WO2012041804A2 - Compositions polymères - Google Patents

Compositions polymères Download PDF

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Publication number
WO2012041804A2
WO2012041804A2 PCT/EP2011/066656 EP2011066656W WO2012041804A2 WO 2012041804 A2 WO2012041804 A2 WO 2012041804A2 EP 2011066656 W EP2011066656 W EP 2011066656W WO 2012041804 A2 WO2012041804 A2 WO 2012041804A2
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Prior art keywords
polymer
modified
groups
filler
composition
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WO2012041804A3 (fr
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Sven Thiele
Sybill Ilisch
Katrin Reincke
Uwe Ferner
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Trinseo Europe GmbH
Polymer Service Merseburg GmbH
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Styron Europe GmbH
Polymer Service Merseburg GmbH
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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives

Definitions

  • the present teachings relate generally to polymer compositions, articles prepared from polymer compositions, and methods for making polymer compositions.
  • a source of hysteresis in vulcanized eiastomeric polymers is believed to be attributable to an insufficient distribution of filler particles in the vulcanized elastomeric polymer composition. Therefore, secondary inorganic compound components which boost processing without being inactive towards polymers also contribute to a low vulcanizate hysteresis.
  • the hysteresis loss of a cross- linked elastomeric polymer composition is related to its Tan ⁇ , at 60 °C, value (see ISO 4664-1 :2005; Rubber, Vulcanized or thermoplastic; Determination of dynamic properties - part i : General guidance).
  • vulcanized elastomeric polymer compositions having relatively small Tan 6 values, at 60 °C, are preferred as having lower hysteresis loss. In the final tire product, this translates to a lower rolling resistance and better fuel economy. It is generally accepted that a lower rolling resistance tire can be made at the expense of deteriorated wet grip properties.
  • both the Tan ⁇ at 60 °C and the Tan ⁇ at 0 °C, are reduced, generally corresponding to improved, rolling resistance and deteriorated wet grip performance of a tire.
  • both the Tan ⁇ at 60 °C and the Tan & at 0 °C are reduced, generally corresponding to improved rolling resistance and deteriorated wet grip performance of a tire. Accordingly, when assessing the rubber vulcanizate performance correctly, both the rolling resistance, related Tan ⁇ at 60 °C, and the wet grip, related Tan ⁇ at 0 °C, should be monitored.
  • Coupled hysteresis loss is to reduce the number of free chain ends of elastomeric polymers.
  • Various techniques are described in the open literature including the use of "coupling agents," such as tin tetrachloride, which may functionalize the polymer chain end and react with components of an elastomeric composition, such as, for example, with a filler or with unsaturated portions of a polymer. Examples of such techniques, along with other documents of interest, are described in the following U.S . patent documents: U .S. Patent Nos, 3,281 ,383; 3 ,244,664 and 3 ,692,874 (for example, tetrachlorosilane); U.S. Patent No.
  • End-functionalization further decreases the polymer hysteresis due to polymer chain-end to polymer interactions, or to polymer chain-end to filler interaction.
  • U .S. Patent No. 6,579,949 describes the use of a similar class of sulfur compounds, including tert-butyl dimethylsi!yI-3-chIoro- l -propyisuIfide to produce a co- chain-end modified elastomeric polymer used as a component in rubber articles having low hysteresis loss.
  • ⁇ -Chain-end modified elastomeric polymers are subsequently blended with fillers, vulcanizing agents, accelerators, oil extenders, and other various additives to produce tires having low hysteresis loss.
  • U.S. Patent No. 5,502, 131 describes a method of preparing a a-chain-end modified polymer comprising polymerizing diolefm monomers and/or monovinyiaromatic monomers in the presence of a polymerization initiator having the general Formula A or B:
  • R' i and R'l are same or different and are selected from alky!s, cycloalkyls and aralkyls, R'3 is a deprotonated allyl, 2-methallyl or xylyl, R is a carbocyclic group, and R' s is an alkyl substituent on a methylene group.
  • Another method of reducing the hysteresis loss consists in a statistical backbone functionalization of polydienes.
  • the number of functionalized positions along the rubber backbone can be higher compared with chain-end modification, where just one or two positions of one base polymer chain can be modified. Accordingly, the interaction of the polymer chain with filler particles can be more intense in the case of a backbone modification, when multiple (more than two) polymer backbone positions are modified.
  • backbone functionalized polydienes have a potential for a lower hysteresis loss and a better compatibility with fillers, such as with carbon black and silica.
  • Typical examples for a polymer backbone modification include U.S. Patent Nos. 6,933,358, and U.S. Patent 7,041 ,761.
  • Polydienes prepared by using an anionic polymerization technology are usually made from butadiene, isoprene and, optionally, styrene as monomer sources.
  • Functionalized conjugated diene or vinylaromatic monomers can be incorporated into the growing polymer chain.
  • Functionalized monomers, representing substituted styrene ( 1 , 2) are shown below.
  • R and R' are individually hydrogen or an alkyl group; x is a number from 1 to 10; and m and n are individually numbers from 0 to 10.
  • Functionalized monomers representing substituted isoprene (1.) are shown below.
  • the substituted styrene and substituted isoprene structures as shown above were incorporated into the elastomeric polydiolefm by being copolymerized with unfunctionalized conjugated dioiefin and, optionally, vinyl aromatic monomers.
  • the functionalized polymers improved the compatibility of the rubber in tires with fillers, such as carbon black and silica. In particular, tire rolling resistance properties and, therefore, hysteresis properties of tires were stated to be improved.
  • Silica turned out to be the better reinforcement agent and, therefore, is increasingly used in high performance passenger car tires.
  • the rubber vulcanizate properties can be tuned u— for example, with respect to a decreased hysteresis loss and improved rolling resistance in tires.
  • German Patent Application No. DE 10208046874 A l reportedly solves some of the aforementioned problems and states success in minimizing the silica particle agglomeration in the rubber vulcanizate. Therefore, the application of the disclosed rubber compositions comprising at least one polar or non-polar rubber, at least one colloidal silica filler component, and further components, to tire manufacturing leads to an improved tire rolling resistance.
  • Preferred rubbers are polyisoprene, polybutadiene and styrene- butadiene rubber.
  • the rubber components may be optionally functionalized or non- funciionaiized.
  • Exemplary rubber compounds comprising colloidal silica (of 22 nm particle size and of 138 m 2 /g surface area according to the CTAB absorption method) containing 13.2 wt% TDAE oil, 0 or 1 phr silaiie, 50 phr Buna CB25 polybutadiene of Lanxess AG and 50 phr Nipol NS 1 16R solution styrene- butadiene rubber of Nippon Zeon corporation was compared with a composition comprising 7 phr precipitated silica grade ULTRASIL VN3 of Evonic industries AG and 1 .2 phr A 1589 silane of Momentive Performance Materials but not containing stated colloidal silica.
  • the examples provided in DE 10208046874 A 1 are at least partially in contrast to the stated invention.
  • the use of the colloidal silica did not increase the rebound values measured as 70 °C. increased rebound values at 70 °C are widely accepted to be an indicator for an improvement of the rolling resistance property in a tire.
  • the reported difference of the rebound resistance at 70 °C and at room temperature reportedly representing the wet braking - rolling resistance balance only improves by 0.9 and 1.6 % versus the ULTRASIL VN3 containing compound reference.
  • the example incorporated in German Patent Application Mo. DE 10208046874 Al demonstrates that an improved rolling resistance property of the vulcanizate in a tire can not be achieved easily.
  • a fraction of carbon black is often added to silica-rubber compositions to achieve an improved tire abrasion resistance performance.
  • Japanese Patent Application No. JP 2006036918 reports on tire compounds comprising 75.6 phr oil extended SBR (VSL 5025), 20 phr polybutadiene (Nipol 1220), 74 phr silica (Nipsil AQ), 5.9 phr silane coupling agent (Si 69), and 8 phr carbon black (Seast 7HM).
  • the vulcanized composition was stated to have a good Lambourn abrasion resistance.
  • Rubber compounds comprising porous glass particles may be beneficial. There are only few examples demonstrating the use of specific glass particle grades in rubber compounds.
  • Japanese Patent No. JP 2554889B2 describes tire rubber compositions comprising (A) solution styrene-butadiene copolymer rubber and low-c v-polybutadiene, (B) titanium oxide coated on silica, alumina, glass flakes or on alternative inorganic materials, and (C) a filler selected from calcium carbonate, clay, talc or syndiotaclic 1 ,2-poS.ybutadiene. Th optioiially used (modified) glass flakes are referred to as mica and represent particles of small plate shape without significant porosity.
  • JP2007275362 describes shoe soles and shoe bodies made from exemplary compounds comprising 85 wt% natural rubber, 15 wt% styrene- butadiene rubber, 15 wt% Nipsil VN3 silica, and 10 wt% silane coupling agent-ireated glass microsphere bubbles S60SH.
  • the preparation of porous glass particles is described in German Patent Application No. DE 1 545065 Al .
  • the glass particles preparation includes a high temperature extrusion process of a glass melt and coarse crushing of the resulting glass foam. Glass particles as described in DE 1 545065 Al were not applied to a rubber-filler compounding process.
  • Zinc oxide is applied to the vulcanization of polymer compositions as an activator for typical vulcanization accelerators.
  • the heavy metal containing zinc oxide is added as a powder in the course of the compounding process. Therefore, tires made by using vulcanized polymer compositions comprise zinc oxide.
  • Zinc oxide comprised in tires also may be released into the environment due to abrasion of tires on the road. Therefore, due to environmental and health concerns, options are sought for avoiding handling of powdery zinc oxide and for reducing the total concentration of zinc (zinc atoms or zinc ions) in tires.
  • German Patent Application No. DEI 02005050764 A l additionally states that zinc sulfide formed in the process of rubber compound vulcanization may block valves and contribute to the formation of bubbles in tires. Accordingly, the use of zinc oxide may negatively impact the rubber compounding process and cause problems with respect to the tire safety on the road. Thus, the replacement of zinc oxide or the reduction of zinc oxide concentration in the course of the rubber-filler vulcanizate and tire manufacturing is beneficial.
  • the preparation of vulcanized rubber compositions using a reduced zinc oxide concentration is described in German Patent Application No. DEI 02005050764 A l .
  • the patent application describes a sulfur vulcanizable composition for use in tires which comprises (1 ) diene rubber, (2) a filler selected from carbon black and. silica, (3) 0.3-2 phi- zinc oxide, and (4) a process aid comprising at least one sodium or potassium soap and at least one compound from the group consisting of mono- and digycerol ester of organic carbon acids.
  • the ratio of sodium and/or potassium soap to mono- and/or digycerol ester preferably amounts to 2 to 4.
  • the zinc oxide concentration of 3 phr could be reduced to 0.9 phr through the addition of, for example, 3 phr Stuktol® HT 207 from Schill & Seilacher AG, representing a mixture of sodium- and potassium soaps and glycerol esters of the palmitin and stearin acid.
  • the reduction of zinc oxide could only be performed through addition of a sodium/potassium soap and mono- and/or digycerol ester containing mixture. Therefore, the reduction of zinc oxide is combined with extra costs for a new component required in the rubber-filler composition. It would be beneficial if the reduction or elimination of zinc oxide could be performed without adding costs for additional components, which do not improve the mechanical properties of vulcanized rubber compositions. It also wouid be beneficial if the reduction of the zinc concentration could be achieved without significantly changing the vulcanization kinetic of rubber composition.
  • a first composition in accordance with the present teachings includes (i) a polymer; (ii) a primary Filler; and (iii) a secondary filler.
  • the secondary filler includes a material selected from the group consisting of a secondary glass powder filler, a zinc-doped secondary glass powder filler, and a combination thereof.
  • FIG . 1 shows a schematic illustration of a coagulator for copolymer suspension
  • a first polymer composition embodying features of the present invention comprises at least one primary filler, at least one polymer, and at least one secondary filler selected from the group consisting of secondary glass powder filler and zinc-doped glass powder filler each as described herein.
  • the compositions have improved processing characteristics
  • a first polymer composition comprises at least one secondary filler selected from the group consisting of secondary glass powder filler and zinc-doped glass powder filler.
  • First polymer compositions comprising zinc-doped secondary glass powder filler do not require the use of zinc oxide as a component of the vulcanization system and, therefore, are environmentally friendly.
  • these first polymer compositions are used in the preparation of second (vulcanized) polymer compositions, and articles prepared from the same.
  • the second (vulcanized) polymer compositions are useful in the preparation of vulcanized— and, therefore, cross-linked— elastomeric compositions having relatively low hysteresis loss.
  • Such compositions are useful in many articles, including tire treads having low rolling resistance in combination with a good balance of other desirable physical and chemical properties including but not limited to wet grip, elongation at break, and processability.
