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WO2003059993A1 - Composition elastomere, procede de preparation de cette composition et motif structural pour composition elastomere - Google Patents

Composition elastomere, procede de preparation de cette composition et motif structural pour composition elastomere Download PDF

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Publication number
WO2003059993A1
WO2003059993A1 PCT/DK2002/000907 DK0200907W WO03059993A1 WO 2003059993 A1 WO2003059993 A1 WO 2003059993A1 DK 0200907 W DK0200907 W DK 0200907W WO 03059993 A1 WO03059993 A1 WO 03059993A1
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Prior art keywords
particles
primer layer
atoms
elastomeric composition
group
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PCT/DK2002/000907
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English (en)
Inventor
Joachim KARTHÄUSER
Bjørn WINTHER-JENSEN
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Nkt Research & Innovation A/S
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Publication date
Application filed by Nkt Research & Innovation A/S filed Critical Nkt Research & Innovation A/S
Priority to AU2002367079A priority Critical patent/AU2002367079A1/en
Publication of WO2003059993A1 publication Critical patent/WO2003059993A1/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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • An elastomeric composition An elastomeric composition, a method of preparing the composition, and a building block for an elastomeric composition
  • the present invention relates to a novel elastomeric composition, a method of preparing it as well as a building block for an elastomeric composition.
  • elastomeric composition includes elastomers, thermoplastics, and cross-linked polymers therefrom. Generally a large amount of different elastomer composition are known. Some of the most used compositions includes rubbers such as polybutadiene, ethylene- propylene rubber, polyisopren and natural rubber; thermoplastics such as polyethylene, polypropylene, polyvinyl, polystyrene and polycarbonate; ionomers such as poly (ethylene-co-methacrylic acid); block co-polymers such as SBS, SIS, SEBS and etc. Other examples of elastomeric compositions are described in EP 626 978, US 4,431,777, US 4,925894 and GB 1,056,247.
  • the objective of the present invention is to provide a novel elastomeric composition, which has relative good properties with respect to mechanical properties such as stress, strength, resistance to chemicals and wear resistance versus its cost compared to known polymeric compositions and thereby provide a further possibility to the constructors when selecting a polymer composition for a specific product.
  • the elastomeric composition according to the invention has furthermore shown to be injection mouldable, which is a major advantage.
  • elastomeric composition includes elastomers, thermoplastics, and cross-linked polymers therefrom which do still exhibit elastomeric properties.
  • the elastomeric composition according to the invention should preferably have an elongation of at least 1%.
  • the elastomeric composition should preferably have a Tg value above room temperature i.e. thermoplastic elastomers are preferred.
  • the Tg value of the elastomeric composition or in case it is a thermoplastic elastomer, blocks of the elastomeric composition comprising block copolymers should have a Tg value below
  • the elastomeric composition according to the invention comprises
  • the particles may in principle be any type of particles solid at room temperature.
  • the particles may preferably solid at a temperature up to at least about 100 °C .
  • the fillers mat thus, e.g. be in the form of inorganic material selected from the group consisting of glass, silica, silicon dioxide, ceramics, carbon, minerals and metal, such as bronze and mixtures thereof.
  • the particles may also be in the form of organic material preferably a polymeric material such as polymers selected from the group consisting of olefins polyolefines such as polyethylene; polystyrene, polivinylacetate, polyviylchloride, polyvinylpyrrolidene, polyacrylonitrile , polymethylmethacrylate , polytetrafluoroethylene, polypropylene, cellulose, nitrocellulose, starch, polysaccharides, natural rubber, butyl rubber, styrene butadiene rubber, silicone rubber, silicates, polysilicates and mixtures thereof
  • olefins polyolefines such as polyethylene; polystyrene, polivinylacetate, polyviylchloride, polyvinylpyrrolidene, polyacrylonitrile , polymethylmethacrylate , polytetrafluoroethylene, polypropylene, cellulose, nitrocellulose, starch, polysaccharides, natural
  • the particles is of a thermoplastic material having a melt point above about 120 °C. In one embodiment it is desired that the particles is of an inorganic material, more preferably of glass or carbon.
