4128510A (en) * 1976-06-28 1978-12-05 Hercules Incorporated Vulcanizing halogen-containing polymers
US20030153652A1 (en) * 1998-06-12 2003-08-14 Daiso Co., Ltd Chlorine-containing polymer vulcanizing composition

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4288576A (en) * 1978-09-15 1981-09-08 Hercules Incorporated 2,5-Dimercapto-1,3,4-thiadiazole as a cross-linker for saturated, halogen-containing polymers
DE4013714A1 (de) * 1990-04-28 1991-10-31 Rhein Chemie Rheinau Gmbh Verfahren zum vernetzen von halogenhaltigen polymeren
US5391621A (en) 1993-10-15 1995-02-21 R. T. Vanderbilt Company, Inc. 1,3,4-thiadiazole curing systems for chlorine containing polymers
DE4424680A1 (de) 1994-07-13 1996-01-18 Rhein Chemie Rheinau Gmbh Poly[2.5-bis(polysulfano)-1.3.4-thiadiazole]
EP0796890A1 (fr) * 1996-03-18 1997-09-24 ENICHEM S.p.A. Composition vulcanisable à base de caoutchouc acrylate
JP3719048B2 (ja) * 1998-06-12 2005-11-24 ダイソー株式会社 塩素含有重合体加硫用組成物
JP2003055513A (ja) * 2001-08-22 2003-02-26 Daiso Co Ltd 低硬度ゴム用組成物、その加硫物およびゴムロール
JP2005036141A (ja) * 2003-07-17 2005-02-10 Daiso Co Ltd ブレンドゴム加硫用組成物
CN100569762C (zh) 2006-06-29 2009-12-16 中国石油化工股份有限公司 二硫代二噻唑酮的合成方法
FR2947549B1 (fr) 2009-07-06 2011-08-05 Mlpc Internat Procede de preparation de bis-dmtd
FR2975996B1 (fr) * 2011-06-06 2013-05-24 Mlpc Internat Composition de vulcanisation pour polymeres insatures

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4128510A (en) * 1976-06-28 1978-12-05 Hercules Incorporated Vulcanizing halogen-containing polymers
US20030153652A1 (en) * 1998-06-12 2003-08-14 Daiso Co., Ltd Chlorine-containing polymer vulcanizing composition

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190002605A1 (en) * 2015-12-23 2019-01-03 Arlanxeo Deutschland Gmbh Low temperature cross linkable polychloroprene compositions
US20190023821A1 (en) * 2015-12-23 2019-01-24 Arlanxeo Deutschland Gmbh Novel polychloroprene compositions
US10899857B2 (en) * 2015-12-23 2021-01-26 Arlanxeo Deutschland Gmbh Polychloroprene compositions
US11001655B2 (en) * 2015-12-23 2021-05-11 Arlanxeo Deutschland Gmbh Low temperature cross linkable polychloroprene compositions

Also Published As

Publication number Publication date
FR2975996A1 (fr) 2012-12-07
US20190194424A1 (en) 2019-06-27
WO2012168642A1 (fr) 2012-12-13
JP2014516116A (ja) 2014-07-07
CN103597022A (zh) 2014-02-19
FR2975996B1 (fr) 2013-05-24
TWI551629B (zh) 2016-10-01
EP2718360A1 (fr) 2014-04-16
CN103597022B (zh) 2016-06-01
TW201313789A (zh) 2013-04-01
US10087308B2 (en) 2018-10-02
US20170121500A1 (en) 2017-05-04
JP5925882B2 (ja) 2016-05-25

Similar Documents

Publication Publication Date Title
US20190194424A1 (en) Vulcanization composition for unsaturated polymers
US20170267841A1 (en) Diphenylguanidine-free rubber mixtures containing polyethylenimine
RU2706609C2 (ru) Не содержащие дифенилгуанидина смеси каучуков, содержащие короткоцепные алкиловые сложные эфиры глицерина
US12091529B2 (en) Process for vulcanizing a reinforced rubber composition
US11292903B2 (en) Rubber mixtures containing sulfur-containing organosilicon compounds
EP3383946B1 (fr) Nouveaux melanges d'additifs de traitement
KR20230166102A (ko) N,N'-다이알킬-p-페닐렌다이아민을 함유하는 고무 혼합물
US6114469A (en) Rubber compositions containing zinc hexasulfide complexes
JP2008274197A (ja) シリカ含有タイヤトレッド用ゴム組成物
CA2607983C (fr) Formule de caoutchouc contenant des sels metalliques d'acides organiques, methode de durcissement, formules durcies et article
JP2000309665A (ja) ゴム組成物
US20240124686A1 (en) Vulcanizable compositions including diresorcinol sulfide and vulcanizates prepared therefrom
JPH11172046A (ja) ゴム組成物
JP2001031797A (ja) ゴム組成物
JP2000336213A (ja) ゴム組成物
US20090215966A1 (en) Rubber composition containing metal salts of organic acids, method of curing, cured compositions, and article
JPH06256603A (ja) ゴム組成物
JP2001164048A (ja) クロロプレン系ゴム組成物
JPH01263133A (ja) ゴム組成物

Legal Events

Date Code Title Description
AS Assignment

Owner name: MLPC INTERNATIONAL, FRANCE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:YARZABAL, ISABELLE;AUBERT, THIERRY;LUGEZ, PIERRE;SIGNING DATES FROM 20131122 TO 20131127;REEL/FRAME:031707/0014

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION