CA2353503C - Improved processability of silica-filled rubber stocks - Google Patents
Improved processability of silica-filled rubber stocks Download PDFInfo
- Publication number
- CA2353503C CA2353503C CA002353503A CA2353503A CA2353503C CA 2353503 C CA2353503 C CA 2353503C CA 002353503 A CA002353503 A CA 002353503A CA 2353503 A CA2353503 A CA 2353503A CA 2353503 C CA2353503 C CA 2353503C
- Authority
- CA
- Canada
- Prior art keywords
- hydrogenated
- silica
- silane
- weight
- elastomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T152/00—Resilient tires and wheels
- Y10T152/10—Tires, resilient
- Y10T152/10495—Pneumatic tire or inner tube
- Y10T152/10855—Characterized by the carcass, carcass material, or physical arrangement of the carcass materials
Abstract
The present invention provides silica-filled, vulcanized elastomeric compoun ds comprising an elastomer mixed with at least a silica filler, a processing aid, and a curing agent, and processes for the preparation of the same. Generally, the present invention provides processin g aids which effectively reduces or replace the amount (i.e., about 10 percent by weight based upon the silica filler) of the processing aid bis [3-triethyoxysilyl)propyl]tetrasulfide ("Si69") used in the production of silica-filled rubber stocks. These new processing aids include alkyl alkoxysilanes, fatty acid esters of hydrogenated and non-hydrogenated sugars and the polyoxyethylene derivatives thereof, and combinations thereof, with or without various non-reinforcing fillers such as mineral fillers. The processing aids do not hinder the physical properties of the compounds and have been found to be excellent substitutes for Si69. The processing aids may be supported on the silica filler or any of the other fillers employed in the composition for improved handling, safe ty and performance. Processes for the preparation of the silica filled vulcanizable elastomers are provided as well as pneumatic tires employing tread stock comprising the novel vulcanizable elastomers.
Description
IMPROVED PROCESSABILITY OF SILICA-FILLED RUBBER
STOCKS
Field of the Invention The present invention relates to the processing and vulcanization of diene polymer and copolymer elastomer-containing rubber stocks and, more particularly, silica-filled rubber stocks using processing aids with or without other reinforcing fillers.
Background of the Invention In the art it is desirable to produce elastomeric compounds exhibiting reduced hysteresis when properly compounded with other ingredients such as reinforcing agents, followed by vulcanization. Such elastomers, when compounded, fabricated and vulcanized into components for constructing articles such as tires, power belts, and the like, will manifest properties of increased rebound, decreased rolling resistance and less heat-build up when subjected to mechanical stress during normal use.
The hysteresis of an elastomer refers to the difference between the energy applied to deform an article made from the elastomer and the energy released as the elastomer returns to its initial, undeformed state. In pneumatic tires, lowered hysteresis properties are associated with reduced rolling resistance and heat build-up during operation of the tire. These properties, in turn, result in lower fuel consumption for vehicles using such tires.
In such contexts, the property of lowered hysteresis of compounded, vulcanizable elastomer compositions is particularly significant.
Examples of such compounded elastomer systems are known to the art and typically include at least one elastomer (that is, a natural or synthetic polymer exhibiting elastomeric properties, such as a rubber), a reinforcing (or non-reinforcing) filler agent (such as finely divided carbon black, thermal black, or mineral fillers such as clay and the like) and a vulcanizing system such as a sulfur-containing vulcanizing (i.e., curing) system.
Recently, precipitated silica has been increasingly used as a reinforcing particulate filler in carbon black-filled rubber components of tires and mechanical goods. While providing excellent properties, including reduced hysteresis, to the rubber stocks, these silica-loaded rubber stocks are unfortunately not easily produced, exhibiting relatively poor processability characteristics.
Summary of the Invention Other work has resulted in improvements in processing characteristics for silica-loaded rubber stocks, particularly that work disclosed in European Patent Publications EP 0 890 603A1 and EP 0 890 606A1. This invention carries forward such work.
The present invention provides reinforcing filler-supported additives, such as a mineral fillers, capable of improving the processability of the formulations of diene polymer elastomers reinforced with silica filler.
The present invention also provides a process for decreasing the level of bis[3-(triethoxysilyl)propyl]tetrasulfide (Si69) in silica-filled elastomeric vulcanizable compounds.
The present invention also provides vulcanizable silica-filled elastomeric compounds having enhanced physical properties, including decreased hysteresis and increased tear strength.
One aspect of the invention is a process for the preparation of a silica-filled, vulcanized elastomeric compound comprising: (a) mixing (1) 100 parts by weight of an elastomer; (2) from about 5 to about 100 parts by weight of a reinforcing filler selected from the group consisting of silica filler or mixtures thereof with carbon black, per 100 parts of said elastomer; (3) from about 0.1 to about 150 percent by weight, based on said silica filler, of a processing aid selected from the group consisting of alkylalkoxysilanes, fatty acid esters of hydrogenated and non-hydrogenated C; and C6 sugars;
polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars and mixtures thereof; (4) optionally from 0 to about 40 parts by weight of a non-reinforcing filler, per 100 parts elastomer, with the provisos that if said processing aid is sorbitan monooleate, then at least one of said polyoxyethylene derivatives or said additional fillers is also present and, that the minimal amount for each said processing aid and said additional filler, if present, is about one part by weight; (5) optionally from 0 to about 20 percent by weight of bis[3-(triethoxysilyl)propyl]tetrasulfide, based upon the weight of said silica filler; and (6) a cure agent; wherein, optionally, said processing aid is first mixed with and supported on at least some of either said reinforcing filler or said non-reinforcing filler prior to mixing with said elastomer; and (b) effecting vulcanization.