  • the particles may have any shape, and it may be porous or nonporous. Preferably the solid particles is essentially non-porous.
  • the particles may e.g. be in the form of fibres, beads and/or powder.
  • the size of the particles measured without coating may vary in dependence of the properties desired in the final elastomeric compositions. In one embodiment it is preferred that at least 90 % by weight of the particles have a size between 1 nm and 1000 ⁇ m, more preferably between 10 and 600 ⁇ m, and even more preferably between 1 and 100 ⁇ m measured using sieving.
  • the solid particles are in the form of glass beads, the size of the beads preferably being so that at least 90 % of the beads are in the interval 5-50 ⁇ m measured using sieving.
  • the particles is partly or totally coated with one or more layers i.e. up to for example 10 layers of a material as will be discussed in further detain below.
  • the innermost layer is designated a primary primer layer
  • the outermost layer is designated a secondary primer layer.
  • the particles is totally coated with at least the outermost layer, and preferably with all layers if more than one layer.
  • the particles are coated with one primer layer only, i.e. this one primer layer constitutes both the innermost primer layer and the outermost primer layer.
  • the particles is coated with two primer layers, wherein these two layers constitute, respectively, the innermost primer layer and the outermost primer layer.
  • the secondary primer layer should comprise C atoms and/or Si atoms.
  • the amount of C atoms and/or Si atoms should preferably be at least 1 per 1000 atoms of the material, more preferably least 1 per 100 atoms of the material. These C atoms and/or Si atoms should preferably be evenly distributed in the material, to provide an essentially homogeneous surface of the outermost primer layer for bonding to the primary polymer chains.
  • the primary primer layer may preferably also comprise C atoms and/or Si atoms, and it is more preferred that the amount of C atoms and/or Si atoms should be at least 1 per 1000 atoms of the material, even more preferably least 1 per 100 atoms of the material.
  • the secondary primer layer is of a material comprising oxygen atoms and/or halogen atoms, preferably in the form of organic groups carrying electronegative group, more preferably selected from the group consisting of ester groups and halogen acid groups .
  • the particles is coated with two or more layers, where these two or more layers being chemically linked to each other, preferably in the form of covalent links.
  • the first primer layer and the secondary primer layer contain hydrogen atoms
  • the first primer layer and the secondary primer layer independently of each other, contain material selected from the group consisting of paraffin's, olefins polyolefines such as polyethylene; polystyrene, polivinylacetate, polyviylchloride, polyvinylpyrrolidene, polyacrylonitrile, polymethylmethacrylate, polytetrafluoroethylene, polypropylene, cellulose, nitrocellulose, starch, polysaccharides, natural rubber, butyl rubber, styrene butadiene rubber, silicone rubber, silicates, polysilicates and mixtures thereof.
  • paraffin's such as polyethylene
  • olefins polyolefines such as polyethylene; polystyrene, polivinylacetate, polyviylchloride, polyvinylpyrrolidene, polyacrylonitrile, polymethylmethacrylate, polytetrafluoroethylene,
  • the first primer layer and the secondary primer layer may furthermore, independently of each other, consist essentially of a polymeric material, whereby said polymeric material can be described as being built up from monomers having a boiling point of up to 80 °C measured at standard conditions (1 atm.) .
  • the secondary primer layer being of a material which is initiable by contact with an anionic initiator to thereby form carbanions .
  • an anionic initiator should preferably be a chemical compound having a pH value above 10, such as an organo-metallic compound e.g.
  • a group I and II organo- metallic compound such as alkali metal alkyl having 2-8 C atoms, alkaline earth metal alkyl having 2-8 C atoms, alkali metal alkene having 2-8 C atoms, alkaline earth metal alkene having 2-8 C atoms alkali metal aryl having 4-10 C atoms, alkaline earth metal aryl having 4-10 C atoms, wherein said alkene and/or said alkyl group (s) being linear or branched.
  • the first primer layer being chemically linked to the particles, to thereby provide an elastomeric composition with a high wearing quality.
  • the chemically links may preferably being covalent links such as one or more of the links C-metal, Si-metal, C-mineral, Si-mineral and more preferably C-C and Si-C links.
  • This chemically bonded layer may e.g. be provide using plasm as described further below.
  • the primary polymer chains may in principle have any length, but preferable the primary polymer chains should comprise at least 500 C atoms, more preferably between 2000 and 10 000 C atoms.
  • the primary polymer chains should be polymerised using anionic polymerisation, more preferably said primary polymer chains being polymerised from monomers selected from the group consisting of dienes having 4-8 C atoms, linear or cyclic olefins having 2-8 C atoms and mixtures thereof.
  • the primary polymer chains is polymerised from monomers comprising and preferably essentially consisting of styrene and dienes having 4-8 C atoms, more preferably from styrene and butadiene and/or isoprene.
  • the primary polymer chains comprises at least one and preferably two double bonds
  • Examples of primary polymer chains include polybutadiene, polyisoprene, styrene-butadien or styrene copolymer, partly or fully halogenated or hydrogenated polydiene and mixtures thereof.
  • the primary polymer chains may be grafted with one or more units in the form of polar compounds, preferably selected from the group consisting of sulphur trioxide, oxides of nitrogen and other oxides .
  • the coated particles is chemically linked via the secondary primer layer to the polymer blocks and optionally to each other, wherein these chemically links e.g. are covalent links such as C-C links or Si-C links.
  • the weight ratio between the coated particles and primary polymer chains should be between 10:90 and 95:5, preferably between 20:80 and 80:20, more preferably between 30:70 and 70:30.
  • the elastomeric composition according to the invention is cross-linked either using a cross-linking agent or by vulcanising.
  • the composition comprises building blocks consisting of the coated particles linked to the primary polymer chains wherein, said building blocks being cross-linked to it self and/or to one or more polymeric cross-linkable units, preferably selected from the group consisting of elastomers such as polyolefin, polybutadiene, polyisoprene, styrene-butadien copolymer, partly or fully halogenated polydiene and mixtures thereof.
  • ⁇ being cross-linked to it self' 1 means being cross-linked to it self or to other building blocks falling under the definition of the building blocks.
  • the building blocks and said one or more polymeric cross-linkable units is vulcanised.
  • the elastomeric composition according to the invention preferably should comprise one or more of the building blocks
  • n represent an integer of at least 1, preferably between 10 and 1000, more preferably between 5 and 100;
  • n represent an integer of at least 1, preferably between 1 and 1000, more preferably between 5 and 100, and y and z represent an integer of preferably 1, and wherein y 0 z or z+1;
  • the elastomeric composition according to the invention may in principle comprise op to about 99 % by weight, such as up to about 75 % or 50 % by weight of other material than the building blocks composed of coated particles and primary chains .
  • This material may in principle be any material provided that an elastomeric composition is formed, preferably an elastomeric composition having a Tg value below 20 °C.
  • composition may therefore comprising up to about 99 % by weight such as up to about 75 % or 50 % by weight of elastomeric polymers preferably selected from the group consisting of polyolefines such as polyethylene; polystyrene, polivinylacetate, polyviylchloride, polyvinylpyrrolidene , polyacrylonitrile , polymethylmethacrylate , polytetrafluoroethylene , polypropylene, cellulose, nitrocellulose, natural rubber, butyl rubber, styrene butadiene rubber, bitumen, silicone rubber, polysilicates and mixtures thereof.
