WO2001004208A1 - Composition contenant nbr et elastomeres thermoplastiques - Google Patents

Composition contenant nbr et elastomeres thermoplastiques Download PDF

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Publication number
WO2001004208A1
WO2001004208A1 PCT/BR2000/000073 BR0000073W WO0104208A1 WO 2001004208 A1 WO2001004208 A1 WO 2001004208A1 BR 0000073 W BR0000073 W BR 0000073W WO 0104208 A1 WO0104208 A1 WO 0104208A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
butadiene
nbr
acrylonitrile
parts
Prior art date
Application number
PCT/BR2000/000073
Other languages
English (en)
Inventor
Maurício MOREIRA NUNES
Mauro Eduardo Costa Braz Pinto
Original Assignee
Nitriflex S/A Indústria E Comércio
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 Nitriflex S/A Indústria E Comércio filed Critical Nitriflex S/A Indústria E Comércio
Priority to EP00940084A priority Critical patent/EP1161493A4/fr
Publication of WO2001004208A1 publication Critical patent/WO2001004208A1/fr

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Classifications

    • 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
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the present invention refers to NBR copolymer thermoset elastomer compositions or mixtures, or NBR copolymers with a crosslinking agent, with the thermoplastic elastomers having improved surface and dullness or opacity properties.
  • Application of these mixtures can be found in the shoes industry, that is, in shoe soles and similar, tubes and hoses, toys, coifs, gaskets and any other article made of rubber.
  • the present invention also relates to vulcanizable NBR and thermoplastic elastomer copolymer or terpolymer mixtures or compositions. BACKGROUND OF THE INVENTION
  • thermoplastic polymers results in a rubber with a brightness aesthetically not accepted by the shoe industry.
  • These mixtures are generally constituted of thermoplastic elastomers such as SBR, SSBR, and so on with polybutadiene . Due resulting brightness in the final product, this would have to be further subjected to a dulling process to produce an aesthetically useful article for shoe soles.
  • these rubbers have poor mechanical properties, such as processability, strain, elasticity, abrasion and elastomeric memory and other properties.
  • the elastomeric mixture technology is rapidly improving, mainly in the case of elastomeric mixtures to produce thermoplastic elastomers. All this shows that this tendency, named technology tendency will grow in the polymer industry. This means that less emphasis will be given to the development of new materials derived from totally new monomers. This means that from now on more improved materials formed from mixtures and composite materials, from known polymers will be produced.
  • thermoplastic rubbers of the prior art Due to a need for obtaining a rubber with vulcanized rubber characteristics, without the disadvantages of the groups of thermoplastic rubbers of the prior art, the present inventors have concentrated their aim at the structural morphology of elastomeric materials, in an attempt to control physical, chemical, rheological and surface properties of thermoplastic materials.
  • the main idea arised from the fact that most polymers, when mixed, wield two phases inside their morphology, this being predominant in all thermoplastics, as they are structured by "soft domain” (polybutadiene) and "hard domain” (styrene) .
  • the polymer found in greater concentration would be the continuous phase with the second polymer soaked between them thus, forming a discrete continuous matrix.
  • Drs Drs .
  • thermoplastic elastomers for specific uses, as for example in shoe products.
  • thermoplastic elastomer mixtures are characterised as materials, which can be processed when, submitted to friction and temperatures and, later, when they are cooled they show properties similar to the vulcanized elastomers .
  • thermoplastic elastomers When most thermoplastic elastomers are compounded or formulated, they must be assisted by additives such as: mineral fillers, plasticizing oils, antioxidants and high tenacity polymeric mixtures (high impact polystyrene) , to improve, as they say, their final properties, such as: abrasion, tearing and stiffness with the circunstancial reduction of their flow property, when using calcium carbonate and silica, thus requiring the use of 5 to 30 parts of high impact polystyrene in the formulation. Then the undesirable fact occurs.
  • additives such as: mineral fillers, plasticizing oils, antioxidants and high tenacity polymeric mixtures (high impact polystyrene)
  • the discrete thermoplastic phase from the polystyrene with a lesser proportion in the diblocked elastomer (styrene butadiene) is increased in a disproportional way and the elastomeric phase of the polybutadiene is diminished.
  • Addition of high impact polystyrene homopolymers, when aggregated to the diblocked polymers increase disproportionately the Yong modules, which normally, with the addition of plasticizing oils cause the reduction of these modules.
  • the diblock SBS thermoplastics are very elastic during their softening in the process phase. This is due to the retention of the two phases and their "interclosed" structures above the glass transition temperature (T g ) of the blocked polystyrenes .
  • thermoplastics Due to this apparent deficiency there is a demand in the shoe industry for lighter and more practical new materials, such as thermoplastics, which would be the ideal candidates for an excellent productivity and a minimal possible loss (vulcanized cuttings) , increasing their versatility and diminishing the labor required for vulcanized elastomers.
  • thermoplastics which would be the ideal candidates for an excellent productivity and a minimal possible loss (vulcanized cuttings) , increasing their versatility and diminishing the labor required for vulcanized elastomers.