Another aspect of the invention is a vulcanizable, silica-filled compound comprising: 100 parts by weight of an elastomer; from about 5 to about 100 parts by weight of a reinforcing filler selected from the group consisting of silica filler or mixtures thereof with carbon black, per 100 parts of said elastomer; optionally from 0 to about 20 percent by weight of bis[3-(triethoxysilyl) propyl]tetrasulfide, based upon the weight of said silica filler;
from about 0.1 to about 150 percent by weight, based on said silica filler, of a processing aid selected from the group consisting of alkylalkoxysilanes, fatty acid esters of hydrogenated and non-hydrogenated C; and C6 sugars;
polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars and mixtures thereof; optionally from 0 to about 40 parts by weight of a non-reinforcing filler, per 100 parts elastomer;
and a cure agent; wherein, optionally, said processing aid is supported on at least some of either said reinforcing filler or said optional non-reinforcing filler;
and with the provisos that if said processing aid is sorbitan monooleate, then at least one of said polyoxyethylene derivatives or said additional fillers is also present and, that the minimal amount for each said processing aid and said additional filler, if present, is about one part by weight.
Another aspect of the invention is a pneumatic tire comprising tread stock vulcanized from the above vulcanizable silica-filled compound.
Another aspect of the invention is a pneumatic tire comprising tread stock obtainable from the above inventive process.
~
A further aspect of the invention is a process for the preparation of a silica-filled, vulcanized elastomeric compound comprising:
= (a)mixing o(1) 100 parts by weight of an elastomer;
o (2) from 5 to 100 parts by weight of a reinforcing filler selected from the group consisting of silica filler or mixtures thereof with carbon black, per 100 parts of said elastomer, wherein the silica filler has a BET surface area of 150 to 220m2/g;
o (3) from 0.1 to 150 percent by weight, based on said silica filler, of a combination of an alkylalkoxysilane and an additional processing aid selected from the group consisting of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars, polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars and mixtures thereof;
o (4) optionally from 0 to 40 parts by weight of a non-reinforcing filler, per 100 parts elastomer;
o (5) optionally from 0 to 20 percent by weight of bis[(triethoxysilyl)-propyl]tetrasulfide, based upon the weight of said silica filler; and o (6) a cure agent;
wherein said alkylalkoxysilane and said additional processing aid are first mixed with and supported on at least some of either said silica reinforcing filler or said non-reinforcing filler prior to mixing with said elastomer, and wherein the minimal amount for the alkylalkoxysilane and said additional processing aid is about one part by weight; and = (b) effecting vulcanization.
Embodiments of the Invention One skilled in the art is directed to the disclosures of European Patent Publications EP 0 890 603A1 and EP 0 890 606A1, wherein one can find full explanations of the work upon which this invention is built. Because of the availability of such publications, the text of those disclosures is not repeated here but is relied upon.
Examples of this invention are provided below, with brief explanations of the embodiments of this invention that emphasize the points of departure from the disclosures of European Patent Publications EP 0 890 603A1 and EP 0 890 606A 1.
In one embodiment, the present invention provides a silica-filled, vulcanizable elastomeric compound useful as tread stocks for pneumatic tires that employs a processing aid as a replacement for Si69, wherein the processing aid is selected from the group consisting of alkyl alkoxysilanes, fatty acid esters of hydrogenated and non-hydrogenated sugars, ethoxylated derivatives of fatty acid esters of hydrogenated and non-hydrogenated sugars, and mixtures thereof and wherein the processing aid is supported on the silica filler or other filler, e.g., either another reinforcing filler such as carbon black, or a non-reinforcing filler such as one of a number of mineral fillers or the like.
In another embodiment, from about 0.1 to about 150 percent by weight of an alkyl alkoxysilane is used in the present invention as a processing aid. Thus, given the amount of silica filler typically preferred in the subject composition, up to about 150 parts by weight of the processing aid, per 100 parts elastomer. may be used, representing a 60/40 ratio of processing aid to silica.
In yet another embodiment, a mixture of a filler and a filler-supported processing aid selected from the group consisting of alkyl alkoxysilanes. fatty acid esters of hydrogenated and non-hydrogenated sugars, ethoxylated derivatives of fatty acid esters of hydrogenated and non-hydrogenated suaars, and mixtures thereof, is preferably added to the elastomer in an amount of about 5 to about 100 parts by weight per 100 parts of the elastomer. It should be stressed that when a silica-supported or carbon black-supported processing aid is used, the non-reinforcing fillers, including mineral fillers or other processing aids are not required in the elastomeric formulation.
However, it will be appreciated that if mineral fillers are used, they may be used to support the processing aid(s). Preferably, the processing aid is added to the silica or other filler in a mixture ratio of from about 1:99 to about 60:40, with a 50:50 mixture being most preferred.
In yet another embodiment, certain additional fillers can be utilized according to the present invention as processing aids which include, but are not limited to, mineral fillers, such as clay (hydrous aluminum silicate), talc (hydrous magnesium silicate), and mica as well as non-mineral fillers such as urea and sodium sulfate. Preferred micas contain principally alumina, silica and potash, although other variants are also useful, as set forth below. The additional fillers are also optional and can be utilized in the amount of from parts to about 40 parts per 100 parts of polymer (phr), preferably in an amount from about I to about 20 phr. It will be understood that these mineral fillers can also be used as non-reinforcing fillers to support the processing aids of the present invention.
Thus, a process for the preparation of a silica-filled, vulcanized elastomeric compound according to the present invention comprises mixing an elastomer with from about 5 to about 100 parts by weight of a reinforcing filler selected from the group consisting of silica filler and mixtures thereof with carbon black, from 0 to about 20 percent by weight, based on said silica filler, of bis[3-(triethoxysilyl)propyl]tetrasulfide, from 0.1 to about 150 percent by weight. based on said silica filler, of an alkylalkoxysilane, and a cure agent;
and, effecting vulcanization.
Further, the present invention also includes a vulcanizable silica-filled compound comprising an elastomer, a silica filler, from 0 to about 20 percent by weight, based on said silica filler, of bis[3-(triethoxvsilyl)propyl]tetrasulfide, from about 0.1 to about 150 percent by weight, based on said silica filler, of an alkylalkoxysilane, and a cure agent.
Preferably, the compound further contains a natural rubber.
Further, the present invention also includes a pneumatic tire comprising tread stock vulcanized from the above compound made from the above process.
The elastomer can be a diene monomer homopolymer or a copolymer of a diene monomer and a monomer selected from the group consisting of monovinyl aromatic monomers and triene monomers.
The alkylalkoxysilane can be represented by the formula (Rl)zSi(OR2)2 or RiSi(OR2)3, wherein each R, independently is selected from the group consisting of C, to about C18 aliphatic, about C; to about C12 cyclo-aliphatic, and about C6 to about C18 aromatic; and wherein the alkoxy groups are the same or are different, each R2 independently containing from one to about 6 carbon atoms.
The alkylalkoxysilane can be selected from the group consisting of octyltriethoxy silane, octyltrimethyloxy silane, (3-glycidoxypropyl)trimethoxy silane, (3-glycidoxypropyl)triethoxy silane, hexyltrimethoxy silane, ethyltrimethyoxy silane, propyltriethoxy silane, phenyltrimethoxy silane, cyclohexyltrimethoxy silane, cyclohexyltriethyoxy silane, dimethyldimethyoxy silane, 3-chloropropyltriethoxy silane, methacroyltrimethoxy silane, and i-butyltriethoxy silane. Preferably, the alkylalkoxysilane is octyltriethoxysilane.
In one option for the above process, one can mix, prior to the vulcanizing step, a processing aid comprising at least one of an ester of a fatty acid or an ester of a polyol. Preferably, that processing aid is selected from the group consisting of at least one sorbitan ester of an oleate, laurate, palmitate and stearate fatty acids, polyoxyethylene derivatives thereof, at least one ester of a polyhydroxy compound, and mixtures thereof. More preferably, that processina aid is sorbitan monooleate.
Preferably for the above process, the elastomer is a styrene butadiene rubber. More preferably. the elastomer is a copolymer of styrene butadiene rubber and butyl rubber. Even more preferably, the elastomer is mixed with carbon black.
The process also optionally includes mixing insoluble sulfur prior to the vulcanizing step.
The present invention also includes a first alternative process for the preparation of a silica-filled, vulcanized elastomeric compound comprising the steps of mixing an elastomer with from about 5 to about 100 parts by weight of a reinforcing filler per 100 parts of elastomer, wherein said reinforcing fillers are selected from the group consisting of silica filler and mixtures thereof with carbon black; from 0 to about 20 percent by weight of bis[3-(triethoxysilyl)propyl]tetrasulfide, based upon the weight of said silica filler;
from about 0.1 to about 150 percent by weight of a processing aid selected from the group consisting of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars, polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars, and mixtures thereof;
from about 0 to about 40 parts by weight of an additional filler other than silica or carbon black, with the provisos that if said processing aid is sorbitan monooleate, then at least one of said polyoxyethylene derivatives or said additional fillers is also present and, that the minimal amount for each said processing aid and said additional filler, if present, is about one part by weight;
and a cure agent; and effecting vulcanization.
The first alternative process utilizes a vulcanizable silica-filled compound which comprises 100 parts by weight of an elastomer; from about 5 to about 100 parts by weight of a reinforcing filler per 100 parts of elastomer, wherein said reinforcing fillers are selected from the group consisting of silica filler and mixtures thereof with carbon black; from 0 to about 20 percent by weight of bis[3-(triethoxysilyl) propyl]tetrasulfide, based upon the weight of said silica filler; from about 0.1 to about 150 percent by weight of a processing aid selected from the group consisting of fatty acid esters of hydrogenated and non-hydrogenated C; and C6 sugars, polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars, and mixtures thereof, from about 0 to about 40 parts by weight of an additional filler other than silica or carbon black; and a cure agent; with the provisos that if said processing aid is sorbitan monooleate, then at least one of said polyoxyethylene derivatives or said additional fillers is also present and, that the minimal amount for each said processing aid and said additional filler, if present, is about one part by weight.
Further, the present invention also includes a pneumatic tire comprising tread stock vulcanized from the above alternative compound made from the above alternative process.
The alternative process and vulcanizable compound are utilize the same preferences of process steps and ingredients, except as noted below.
The alternative process can include an additional step of adding a natural rubber.
Preferably, silica filler used in the alternative process and compound has a surface area of about 32 to about 400 m2/g and a pH of about 5.5 to about 7.
Preferably, the alternative process and compound has an amount of said carbon black reinforcing filler ranging from about 0 to about 50 parts by weight, per 100 parts by weight of elastomer, and an amount of said reinforcing silica filler ranging from about I to 100 parts, per 100 parts of elastomer, with the proviso that where carbon is 0, at least 30 phr of silica is employed.
Preferably, the fatty acid esters of hydrogenated and non-hydrogenated C; and C6 sugars are selected from the group consisting of sorbitan monooleate, sorbitan dioleate, sorbitan trioleate, sorbitan sesquioleate, sorbitan laurate. sorbitan palmitate and sorbitan stearate. while the polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C; and C6 sugars are selected from the group consisting of POE
(20) sorbitan stearate; POE (20) sorbitan oleate; POE (20) sorbitan tri-oleate;
POE (20) sorbitan sesquioleate; POE (20) sorbitan laurate and POE (20) sorbitan palmitate. More preferably, the processing aid comprises a mixture of at least one fatty acid ester of hydrogenated and non-hydrogenated C5 and C6 sugars and at least one polyoxyethylene derivative of a fatty acid ester of hydrogenated and non-hydrogenated C5 and C6 sugars.
Preferably, the additional filler is selected from the group consisting of mica, talc, urea, clay, sodium sulfate and mixtures thereof and more preferably, is included with the mixture of at least one fatty acid ester of hydrogenated and non-hydrogenated C5 and C6 sugars.
The present invention provides a second alternative process for the preparation of a silica-filled, vulcanized elastomeric compound comprising mixing 100 parts by weight of an elastomer with from about 5 to about 100 parts by weight of a reinforcing filler selected from the group consisting of silica filler or mixtures thereof with carbon black, per 100 parts of said elastomer; from about 0.1 to about 150 percent by weight, based on said silica filler, of a processing aid selected from the group consisting of alkylalkoxysilanes, fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars; polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars and mixtures thereof; from 0 to about 40 parts by weight of a non-reinforcing filler, per 100 parts elastomer; and a cure agent: wherein said processing aid is first mixed with and supported on at least some of either said reinforcing filler or said non-reinforcing filler prior to mixing with said elastomer; and effecting vulcanization.
The second alternative process utilizes a vulcanizable, silica-filled compound comprising 100 parts by weight of an elastomer; from about 5 to about 100 parts by weight of a reinforcing filler selected from the group consisting of silica filler or mixtures thereof with carbon black, per 100 parts of said elastomer; from about 0.1 to about 150 percent by weight, based on said silica filler. of a processing aid selected from the group consisting of alkylalkox-,,silanes, fatty acid esters of hydrogenated and non-hydrogenated and C6 suQars; polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars and mixtures thereof; from 0 to about 40 parts by weight of a non-reinforcing filler, per 100 parts elastomer; and a cure agent; wherein said processing aid is supported on at least some of either said reinforcing filler or said non-reinforcing filler.
Further, the present invention also includes a pneumatic tire comprising tread stock vulcanized from the above second alternative compound made from the above second alternative process.
The second alternative process and vulcanizable compound are utilize the same preferences of process steps and ingredients as the first alternative process and vulcanizable compound, except as noted below.
As with the initial process and vulcanizable compound described above, the alkyl alkoxysilanes are selected from the group consisting of octyltriethoxy silane, octyltrimethyloxy silane, (3-glycidoxypropyl)trimethoxy silane, (3-glycidoxypropyl)triethoxy silane, hexyltrimethoxy silane, ethyltrimethyoxy silane, propyltriethoxy silane, phenyltrimethoxy silane, cyclohexyltrimethoxy silane, cyclohexyltriethyoxy silane, dimethyldimethyoxy silane, 3-chloropropyltriethoxy silane, methacroyltrimethoxy silane, and i-butyltriethoxy silane.
Preferably, for the second alternative vulcanizable silica-filled compound, the silica or carbon black-support processing aid is provided as a 50/50 mixture of processing aid to support.
The following examples amplify upon these embodiments.
Examples Testing of silica-filled vulcanizable elastomeric compounds was conducted to determine the effect silica-supported and carbon black-supported alkyl alkoxysilanes and polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated sugars as processing aids in the elastomeric stock formulations. The basic formulation. C-CC, of the elastomeric stock formulation is shown and described in Table I below.
The physical properties of the Example Nos. 1-6 and the control, C-DD, are shown and described in Table II, below. Example Nos. 2-6 indicated a Mooney viscosities (ML 1+4/100 C) comparable to the control, C-DD, with 3 phr of Si69 processing aid. Tensile properties of the cured elastomeric stocks, containing processing aids comprising octyl triethoxy silane and sorbitan oleate supported on silica are comparable to the tensile properties of the controi elastomeric stock formulation, C-DD, containing 3 phr of Si69 processing aid.
Curing at 171 C for 20 minutes was used to obtain the physical properties set forth below.
TABLE I
Basic Formulation of Elastomeric Stock (C-CC) Component Parts Oil 15 carbon black 35 silica VARIABLE
stearic acid 1.5 wax 1.0 process aid VARIABLE
antioxidant 0.95 sulfur 1.7 CBS 1.5 DPG 0.5 Zinc oxide 2.5 Table I Continued Final Elastomeric Stock Formulations Examples C-DD and 1-6 Example C-DD 1 2 3 4 5 6 46% SO on Silica" C 3.3 13 --- --- --- ---Table I Continued Final Elastomeric Stock Formulations Examples C-DD and 1-6 Example C-DD 1 2 3 4 5 6 47% OS on Silica --- 1.5 2.5 --- ---SO/3.8% OS on Silicac --- --- --- 32.9 --- --- ---5%
5% SO/3.8% OS on Silica --- --- --- --- 32.9 --- ---Sorbitan Oleate (SO) --- --- --- --- --- 1.65 1.65 Octyl triethoxysilane (OS) --- --- --- --- --- 1.25 1.25 a Flogard SP (712-090) b Flogard SP (712-091) c Flogard SP (712-097) d HiSil (712-098) Table II
Physical Properties of Elastomeric Formulations Example C-DD 1 2 3 4 5 6 Mooney Viscosity ML 1+4/100 C 77.6 132.4 75.2 77.9 80.8 64.6 72.9 T80 9.7 43.5 7.5 8.5 9.3 6.5 7.4 MDR Monsanto Cure at 165 C
ML 11.01 3.86 3.48 3.7 3.75 3.13 3.32 MH 35.37 20.42 19.39 19.67 20.28 18.89 19.1 ts2 2:36 2:08 2:16 2:26 2:16 2:22 2:24 tc90 17:06 13:55 l i: I4 10:37 11:14 10:41 10:02 tan 6 at MH -- 0.144 0.145 0.158 0.15 0.134 0.135 Ring Tensile at 24 C
50% Modulus,psi 221 256 230 1209 219 207 227 100% Modulus, psi 322 403 360 331 356 331 360 * comparative Table II
Physical Properties of Elastomeric Formulations Example C-DD 1 2 3 4 5 6 200% Modulus, psi 615 819 766 678 739 697 765 300% Modulus,psi 1008 1407 1338 1177 1279 1234 1335 Tensile Strength, psi 1852 2082 1899 1726 1959 1840 1886 % Elongation 474 400 386 392 407 395 381 Break energy, 4012 3762 3229 3013 3549 3156 3166 in-lbs/in' Ring Tensile at 100 C
50% Modulus,psi 189 229 208 212 196 193 190 100% Modulus, psi 263 350 323 312 303 296 300 200% Modulus, psi 518 685 654 632 607 614 604 300% Modulus,psi 869 1140 1107 1022 1025 1070 1023 Tensile Strength, psi 1299 1248 1227 1203 1075 1097 1 148 % Elongation 412 322 322 327 310 308 326 Break energy, 2496 1894 1837 1813 1557 1552 1761 in-lbs/in' Ring Tear at 171 C, psi 184.9 175.6 140.8 152.2 108.2 118.4 154 Wet Stanley 59/53 57/52 57/52 58/52 58/52 57/52 57/52 London(#/std) Shore A, at RT ---- 72 70 67 67 67 66 Shore A at 50 C ---- 67 67 65 67 66 65 Rheometrics at 7% Strain tan 6 at 24 C 0.193 0.195 0.169 0.173 0.175 0.166 0.180 o G' x 10-7 at 24 C 4.239 4.506 4.879 5.267 4.718 3.94 4.712 Table II
Physical Properties of Elastomeric Formulations Example C-DD 1 2 3 4 5 6 24 C G' x 10-' at 14.5% 3.006 3.138 3.261 3.01 3.127 2.856 3.422 tan S at 65 C 0.152 0.153 0.155 0.143 0.145 0.138 0.149 6 G' x 10-' at 65 C 2.689 3.779 5.667 3.939 4.554 4.172 3.836 50 C G' x 10-' at 14.5% 2.42 2.736 2.77 2.731 2.992 2.509 2.6 Mr, g/mol from 13680 10440 ---- 11320 ---- ---- ----Tensile Retraction Further testing of silica-filled vulcanizable elastomeric stock formulations was conducted to determine the effects of the silica and carbon black-supported processing aids on the physical properties and processability of the elastomeric formulations after six months of ambient storage.
The elastomeric stock formulations were prepared according to Table III, below, and the physical properties were evaluated after curing at 170 C for 20 minutes, followed by six months of ambient aging. The data for the physical properties and processability of the elastomeric formulations for the ambient aging study are shown in Table IV, below.
TABLE III
Basic Formulation of Elastomeric Stock (C-CC) Component Parts Oil 15 carbon black 35 si{ica VARIABLE
stearic acid 1.5 TABLE III
Basic Formulation of Elastomeric Stock (C-CC) Component Parts wax 1.0 process aid VARIABLE
antioxidant 0.95 sulfur 1.7 CBS 1.5 DPG 0.5 Table III Continued Final Elastomeric Stock Formulations Examples 7-12 Example 7 8 9 10 11 12 46% SO on Sitica' 3.3 3.3 --- ---47% --- ---OS on Silica -- 2.5 --- --- --- ---5% SO/3.8% OS on Silica` - --- 32.9 --- --- ---5% SO/3.8% OS on Silica --- --- --- 32.9 --- ---Sorbitan Oleate (SO) --- --- --- --- 1.65 1.65 Octyl triethoxysitane (OS) 1.25 --- --- --- 1.25 1.25 Table IV
Physical Properties of Elastomeric Formulations After Ambient aging for 6 months Example 7 8 9 10 11 12 Mooney Viscosity ML 1+4/100 C 77 80.8 78.9 78.9 74.8 78.1 MDR Monsanto Cure at 165 C
ML 2.97 3.62 3.5 3.69 3.29 3.47 MH 16.12 19.65 19.02 19.62 18.72 16.49 ts2 2:52 2:42 3:04 3:05 2:49 2:54 tc90 14:27 10:47 9:37 9:11 9:41 14:00 tan S at MH 0.2 0.093 0.102 0.103 0.091 0.189 Ring Tensile at 24 C
50% Modulus,psi 181 159 172 166 171 165 100% Modulus, psi 333 286 316 296 310 294 200% Modulus, psi 778 676 754 691 740 696 300% Modulus,psi 1415 1242 1389 1273 1375 1288 Tensile Strength, psi 2551 2233 2442 2298 2548 2438 % Elongation 448 445 441 447 454 461 Breakes4735 4088 4521 4235 4731 4605 in-lbs/in' Ring Tensile at 100 C
50% Modulus,psi 131 131 146 153 146 139 100% Modulus, psi 244 240 267 274 266 250 200% Modulus. psi 541 532 596 596 590 546 Table IV
Physical Properties of Elastomeric Formulations After Ambient aging for 6 months Example 7 8 9 10 11 12 300% Modulus, psi 973 963 1073 1076 1069 982 Tensile Strength, psi 1285 1400 1356 1433 1430 1396 % Elongation 367 394 356 369 371 388 Break energy, 2024 2353 2069 2266 2270 2330 in-lbs/in 2 New Lambourn at 179 181 157 147 158 149 65%, g lost New Lambourn at 0.145 0.148 0.1456 0.1506 0.1454 0.1481 65%, INDEX
Ring Tear at 171 C, 0.97 0.95 0.96 0.93 0.96 0.95 psi Wet Stanley 53/48.5 57/48.5 53/48.5 53/48.5 56/48.5 53/48.5 London(#/std) Shore A, at RT 66.4 67 67.7 67.5 65.8 64.1 Shore A at 50 C 63.6 64.3 64.8 64.9 63.9 64.1 Rheometrics at 7% Strain Tan S at 24 C 0.1779 0.169 0.181 0.1843 0.159 0.1724 24 C G' x 10' at 7% 0.628 0.605 0.657 0.739 0.491 0.577 S G' x 10" at 24 C 4.772 4.224 5.233 5.909 3.13 4.087 24CG'x10' at 14.5% 2.652 2.779 2.779 3.009 2.48 2.572 tan S at 50 C
0.15 0.1391 0.1524 0.1544 0.1417 0.1412 50 C G' x 10' at 7% 0.462 0.441 0.482 0.521 0.38 0.401 S G' x 10-" at 50 C
STOCKS
Field of the Invention The present invention relates to the processing and vulcanization of diene polymer and copolymer elastomer-containing rubber stocks and, more particularly, silica-filled rubber stocks using processing aids with or without other reinforcing fillers.
Background of the Invention In the art it is desirable to produce elastomeric compounds exhibiting reduced hysteresis when properly compounded with other ingredients such as reinforcing agents, followed by vulcanization. Such elastomers, when compounded, fabricated and vulcanized into components for constructing articles such as tires, power belts, and the like, will manifest properties of increased rebound, decreased rolling resistance and less heat-build up when subjected to mechanical stress during normal use.
The hysteresis of an elastomer refers to the difference between the energy applied to deform an article made from the elastomer and the energy released as the elastomer returns to its initial, undeformed state. In pneumatic tires, lowered hysteresis properties are associated with reduced rolling resistance and heat build-up during operation of the tire. These properties, in turn, result in lower fuel consumption for vehicles using such tires.
In such contexts, the property of lowered hysteresis of compounded, vulcanizable elastomer compositions is particularly significant.
Examples of such compounded elastomer systems are known to the art and typically include at least one elastomer (that is, a natural or synthetic polymer exhibiting elastomeric properties, such as a rubber), a reinforcing (or non-reinforcing) filler agent (such as finely divided carbon black, thermal black, or mineral fillers such as clay and the like) and a vulcanizing system such as a sulfur-containing vulcanizing (i.e., curing) system.
Recently, precipitated silica has been increasingly used as a reinforcing particulate filler in carbon black-filled rubber components of tires and mechanical goods. While providing excellent properties, including reduced hysteresis, to the rubber stocks, these silica-loaded rubber stocks are unfortunately not easily produced, exhibiting relatively poor processability characteristics.
Summary of the Invention Other work has resulted in improvements in processing characteristics for silica-loaded rubber stocks, particularly that work disclosed in European Patent Publications EP 0 890 603A1 and EP 0 890 606A1. This invention carries forward such work.
The present invention provides reinforcing filler-supported additives, such as a mineral fillers, capable of improving the processability of the formulations of diene polymer elastomers reinforced with silica filler.
The present invention also provides a process for decreasing the level of bis[3-(triethoxysilyl)propyl]tetrasulfide (Si69) in silica-filled elastomeric vulcanizable compounds.
The present invention also provides vulcanizable silica-filled elastomeric compounds having enhanced physical properties, including decreased hysteresis and increased tear strength.
One aspect of the invention is a process for the preparation of a silica-filled, vulcanized elastomeric compound comprising: (a) mixing (1) 100 parts by weight of an elastomer; (2) from about 5 to about 100 parts by weight of a reinforcing filler selected from the group consisting of silica filler or mixtures thereof with carbon black, per 100 parts of said elastomer; (3) from about 0.1 to about 150 percent by weight, based on said silica filler, of a processing aid selected from the group consisting of alkylalkoxysilanes, fatty acid esters of hydrogenated and non-hydrogenated C; and C6 sugars;
polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars and mixtures thereof; (4) optionally from 0 to about 40 parts by weight of a non-reinforcing filler, per 100 parts elastomer, with the provisos that if said processing aid is sorbitan monooleate, then at least one of said polyoxyethylene derivatives or said additional fillers is also present and, that the minimal amount for each said processing aid and said additional filler, if present, is about one part by weight; (5) optionally from 0 to about 20 percent by weight of bis[3-(triethoxysilyl)propyl]tetrasulfide, based upon the weight of said silica filler; and (6) a cure agent; wherein, optionally, said processing aid is first mixed with and supported on at least some of either said reinforcing filler or said non-reinforcing filler prior to mixing with said elastomer; and (b) effecting vulcanization.
Another aspect of the invention is a vulcanizable, silica-filled compound comprising: 100 parts by weight of an elastomer; from about 5 to about 100 parts by weight of a reinforcing filler selected from the group consisting of silica filler or mixtures thereof with carbon black, per 100 parts of said elastomer; optionally from 0 to about 20 percent by weight of bis[3-(triethoxysilyl) propyl]tetrasulfide, based upon the weight of said silica filler;
from about 0.1 to about 150 percent by weight, based on said silica filler, of a processing aid selected from the group consisting of alkylalkoxysilanes, fatty acid esters of hydrogenated and non-hydrogenated C; and C6 sugars;
polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars and mixtures thereof; optionally from 0 to about 40 parts by weight of a non-reinforcing filler, per 100 parts elastomer;
and a cure agent; wherein, optionally, said processing aid is supported on at least some of either said reinforcing filler or said optional non-reinforcing filler;
and with the provisos that if said processing aid is sorbitan monooleate, then at least one of said polyoxyethylene derivatives or said additional fillers is also present and, that the minimal amount for each said processing aid and said additional filler, if present, is about one part by weight.
Another aspect of the invention is a pneumatic tire comprising tread stock vulcanized from the above vulcanizable silica-filled compound.
Another aspect of the invention is a pneumatic tire comprising tread stock obtainable from the above inventive process.