  • polyolefines such as polyethylene; polystyrene, polivinylacetate, polyviylchloride, polyvinylpyrrolidene , polyacrylonitrile , polymethylmethacrylate , polytetrafluoroethylene , polypropylene, cellulose, nitrocellulose, natural rubber, butyl rubber, st
  • the composition may comprise up to about 50% by weight such as up to about 40 % or 25 % by weight of fillers preferably selected from the group consisting of carbon black, glass particles, mineral fibres, talcum, carbonates, mica, and silicates. It should be noted that the coated fibres chemically incorporated in the composition do not represent a filler material in this context .
  • the invention also relates to the building block as defined in the claims, wherein said building block preferably has the formula (I) or (II) as described above
  • the elastomeric composition may preferably be prepared according to the method defined in the claims. This method comprise the steps of i. providing solid particles of inorganic or organic material,
  • the innermost layer is designated a primary primer layer
  • the outermost layer is designated a secondary primer layer
  • said secondary primer layer comprising C atoms and/or Si atoms
  • the solid particles (type, size, shape etc.) and the one or more layers (type, combinations etc.), may be as described above when describing the elastomeric composition.
  • the one or more layers may be applied by any method as known in the art, e.g. as described in US 2448391, US 5798142 and US 5665424.
  • At least one of said one or more layers being applied to said particles using a plasma process. Usually it is preferred that all layers if more than one, are applied using a plasma method.
  • the method therefore preferably includes a step of activating the surfaces by generating radicals on the surfaces of the particles by subjecting the surfaces to a reducing gas plasma and forming a layer on the substrate surface using a plasma enhanced polymerisation process employing one or more monomers with a sufficient low molecular weight for them to be in their gaseous state in the gas plasma.
  • Prior to the step of activating the surfaces of the particles may preferably be cleaned by subjecting the surface to reducing gas plasma without monomers .
  • At least the innermost primer layer should be applied to particles using a plasma process, thereby a covalent bonding between the particles and the primary polymer chains can be provided.
  • the monomers for the plasma treatment may preferably be selected from the group consisting of C ⁇ C ⁇ alkanes, C 2 - C 16 alkenes, C 2 -C 16 alkynes, C 2 -C 16 alkynes, styrene, aromatic monomers of styrene compounds, monomers of vinyl- and acrylate- compounds.
  • the step of providing and chemically linking at least one primary polymer chain to said outermost primer layer may in principle be carried out using two different sub- methods .
  • the step of providing and chemically linking at least one primary polymer chain to said outermost primer layer includes the sub-steps
  • the surface of the outermost primer layer is initiated by the contact with the anionic initiator and C “ and/or Si " ions exposed on the surface, onto these ions the monomers are directly polymerised using anionic polymerisation to finally provide at least one primary chain linked to said outermost primer layer.
  • the secondary primer layer should preferably further comprise organic groups carrying electronegative group, preferably selected from the group consisting of ester groups and halogen acid groups, the second sub-method includes the sub-steps
  • the primary polymer chain (s) are polymerised using an anionic initiator, where after the coated particles are added and due to the anionic polymerisation the primary polymer chains will still be activated i.e. comprising C " and/or Si " ions, which ions will react with electronegative group exposed on the surface of the outermost primer layer to thereby link the primary polymer chain (s) to the coated particles and to finally provide at least one primary chain linked to the outermost primer layer.
  • the primary polymer chain may in length, type, composition and other be as described above when describing the elastomeric composition.
  • the anionic initiator may be any type of anionic initiator.
  • the anionic initiator includes a chemical compound having a pH value above 10, more preferably an organo-metallic compound even more preferably group I and II organo-metallic compounds such as alkali metal alkyl having 2-8 C atoms, alkaline earth metal alkyl having 2-8 C atoms, alkali metal alkene having 2-8 C atoms, alkaline earth metal alkene having 2- 8 C atoms alkali metal aryl having 4-10 C atoms, alkaline earth metal aryl having 4-10 C atoms, wherein said alkene and/or said alkyl group (s) being linear or branched.