  • vulcanized cuttings vulcanized cuttings
  • the present inventors developed a rubber from a mixture of thermoplastic with NBR or a pre - crosslinked NBR, in which addition of NBR or pre - crosslinked NBR (NBR + monomer + crosslinked agent) provide dull thermoplastic elastomers.
  • ABSTRACT OF THE INVENTION The present invention consists of a thermoset NBR copolymer polymeric elastomer composition or a NBR copolymer plus a crosslinking agent, with thermoplastic elastomers, wherein they exhibit improved mechanical and surface properties, as well as a final dull product.
  • the present invention also refers to a vulcanizable polymeric composition.
  • the object of the present invention is to provide a polymeric composition, comprising from 5 to 95 parts of NBR per 100 parts of the composition with thermoplastic elastomer.
  • Another object of the invention is to provide a polymeric composition
  • a polymeric composition comprising from 5 to 95 parts of NBR terpolymer - crosslinking agent per 100 parts of the composition with polymeric elastomer, in which the elastomer is selected from monoblocked, diblockerd, triblocked, radial or linear thermoplastic elastomers.
  • Another object of the invention is to provide a vulcanizable polymeric composition
  • a vulcanizable polymeric composition comprising from 5 to 95 parts of (NBR) butadiene-acrylonytrile copolymer or a terpolymer of butadiene-acrylonytrile-butadiene (NBR) - crosslinking monomer per 100 parts of the composition with thermoplastic elastomer and an effective amount of a vulcanized system.
  • the crosslinking agent used in the composition is selected from monomers with a functionality equal or higher than 3.
  • the agents or crosslinking monomers are selected from divinyl benzene, trimethylol propane trimetacrylate, ethylene glycol dimetacrylate and triallyl isocianurate .
  • elastomeric material it is meant the one, which can be drawn to 100% of its original size, without losing its return, that is, it returns to its original size in a short period of time.
  • thermoplastic elastomers and NBR thermoplastic elastomers and NBR, with the difference that the modules diminish proportionally to the crosslinkage degree and' to the amount of acrylonitrile used in the NBR copolymer, which does not occur in thermoplastic elastomers without the presence of NBR.
  • thermoplastic elastomers and thermoelastic mixtures exhibit strain/deformation features, this fact being proved in thermoplastic elastomers as they have low modules, typical of crosslinked elastomers (C curve) and other high modules producing materials undergo from a high degree of plastic deformation (B curve) .
  • polymeric mixtures By using the polymeric mixtures, physical properties can be altered thus, producing materials, which can be used in a great number of applications in several different industries.
  • crosslinking monomer includes conventionally known monomers in the art as polymerizable crosslinking agents, in combination with other traditional monomers.
  • these crosslinking monomers include monomers with a functionality equal or higher than 3, such as divinyl benzene, trimethylol propane trimethacrylate, ethylene glycol dimethacrylate and triallyl isocyanate, 1, 3 dimethacrylate butilene, alyl metacrylate, or any other crosslinking agent known from the art.
  • the term "NBR copolymer or terpolymer of butadiene-acrylonitrile-crosslinking monomers agent" is simply called NBR.
  • the polar acrylonytrile monomer content can vary from 1 to 60%, preferably from 5 to 50% and more preferably form 15 to 45% by weight based on the butadiene weight.
  • the crosslinking agent varies from 0 to 20%, preferably from 0 to 10% and more preferably from 0 to 5% by weight based on the weight of acrylonytrile and butadiene.
  • copolymers or terpolymers are capable of producing effects only presently found by using syndiotactic polybutadiene polymers when mixed with some blocked, diblocked, triblocked polymer thermoplastics (styrene butadiene - styrene, (SBS) , styrene - isoprene-butadiene- styrene (SSBS) , styrene - isoprene - butadiene - styrene (SIBS) , styrene- isoprene-styrene (SIS) , independently if they are linear or radial in their basic structure.
  • SBS styrene butadiene - styrene
  • SIBS styrene - isoprene-butadiene- styrene
  • SIBS styrene- isoprene-styren
  • NBR in the polymeric composition presents an excellent compatibility in concentrations from 5 to 50 parts, preferably from 5 to 40 parts, more preferably from 5 to 30 parts, and much more preferably from 5 to 20 parts per 100 parts of elastomer, exhibiting superior or equal physical and mechanical characteristics in different used proportions when compared with syndiotactic polybutadiene conventionally used in thermoplastic elastomer compositions, so as to produce the desired effects in the shoe industry, mainly when partially crosslinked NBR copolymers with shrinkage values between 0 and 15%, 0 and 20%, 0 and 30% or 0 and 40% are used.
  • thermoplastic elastomer final mixtures with varied NBRs present mechanical properties on the same level or superior to those produced by thermoplastic elastomers and syndiotactic polybutadiene.
  • Syndiotactic polybutadiene is world-wide produced only by "Japan Synthetic Rubber Co.”, and nowadays this company cannot supply the worldly demands. Customers from all over the world purchase such products under share regime, due to the fact that annual production of syndiotactic polybutadiene is not capable of attending the world requirements. It is also an object of the present invention to offer to the market an alternative to the shortage of this product, also providing the development of new applications of thermoplastic rubbers not so much explored until now.