~
A further aspect of the invention is a process for the preparation of a silica-filled, vulcanized elastomeric compound comprising:
= (a)mixing o(1) 100 parts by weight of an elastomer;
o (2) from 5 to 100 parts by weight of a reinforcing filler selected from the group consisting of silica filler or mixtures thereof with carbon black, per 100 parts of said elastomer, wherein the silica filler has a BET surface area of 150 to 220m2/g;
o (3) from 0.1 to 150 percent by weight, based on said silica filler, of a combination of an alkylalkoxysilane and an additional processing aid selected from the group consisting of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars, polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars and mixtures thereof;
o (4) optionally from 0 to 40 parts by weight of a non-reinforcing filler, per 100 parts elastomer;
o (5) optionally from 0 to 20 percent by weight of bis[(triethoxysilyl)-propyl]tetrasulfide, based upon the weight of said silica filler; and o (6) a cure agent;
wherein said alkylalkoxysilane and said additional processing aid are first mixed with and supported on at least some of either said silica reinforcing filler or said non-reinforcing filler prior to mixing with said elastomer, and wherein the minimal amount for the alkylalkoxysilane and said additional processing aid is about one part by weight; and = (b) effecting vulcanization.
Embodiments of the Invention One skilled in the art is directed to the disclosures of European Patent Publications EP 0 890 603A1 and EP 0 890 606A1, wherein one can find full explanations of the work upon which this invention is built. Because of the availability of such publications, the text of those disclosures is not repeated here but is relied upon.
Examples of this invention are provided below, with brief explanations of the embodiments of this invention that emphasize the points of departure from the disclosures of European Patent Publications EP 0 890 603A1 and EP 0 890 606A 1.
In one embodiment, the present invention provides a silica-filled, vulcanizable elastomeric compound useful as tread stocks for pneumatic tires that employs a processing aid as a replacement for Si69, wherein the processing aid is selected from the group consisting of alkyl alkoxysilanes, fatty acid esters of hydrogenated and non-hydrogenated sugars, ethoxylated derivatives of fatty acid esters of hydrogenated and non-hydrogenated sugars, and mixtures thereof and wherein the processing aid is supported on the silica filler or other filler, e.g., either another reinforcing filler such as carbon black, or a non-reinforcing filler such as one of a number of mineral fillers or the like.
In another embodiment, from about 0.1 to about 150 percent by weight of an alkyl alkoxysilane is used in the present invention as a processing aid. Thus, given the amount of silica filler typically preferred in the subject composition, up to about 150 parts by weight of the processing aid, per 100 parts elastomer. may be used, representing a 60/40 ratio of processing aid to silica.
In yet another embodiment, a mixture of a filler and a filler-supported processing aid selected from the group consisting of alkyl alkoxysilanes. fatty acid esters of hydrogenated and non-hydrogenated sugars, ethoxylated derivatives of fatty acid esters of hydrogenated and non-hydrogenated suaars, and mixtures thereof, is preferably added to the elastomer in an amount of about 5 to about 100 parts by weight per 100 parts of the elastomer. It should be stressed that when a silica-supported or carbon black-supported processing aid is used, the non-reinforcing fillers, including mineral fillers or other processing aids are not required in the elastomeric formulation.
However, it will be appreciated that if mineral fillers are used, they may be used to support the processing aid(s). Preferably, the processing aid is added to the silica or other filler in a mixture ratio of from about 1:99 to about 60:40, with a 50:50 mixture being most preferred.
In yet another embodiment, certain additional fillers can be utilized according to the present invention as processing aids which include, but are not limited to, mineral fillers, such as clay (hydrous aluminum silicate), talc (hydrous magnesium silicate), and mica as well as non-mineral fillers such as urea and sodium sulfate. Preferred micas contain principally alumina, silica and potash, although other variants are also useful, as set forth below. The additional fillers are also optional and can be utilized in the amount of from parts to about 40 parts per 100 parts of polymer (phr), preferably in an amount from about I to about 20 phr. It will be understood that these mineral fillers can also be used as non-reinforcing fillers to support the processing aids of the present invention.
Thus, a process for the preparation of a silica-filled, vulcanized elastomeric compound according to the present invention comprises mixing an elastomer with from about 5 to about 100 parts by weight of a reinforcing filler selected from the group consisting of silica filler and mixtures thereof with carbon black, from 0 to about 20 percent by weight, based on said silica filler, of bis[3-(triethoxysilyl)propyl]tetrasulfide, from 0.1 to about 150 percent by weight. based on said silica filler, of an alkylalkoxysilane, and a cure agent;
and, effecting vulcanization.
Further, the present invention also includes a vulcanizable silica-filled compound comprising an elastomer, a silica filler, from 0 to about 20 percent by weight, based on said silica filler, of bis[3-(triethoxvsilyl)propyl]tetrasulfide, from about 0.1 to about 150 percent by weight, based on said silica filler, of an alkylalkoxysilane, and a cure agent.
Preferably, the compound further contains a natural rubber.
Further, the present invention also includes a pneumatic tire comprising tread stock vulcanized from the above compound made from the above process.
The elastomer can be a diene monomer homopolymer or a copolymer of a diene monomer and a monomer selected from the group consisting of monovinyl aromatic monomers and triene monomers.
The alkylalkoxysilane can be represented by the formula (Rl)zSi(OR2)2 or RiSi(OR2)3, wherein each R, independently is selected from the group consisting of C, to about C18 aliphatic, about C; to about C12 cyclo-aliphatic, and about C6 to about C18 aromatic; and wherein the alkoxy groups are the same or are different, each R2 independently containing from one to about 6 carbon atoms.
The alkylalkoxysilane can be selected from the group consisting of octyltriethoxy silane, octyltrimethyloxy silane, (3-glycidoxypropyl)trimethoxy silane, (3-glycidoxypropyl)triethoxy silane, hexyltrimethoxy silane, ethyltrimethyoxy silane, propyltriethoxy silane, phenyltrimethoxy silane, cyclohexyltrimethoxy silane, cyclohexyltriethyoxy silane, dimethyldimethyoxy silane, 3-chloropropyltriethoxy silane, methacroyltrimethoxy silane, and i-butyltriethoxy silane. Preferably, the alkylalkoxysilane is octyltriethoxysilane.