  • the most used and preferred anionic initiator is organo- lithium, preferably selected from the group consisting of alkyl-lithium and phenyl-lithium. This initiator is thus both effective and not too expensive.
  • the anionic initiator may preferably be brought into contact with the outermost primer layer when using the first sub-method or may be mixed with said monomers when using the second sub-method in the form of a solution or dispersion in an solvent .
  • the solvent is a paraffinic solvents including linear and cyclic C4-C8 compounds, more preferably selected from the group consisting of hexane, cyclohexane, pentane and cyclopentane .
  • the solution wherein the polymerisation takes place should preferably be free of water or other anion-terminating component, as this may reduce or terminate the polymerisation .
  • the weight ratio between the coated particles and primary polymer chains may be as described above when describing the elastomeric composition.
  • the method further includes the step of cross-linking the elastomeric composition either using a cross-linking agent or by vulcanising.
  • the method of cross-link may be carried out using any conventional process.
  • the method includes the step of cross-linking the building blocks to it self and/or to one or more polymeric cross- linkable units, preferably selected from the group consisting of elastomers such as polyolefin, polybutadiene, polyisoprene, styrene-butadien copolymer, partly or fully halogenated polydiene and mixtures thereof .
  • elastomers such as polyolefin, polybutadiene, polyisoprene, styrene-butadien copolymer, partly or fully halogenated polydiene and mixtures thereof .
  • the building blocks may preferably be as described above when describing the elastomeric composition.
  • the method according to the invention may further comprise the step of mixing the elastomeric material with other materials to obtain an elastomeric composition comprising at least 1 % by weight of the coated particles linked to primary chains.
  • the additional material may be as described above when describing the elastomeric composition.
  • the invention also relates to an elastomeric composition obtainable according to the method as defined in the claims as well as an elastomeric composition comprising a building block as defined in the claims.
  • the elastomeric composition may be used in almost any materials, such as for preparing and modifying asphalt as used in road construction, roofing and waterproofing membranes, for preparing and modifying heavy duty-rubber products such as tires, carrier belts, drive belts, for preparing and modifying adhesives, sealant and coatings, and for preparing and modifying polymer formulations and compounds useful for injection moulding, extrusion and calendering of elastic items.
  • FIGURES for preparing and modifying asphalt as used in road construction, roofing and waterproofing membranes, for preparing and modifying heavy duty-rubber products such as tires, carrier belts, drive belts, for preparing and modifying adhesives, sealant and coatings, and for preparing and modifying polymer formulations and compounds useful for injection moulding, extrusion and calendering of elastic items.
  • Figure 1 is a schematic illustration of the process of linking polymer chains to a solid bead.
  • Figure 2 illustrate a building block comprising solid particle with isoprene/butadien and styrene blocks.
  • Figure 3 illustrates an elastomer with soft and hard domains, where some of the hard domains are made from solid particles.
  • the elastomeric building blocks according to the invention may be produced by selecting a solid particle e.g. a glass bead 1, and coating it with a monomer using plasma as described above, to thereby provide a polymer coating 2 which is chemically linked to the surface of the bead. Thereafter the polymer coating it treated with organo-metallic compound in the presence of diene monomer whereby an anionic polymerisation is initiated to provide primary polymer chains 3 linked to the polymer coating 3.
  • the building block may be further modified by adding styrene monomer and re-initiate by adding further BuLi.
  • FIG. 1 illustrates a similar building block.
  • the solid particle 12 which may e.g. be a glass fibre comprise several primary chains composed of soft domains (isoprene and/or butadiene) and hard domains (styrene) .
  • the soft blocks may e.g. have a length of 100- 300 n and the styrene blocks may e.g. have a length of around 100 nm.
  • Figure 3 is an illustration of an elastomer comprising solid particles in the form of glass beads 20.