  • thermoplastic elastomer matrix in combination with the intermolecular linkages of the butadiene-acrylonytrile-crosslinking monomer terpolymer, generate a crosslinked structure in three dimensions, which upon melting during the moulding step returns to its original position after melting.
  • the intermolecular linkages and the intramolecular linkages play fundamental role either in maintaining a good level of mechanical properties or in the dullness showed by the mixture.
  • Crosslinkages withstand the melting process without tearing. Thus, after their post-melting cooling, these crosslinkages maintain the interclosed structures of the mixture stiffening the polymeric structure, now cold, thus producing a microscopic wrinkling on the artifact surface.
  • This multifaceted surface on a microscopic level is responsible for the chaotically incident light refraction, exhausting the artifact brightness, so as to give it the final dull appearance. If there is not such a type of “anchoring” or “fastening” of chains, after their relaxing in the melting step, there is no sufficient elastic memory to pull these chains and create a superficial microwrinkling, responsible for the final dull appearance of the artifacts, after moulding.
  • NBR /thermoplastic elastomer compositions of the present invention as they have allyl carbons in both compounding basic polymers, in relation to the mere coming from butadiene, can also be submitted to the same conventional process steps as the non thermoplastic elastomers are submitted, i.e., they can be vulcanized with systems based on sulphur or its donors or with peroxide based systems, with or without the use of co-agents, then resulting in the polymeric composition mentioned before. Further, the present compositions can be moulded by conventional rubber industry processes.
  • Vulcanization system is selected from the following products conventionally utilised in the vulcanized rubber manufactures, such as: sulphur and/or its donors, primary accelerators, secondary accelerators, tertiary accelerators, peroxides, sylanes, crosslinking agents and their mixtures and electron accelerators.
  • the expression "efficient amount of vulcanizing system” means the amount routinely used in the field of vulcanized rubber manufacture. This amount will depend on the vulcanizing system used and also on the origin of the products employed in the vulcanizing system. These amounts are only given for illustrative purposes.
  • Sulphur based vulcanizing systems and/or its donors in general, can be classified as in the following table : enxofre (S) : sulphur (S) accelerator (A) convencional : conventional semi - e: half effective e: effective
  • compositions of the invention can also comprise pigments, accelerators, cure agents, fillers, plasticizers, flux agents, anti oxidants, anti ozonants, cure co-agents and so on, selected under those conventionally used in the rubber production technique;
  • the present invention will be illustrated, but not limited, by the following examples:
  • the material was injected at 190 °C (Battenfelf extrusion machine BA 250/050 CDC) .
  • the material was injected at 190 °C (Battenfelf extrusion machine BA 250/050 CDC) .
  • snorkels belts, air ducts and diving masks
  • blends (mixtures) present special properties and can be used in all above mentioned applications. Such applications are mentioned herein for as an example, illustrative purposes only.
  • thermoplastic NBR rubber composite can be produced in many ways. The most usual is by mixing NBR powder with TR powder in speedy mixers, "Henschel" type or helical mixers, concrete mixers or also by simple drumming, which consists of physically mixing the two components in any type of drum, container, bucket, etc. After this step, the mixture can be added to any kind of extrusion machine, mono or double screw extrusion machine, co-rotating or counter-rotating, extruded, then pelletized for subsequent processing in thermoplastic transforming industry equipment.
  • the final blended form, in powder, pellets, grumps, mats or wires is not obstructive nor restrictive for their posterior use and do not influence the final properties claimed in the artefact produced by them.
  • NBR as a dulling or opacity agent
  • the material was injected at 190 °C (Battenfelf extrusion machine BA 250/050 CDC) .
  • the material was injected at 190 °C (Battenfelf extrusion machine BA 250/050 CDC) .
  • thermoset rubber industry With the ready mixture, in any kind of mixing equipment largely used in the thermoset rubber industry, it can be processed afterwards in any kind of mono or double screw, co-rotational or counter-rotational extrusion machine, extruded and pelletized for subsequent processing in thermoplastics transforming industry equipment.
  • thermoplastic rubber industry mixing equipment in case adhesives and conventional additives components of said industry field are added, such as sulphur, vulcanization agents, primary accelerators, secondary accelerators, plasticizers, flow adjuvants, activators, fillers, antiozonants , antioxidants, etc., a vulcanizable composition can be obtained in any kind of equipment, such as simple presses or transferring presses, injection machines, autoclaves, vulcanizing tunnels, etc., which render superior final properties to the same products when employing the prior art techniques, notably in their solvent and abrasion resistance properties.
  • test samples were vulcanized in specific moulds in a press, after the rheometric curve @ 160 ° .
  • Results of the reference composition example 05 analysis are given in Table below.
  • composition of the invention presents a superior non-polar solvent resistance, compared with those compositions in which a polymer of the prior art is used.
  • composition of the invention is particularly appropriate for making parts, such as hoses, gaskets, sealings, coifs profiles, etc., in which a high organic solvent resistance is required.