  • a first polymer composition comprises:
  • a primary filler selected from the group consisting of silica, carbon-silica dual phase filler, carbon black, carbon nano-tube filler, lignin, and combinations thereof;
  • a secondary filler selected from the group consisting of:
  • a secondary glass powder filler which, in some embodiments, comprises glass fillers of mean diameter ⁇ 20 ⁇ and BET-surface > 0.5 m 2 /g, in some embodiments of mean diameter ⁇ 10 pm and BET-surface > l .O nrVg, and in some embodiments of mean diameter ⁇ 5 pm and BET-surface > 2.0 m 2 /g; and
  • a secondary zinc-doped glass powder filler which, in some embodiments, comprises glass fillers of mean diameter ⁇ 20 pm, BET-surface > 0.5 m 2 /g, and a zinc concentration in the pores and on the surface of the glass particles of 0.2 to 30 percent by weight of the glass powder filler, in some embodiments of mean diameter ⁇ 10 pm, BET-surface > 1 .0 m 2 /g, and a zinc concentration in the pores and on the surface of the glass particles of 0.5 to 20 percent by weight of the glass powder filler, and in some embodiments of mean diameter ⁇ 5 pm, BET-surface > 2.0 m 2 /g, and a zinc concentration in the pores and on the surface of the glass particles of 1.0 to 1 0 percent by weight of the glass powder filler;
  • the polymer is selected from the group consisting of polybutadiene; modified-polybutadiene; poiyisoprene; modified-polyisoprene; styrene/butadiene copolymers with styrene contents of 1 0 to 50, including SSBR wherein the polymer was prepared in solution; modified-styrene/butadiene copolymers (SSBR), with styrene contents of 10 to 50, including modified-SSBR wherein the polymer was prepared in solution; styrene/isoprene copolymers with styrene contents of 10 to 50; modified styrene/isoprene copolymers (SIR) with styrene contents of 10 to 50, including SSIR wherein the poiymer was prepared in solution; isoprene/butadiene copolymers; modified- isoprene butadiene copolymers; and combinations thereof
  • the first composition further comprises a silane coupling agent. In some embodiments, the first composition further comprises an oil. In some embodiments, the first composition further comprises a processing aid. In some embodiments, the first composition further comprises a vulcanization agent.
  • the present teachings also provide a second (vulcanized) polymer composition comprising the reaction product of; ( 1 ) a vulcanization agent; and (2) a first composition as described herein.
  • the present teachings also provide a method for making a vulcanized polymer composition comprising reacting: ( 1) a vulcanization, agent; and (2) a first composition as described herein.
  • a first composition in accordance with the present teachings comprises a combination of two or more embodiments as described herein.
  • a vulcanized composition in accordance with the present teachings comprises a combination of two or more embodiments as described herein.
  • the primary filler comprises carbon black. In some embodiments, the primary filler comprises silica. In some embodiments, the primary' filler comprises carbon-silica dual-phase filler. In some embodiments, the secondary glass powder filler comprises a borosilicate glass. In some embodiments, the secondary glass powder filler comprises a soda-lime-glass. In some embodiments, the zinc-doped secondary glass powder filler comprises a borosilicate glass. In some embodiments, the zinc-doped secondary glass powder filler comprises a soda-lime-glass.
  • Representative uncrossliiiked elastomeric polymers in accordance with the present teachings include ones that are prepared from the following list of representative monomers: conjugated olefins and olefins selected from a-olefins, internal olefins, cyclic olefins, poiar olefins, nonconjugated diolefms, and combinations thereof.
  • conjugated unsaturated monomers include but are not limited to conjugated dienes, such as 1 ,3-butadiene, 2-alkyl-l ,3-butadiene, isoprene (2-methy 1- 1 ,3 - butadiene), 2,3-dimethyl- 1 ,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1 ,3-hexadiene, 1 .3- heptadiene, 1,3-octadiene, 2-methy1-2,4-pentadiene, cyclopentadiene, 2,4-hexadiene, 1 ,3- cyclooctadiene, and combinations thereof.
  • conjugated dienes such as 1 ,3-butadiene, 2-alkyl-l ,3-butadiene, isoprene (2-methy 1- 1 ,3 - butadiene), 2,3-dimethyl- 1 ,3-buta
  • Representative olefins include but are not limited to C2-20 a-olefms, including but not limited to long chain macromolecular ⁇ .-olefms—especially aromatic vinyl compounds.
  • aromatic vinyl compounds include but are not limited to styrene, including but not limited to CM alkyl substituted styrenes, such as 2-meth Istyrene, 3- methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4.6-trimethylstyrene, a- methylstyrene and stilbene, 2 J 4-d.iisopropylstyrene,4-tert-butyistyrene, vinyl benzyl dimethylamme, (4 ⁇ vmylbenzyl)dimefhyl aminoethyl ether, ⁇ , ⁇ -dimethylaminoethyl styrene, tert-butoxystyrene, vinylpyridine, and combinations thereof.
  • styrene including but not limited to CM alkyl substituted styrenes, such as 2-meth Istyrene, 3- methylstyrene, 4-methylsty
  • Representative polar olefins include but are not limited to acrylonitrile, methacrylates, methylniethacrylate, and combinations thereof.
  • Nonconjugated olefins include but are not limited to C 4 . 2 o diolefms, especially norbornadiene, ethylidenenorbornene, 1 ,4-hexadiene, 1 ,5-hexadiene, 1 ,7- octadiene, 4-vinyicyclohexene, divinylbenzene including 1 ,2-divinylbenzene, 1 ,3- divinylbenzene and 1 ,4-dsvinylbenzene, and combinations thereof.
  • Representative conjugated dienes include but are not limited to butadiene, isoprene, cyclopentadiene, and combinations thereof.
  • Representative aromatic a-olefins include but are not limited to styrene, 4-methylstyrene, and a combination thereof.
  • Representative uncross! inked elastomeric polymers include but are not limited to homopolymers of conjugated dienes. especially butadiene or isoprene, and random or block co- and terpolymers of at least one conjugated diene, especially butadiene or isoprene, with at least one conjugated diene or with at least one aromatic a-olefin. and especially styrene and 4-methylstyrene, aromatic diolefm, especially divinylbenzene.
  • Examples of applicable uncrosslinked elastomeric modified polymers include but are not limited to: modified BR-polybutadiene; butadiene/Cl-C4-alkyl acrylate copolymers; modified LR-polyisoprene; modified SBR-styrene/butadiene copolymers with styrene contents of 1 to 60, in some embodiments 10 to 50 weight percent, including SSBR wherein the polymer was prepared in solution; modified SiR-styrene/isoprene copolymers with styrene contents of 1 to 60, in some embodiments 10 to 50 weight percent including SSIR wherein the polymer was prepared in solution; modified IIR-isobutylene/isoprene copolymers; modified lBR-isoprene/butadiene copolymers; modified NBR- butadiene/acrylonitrile copolymers; modified H BR-partialiy hydrogenated or fully hydrogenated NBR rubber: EP
  • the modified polymer comprises a modified poiybutadiene. In some embodiments, the modified polymer comprises a modified butadiene/Cl -C4- alkyl acrylate copolymer.
  • the modified poiymer comprises a modified butadiene/styrene copolymer.
  • the modified polymer comprises a modified butadiene/styrene copolymer (SSBR) prepared in solution.
  • SSBR modified butadiene/styrene copolymer
  • the modified polymer comprises a modified isoprene/styrene copolymer (SSIR) prepared in solution.
  • SSIR modified isoprene/styrene copolymer
  • the modified polymer comprises a modified butadiene/isoprene copolymer.
  • the modified polymer comprises a modified po!ychloroprene.
  • the modified polymer comprises a modified polyisoprene, including synthetic polyisoprene and natural rubber.
  • the modified polymer comprises a modified styrene/butadiene copolymer with a styrene unit content from 1 to 60 weight percent in some embodiments from 10 to 50 weight percent, based on the total weight of the copolymer.
  • the modified polymer comprises a modified styrene/butadiene copolymer with a 1 ,2-polybutadiene unit content from 5 to 70 weight percent, in some embodiments from 50 to 70, or 5 to 27 weight percent, based on the total weight of polybutadiene unit fraction of the copolymer.
  • the modified polymer comprises a modified styrene/isoprene copolymer with a styrene unit content from 1 to 60 weight percent, in some embodiments from 10 to 50 weight percent, based on the total weight of the copolymer.
  • the modified polymer comprises a modified styrene/isoprene copolymer with a 1 ,2-polyisoprene unit content from 5 to 70 weight percent, in some embodiments from 50 to 70, or 5 to 25 weight percent, based on the total weight of polybutadiene unit fraction of the copolymer.
  • the modified polymer comprises a modified butadiene/isoprene copolymer with an isoprene unit content from 0.1 to 70 weight percent, in some embodiments from 5 to 50 weight percent, based on the total weight of the copolymer.
  • the modified polymer comprises a modified isobutylene/isoprene copolymer.
  • the modified polymer comprises a modified partially hydrogenated butadiene.
  • the modified polymer comprises a modified partially hydrogenated styrene-butad iene copolymer.
  • Such representative uncrosslinked elastomeric modified polymers comprise functional groups which, in some embodiments, are attached to one or both polymer chain ends to the branching point of the polymer or to the polymer backbone.
  • the functional groups are selected from the following and combinations thereof:
  • thiol groups (HS- or HS-R"-); protected thiol groups including but not limited to hydrocarbyl thioethers (RS- or RS-R" -) > trihydrocarbylsilyl-thioethers ((RjSi)S- or (R 3 Si)S- R"-), and trihydrocarbylstannyl-thioethers ((R 3 Sn)S » or (R 3 Sn)S-R"-);
  • primary amine groups H 2 N- or H2N-R"-
  • protected primary amino groups including but not limited to bis rihydrocarbylsilyl-amino groups
  • hydrocarbyl amino groups (R(H)N- or R(H)N-R"-); protected hydrocarbyl amino groups including but not limited to tiihydrocarbylsilyl-hydrocarbyl-amino groups ((R(R' 3 Si)N- or and trihydrocarbytstannyl-hydrocarbyl-amino groups ((R(R ! 3 Sn)N- or (R(R' 3 Sn)N-R");
  • cyclic amine groups including but not limited to the following groups
  • primary phosphane groups H 2 P- or H 2 P-R"-
  • protected primary phosphane including but not limited to bis-trihydrocarbylsilyl-phosphane groups R"-), bis-trihydrocarbylstannyl-phosphane groups ⁇ (R 3 Sn or (RjSif P-R"-), irihydrocarbylsilyl-phosphane groups ((R 3 Si)(B)P ⁇ or (R 3 Si)(H)P-R"-) ! and bis- tribydrocarbylstannyl-phosphane groups ((R 3 Sn)(H)P- or (R 3 Sn)(PI)P-R"-);
  • hydrocarbyl phosphane groups (R(H)P- or R(H)P-R"-); protected hydrocarbyl pbosphane groups including but not limited to trihydrocarbylsilyl-hydrocarbyi-phosphane groups ((R(R'3Si)P- or (RfR'jS P-R"-) and trihydrocarbyistannyi-hydrocarbyl-phosphane groups ((R(R' 3 Sn)P- or (RfR ⁇ S ⁇ P-R' 5 - ⁇ ;
  • alcohol groups (HO- or HO-R"-); protected alcohol groups incl uding but not limited to trihydrocarbylsilyl-ethers (R 3 S1-O- or R 3 Si-0-R " -) and trihydrocarbylstannyl-ethers (R 3 Sn-0- or R 3 Sn-0-R"-);
  • HOOC- or HOOC-R carboxyl groups
  • ROOC- or ROOC-R carbon acid hydrocarbylesters
  • hydrocarboxysilyl groups including but not limited to trihydrocarboxysilyl groups ((RO) 3 Si- or (RO) 3 Si-R"-), hydrocarbyl-dihydrocarboxysilyl groups (R'(RO) 2 Si- or R'( O)2Si-R , , ”) ! and dihydrocarbyS-hydrocarboxysilyl groups (R'2(RO)Si ⁇ R"-);
  • dihydrocarbylsilanol groups ((HO)(R2)Si- or (HO)(R2)Si-R"- ⁇ ; hydrocarbyldisilanol groups ((HQ) 2 (R)Si- or (HO) 2 (R)Si-R"-);
  • hydrocarbyl or dihydrocarbylolegosiloxane groups including but not limited to groups formed through reaction of tris-dimethylsiloxane (((CHs ⁇ SiO ⁇ ) with living anionic polymer chains;
  • R and R' are independently selected hydrocarbyl groups and R" is a divalent hydrocarbon group.
  • One or more types of the aforementioned functional groups may be attached to the polymer.
  • Representative uncrosslinked eiastomeric modified polymers comprising thiol groups and/or protected thiol groups are described in international Patent Publication Nos. WO 2007047943 and WO 2008076875, International Patent Application Nos. PCT/US09/045553 and PCT/US09/063961 , and U.S. Provisional Application Serial Nos. 61 /288,51 9 and 61 /288.697.
  • Representative uncrosslinked modified polymers comprising dihydrocarbylamino groups are described in. DD 237513 Al ; DD242232 Al ; DD23632 I A l; in U.S. Patent Nos.
  • Patent Application Publication No. 2009/01567 1 and in the manuscript of the 170 th technical meeting of the rubber division of the American chemical society (1 -25, 2006; ISSN: 15471977).
  • Representative uncrosslinked modified polymers comprising alkoxysilane groups are described in U.S. Patent No. 6,566,480 and in the manuscript of the 143rd technical meeting of the rubber division of the American chemical society at Denver, Colorado (May 18.21 , 1993 ; title: Chemical modification of short polystyrene b lock-SB R with alkoxysilane, presented by I. Hattori and M. Sakalibara, Japan Synthetic Rubber Co., Ltd.).
  • the functional groups of the applicable modified polymers are reactive with fillers (such as silica and/or carbon black) present. Further interaction can be referred to intermoleciilar reactions of functional groups or to reactions of functional groups with unsaturated portions of the polymer backbone.
  • the reaction of the functional groups with fillers is believed to result in the formation of bonds with filler particles or, in the case of some filler particles, in electrostatic interactions, which result in more homogeneous distributions of filler within the polymer compositions.
  • Intermolecular interaction of polymer bound functional groups with other polymer-chain backbones or with functional groups attached to other polymer chains leads to deteriorated processing characteristics of the polymers in polymer compounds. T raditional ly, processing difficulties were counteracted through the use of processing aids.
  • Representative uncrosslinked modified polymers exclusively comprising functional groups at one or more of the alpha-chain-end position, the omega-chain-end position, and at the branching point of polymer chains comprise functional groups typically in a total amount from 0.0001 to 1.50 mmol/gram of polymer, in some embodiments from 0.0005 to 0.75 mmol/gram, in some embodiments from 0.0010 to 0.45 mmol/gram, and in some embodiments from 0.0020 to 0.1 8 mmol/gram of polymer.
  • Representative uncrosslinked modified polymers comprising functional groups at positions different to the alpha-chain- end position, the omega-chain-end position or to the branching point of polymer chains are modified at the poiymer backbone.
  • Backbone modified polymers comprise functional groups typically in a total amount up to 5 wt%, in some embodiments up to 2,5 wt , in some embodiments up to 1.5 wt%, and in some embodiments up to 0.75 wt% of the total polymer molecular weight.
  • the modified poiymer is preferably a homopoiymer derived from a conjugated, diolefm, a copolymer derived from a conjugated di olefin monomer with an aromatic vinyl monomer, and/or a terpolymer of one or two types of conjugated diolefms with one or two types of aromatic vinyl compounds.
  • the vinyl bond content of 1 ,2 -bonds and/or 3.4-bonds (hereinafter called "vinyl bonds”) of the conj ugation diolefm portion of the (elastomeric) poiymer is from 10 to 90 weight percentage, and in some embodiments from 15 to 80 weight percentage (based on total weight of polymer). If the vinyl bond content in a poiymer is less than 10 weight percentage, the resulting product may have inferior wet skid resistance. If the vinyl content in the (elastomeric) polymer exceeds 90 weight percentage vinyl bonds, the product may exhibit compromised tensile strength and abrasion resistance, and relatively large hysteresis loss.
  • the aromatic vinyl monomers comprise from 5 to 60 weight percentage of the total monomer content, and in some embodiments from 10 to 50 weight percentage (based on total weight of polymer). Values less than 5 weight percentage may lead to reduced wet skid properties, abrasion resistance, and tensile strength; whereas values more than 60 weight percentage may lead to increased hysteresis loss.
  • the modified (elastomeric) polymer may be a block or random copolymer, and in some embodiments 40 weight percentage or more of the aromatic vinyl compound units are linked singly, and 30 weight percentages or less are of "blocks" in which eight or more aromatic vinyl compounds are linked successively.
  • Copolymers fa!iing outside this range often exhibit increased hysteresis.
  • the length of successively linked aromatic vinyl units can be measured by an ozonolysis-gel penrseation chromatography method developed by Tanaka, et al. (Polymer, 1981, 22, 1721 - 1723).
  • polymers including the group of modified polymers in accordance with the present teachings have, in some embodiments, a Mooney viscosity (ML 1+4, 100 °C, as measured in accordance with ASTM D 1646 (2004)), in the range from 20 to 1.50, and in some embodiments from 30 to 100, using a Monsanto MV2000 instrument, if the Mooney viscosit ⁇ ' (ML 1 +4, 100 °C) is less than 20, abrasion resistance and hysteresis loss properties may be compromised. Moreover, tack and cold flow of the uncrossiinked elastomeric polymer are increased, resulting in difficult handling, poor green strength, and poor dimensional stability during storage.
  • Mooney viscosity (ML 1 +4, 100 °C) of the polymer is more than 150 MU, processability (filler mcorporation and heat build up in the internal mixer, banding on the roll mill, extrusion rate, extrudate die swell, smoothness, etc.) is negatively impacted because compounding machinery used at the manufacturer of tires are not designed to handle such high Mooney rubber grades, and the cost of processing increases.
  • the preferred molecular weight distribution of the modified polymer represented by the ratio of the weight average molecular weight to the number average molecular weight, (M w /M n ), ranges in some embodiments from 1.2 to 3.0.
  • the one or more uncrossiinked elastomeric polymer(s)— including but not limited to the group of modified polymers— is (are) combined and reacted with secondary filler selected from, the group consisting of secondary glass powder filler and zinc-doped glass powder filler, primary filler component(s) selected from the group consisting of silica, carbon-silica dual phase filler, carbon black, carbon nano-tube filler, lignin, in some embodiments silica and vulcanization agent, and, optionally, additional constituents including but not limited to oils, accelerators and silane coupling agents.
  • secondary filler selected from, the group consisting of secondary glass powder filler and zinc-doped glass powder filler
  • primary filler component(s) selected from the group consisting of silica, carbon-silica dual phase filler, carbon black, carbon nano-tube filler, lignin
  • silica and vulcanization agent in some embodiments silica and vulcanization agent
  • additional constituents including but not limited to
  • the total elastomeric polymer present (including oil extended embodiments) in the glass powder and alternative filler comprising polymer compound comprises at least 30 weight percentage, and more preferably at least 50 weight percentage of modified elastomeric polymer.
  • the remaining portion of the total elastomeric polymer present in the polymer compound is unmodified eiastomeric polymer. Examples of preferred unmodified elastomeric polymers are listed in International Patent Publication No. WO 2009/148932 (Attorney Docket No.
  • the composition in accordance with the present teachings includes secondary filler selected from the group consisting of secondary glass powder filler and zinc-doped glass powder filler and primary fillers, which serve as reinforcement agents.
  • Oils may be used in combination with the uncrosslinked elastomeric polymers to reduce viscosity or Mooney values, or to improve processability of first polymer compositions in accordance with the present teachings and various performance properties of (vulcanized) second polymer compositions products in accordance with the present teachings.
  • the oil(s) can be added to the polymer prior to the end of the polymer preparation process and as a separate component of the first or second polymer composition preparation process in accordance with the present teachings.
  • oils see International Patent Application No. PCT/US09/045553 and U.S. Patent Application Publication No. 2005/0159513, each of which is incorporated herein by reference in its entirety.
  • oils include but are not limited to MES (Mild Extraction Solvate), TDAE (Treated Distillate Aromatic Extract), RAE (Residual Aromatic Extract) including but not limited to T-RAE and S-RAE, DAE including T-DAE and NAP (light and heavy naphthenic oils), including but not limited to Nytex 4700, Nytex 8450, Nytex 5450, Nytex 832, Tufflo 2000, and Tufflo 1200.
  • native oils including but not limited to vegetable oils, can be used as extender oils.
  • Aforementioned oils comprise different concentrations of polycyclic aromatic compounds, parafmics, naphthenics and aromatics, and have different glass transition temperatures. The above mentioned types of oil have been characterized (Kaulschuk Kunststoffe, vol. 52, pages 799-805).
  • the MES, RAE and TDAE are extender oils for rubber.
  • Processing aids can be optionally added to the first polymer compositions in accordance with the present teachings. Processing aids are usually added to reduce the first polymer composition viscosity. As a result, the mixing period is decreased and/or the number of mixing steps is reduced and, consequently, less energy is consumed and/or a higher throughput in the course of the rubber compound extrusion process is achieved.
  • processing aids which can optionally be used as a component in the first polymer compositions in accordance with the present teachings are described in the Rubber Handbook, SGF, The Swedish Institution of Rubber Technology 2000 and in Werner leemann, Kurt Weber, Elast kauKennhong und Be sacredsmethoden, Deutscher Verlag fur Grundstoffmdustrie (Leipzig, 1990), each of which is incorporated herein by reference in its entirety.
  • Examples of representative possessing aids which can optionally be used as component in the first polymer compositions in accordance with the present teachings can be classified as follows;
  • (A) fatty acids including but not limited to oleic acid, priolene, pristerene and stearinsyra;
  • (B) fatty acid salts including but not limited to Aktiplast GT, PP, ST, T, T-60, 8, F; Deoflow S; Kettlitz Dispergator PL, FL Plus; Dispergum 18.
  • (C) dispersing agents and processing aids including but not limited to Afiux 12, 16, 42, 54, 25 ; Deofiow A, D; Deogum 80; Deosol H; Kettlitz Dispergator DS, KB, OX; Kettlitz-Mediaplast 40, 50, Pertac/GR; Kettlitz-Dispergator SI; Struktol PL and WB 212; and
  • (D) dispersing agents for highly active white fillers including but not limited to Struktol W33 and WB42.
  • Bifunctionalized silanes and monofunctional silanes (herein also called “silane coupling agents") are aiso occasionally refeixed to as processing aids but are separately described below.
  • a silane coupling agent (used for compatibilization of polymer and stated fillers) is added to the composition containing modified polymer as described herein and silica or carbon-silica dua!-phase filler, which is used as filler component.
  • the typical amount of a silane coupling agent added is from about 1 to about 20 parts by weight and, in some embodiments, from about 5 to about 15 parts by weight for 1 00 parts by weight of the iota! amount of silica and/or carbon-silica dual-phase filler.
  • Silane coupling agents can be classified according to the Fritz Rothemeyer, Franz Sommer: Kautschuk Technologie s (Carl Hanser Verlag 2006):
  • silane coupling agents are given in International Patent Application No. PCT/US2009/045553, and inciude but are not limited to bis-(3-hydroxy-dimethylsilyl- propyl)tetrasulfide, bis-(3-hydroxy-dimethyI.silyl-propyl)-disuIfjde, bis-(2-hydroxy- dimethylsjl.yl-ethyi)tetrasulfide, bis-(2 -hydrox -dimethylsilyl-ethyl)disulfide, 3-hydroxy- dimethylsilyl-propyl-N.N-dimethylthiocarbamoyltetrasulfide, and 3-hydroxy-di.methylsilyl- propylbenzothiazole tetrasulfide.
  • Sulfur, sulfur-containing compounds acting as sulfur-donors, sulfur-accelerator systems, and peroxides are the most common vulcanizing agents.
  • sulfur- containing compounds acting as sulfur-donors inciude but are not limited to dithiodimorpholine (DTDM), tetramethylthiuramdisuiphide (TMTD), tetraethylthiuramdisulphide (TETD), and dipentamethylenthiuramtetrasulphide (DPTT).
  • sulfur accelerators include but are not limited to amine derivates, guanidine derivates, aldehydeamine condensation products, thiazoles. thiuram sulphides, dithiocarbamates and thiophospahtes.
  • peroxides used as vulcanizing agents include bu are not limited to di-/e; . -butyl-peroxides, di-(fcrf. ⁇ butyl-peroxy-trimethyl- cyclohexane), di-(iert.-butyl-peroxy-isopropyl-)benzene, dichloro-benzoy!peroxide, dicumylperoxides, ierf.-butyl-cumyl-peroxide, dimethyl-di(/e7-z.-butyl-peroxy)hexane and dimethyi-di( eri.-butyl-peroxy)hexine and butyl-di( eri.-buty!-peroxy)valerate (Rubber Handbook, SGF, The Swedish Institution of Rubber Technolgy 2000),
  • vulcanizing agents can be found in irk-Othmer, Encyclopedia of Chemical technology 3 nl , Ed., (Wiley Interscience, N.Y. 1982), volume 20, pp. 365-468, (specifically "Vulcanizing Agents and Auxiliary Materials” pp. 390-402).
  • A. vulcanizing accelerator of sulfene amide-type, guanidine-type, or thiuram-type can be used together with a vulcanizing agent as required.
  • Other additives such as zinc white, vulcanization auxiliaries, aging preventives, processing adjuvants, and the like may be optionally added.
  • a vulcanizing agent is typically added to the polymer composition in an amount from 0.5 to 10 parts by weight and, in some embodiments, from 1 to 6 parts by- weight for 100 parts by weight of the total elastomertc polymer. Examples of vulcanizing accelerators, and the amount of accelerator added with respect to the total polymer, are given in International Patent Publication No. WO 2009/148932.
  • the elastomeric composition in accordance with the present teachings includes primary fillers, which serve as reinforcement agents.
  • Primary fillers which serve as reinforcement agents.
  • Carbon black is manufactured by a furnace method and in some embodiments a nitrogen adsorption specific surface area of 50-200 m7g and DBP oil absorption of 80-200 ml/100 grams, for example, FEF; HAF. 1SAF, or SAF class carbon black, is used. In some embodiments, high agglomeration type carbon black is used. Carbon black is typically added in an amount from 2 to 100 parts by weight, in some embodiments from 5 to 100 parts by weight, in some embodiments from. 1.0 to 100 parts by weight, and in some embodiments from 10 to 95 parts by weight for 100 parts by weight of the total elastomeric polymer.
  • silica fillers include but are not limited to wet process silica, dry process silica, synthetic silicate-type silica, and combinations thereof.
  • Silica with a small particle diameter exhibits a high reinforcing effect.
  • Small diameter, high agglomeration-type silica i.e., having a large surface area and high oil absorptivity
  • An average particle diameter of silica in terms of a primary particle diameter, is in some embodiments from 5 to 60 nm, and in some embodiments from 10 to 35 nm.
  • the specific surface area of the silica particles is in some embodiments from 35 to 300 m 2 /g.
  • Silica is added in an amount from 1 0 to 100 parts by weight, in some embodiments from 30 to 100 parts by weight, and in some embodiments from 30 to 95 parts by weight for 100 parts by weight of the total, elastomeric polymer.
  • Carbon biack and silica may be added together; in which case the total amount of carbon black and silica added is from 30 to 1 00 parts by weight and, in some embodiments, from 30 to 95 parts by weight for 100 parts by weight of the total elastomeric polymer. So long as such fillers are homogeneously dispersed in the elastomeric composition, increasing quantities (within the above cited ranges) result in compositions having excellent rolling and extruding processability, and vulcanized products exhibiting favorable hysteresis loss properties, rolling resistance, improved wet skid resistance, abrasion resistance, and tensile strength.
  • Carbon-silica duai-phase-filler may be used either independently or in combination with carbon black and/or silica in accordance with the present teachings. Carbon-silica dual- phase-filler can exhibit the same effects as those obtained by the combined use of carbon biack and silica, even in the case where it is added alone. Carbon-silica dual-phase-filler is so called silica-coated-carbon black made by coating silica over the surface of carbon black, and is commercially available under the trademark CRX2Q00, CRX2002. or C.RX2006 (products of Cabot Co.). Carbon-silica dual-phase-filler is added in the same amounts as previously described with respect to silica.
  • Carbon-silica dual -phase- filler can be used in combinations with other fillers including but not limited to carbon black, silica, clay, calcium carbonate, magnesium carbonate, and combinations thereof. In some embodiments, carbon black and silica, either individually or in combination, are used.
  • Silica, carbon black or carbon black-silica duai-phase-fillers or combinations thereof can be used in combination with natural fillers including but not limited to starch or lignin.
  • the silica incorporated in the rubber compound has a surface area by nitrogen adsorption (hereinafter referred to as "N2A") of from 150 to 300 m 2 /g.
  • N2A nitrogen adsorption
  • a silica having N2A of less than 150 m 2 /g leads to an unfavorably low reinforcing effect.
  • a silica having 2A of more than 300 nr/g provides a rubber compound with an increased viscosity and a deteriorated processabil ity.
  • a N2A from 60 to 150 m 2 /g is suitable.
  • a carbon black having N2A of less than 60 nr/g leads to a low reinforcing effect.
  • a carbon black having N2A of more than 150 m 2 /g provides a rubber compound with an increased hysteresis ioss and a deteriorated processabiiity.
  • Carbon black is typically added in an amount from 2 to 100 parts by weight, in some embodiments from 5 to 100 parts by weight, in some embodiments from 10 to 100 parts by weight, and in some embodiments from 10 to 95 parts by weight for 100 parts by weight of the total polymer.
  • silica filler diameters, particle sizes, and BET surfaces see International Patent Application No, PCT/US2009/045553.
  • silica is added in an amount from 10 to 100 parts by weight, in some embodiments from 30 to 100 parts by weight, and in some embodiments from 30 to 95 parts by weight for 1 00 parts by weight of the total polymer.
  • carbon black and silica are added together, in which case the total amount of carbon black and silica added is from 30 to 100 parts by weight and, in some embodiments, from 30 to 95 parts by weight for 100 parts by weight of the total polymer.
  • Secondary fillers are selected from the group consisting of ( ⁇ ⁇ ) secondary glass powder filler and (A2) zinc-doped glass powder filler.
  • Secondary glass powder fillers are made from glass foam.
  • the glass powder filler is manufactured as a result of a high-temperature extrusion process of giass to porous, amorphous glass foam according to a method described in German Patent Application No. DE 19545065 C2, which is incorporated herein by reference in its entirety. After coarse crushing of the glass foam, the resulting intermediate product is ground and classified.
  • types of glass which can be applied to the method of secondary giass powder filler preparation and representative types include but are not limited to those types of glass described in DE 1 9545065 C2.
  • the type of glass is soda-lime-glass, borosilicate glass or glass compositions comprising soda- lime-glass or borosilicate giass.
  • soda-lime-glass or borosilicate glass is used, in some embodiments, borosilicate glass is used.
  • borosilicate glass filler comprises 55.0 to 60.0 percent by weight S 8.0 to 1 1.0 percent by weight B2O5, 9.5 to 13.5 percent by weight NaiO, 1.0 to 4.0 percent by weight K 2 0, 0 to 2.0 percent by weight MgO, 1 .0 to 5.0 percent by weight CaO, 4.0 to 7.0 percent by weight AI2O3, 2.0 to 5.0 percent by weight ZnO, and 3.0 to 6.0 percent by weight BaO
  • the mean diameter (djo) of the glass particles made from glass foam according to DE 1 545065 C2 is ⁇ 20 ⁇ , in some embodiments ⁇ 10 ⁇ , in some embodiments ⁇ 5 pm and in some embodiments ⁇ 3 ⁇ .
  • the moisture content of the glass powder filler is lower than 0.5 percent by weight.
  • Soda-lime-giass in some embodiments comprises 71.0 to 74.0 percent by weight SiCb, 9.0 to 1 4.0 percent by weight ⁇ a ⁇ -C ).
  • the mean diameter dso) of the glass particles made from giass foam according to DE 19545065 C2 is ⁇ 20 pm, in some embodiments ⁇ 10 pin, in some embodiments ⁇ 5 ⁇ and in some embodiments ⁇ 3 pm.
  • the moisture content of the glass powder filler is lower than 0.5 percent, by weight.
  • the BET-surface of the glass particles made from glass foam according to DE 1 9545065 C2 is > 0.5 m /g, in some embodiments > 1 m 2 /g and in some embodiments > 2 m 2 /g.
  • Secondary glass powder fil ler is typically added in an amount from 0.1 to 100 parts by weight and, in some embodiments, from 0.5 to 60 parts by weight for 100 parts by weight of the total polymer.
  • secondary glass powder filler is typically added in an amount from 0.5 to 30 parts by weight for 100 parts by weight of the total polymer.
  • secondary glass powder filler is typically added in an amount from 30 to 60 parts by weight for 100 parts by weight of the total polymer.
  • zinc-doped secondary glass powder filler is added in an amount from 0.5 to 15 parts by weight for 100 parts by weight of the total polymer.
  • the glass particles can be doped with aluminium salt to (i) change the siianol group density on the secondary glass powder filler surface or to (ii) change the pH value of the secondary glass powder Filler.
  • secondary glass powder fillers can be used as support for vulcanization accelerators including but not limited to CBS (N- cyclohexyl-2-benzothiazylsulfenamid sold under the tradename Vulcacit CZ/EG), and subsequently applied to the preparation of the first polymer compound or to the preparation of the second polymer compound.
  • Secondary zinc-doped glass powder fillers comprise an increased concentration of zinc-ions with the additional zinc-ions in some embodiments being located in the pores of the filler.
  • the secondary zinc-doped glass powder fillers are made from secondary glass powder fillers of relatively lower zinc concentration or from secondary glass powder fillers not comprising zinc. Therefore, the choice of glass subsequently used for the preparation of secondary glass powder filler of relatively lower zinc-ion concentration also applies for zinc- doped secondary glass powder filler with relatively higher zinc-ion concentration.
  • soda-iime-giass, borosilicate glass or glass compositions comprising soda-iime-glass or borosilicate glass are used.
  • soda- lime-glass or borosilicate glass is used.
  • borosilicate glass is used.
  • the secondary zinc-doped glass powder fillers can be made, for example, from secondary glass powder fillers of relatively lower zinc concentration through subsequent treatment with an aqueous zinc salt solution.
  • the selected secondary glass powder filler of relatively low zinc-ion concentration is mixed with a solution of a water soluble zinc salt.
  • Zinc salts useful for the glass powder modification include all soluble zinc salts, with representative examples including but not limited to zinc bromide, zinc sulphate, zinc iodide, zinc fluoride, zinc nitrate, zinc chloride and organic zinc salts including but not limited to zinc acetate. In some embodiments, zinc chloride solution is used.
  • the concentration of the zinc salt in water ranges in some embodiments from 5 to 1000 mmol (zinc chloride)/mL of water, and in some embodiments from 50 to 200 mmol (zinc chloride) / iisL of water.
  • the aqueous zinc solution comprising glass powder is dried in an oven. After drying, the moisture content of the resulting zinc- doped secondary glass powder filler is lower than 0.5 percent by weight.
  • the zinc fraction which has been added as aqueous zinc salt solution is in some embodiments accumulated in the pores and on the surface of the glass particles.
  • the concentration of zinc located in pores and on the surface of the glass particles amounts to 0.2 to 30 percent by weight, in some embodiments to 0.5 to 20 percent by weight, and in some embodiments to 1 to 10 percent by weight of the glass.
  • Zinc potentially located in the bonding structure of glass is not soluble and not derived from zinc added as aqueous solution.
  • the composition corresponds to those described above in the section entitled "Secondary Glass Powder Filler".
  • the mean diameter (dso) of the zinc-doped secondary glass powder filler particles comprising zinc is ⁇ 20 ⁇ , in some embodiments ⁇ 10 ⁇ , in some embodiments ⁇ 5 ⁇ , and in some embodiments ⁇ 3 ⁇ .
  • the BET-surface of the zinc- doped secondary glass powder filler particles comprising zinc is > 0.5 m 2 /g, in some embodiments > 1 m 2 /g. and in some embodiments > 2 m 2 /g.
  • zinc-ions in zinc-doped secondary giass powder fillers located in the filler pores are relatively well distributed, and act as activator of typical vulcanization accelerators. Therefore, state of the art zinc oxide can be replaced as a component in the first polymer compositions in accordance with the present teachings. Due to the relativel higher activity of the zinc-ions in zinc-doped secondary giass powder filler with respect to the relatively lower activity of zinc added to the first polymer composition as zinc oxide, the total zinc concentration can be reduced in the process of the preparation of the second polymer composition (vulcanized polymer composition) in accordance with the present teachings.
  • the polymer composition in accordance with the present teachings can be prepared by kneading the above-described polymers (including oil extended varieties), in some embodiments comprising modified polymers (including oil extended varieties), primary fillers (carbon black, silica, carbon-silica dual-phase filler, etc.), secondar ⁇ ' filler selected from the group consisting of secondary glass powder filler and zinc-doped glass powder filler, optionally processing aids, oils, silane coupling agents, and other additives, in a kneader at 140 °C to 180 °C, to form a filler containing formulation.
  • polymer compositions in accordance with the present teachings can be prepared by kneading the above-described polymers (including oil extended varieties) already comprising the secondary fillers selected from the group consisting of secondary glass powder fillers and zinc-doped glass powder fillers with primary fillers (carbon black, silica, carbon-silica dual-phase filler, etc.) and, optionally, with processing aids, oils, silane coupling agents, and other additives in a kneader at 140 °C to 180 °C to form a filler containing formulation.
  • the secondary fillers selected from the group consisting of secondary glass powder fillers and zinc-doped glass powder fillers with primary fillers (carbon black, silica, carbon-silica dual-phase filler, etc.) and, optionally, with processing aids, oils, silane coupling agents, and other additives in a kneader at 140 °C to 180 °C to form a filler containing formulation.
  • the polymer composition can be prepared by kneading the above-described modified polymers (including oil extended varieties) already comprising the secondary filler selected from the group consisting of secondary glass powder filler and zinc-doped glass powder filler with primary fillers (carbon black, silica, carbon-silica dual-phase filler, etc.) and, optionally, with processing aids, oils, silane coupling agents, and other additives in a kneader at 140 °C to 180 °C to form a filler containing formulation.
  • the secondary filler selected from the group consisting of secondary glass powder filler and zinc-doped glass powder filler with primary fillers (carbon black, silica, carbon-silica dual-phase filler, etc.) and, optionally, with processing aids, oils, silane coupling agents, and other additives in a kneader at 140 °C to 180 °C to form a filler containing formulation.
  • Polymer compositions already comprising the secondary fillers selected from the group consisting of secondar glass powder fillers and zinc-doped glass powder fillers are prepared by adding the secondary fillers into a polymer solution (e.g., during agitation) followed by an azeotropic (sol vent/ water-steam) solvent removal process, followed by drying the secondary filler comprising polymer at an. elevated temperature.
  • a polymer solution e.g., during agitation
  • azeotropic sol vent/ water-steam
  • a polymer composition in accordance with the present teachings comprises at least 30-60 parts by weight in some embodiments 30-45 parts by weight, for 100 parts by weight of the total polymer of a secondary glass powder filler, 10- 100 parts by weight, in some embodiments 30-95 parts by weight, for 100 parts by weight of the total polymer of silica, 30-90 parts by weight, in some embod iments 40-80 parts by weight, for 100 parts by weight of the total polymer content of a polymer selected from the group consisting of SBR, SIR.
  • S-SBR or S-SIR 5-60 parts by weight in some embodiments 10-50 parts by weight, for 100 parts by weight of the total polymer of a polymer selected from the group consisting of polybutadiene, polyisoprene or natural rubber or conjugated poiydiene, and 1 -25 parts by weight, in some embodiments 3- 15 parts by weight, of a silane coupling agent.
  • a polymer composition in accordance with the present teachings comprises at least 0.5-30 parts by weight, in some embodiments 3-20 parts by weight, for 100 parts by weight of the total polymer of a secondary glass powder filler, 1 0- 1 10 parts by weight, in some embodiments 30-95 parts by weight, for 100 parts by weight of the total polymer of silica, 30-95 parts by weight, in some embodiments 40-80 parts by weight, for 100 parts by weight of the total polymer content of a polymer selected from the group consisting of SBR, SIR.
  • S-SBR or S-SIR 5-60 parts by weight, in some embodiments 10-50 parts by weight, for 100 parts by weight of the total polymer of a polymer selected from the group consisting of polybutadiene, polyisoprene or natural rubber or conjugated poiydiene and 1 -25 parts by weight, in some embodiments 3- 15 parts by weight of a silane coupling agent.
  • a polymer composition in accordance with the present teachings comprises at least 0.1 -25 parts by weight, in some embodiments 0.5-15 parts by weight, for 100 parts by weight of the total polymer of a zinc-doped secondary glass powder filler, 10-1 10 parts by weight, in some embodiments 30-95 parts by weight, for 100 parts by weight of the total polymer of silica, 30-95 parts by weight, in some embodiments 40-80 parts by weight, for 100 parts by weight of the total polymer content of a polymer selected from the group consisting of SBR, SIR, S-SBR or S-SIR; 5-60 parts by weight, in some embodiments 10-50 parts by weight, for 100 parts by weight of the total polymer of a polymer selected from the group consisting of polybutadiene, polyisoprene or natural rubber or conjugated poiydiene and 1 -25 parts by weight, in some embodiments 3-15 parts by weight, of a silane coupling agent.
  • a polymer composition in accordance with the present teachings comprises at least 0.5-30 parts by weight, in some embodiments 3-20 parts by weight, for 100 parts by weight of the total polymer of a secondary glass powder filler, 10- 1 1 0 parts by weight, in some embodiments 30-95 parts by weight, for 100 parts by weight of the total polymer of carbon black, 30-95 parts by weight, in some embodiments 40-80 parts by weight, for 100 parts by weight of the total polymer content of a polymer selected from the group consisting of SBR, SIR, S-SBR or S-SIR; 5-60 parts by weight, preferably 10-50 parts by weight, for 100 parts by weight of the total polymer of a polymer selected from the group consisting of polybutadiene, polyisoprene or natural rubber or conjugated polydiene and 1 -50 parts by weight, in some embodiments 3-30 parts by weight, of an oil.
  • a polymer composition in accordance with the present teachings comprises at least 0.5-30 parts by weight, in some embodiments 3-20 parts by weight, for 100 parts by weight of the total polymer of a zinc-doped secondary glass powder filler, 1 0-1 10 parts by weight, in some embodiments 30-95 parts by weight, for 100 parts by weight of the total polymer of carbon black, 30-95 parts by weight, in some embodiments 40-80 parts by weight, for 1.00 parts by weight of the total polymer content of a polymer selected from the group consisting of SBR, SIR, S-SBR or S-SIR; 5-60 parts by weight, in some embodiments 1 0-50 parts by weight, for 100 parts by weight of the total polymer of a polymer selected from the group consisting of polybutadiene, polyisoprene or natural rubber or conjugated polydiene and 1-50 parts by weight, in some embodiments 3-30 parts by weight, of an oil.
  • a polymer composition in accordance with the present teachings comprises at least 30-60 parts by weight, in some embodiments 30-45 parts by weight for 100 parts by weight of the total polymer of a secondary glass powder filler, 10- 100 parts by weight, in some embodiments 30-95 parts by weight, for 100 parts by weight of the total polymer of carbon black, 30-90 parts by weight, in some embodiments 40-80 parts by weight, for 100 parts by weight of the total polymer content of a polymer selected from the group consisting of SBR.
  • SIR, S-SBR or S-SIR 5-60 parts by weight, in some embodiments 10-50 parts b weight, for 100 parts by weight of the total polymer of a polymer selected from the group consisting of polybutadiene, polyisoprene or natural rubber or conjugated polydiene and 1 -50 parts by weight, in some embodiments 3-30 parts b ⁇ ' weight, of an oil.
  • a polymer composition in accordance with the present teachings comprises at least 0.5-30 parts by weight, in some embodiments 3-20 parts by weight, for 100 parts by weight of the total polymer of a secondary glass powder filler, 10- 100 parts by weight, in some embodiments 30-95 parts by weight, for 100 parts by weight of the total polymer of silica and carbon black, 30-95 parts by weight, in some embodiments 40-80 parts by weight for 100 parts by weight of the total polymer content of a polymer selected from the group consisting of SBR, SIR, S-SBR or S-SIR; 5-60 parts by weight, in some embodiments 10-50 parts by weight, for 1 00 parts by weight of the total polymer of a polymer selected from the group consisting of polybutadiene, polyisoprene or natural rubber or conjugated polydiene and 1 -20 parts by weight, in some embodiments 3-12 parts by- weight of a silane coupling agent.
  • a polymer composition in accordance with the present teachings comprises at least 0.5-30 parts by weight, in some embodiments 3-20 parts by weight, for 100 parts by weight of the total polymer of a zinc-doped secondary glass powder filler, 10- 100 parts by weight, in some embodiments 30-95 parts by weight, for 100 parts by weight of the total polymer of silica and carbon black, 30-95 parts by weight, in some embodiments 40-80 parts by weight for 100 parts by weight of the total polymer content of a polymer selected from the group consisting of SBR, SIR, S-SBR or S-SIR: 5-60 parts by weight, in some embodiments 10-50 parts by weight for 100 parts by weight of the total polymer of a polymer selected from the group consisting of polybutadiene, polyisoprene or natural rubber or conjugated polydiene and 3 -20 parts by weight, in some embodiments 3- 12 parts by weight, of a silane coupling agent.
  • a polymer composition in accordance with the present teachings comprises at least 30-60 parts by weight, in some embodiments 30-45 parts by weight, for 100 parts by weight of the total polymer of a secondary glass powder filler, 10- 100 parts by weight, in some embodiments 30-95 parts by weight, for 100 parts by weight of the total polymer of silica and carbon black, 30-90 parts by weight, in some embodiments 40-80 parts by weight, for 100 parts by weight of the total polymer content of a polymer selected from the group consisting of SBR, SIR, S-SBR or S-SIR; 5-60 parts by weight, in some embodiments 10-50 parts by weight, for 1 00 parts by weight of the total polymer of a polymer selected from the group consisting of polybutadiene, polyisoprene or natural rubber or conjugated polydiene and 1-20 parts by weight, in some embodiments 2- 10 part by weight of a silane coupling agent.
  • the typical primary filler content is reduced when secondary filler selected from the group consisting of secondary glass powder filler and zinc-doped glass powder filler is added to the polymer composition.
  • secondary filler selected from the group consisting of secondary glass powder filler and zinc-doped glass powder filler is added as a component to the polymer composition
  • the primary filler content (silica, carbon, black, silica-carbon black dual filler) in the polymer composition can be optionally reduced by 20 parts by weight for 100 parts by weight of the total polymer content in a polymer composition.
  • the silica filler content is reduced as result of the secondary Filler addition, there is the option to reduce the silane coupling agent concentration of the polymer composition as well.
  • the silane coupling agent concentration is usually calculated with respect to the surface area of all silicon-hydroxy (Si-OH) groups containing fillers comprised in the polymer composition. Therefore, in an exemplary polymer composition in accordance with the present teachings comprising silica and secondary filler selected from the group consisting of secondary glass powder filler and zinc-doped glass powder filler, the silane coupling agent concentration can be calculated with respect to the surface area of the total silica and secondary glass powder filler present: in the polymer composition.
  • the silane coupling agent concentration can be reduced. Therefore, beneficially, expenses on silane coupling agents can be saved, when secondary filler selected from the group consisting of secondary glass powder filler and zinc-doped glass powder filler is applied as a constituent to a silica- containing polymer composition.
  • vulcanizing agents such as sulfur, vulcanizing accelerators, and the like, are added to the aforementioned filler-containing formulation, and the resulting mixture is blended using a Brabender mixer, Banbury mixer or open roll mill to form the desired shape, and the mixture is vulcanized at 140 °C to 1 80 °C, to obtain a vulcanized article.
  • a composition in accordance with the present teachings comprising at least (A) secondary filler selected from the group consisting of (A l ) secondary glass powder filler and (A2) zinc-doped glass powder filler, (B) primary filler component(s) selected from the group consisting of silica, carbon-silica dual-phase filler, carbon black, carbon nano-tube filler, lignin (in some embodiments silica), and (C) one or more types of polymers including but not limited to the group of modified polymers is used for vulcanized (or cross-linked) elastomeric polymer compositions, and articles made from such compositions, such as pneumatic tires, tire treads, belts, footwear components, and the like.
  • the second polymer compositions in accordance with the present teachings comprising secondary filler selected from the group consisting of secondary glass powder filler and zinc- doped glass powder filler exhibit lower Tan ⁇ at 60 °C values or higher Tan ⁇ at 0 °C values, and a good balance of physical properties including but not limited to one or more of abrasion resistance, tensile and tear strength, modulus, and heat buildup when compared with second polymer compositions (or cross-linked polymer compositions) not comprising secondary filler selected from the group consisting of secondary glass powder filler and zinc- doped glass powder filler.
  • the second polymer compositions in accordance with the present teachings also exhibit lower Tan ⁇ at 60 °C values, higher Tan ⁇ at 0 °C val ues or higher Tan ⁇ at - 10 °C values, and a good balance of physical properties including but not limited to one or more of abrasion resistance, tensile and tear strength, modulus, and heat buildup when in the first polymer compositions in accordance with the present teachings at the same time silica is partially replaced by secondary filler selected from the group consisting of secondary glass powder filler and zinc-doped glass powder filler, and the silane coupling agent concentration is reduced. Therefore, the second polymer compositions in accordance with the present teachings can be manufactured by using a reduced amount of relatively expensive silane coupling agent.
  • compositions in accordance with the present teachings are useful in preparing tire treads having lower rolling resistance, higher wet grip, higher ice grip, and/or lower heat buildup while maintaining good wear properties. Therefore, compositions in accordance with the present teachings are useful in preparing tires with improved fuel economy and safety in terms of a reduced braking distance.
  • first polymer compositions in accordance with the present teachings comprising secondary filler selected from the group consisting of secondary glass powder filler and zinc-doped glass powder filler exhibit improved processing characteristics as represented by decreased first poiymer composition Mooney value, when compared with first polymer compositions not comprising secondary filler selected from the group consisting of secondary glass powder filler and zinc-doped glass powder filler. Therefore, the composition in accordance with the present teachings exhibits improved processing characteristics for tire manufacturers. The improved processing characteristic leads to a reduced mixing period and a higher throughput in the course of the rubber compound extrusion process.
  • compositions in accordance with the present teachings including secondary filler selected from the group consisting of secondary giass powder filler and zinc- doped glass powder filler, primary fillers such, as silica, carbon black, carbon nano-tube, carbon-silica dual, phase filler, softener, vulcanizing agents and the like, and the (vulcanized elastomeric) second polymer compositions in accordance with the present teachings are particularly useful in the preparation of tires.
  • secondary filler selected from the group consisting of secondary giass powder filler and zinc- doped glass powder filler
  • primary fillers such, as silica, carbon black, carbon nano-tube, carbon-silica dual, phase filler, softener, vulcanizing agents and the like
  • the (vulcanized elastomeric) second polymer compositions in accordance with the present teachings are particularly useful in the preparation of tires.
  • the present teachings also provide a method to replace zinc oxide added in powder form to first polymer compositions through the application of zinc-doped secondary glass powder filler. Therefore, the handling of powdery zinc oxide, which is classified as environmentally dangerous according to EG 67/548/EEC, in the process of the preparation of first polymer compositions can be avoided.
  • the present teachings further provide second polymer compositions (and first polymer compositions) with reduced zinc concentration.
  • Zinc provided through the application of zinc-doped secondary glass powder filler in the first polymer compositions in accordance with the present teachings more efficiently activates typical vulcanization accelerators. Therefore, the total zinc concentration required for performing the vulcanization of first polymer compositions can be reduced if zinc oxide is replaced by zinc- doped secondary glass powder filler.
  • the present teachings also provide an article comprising at least one component formed from a composition in accordance with the present teachings, in some embodiments, the article comprises a tire. In some embodiments, the article comprises a tire tread. In some embodiments, the article comprises a tire side wall. In some embodiments, the article comprises an automotive part. In some embodiments, the article comprises a footwear component. In some embodiments, the inventive article comprises a belt, a gasket, a seal, or a hose.
  • the following polymers are of particular interest: natural rubber; emulsion SBR and solution SBR rubbers with a glass transition temperature above -50 °C; polybutadiene rubber with a high cis 1,4-unit content (>90%), which has been prepared using catalysts based on nickel, cobalt, titanium, vanadium, gadolinium or neodymium; and polybutadiene rubber with a vinyl content of 0 to 75%; and combinations thereof.
  • polystyrene rubber with a high trans 1 ,4-unit content (>75%)
  • SBR polybutadiene rubber with a high trans 1 ,4-unit content (>75%)
  • SBR polybutadiene rubber with a high trans 1 ,4-unit content (>75%)
  • SBR polybutadiene rubber with a high trans 1 ,4-unit content (>75%)
  • SBR polybutadiene rubber with a high trans 1 ,4-unit content (>75%)
  • SBR containing in some embodiments between 5 and 40 wt% styrene and a high trans 1 ,4-polybutadiene content (>75%) of the polybutadiene fraction of the copolymer
  • each type of polymer SBR or BR
  • initiator compounds comprising earth alkaline metal compounds, such as described for example in U.S.
  • the gel content in some embodiments is greater than 50 weight percent, in some embodiments greater than 75 weight percent, and in some embodiments greater than 90 weight percent based on the weight of the polymer.
  • Gel content can be determined by dissolving about 0.2 grams of poiymer in 150 ml of toluene for 24 hours at ambient temperature, separating the insolubles, drying the insolubles, and measuring the amount of insolubles.
  • alkyl refers to at least one aliphatic group, and may also refer to two or more aliphatic groups.
  • the alkyl group may be linear, branched, cyclic, or a combination thereof, and saturated or unsaturated, in some embodiments, the alkyl group is linear, branched, cyclic or a combination thereof, and saturated, in some embodiments, the alkyl group is linear and saturated or branched and saturated.
  • alkyr is understood to include both straight chain, aliphatic hydrocarbon groups, (for example, methyl (Me), ethyl (Et), n-propyl (Pr), n-butyl (Bu), n-pentyl, n-hexyL etc.).
  • branched aliphatic hydrocarbon groups for example, isopropyl, tert-butyl, etc.
  • carbon-based non-aromatic rings aliphatic hydrocarbon groups in some embodiments, "alkyl” refers to saturated linear, branched, cyclic, or combinations thereof, aliphatic hydrocarbon groups, and unsaturated, linear, branched, cyclic, or combinations thereof, aliphatic hydrocarbon groups.
  • alkoxy is understood to include methoxy (MeO), ethoxy (EtO), propoxy (PrO), butoxy (BuO), isopropoxy (iPrO), isobutoxy (z ' BuO), pentoxy, and the like.
  • aralkyl refers to at least one aromatic ring, and also at least one alkyl group.
  • the term “aralkyl” is understood to mean an ary! group bonded to an alkyl .
  • hydrocarbon groups is understood to include any group, including saturated, unsaturated, linear, branched, cyclic, aromatic groups, which only consist of the elements hydrogen and carbon.
  • the following examples and representative procedures illustrate features in accordance with the present invention, and are provided, solely by way of illustration. They are not intended to limit the scope of the appended claims or their equivalents.
  • the Examples include the preparation of the glass fillers, the preparation of polymers, and the preparation and testing of uncrosslinked. as well as cross-linked, poiymer compositions. Unless stated to the contrary, all parts and percentages are expressed on a weight basis. The polymerizations were performed under the exclusion of moisture and oxygen, in a nitrogen atmosphere. Various methods were used to test and measure the examples. A brief description of each technique is provided.
  • Bonded sty ene content A calibration curve was prepared by IR absorption spectrum (IFS 66 FT-IR spectrometer of Bruker Analytik GmbH). The IR samples were prepared using CS2 as swelling agent. For the IR determination of the bound styrene in styrene- butadiene copolymers are four bands viewed: a) band for trans- 1.4-polybutadiene units at 966 cm "1 , b) band for cis-1.4-polybutadiene units at 730 cm " ' , c) band for 1.2-polybutadiene units at 910 cm "1 and band for bound styrene (styrene aromatic bond) at 700 cm "1 .
  • the band heights are normed according to the appropriate extinction coefficients and summarized to a total of 100%.
  • the normation is done via ⁇ - and , C-NMR.
  • the ID NMR spectra were collected on a Bruker Avance 200 NMR spectrometer (BRUKER BioSpin GmbH) using a 5 mm dual detection probe, The field homogeneity was optimized by maximizing the deuterium lock signal. The samples were shimmed by optimizing the deuterium lock signal. The samples were run at room temperature (298 ).
  • GPC-Method SEC calibrated with narrow distributed polystyrene standard.
  • each G PC-device three columns were used in a connected mode.
  • the length of each of the columns 300 mm;
  • GPC Standards EasiCal PS- 1 Polystyrene Standards, Spatula A ⁇ B
  • Mw/ n Polydispersity
  • the Mpl, Mp2, Mp3 correspond to the (maximum, peak) molecular weight measured at the first, second or third peaks of the GPC curve [the first peak Mpl (lowest molecular weight) is located on the right side of the curve, and the last peak (highest molecular weight) is located on the left side of the curve], respectively.
  • Maximum peak molecular weight means the molecular weight of the peak at the position of maximum peak intensity.
  • the Mp2 and Mp3 are two or three polymer chains coupled to one macromolecule.
  • Mpl is one polymer chain (base molecular weight— no coupling of two or more polymer chains to one macromolecule).
  • the total coupling rate represents the sum of the weight fractions of coupled polymers relative to the total polymer weight, including the sum of the weight fractions of all coupled polymers and the uncoupled polymer.
  • the total coupling rate is calculated as shown below.
  • CR( total) (£Area fraction of all coupled peaks [Peak with maximum M.p2 to peak with highest indexed, peak maximum])/( ⁇ Area fraction of all peaks [Peak with peak maximum Mp l to peak with highest indexed peak maximum]).
  • the individual coupling rate (e.g. two polymer arms coupled corresponding to the peak with peak maximum Mp2) is calculated as depicted below
  • CR(2arms) (Area fraction of peak with peak maximum Mp2)/ ( ⁇ Area fraction of all peaks [Peak with, peak maximum Mp l to peak with highest indexed peak maximum]).
  • the Mooney viscosity of the polymer was measured according to ASTM D 1646 (2004), with a preheating time of one minute and a rotor operation time of 4 minutes, at a temperature of 100 °C [ML1+4(100 °C)], on a MV 2000E from Alpha Technologies UK.
  • the rubber Mooney viscosity measurement is performed on dry (solvent free) raw polymer (wow-vulcanized rubber).
  • composition of the glass grades was determined through atomic absorption spectroscopy on a Nova A A 350 from Analytik Jena AG and X-ray fluorescence analysis using a SEA 1200VX from Seiko Instruments Inc. according to DIN ISO 52340.
  • the particle size of the glass particles was determined through application of laser diffraction using a Sympatec Helos device (Type H2023) according to DIN ISO 1332- 1.
  • D50 is the particle size, when 50 percent of the particles have smaller or equal size.
  • D99 is the particle size, when 99 percent of the particles have smaller or equal size.
  • the pH-value was determined by using an aqueous solution (also called eluate) prepared from 1 0 g glass powder and 90 g distilled water. The p.H-value measurement was performed at room temperature following DIN EN ISO 787-9. The pH-value was determined using a PM 2000 with pH-electrode from the company Ingenieurgesellschaft GmbH.
  • the conductivity was determined by using an aqueous solution (also called eluate) prepared from 10 g glass powder and 90 g distilled water. The conductivity was measured at room temperature according to DIN EN ISO 787- 14 using the device PM. 2000 with a conductivity-measuring cell from the company ingenieurgesellschaft mbH.
  • the moisture content of the glass particles was determined according to ISO 787-2 after two hours drying of the glass samples in a drying chamber of VEB Elektroindustrieofenbau Romhild type RE 100 at a temperature of 105 °C.
  • BET Brunauer, Emmett and Teller nitrogen surface area of glass was determined with a gas adsorption meter of Sirohlein Kaarst, model Bb. according to DIN ISO 9277. Void volume and pore diameter of the glass particles were determined with mercury porosimetry of Thermo Electro Corporation Mailand, Type Pascal 140.
  • the density of silanol groups on the glass surface was determined by acid-base- titration, according to the description by G. W. Sears (see analytical Chemistry, Volume 28, No. 12, 1 56). The determination method is based on the chemical reaction below, "Si-OH" representing silanol groups on the glass particle surface:
  • Rubber compounds were prepared by combining the constituents listed below in Tables 6 to 17, in a laboratory mixer Brabender Plasticorder PL 2000 (Brabender GmbH & Co. KG, Duisburg, Germany) with a thermostat heated mixing chamber N50 with Banbury rotors and a chamber volume of 75 cm" following a two-stage mixing process.
  • stage 1 all components were mixed together, except the components of the vulcanization package, to form a stage 1 formulation, in stage 2, the components of the vulcanization package were mixed into the stage 1 formu!ation to form a stage 2 formulation.
  • the energy input W5 measured in ki during the two mixing steps is listed in Tables 20, 23, 25 and 28.
  • the vulcanization curve and rubber compound viscosity was measured with a rotorless vulcameter Goettfert Elastograph, type: Vario according to ASTM D5269 and ISO 6502 (Goettfert Maschinenstoffpriifmaschinen GmbH, Buchen, Germany, Frequency 50 min " ', operation angle 0.5°, gap 150 micrometer, temperature 160 °C).
  • the scorch time (TS2) and time to cure (TC90) are listed in Tables 20, 23, 25 and 28.
  • the rheometer measurements were performed at a constant temperature of 160 °C on the unvulcanized second stage polymer formulations, according to Tables 20, 23, 25 and 28.
  • the amount of polymer sample is about 4.6 g.
  • Sample shape and shape preparation are standardized and defined by the measurement device (vulcameter Goettfert Elastograph, type Vario, see above).
  • the "TC 90" is the respective time required to achieve 90% conversion of the vulcanization reaction.
  • the torque is measured as a function of time of reaction.
  • the vulcanization conversion is automatically calculated from the generated torque versus time curve.
  • the "TS 2" is the respective time required to increase the torque by 0.02 Nm above the respective torque minimum (ML) during vulcanization.
  • TS 2 is > 2.5 minute (listed in Tables 20. 23 , 25 and 28) and TC 90 (listed in Tables 20, 23, 25 and 28) is from 8 to 19 minutes. All mechanical property tests on cured (vulcanized) materials were performed with specimens from vulcanized plates. The rubber mixtures were prepared during a two-stage process with compositions according the Tables 7, 8, 9, 10, 1 1, 12. 13, 14, 15, 16 and 17.
  • the vulcanization of plates was performed for a period of 16 to 25 minutes at a temperature of 160 °C to TC 90 (90% vulcanization conversion: see cure data in Tables 20, 23, 25 and 28).
  • the process leads to the formation of visually "bubble free,'" homogeneous cured rubber plates of 100 mm x 100 mm x 2 mm for DMA tests, tensile tests, tear tests, instrumented tensile-impact tests and Shore A hardness testing and discs of 60 mm diameter and 10 mm height for abrasion tests.
  • the specimens of the necessary geometry were prepared out of the aforementioned plates by punching and drilling out (abrasion test), respectively.
  • Tables 21 , 24, 26 and 29 summarize the results of the tensile and tear tests, of hardness testing, as well as of toughness tests.
  • Tensile strength GM, elongation at break ER and stress at 100% and 300% strain were determined by tensile tests according to ISO 37 (2005-07), using S2 dumbbell test specimens on a ZWIC Z020 universal testing machine. Furthermore, the maximum stress ⁇ ⁇ (tensile strength) as well as the tensile strain at break 8 were determined for each specimen. The tensile tests were performed at room temperature with five (5) specimens for each material. The tensile strength should be at least 12 MPa and the tensile strain at break at least 400%. Tables 21. 24. 26 and 29 summarize the results of the tensile tests.
  • the hardness testing was performed according to DIN 53505 (2000-08) at room temperature with the Shore A tester ZWIC 3150. As a result, the Shore A hardness was determined as the mean value of 10 single measurements for each material. For the tests, 3 pieces of the material were stacked to reach the minimum thickness for the test of 6 mm. The minimum value of the Shore A hardness should be 60. Tables 21 , 24, 26 and 29 summarize the results of the hardness testing.
  • the tear resistance T ⁇ was determined at room temperature according to ISO 34-1 (2005-07) by using the universal testing machine ZW1CKI.
  • the crosshead speed was 100 mm/min, and for each material, 5 trouser specimens with a thickness of 2 mm were used.
  • Tables 21. 24, 26 and 29 summarize the results of the tear tests.
  • Rubber compounds were prepared by combining the constituents listed below in Table 18 and 19 in a "380 cc Banbury mixer (Labstation 3 0S from Brabender GmbH&Co KG)," following a two-stage mixing process.
  • the Mooney viscosity of the rubber compound was measured according to ASTM D 1646 (2004), with a preheating time of one minute and a rotor operation time of 4 minutes, at a temperature of 100 °C [ML 1 +4( 1 00 °C)], on a MV 2000E shear disc-viscosimeter from Alpha Technologies UK.
  • the rubber Mooney viscosity measurement is performed on an uncured (unvulcanized) second state polymer compound sample prepared according to Tables 18 and 19.
  • the Compound Mooney values are listed in Table 3 1.
  • Measurement of unvulcanized rheological properties on finalized first stage rubber compounds prepared according to Tables 18 and 19 was performed according to AST D 5289-95 (reapproved 2001 ) using a rotor-less shear rheometer (MDR 2000 E from Alpha Technologies UK; MDR Moving Disc Rheometer) to measure Scorch Time (TS) and Time to Cure (TC).
  • MDR 2000 E from Alpha Technologies UK
  • MDR Moving Disc Rheometer
  • the rheometer measurement was performed at a constant temperature of 160 °C on an unvulcanized second stage polymer formulation, according to Table 3 1 .
  • the unvulcanized first stage rubber compound rheological properties are listed in Table 31.
  • the "TC 50" is the respective time required to achieve 50% conversion of the vulcanization reaction.
  • the “TS ' is the respective time required to increase the torque by 0.01 Nm above the respective torque minimum (ML) during vulcanization.
  • TS 1 is > 1.5 minute, and TC 50 is from 3 to 8 minutes.
  • Tensile strength O , elongation at break E and stress at 300% strain were determined by tensile tests according to AST D 41 2-98A (reapproved 2002). using a dumbell die C test pieces on a Zwick ZO I O. Of the standardized dumbbell die C test pieces, those of "2 mm thickness" were used. The tensile strength measurement was performed at room temperature on a cured (vulcanized) second stage polymer sample prepared according to Table 18. Stage 2 formulations were vulcanized within 16-25 minutes at 160 °C to TC 95 (95% vulcanization conversion) (see cure data in Table 31 ).