  • the glass beads are coated as described above and broad into contact with monomers including styrene and diene and an initiator for providing a net-work of diene blocks 22, and styrene blocks 21.
  • a primary primer coating is of paraffinic nature whilst a secondary primer coating is a plasma coating, which is different from #3 to dictate, and consists of (a) epoxy groups, (b) chlorine groups and (c) ester groups.
  • the plasma coatings on the fibers treated in this way cannot be extracted from the fibers or removed by solvents, indicating that strong (covalent) chemical links is formed between the fibers and the coatings.
  • the total weight of the plasma coating (all layers) is 0.2 % of the weight of the fibers.
  • the fibers are transferred to a vessel suitable for chemical syntheses under exclusion of moisture.
  • the fibers are dried at elevated temperature and high vacuum (150-200 °C, ⁇ 1 ⁇ bar) for 8 hours. After drying, the fibers are not acting as agents preventing anionic polymerisation reactions, indicating both full coverage of the glass fiber surfaces, and absence of any residual water and residual hydroxyl groups from the glass fiber surfaces.
  • ''living polymer'' composed of lithium salts of diblock copolymers consisting of (a) polyisoprene and (b) polyisoprene coupled to polystyrene is added.
  • the living polymer being prepared from styrene or styrene/isoprene and an anionic initiator BuLi as it is generally known in the art.
  • the weight ratio between glass fibers and living polymer being 20:80.
  • the elastomeric composition formed is analysed for mol weight distribution. Based on the results, the reactivity of plasma coatings in coupling reactions with bulky anions can be ranked as follows:
  • a primary primer coating is of paraffinic nature whilst secondary primer coating is varied and consists of (a) vinyl double bonds, (b) other, partly conjugated double bonds on the basis of acetylene or diolefins and (c) ester and carbonyl groups.
  • the plasma coatings on the fibers treated in this way cannot be extracted from the fibers or removed by solvents, indicating that strong (covalent) chemical links are formed between the fibers and the coatings.
  • the total weight of the plasma coating (all layers) is 0.2 % of the weight of the fibers.
  • the fibers are transferred to a vessel suitable for chemical syntheses under exclusion of moisture.
  • the fibers are dried at elevated temperature and high vacuum (150-200 °C, ⁇ 1 ⁇ bar) for 8 hours. After drying, the fibers are not acting as agents preventing anionic polymerisation reactions, indicating both full coverage of the glass fiber surfaces, and absence of any residual water and residual hydroxyl groups from the glass fiber surfaces.
  • a paraffinic solvent cyclopentane
  • a quantity of strong base lithiumbutyl
  • isoprene is fed into the reactor, leading to polymerisation starting from the glass beads, however, in a competitive reaction also from the dissolved feedstock monomer.
  • the polymer formed is analysed for mol weight distribution. Based on those results, the suitability of plasma coatings for maximum polymerisation starting from the glass beads can be ranked as follows:

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Abstract

L'invention concerne une composition élastomère comportant des particules solides partiellement ou totalement enrobées et des chaînes polymères primaires. Les particules sont enrobées d'une ou de plusieurs couches, la couche la plus extérieure incluant des atomes de C et/ou de Si ; ces particules enrobées sont liées chimiquement, par l'intermédiaire de la couche la plus extérieure, aux chaînes polymères primaires, et éventuellement entre elles de manière à former un réseau. Les liaisons chimiques sont de préférence des liaisons covalentes telles que des liaisons C-C ou Si-C. L'enrobage de ces particules solides est de préférence lié à la particule de façon covalente. L'invention a également trait à un procédé de production de ces particules élastomères et à un produit intermédiaire utile dans celui-ci. Cette composition élastomère possède une résistance accrue à l'usure et est relativement bon marché par rapport à des élastomères comparables.
PCT/DK2002/000907 2001-12-28 2002-12-23 Composition elastomere, procede de preparation de cette composition et motif structural pour composition elastomere WO2003059993A1 (fr)

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