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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 une composition de copolymères NBR et d'élastomères thermoplastiques. L'invention concerne également une composition de copolymères NBR pré-réticulés et d'élastomères thermoplastiques, dans laquelle le NBR est pré-réticulé par addition à la composition d'un monomère de réticulation ayant une fonctionnalité supérieure ou égale à 3, ledit monomère étant sélectionné parmi divinyl-benzène, triméthylol propane triméthacrylate, éthylène glycol diméthacrylate et isocyanate de triallyle. Lesdites compositions sont particulièrement utiles dans l'industrie des chaussures, des jouets, des coiffes, des joints et de tout autre article fait de caoutchouc. Ce dernier, lorsqu'il est fabriqué selon la présente invention, possède des propriétés mécaniques, chimiques et d'opacité améliorées.
PCT/BR2000/000073 1999-07-13 2000-07-12 Composition contenant nbr et elastomeres thermoplastiques WO2001004208A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP00940084A EP1161493A4 (fr) 1999-07-13 2000-07-12 Composition contenant nbr et elastomeres thermoplastiques

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
BRPI9902743-7 1999-07-13
BR9902743A BR9902743C1 (pt) 1999-07-13 1999-07-13 Composição de copolìmeros de nbr carboxilados ou não e copolìmero de etileno vinil acetato (eva) e composição vulcanizável de copolìmeros de nbr carboxilados ou não e eva
BRCI9902743-7 2000-07-07

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Publication Number Publication Date
WO2001004208A1 true WO2001004208A1 (fr) 2001-01-18