  • Rubber compound tensile strength ⁇ ⁇ , elongation at break E R and stress at 300% strain data are listed in Table 32.
  • the abrasion measurement was performed on a vulcanized, second stage polymer formulation according to Tables 18 and 19. Stage 2 formulations were vulcanized at 160 °C to TC 95 (95% vulcanization conversion) (see cure data in Table 31 .
  • Tan ⁇ at 60 °C and Tan 5 at 0 °C measurements were performed cylindrical specimens using a dynamic mechanical thermal spectrometer Epiexor 150N manufactured by Gabo Qualimeter Testanlagen GmbH, Ahiden, Germany , by applying a compression dynamic strain of 0.2%. at a frequency of 2 Hz, respectively, at the respective temperatures. Rubber compound vulcanizate Tan ⁇ at 60 °C and Tan ⁇ at 0 °C are listed in Table 32.
  • Tan ⁇ (0 °C) and Tan o (- 10 °C) were measured using the same equipment and load conditions at 0 °C and -10 °C, respectively.
  • Tan ⁇ at 60 °C, Tan ⁇ at 0 °C and Tan ⁇ at -1.0 °C index values are listed in Tables 32).
  • Glass is transferred into a porous, amorphous glass foam according to patent DE 19545065 C2 incorporated herein by reference in its entirety.
  • the reference describes that glass is first melted and then extruded using a high temperature extrusion process. Subsequently, the resulting glass foam is coarse crushed and subsequently ground. In a last step according to DE 02452693 B4. the glass particles are classified with, respect to resulting average particle size.
  • Zinc-(Il)-chloride is dissolved in distilled water.
  • TROVO® powder (952 g) is exposed to a solution of 48 g zinc chloride in 56 mL water to get free-flowing glass powder with even distribution of zinc (Type G4).
  • exemplary concentrations of zinc are 2.3 (G4) and 4.6 (G5) percent by weight.
  • the resulting mixture is distributed on a stainless steel sheet (thickness of the sheet ⁇ 5 mm) and stored in an oven at a temperature of 190 °C for two hours. Subsequently the dried glass powder was deagglomerated in a split mill.
  • the eluate is made from 10 g glass-powder and 90 g distilled water,
  • the OH groups are determined with the method for the SEARS number (titration),
  • BET nitrogen surface area are determined with area meter (company Str hlein from Kaarst, model Bb) according to DIN ISO 9277.
  • Zinc oxide concentrations are calculated from zinc concentrations measured using X-ray fluorescence analysis
  • butadiene unit concentration is referred to the total iiornopolyrrser or copolymer
  • Vinyl Concentration means the L2-poiybutadiene umt concentration is referred to the totai butadsene fraction of the copolymer or to the total homopolymer
  • J Styrene unit concentration is referred to the total homopolymer or copolymer
  • phr means parts per weight per hundred parts per weight of rubber
  • Coupling agents The following coupling agents were applied to polymer P0GT and P002 preparation:
  • Coupling agent 2 (C2): n-methylpyrrolidine
  • Coupling agent 3 (C3): 3-meihoxy-3-methyl-8,8-dioctyl-2-oxa-7-thia-3,8-disila-octadecane
  • Preparation of the polymer solution P001 The co-polymerizations of styrene and butadiene were performed in a double wall 40 liter steel reactor, which was first purged with nitrogen, before the addition of organic solvent, monomers, polar coordinator compound, initiator compound or other components.
  • the polymerization reactor was tempered to 60 °C, unless stated otherwise.
  • the following components were than added in the following order: cyclohexane solvent (22.43 kilograms); butadiene monomer, styrene monomer, and tetramethylethylene diamine (TMEDA). The mixture was stirred for one hour, followed by titration with n-butyl lithium to remove traces of moisture or other impurities.
  • the polymerization initiator n-butyl lithium was added to initiate the polymerization reaction.
  • the polymerization was performed for 80 minutes, not allowing the polymerization temperature to exceed 60 °C. Afterwards, 0.5% of the total butadiene monomer amount were added, followed by the addition of coupling agent 1 .
  • the mixture was stirred for 20 minutes. Subsequently, 1.8% of the total butadiene monomer amount were added, followed by the addition of the coupling agent 2 (in case of PI ) or of coupling agent 3 (in case of P2).
  • the polymer solution was transferred, after 45 minutes, into a separate double wall, steel reactor, containing 100 mL ethanol. and 5 g IRGANOX 1520 as stabilizer for the polymer. This mixture was stirred for 1.5 minutes.
  • Table 4 Com osition of Examples - amounts of rea ents for ol merization
  • vinyl content is that of the 1.2-polybutadiene unit content of the final copolymer, and is determined by IR spectroscopy
  • Coagulation Procedure 135 kg water containing 60 ppm Pluronic PE6400 from BASF AG surfactant were heated up using low pressure steam (central company suppiy, steam pressure: 4 bar, steam temperature: 130 °C) until a. temperature of about 97-99 °C was reached in the coagulator vessel.
  • the coagulator vessel (fabrication no. 09998256. year of construction: 2000, from SRI Hoi land/ Veen wouden - Speciaal Roestvrijstaal Industrie Veenwouden) is of 206 L size.
  • the coagulator is connected, with a nozzle pipe.
  • the nozzle pipe contains a nozzle for transferring the polymer suspension in perpendicular direction and an outlet for Kondensat. In the right angle to the polymer suspension transfer nozzle and to the outlet for Kondensat, there is a steam transfer nozzle. After the coagulator temperature is reached steam was released via the steam nozzle into the coagulator vessel. The steam pressure in the coagulator was adjusted to 4 bar. The steam velocity amounted to 15.0 kg/hr. In addition. Kondensat containing 60 ppm Pluoronic surfactant is fed continuously via the nozzle pipe into the coagulator.
  • One of the nozzies, the steam transfer nozzle has a nozzle exit surface of 22 mm2.
  • the nozzle is of a trench shape.
  • the other nozzle, the polymer solution transfer nozzle has a nozzle exit surface of 15.2 mm2.
  • the hole of the polymer solution transfer nozzle is of circular shape and has a diameter of 4.4 mm. Both nozzles only have only one hole.
  • the coagulation process was performed for a period of 35 min. Afterwards the polymer solution and the Kondensat transfer into the coagulator vessel was stopped, while steam was fed for further 5 min into the coagulator vessel to remove residues of cyclohexane solvent. Then the steam feed stream into the coagulator was stopped as well, and the glass-polymer composite crumbs were removed from the coagulator. The glass-rubber crumbs were than dried for 12 hours at room temperature, further 30 min at a temperature of 70 °C and then another two days at room temperature.
  • the final glass-in-rubber concentration, calculated from the glass-rubber composite ash content and the glass-rubber composite Mooney value are listed in Table 6.
  • Table 6 Com osition of Examples - amounts of reagents for pol merization and characteristics
  • glass concentration solvent- free polymer composite was calculated from the dosed amount of glass and the ash content of the rubber composite (The ash content of e.g. the glass free PC rubber only amounts to 0.25 wt%. The ash content contribution of P5 and P6 was considered not significant and thus, was neglected.)
  • Polymer Compositions Poiymer compositions were prepared by combining and compounding the constituents listed below in Table 7 and 9 in a N50 cc Banbury mixer, and vulcanized at 160 °C for T90. Vulcanization process data and physical properties for the each composition example are provided in Tables 20, 21 and 22.
  • Polymer compositions M10-M 1 8 were prepared by combining and compounding the constituents listed below in Table 8 and 9 in a N50 Brabender mixer, and vulcanized at 160 °C for T90. Vulcanization process data and physical properties for the each composition example are provided in Tables 20, 21 and 22, Table 8: Pol mer Com osition usin Pol mers P2 and P3
  • VI-B Compounds Based on Oil Free Rubber Grades (Compositions individually added to the Brabender mixer according to T ables 10 and 1 1 include a separately prepared glass filler containing SSBR composite component)
  • Additional polymer compositions were prepared by combining and compounding the constituents listed below in Table 10 and 1 1 in a N50 Brabender mixer, and vulcanized at 160 a C for T90. Vulcanization process data and physical properties for the each composition example are provided in Tables 23 , 24 and 25.
  • VI-C Compounds based on Oil extended Rubber Grades
  • Additional polymer compositions were prepared by combining and compounding the constituents listed below in Table 12 and 14 in a N50 Brabender mixer, and vulcanized at 60 °C for T90. Vulcanization process data and physical properties for the each composition example are provided in Tables 25, 26 and 27.
  • Additional polymer compositions were prepared by combining and compounding the constituents listed below in Table 13 and 14 in a N50 Brabender mixer, and vulcanized at 160 °C for T90. Vulcanization process data and physical properties for the each composition example are provided in Tables 25. 26 and 27.
  • VI-D Compounds Based on Oil Free Rubber Grades and on Zinc-Doped Glass Filler Component (compounds do not comprise Zinc oxide)
  • Polymer compositions were prepared by combining and compounding the constituents listed be!ow in Table 15 and 1 7 in a N50 Brabender mixer, and vulcanized at 160 °C for T 90. Vulcanization process data and physical properties for the each composition example are provided in Tables 28, 29 and 30.
  • Polymer compositions were prepared by combining and compounding the constituents listed below in Table 16 and 17 in a N50 Brabender mixer, and vulcanized at 160 °C for T90. Vulcanization process data and plwsical properties for the each composition example are provided in Tables 28, 29 and 30.
  • Polymer compositions were prepared by combining and compounding the constituents iisted beiow in Table 18 and 19 in a 350 cc Banbury mixer, and vulcanized at 160 °C for T 90. Vulcanization process data and physical properties for the each composition example are provided in Tables 31 , 32 and 33.
  • Tabie 1.8 Polymer Composition M40-M53 using polymers PI and P7 and glass grades Gl and
  • VI1-A Compound Vuicanisates Based on Oil Free Rubber Grades (vuicanizates made from polymer compounds in a Brabender mixer through separate addition of all individual components listed in Tables 7. 8 and 9)
  • Table 20 Silica/Giass Containing Pol mer Vuicanizate Composition Process Data
  • n.d. means not determined
  • Vll-B Compound Vulcanizates Based on Oil Free Rubber Grades (vulcanizates made from polymer compounds in a Brabender mixer through separate addition of ail individual components comprising a glass filler containing SSBR composite component as listed in Tables 10 and 1 1 )
  • Vll-C Compound Vulcanizates based on Oil extended Rubber Grades (vulcanizates made from polymer compounds in a Brabender mixer through separate
  • V1I-D Compound Vulcanizates Based on Oil Free Rubber Grades and on Zinc- Doped Glass Filler Component (compounds do not comprise Zinc oxide; vulcanizates made from polymer compounds in a Brabender mixer through separate addition of all individual components listed in Tables 15, 16 and 1 7)
  • VII -E Compound Vulcanizates Based on Oil Free Rubber Grades, Prepared With a Reduce Silane Coupling Agent Content (vulcanizates made from polymer compounds in a 350 cc Banbury mixer through separate addition of all individual components listed in Tables 1 8 and 19)
  • first polymer compositions non-crosslinked elastomeric polymer compositions
  • first polymer compositions comprising at least one primary filler, at least one secondary glass powder filler, and at least one polymer having lower first polymer composition Mooney values and lower energy input during first polymer composition processing when compared with first polymer compositions not comprising secondary glass powder filler.
  • the lower Mooney values and the lower energy input of the first polymer composition in accordance with the present teachings enables use of the first polymer composition in mixing steps of reduced mixing periods and/or a reduced number of mixing steps and, therefore, in iess energy consuming mixing steps and in higher throughput rubber compound extrusion processes.
  • first polymer compositions having improved polymer processing characteristics as evidenced in reduced Mooney viscosity and reduced energy input (or reduced energy consumption) W5 during two mixing steps for a speed of the rotor biades in the mixer of 60 rpm during the first mixing step and 50 rpm during the second mixing step in the process of formation of the first polymer composition, when compared with polymeT compositions not comprising secondary glass powder fillers.
  • the use of the first polymer composition in accordance with the present teachings leads to decreased mixing periods and/or to a reduced number of mixing steps and, consequently, less energy is consumed and/or a higher throughput in the course of the rubber compound extrusion process is achieved.
  • second polymer compositions vulcanized or crosslinked elastomeric polymer compositions
  • first polymer compositions non-crossiinked elastomeric polymer compositions
  • at least one vulcanization agent having lower "Tan ⁇ at 60 °C” values and/or higher "Tan ⁇ at 0 °C " values. If one of the-two values, which relate to tire rolling resistance or to tire wet grip performance, is improved, the other value as well as other physical properties, such as abrasion resistance and processability should not be negatively impacted to improve the key tire performance properties.
  • Tire treads made from polymer compositions having lower "Tan 6 at 60 °C" values have corresponding lower rolling resistance, while those with higher "Tan ⁇ at 0 °C” values have corresponding better wet skid properties.
  • (vulcanized) second polymer compositions in accordance with the present teachings in tire treads leads to an improved low rolling resistance (high wet grip balance of a tire when compared with tires based on vulcanized second polymer compositions not comprising secondary glass powder fillersO.
  • vulcanized second polymer compositions in accordance with the present teachings having an improved low rolling resistance-high wet grip balance as discussed above can be prepared from first polymer compositions comprising at least one polymer, at least one silica filler selected from the group consisting of primary fillers and at least one secondary glass powder filler and from at least one vulcanization agent comprising a relatively reduced silane coupling agent concentration, when compared with second polymer compositions made from first polymer compositions comprising silica filler, but not comprising a secondary glass powder filler, which have a relatively higher silane coupling agent concentration.