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1426411A1 (fr) * 2002-12-06 2004-06-09 KRATON Polymers Research B.V. Compositions de polymères à blocs de styrène pour la préparation de films transparents exempts de gel
WO2005082996A1 (fr) * 2004-02-24 2005-09-09 Arkema France Composition reticulee comprenant un copolymere sequence triblocs, son procede d'obtention et ses utilisations
EP1757668A1 (fr) * 2004-06-18 2007-02-28 Sunstar Giken Kabushiki Kaisha Materiau d'etancheite pour portiere d'automobile
JP2011099103A (ja) * 2009-11-09 2011-05-19 Evonik Degussa Gmbh 熱可塑性エラストマー混合物
US8173740B2 (en) * 2006-11-20 2012-05-08 Tsrc (Usa) Investment Corporation Styrene tetrablock copolymers and polymer blend compositions based upon such copolymers
CN114479213A (zh) * 2020-10-23 2022-05-13 中国石油化工股份有限公司 Nbr/pp热塑性弹性体及其制备方法和应用

Citations (1)

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US5055519A (en) * 1986-06-27 1991-10-08 Shell Internationale Research Maatschappij B.V. Thermoplastic elastomer compositions and process for the preparation thereof

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FR2590586B1 (fr) * 1985-11-26 1988-01-15 Atochem Compositions elastomeriques a base de polyetheramide et de caoutchouc nitrile et leur procede de fabrication
JPH0692521B2 (ja) * 1988-03-10 1994-11-16 旭化成工業株式会社 熱可塑性を有するエラストマー組成物
FR2685660A1 (fr) * 1991-12-31 1993-07-02 Atochem Procede de preparation de materiau composite forme d'un elastomere vulcanise associe a un elastomere thermoplastique a sequences polyamides et materiau composite ainsi constitue.
US5536774A (en) * 1994-12-02 1996-07-16 The Goodyear Tire & Rubber Company Use of maleated styrene-ethylene-butylene-styrene triblock polymer for improved adhesion
JPH115875A (ja) * 1997-06-17 1999-01-12 Mitsuboshi Belting Ltd 衝撃吸収ゲル材

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US5055519A (en) * 1986-06-27 1991-10-08 Shell Internationale Research Maatschappij B.V. Thermoplastic elastomer compositions and process for the preparation thereof

Non-Patent Citations (1)

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Title
See also references of EP1161493A4 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1426411A1 (fr) * 2002-12-06 2004-06-09 KRATON Polymers Research B.V. Compositions de polymères à blocs de styrène pour la préparation de films transparents exempts de gel
WO2004052989A1 (fr) * 2002-12-06 2004-06-24 Kraton Polymers Research B.V. Compositions de copolymere bloc styrene a utiliser pour la production de films transparents, sans gel
US7838598B2 (en) 2002-12-06 2010-11-23 Kraton Polymers U.S. Llc Styrenic block copolymer compositions to be used for the manufacture of transparent, gel free films
WO2005082996A1 (fr) * 2004-02-24 2005-09-09 Arkema France Composition reticulee comprenant un copolymere sequence triblocs, son procede d'obtention et ses utilisations
EP1757668A1 (fr) * 2004-06-18 2007-02-28 Sunstar Giken Kabushiki Kaisha Materiau d'etancheite pour portiere d'automobile
EP1757668A4 (fr) * 2004-06-18 2010-09-29 Sunstar Engineering Inc Materiau d'etancheite pour portiere d'automobile
US8173740B2 (en) * 2006-11-20 2012-05-08 Tsrc (Usa) Investment Corporation Styrene tetrablock copolymers and polymer blend compositions based upon such copolymers
JP2011099103A (ja) * 2009-11-09 2011-05-19 Evonik Degussa Gmbh 熱可塑性エラストマー混合物
EP2325249A1 (fr) * 2009-11-09 2011-05-25 Evonik Degussa GmbH Mélanges élastomères thermoplastiques
US8779031B2 (en) 2009-11-09 2014-07-15 Evonik Degussa Gmbh Thermoplastic elastomer mixtures
CN114479213A (zh) * 2020-10-23 2022-05-13 中国石油化工股份有限公司 Nbr/pp热塑性弹性体及其制备方法和应用
CN114479213B (zh) * 2020-10-23 2024-02-13 中国石油化工股份有限公司 Nbr/pp热塑性弹性体及其制备方法和应用

Also Published As

Publication number Publication date
EP1161493A4 (fr) 2004-06-23
EP1161493A1 (fr) 2001-12-12
BR9902743A (pt) 2001-03-06
BR9902743C1 (pt) 2001-05-22

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