  • first polymer compositions non-crosslinked and thus non- vulcanized elastomeric po!ymer compositions
  • first polymer compositions which are made from at least one (elastomeric) polymer, at least one primary filler and at least one zinc-doped secondary' glass powder filler, selected from the group consisting of secondary glass powder fillers having a reduced total concentration of the heavy metal zinc and a reduced (or eliminated) concentration of zinc oxide.
  • the reduced concentration of zinc, partly or completely located in the pores or on the surface of zinc-doped secondary glass powder fillers comprised in the first polymer compositions reduces or eliminates the amount of powdery zinc oxide, which is classified as environmentally dangerous according to EG 67/548/EEC, and which is handled in the process of preparing first polymer compositions. Furthermore, the reduced total concentration of zinc in second polymer compositions in accordance with the present teachings reduces the total amount of zinc released into the environment through abrasion of vulcanizates, including but not limited to the abrasion of tire treads, in comparison with zinc oxide-containing second polymer compositions, without affecting typical (vulcanized) second polymer composition performance properties. Therefore, the preparation of specific first polymer compositions and second polymer compositions in accordance with the present teachings and articles made therefrom is considered to be more environmentally friendly.
  • first polymer compositions and second polymer compositions in accordance with the present teachings additionally comprising at least one vulcanization agent, having a decreased total zinc concentration and having a decreased or eliminated zinc oxide concentration compared with first polymer compositions and second polymer compositions not comprising zinc-doped secondary glass powder filler.
  • the reduced zinc oxide concentration and the reduced total zinc concentration in first polymer compositions in accordance with the present teachings does not negatively impact parameters, such as for example scorch, time (TS2), vulcanization conversion (TC90) or crossiinking (MH- L), describing the vulcanization kinetic of the first polymer compositions or processing characteristics of the first polymer compositions.
  • the reduced zinc oxide concentration and the reduced total zinc concentration in second polymer compositions in.
  • vulcanized second polymer composition performance properties such as for example, polymer hysteresis properties, such as determined by tan ⁇ @ 60 °C and by tan 6 @ 0 °C measurements, heat buildup, elongation at break, or abrasion resistance performance values.
  • one significant appiication for the (non-vulcanized elastomeric) first polymer compositions in accordance with the present teachings which are made from at least one (elastomeric) polymer, at least one primary filler and at least one secondary glass powder filler, is their use in preparing (vulcanized elastomeric) second polymer compositions in accordance with the present teachings, and which have one or more of the following three key characteristics: reduced rolling resistance and/or increased wet skid performance, as represented by compositions having relatively lower (or reduced) values of Tan ⁇ at 60 °C; improved wet skid resistance, as represented by compositions having relatively higher values of Tan 5 at 0 °C; improved processing characteristics and, in the case of silica-containing compositions, relatively decreased silane coupling agent concentration.
  • the at least one primary filler, and the at least one secondary glass powder filler on the (non-vulcanized) first polymer composition and on the (vulcanized) second polymer composition one, two, three or four of the aforementioned property values can be improved, without any of the above Tan ⁇ values or processing characteristics being significantly deteriorated.
  • the polymer preparation and the polymer characteristics of those polymers used for the preparation of compositions containing the primary filler silica and secondary glass powder filler as well as vulcanizates formed from the same, are stated in Table 3, Table 4 and Table 5.
  • composition of the secondary glass powder filler grades used for the preparation of compositions containing the primary filler silica and vulcanizates formed from the same are stated in Table 2.
  • the polymer-secondary glass powder filler compositions made by adding the secondary glass powder filler into the polymer solution following low pressure solvent removal used for the preparation of compositions containing the primary filler silica and vulcanizates formed from the same, are stated in Table 6.
  • the compounding and vulcanization formulations are stated in Table 7 to Table 19.
  • the corresponding vuicanizate composition process data and vuicanizate composition performance properties are stated in Table 20 to Table 33.
  • sica-containing' ' polymer compositions are prepared from oil-free modified polymers, silica primary filler, zinc oxide, and secondary glass powder filler.
  • the corresponding vuicanizate composition process data are stated in Table 20 and the corresponding vuicanizate composition performance properties are stated in Table 21 and Table 22.
  • first polymer compositions in accordance with the present teachings are easier to process than comparable polymer compositions not comprising secondary glass powder filler.
  • Exemplar ⁇ ' polymer compositions M5, M7, M6 and M8 each contain polymer P I , modified polymer P3, and silica primary filler.
  • the polymer compositions furthermore contain an increasing amount of the secondary glass powder filler grade Gl of 0 phr (M5, reference without Gl ), 4 phr (M7). 12 phr (M6) or 20 phr (MS) as stated in Table 9.
  • Table 20 shows the decreasing energy uptake W5 during mixing of the first and second polymer compositions of 104.9 kJ (composition MVS made from M5 composition ingredients), 96.3 Id ( V7 made from. 7), 86.7 kJ (MV6 made from M6), and 78.7 ki (MVS made from M8).
  • the examples demonstrate the possibility of saving energy in the process of preparing the compositions in accordance with the present teachings.
  • the vulcanized compositions MV5, MV7, MV6, and MV8 also indicate, as already stated above, an improved rolling resistance performance as represented by improved data of Tan ⁇ @ 60 °C, when the concentration of the secondary glass powder filler grade is increased.
  • Tan ⁇ @ 60 °C values decrease for MY5, MV7, MV6 and MVS in the order 0.1488, 0.1347, 0.1251 , and 0.1 191 , while the corresponding Tan ⁇ @ 0 °C values do not or do not significantly change with increasing Gl concentration.
  • "silica-containing" polymer compositions are prepared from secondary glass powder filler containing oil-free modified polymers, silica primary filler, zinc oxide, and secondary glass powder filler.
  • the corresponding vuicanizate composition process data are stated in Table 23 and the corresponding vuicanizate composition performance properties are stated in Table 24.
  • "silica-containing" polymer compositions are prepared from oil-free modified polymers, silica primary filler, zinc oxide and secondary glass powder filler and a reduced silane coupling agent concentration.
  • the corresponding vulcanizate composition process data are stated in Table 31 and the corresponding vulcanizate composition performance properties are stated in Table 32 and Table 33.
  • the first polymer compositions in accordance with the present teachings are easier to process than comparable polymer compositions not comprising secondary glass powder filler.
  • Exemplary polymer compositions M48, M49 and M50 each contain polymer PI, modified polymer P7 and siiica primary filler.
  • the polymer compositions furthermore contain an increasing amount of the secondary glass powder filler grade G2 of 5 phr (M48), 15 phr (M49) or 25 phr (M50) (see Table 19).
  • Table 31 shows decreasing compound Mooney viscosities of the polymer composition with increasing secondary glass powder filler grade G2 of 73.5 MU (MV48 made from M48 ingredients), 66.1 MU (MV49 made from M49 ingredients), and 56.4 MU (MV50 made from TV! 50 ingredients).
  • the examples demonstrate the reduction of the polymer composition viscosity in case an increased secondary glass powder filler concentration is applied to the composition manufacturing process.
  • the vulcanized compositions MV47 (reference without G2), MV48, MV49. and MV50 also indicate an improved rolling resistance-wet grip performance balance as indicated, by improved data of Tan ⁇ @ 60 °C at only slightly decreased Tan ⁇ @ 0 °C values, when the concentration of the secondary glass powder filler grade G2 is increased and the silane coupling agent concentration is decreased.
  • the Tan ⁇ @ 60 °C values clearly overcompensate the impaired Tan ⁇ @, 0 °C values.
  • the Tan ⁇ @ 60 °C values decrease for MV47, MV48, MV49, and MV50 in. the order 0.090 (MV47 reference value), 0.082 (MV48, 9% improvement vs.
  • MV47 0.070
  • MV49 22% improvement vs. MV47
  • 0.052 MV50, 42% improvement vs. MV47
  • Tan ⁇ @ 0 °C are only impaired by 1 % (MV48), 9% (MV49) and 17% (MV50) with increasing G2 concentration.
  • the increasing secondary glass powder filler grad concentration is accompanied with a decreasing silane coupling agent concentration.
  • the reference composition M47 comprised 9.70 phr silane coupling agent while only 6.90 phr silane coupling agent were added to composition M50 containing the highest concentration of G2.
  • Tables 12, 13 and 14 "silica-containing" polymer compositions are prepared from oil -containing polymers, silica primary filler, zinc oxide, and secondary glass powder filler. The corresponding vulcanizate composition process data are stated in Table
  • the first polymer compositions in accordance with the present teachings are easier to process than comparable polymer compositions not comprising secondary glass powder filler.
  • Exemplary polymer compositions M22, M23, M24 and M25 each contain, polymer PI , oil-extended polymer P7, and silica primary filler.
  • the polymer compositions furthermore contain an increasing amount of the secondary glass powder filler grade Gl of 0 phr (M22), 4 phr (M23), 12 phr (M24), and 20 phr (M25) (see Table 14).
  • Tabie 25 shows the decreasing energy uptake W5 during mixing of the first and second polymer compositions of 107.2 id (reference, composition MV22 made from M22 ingredients), 99.4 kJ (MV23 made from M23), 90.5 kJ (MV24 made from M24), and 82.4 Id (MV25 made from M25).
  • the examples demonstrate the possibility of saving energy in the process of preparing the compositions in accordance with the present teachings.
  • the vulcanized compositions MV23, MV24, and MV25 also indicate, as already stated above, an improved rolling resistance performance as indicated by improved data of Tan ⁇ @ 60 °C, when the concentration of the secondary glass powder filler grade is increased.
  • Tan ⁇ @ 60 °C value decreases for MV23, MV24, and MV25 in the order 0.1 414, 0.1323, and 0.1077, while the corresponding Tan ⁇ (3 ) . 0 °C values do not or do not significantly change with increasing Gl concentration (see Table 27).
  • ''silica-containing'' polymer compositions are prepared from oil -free modified po!ymers, silica primary filler, and secondary zinc-doped glass powder filler.
  • the corresponding vulcanizate composition process data are stated in Table 28 and the corresponding vulcanizate composition performance properties are stated in Tabie 29 and Table 30.
  • Exemplary compounds 30 (reference).
  • 31 , and 32 comprise silica primary filler, modified polymer P3, and polymer PI .
  • M36 and M37 additionally contain 5 phr and 10 phr zinc-doped secondary glass powder fillers G4 and G5. respectively (see Table 17).
  • the crosslinking density (MH- L) of the corresponding vulcanized compositions MV30, MV31, and MV32 of 1 .07, 1.19, and 0.92 are in a comparable order.
  • the scorch time TS2 is similar (1.1 min for MV30, 1.5 min for MV31 and 1.1 min for MV32).
  • the period to achieve 90% vulcanization conversion represented by the TC90 value somewhat decreases with increasing zinc concentration of the secondary glass powder fillers (zinc pore/surface concentration, G4 : 2.1 wt% zinc and G5 : 4.5 wt% zinc) in the order 20 min (MV30), 16.5 min (MV31 ), and 14 min (MV32).
  • the reduced TC90 value is, however, still acceptable for a technical vulcanization process.
  • the application of zinc-doped secondary glass powder fillers does not significantly influence the composition vulcanization kinetic.
  • the vulcanized compositions MV30, MV3 1 , and MV32 also indicate, as already stated above, an improved rolling resistance performance as indicated by improved data for Tan ⁇ @ 60 °C, when the concentration of the secondary glass powder filler grade is increased.
  • Tan ⁇ @, 60 °C value decreases for MV30, V31 , and MV32 in the order 0.1 488, 0.1064, and 0.1.230 with increasing G l concentration (see Table 30).
  • the corresponding Tan ⁇ @ 0 °C value is in the range of the MV30 reference value for V3 or is improved in case of MV32.
  • Modified polymers are reported, when used as components of vulcanized compositions, to improve the rolling resistance-wet grip performance balance in compounds only comprising silica or carbon black as filler.
  • Secondary glass powder fillers and zinc- doped secondary glass powder fillers are demonstrated, when contained in vulcanized polymer-filler compositions in accordance with the present teachings, also to improve the rolling resistance-wet grip performance balance. Therefore, it is furthermore advantageous that the application of second polymer compositions in accordance with the present teachings comprising both modified polymers and secondary glass powder fillers or zinc- doped secondary glass powder fillers leads to vulcanizates with especially low hysteretic energy loss.

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Abstract

La présente invention concerne une composition comprenant i) un polymère ; ii) une charge primaire ; et iii) une charge secondaire. La charge secondaire comprend une substance choisie dans le groupe constitué par une charge secondaire de poudre de verre, une charge secondaire de poudre de verre dopée au zinc, et une combinaison de celles-ci.
PCT/EP2011/066656 2010-09-30 2011-09-26 Compositions polymères Ceased WO2012041804A2 (fr)

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CN112029165A (zh) * 2020-08-27 2020-12-04 茂泰(福建)鞋材有限公司 一种耐臭氧老化的浅色橡胶鞋底及其制备方法
CN113165424A (zh) * 2018-11-28 2021-07-23 倍耐力轮胎股份公司 轮胎用胶料的制备方法和包含它们的轮胎
CN116102889A (zh) * 2022-12-27 2023-05-12 双安电力科技有限公司 一种高强度复合绝缘子用混炼硅橡胶及其制备方法

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