In one option for the above process, one can mix, prior to the vulcanizing step, a processing aid comprising at least one of an ester of a fatty acid or an ester of a polyol. Preferably, that processing aid is selected from the group consisting of at least one sorbitan ester of an oleate, laurate, palmitate and stearate fatty acids, polyoxyethylene derivatives thereof, at least one ester of a polyhydroxy compound, and mixtures thereof. More preferably, that processina aid is sorbitan monooleate.
Preferably for the above process, the elastomer is a styrene butadiene rubber. More preferably. the elastomer is a copolymer of styrene butadiene rubber and butyl rubber. Even more preferably, the elastomer is mixed with carbon black.
The process also optionally includes mixing insoluble sulfur prior to the vulcanizing step.
The present invention also includes a first alternative process for the preparation of a silica-filled, vulcanized elastomeric compound comprising the steps of mixing an elastomer with from about 5 to about 100 parts by weight of a reinforcing filler per 100 parts of elastomer, wherein said reinforcing fillers are selected from the group consisting of silica filler and mixtures thereof with carbon black; from 0 to about 20 percent by weight of bis[3-(triethoxysilyl)propyl]tetrasulfide, based upon the weight of said silica filler;
from about 0.1 to about 150 percent by weight of a processing aid selected from the group consisting of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars, polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars, and mixtures thereof;
from about 0 to about 40 parts by weight of an additional filler other than silica or carbon black, with the provisos that if said processing aid is sorbitan monooleate, then at least one of said polyoxyethylene derivatives or said additional fillers is also present and, that the minimal amount for each said processing aid and said additional filler, if present, is about one part by weight;
and a cure agent; and effecting vulcanization.
The first alternative process utilizes a vulcanizable silica-filled compound which comprises 100 parts by weight of an elastomer; from about 5 to about 100 parts by weight of a reinforcing filler per 100 parts of elastomer, wherein said reinforcing fillers are selected from the group consisting of silica filler and mixtures thereof with carbon black; from 0 to about 20 percent by weight of bis[3-(triethoxysilyl) propyl]tetrasulfide, based upon the weight of said silica filler; from about 0.1 to about 150 percent by weight of a processing aid selected from the group consisting of fatty acid esters of hydrogenated and non-hydrogenated C; and C6 sugars, polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars, and mixtures thereof, from about 0 to about 40 parts by weight of an additional filler other than silica or carbon black; and a cure agent; with the provisos that if said processing aid is sorbitan monooleate, then at least one of said polyoxyethylene derivatives or said additional fillers is also present and, that the minimal amount for each said processing aid and said additional filler, if present, is about one part by weight.
Further, the present invention also includes a pneumatic tire comprising tread stock vulcanized from the above alternative compound made from the above alternative process.
The alternative process and vulcanizable compound are utilize the same preferences of process steps and ingredients, except as noted below.
The alternative process can include an additional step of adding a natural rubber.
Preferably, silica filler used in the alternative process and compound has a surface area of about 32 to about 400 m2/g and a pH of about 5.5 to about 7.
Preferably, the alternative process and compound has an amount of said carbon black reinforcing filler ranging from about 0 to about 50 parts by weight, per 100 parts by weight of elastomer, and an amount of said reinforcing silica filler ranging from about I to 100 parts, per 100 parts of elastomer, with the proviso that where carbon is 0, at least 30 phr of silica is employed.
Preferably, the fatty acid esters of hydrogenated and non-hydrogenated C; and C6 sugars are selected from the group consisting of sorbitan monooleate, sorbitan dioleate, sorbitan trioleate, sorbitan sesquioleate, sorbitan laurate. sorbitan palmitate and sorbitan stearate. while the polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C; and C6 sugars are selected from the group consisting of POE
(20) sorbitan stearate; POE (20) sorbitan oleate; POE (20) sorbitan tri-oleate;
POE (20) sorbitan sesquioleate; POE (20) sorbitan laurate and POE (20) sorbitan palmitate. More preferably, the processing aid comprises a mixture of at least one fatty acid ester of hydrogenated and non-hydrogenated C5 and C6 sugars and at least one polyoxyethylene derivative of a fatty acid ester of hydrogenated and non-hydrogenated C5 and C6 sugars.
Preferably, the additional filler is selected from the group consisting of mica, talc, urea, clay, sodium sulfate and mixtures thereof and more preferably, is included with the mixture of at least one fatty acid ester of hydrogenated and non-hydrogenated C5 and C6 sugars.
The present invention provides a second alternative process for the preparation of a silica-filled, vulcanized elastomeric compound comprising mixing 100 parts by weight of an elastomer with from about 5 to about 100 parts by weight of a reinforcing filler selected from the group consisting of silica filler or mixtures thereof with carbon black, per 100 parts of said elastomer; from about 0.1 to about 150 percent by weight, based on said silica filler, of a processing aid selected from the group consisting of alkylalkoxysilanes, fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars; polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars and mixtures thereof; from 0 to about 40 parts by weight of a non-reinforcing filler, per 100 parts elastomer; and a cure agent: wherein said processing aid is first mixed with and supported on at least some of either said reinforcing filler or said non-reinforcing filler prior to mixing with said elastomer; and effecting vulcanization.
The second alternative process utilizes a vulcanizable, silica-filled compound comprising 100 parts by weight of an elastomer; from about 5 to about 100 parts by weight of a reinforcing filler selected from the group consisting of silica filler or mixtures thereof with carbon black, per 100 parts of said elastomer; from about 0.1 to about 150 percent by weight, based on said silica filler. of a processing aid selected from the group consisting of alkylalkox-,,silanes, fatty acid esters of hydrogenated and non-hydrogenated and C6 suQars; polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars and mixtures thereof; from 0 to about 40 parts by weight of a non-reinforcing filler, per 100 parts elastomer; and a cure agent; wherein said processing aid is supported on at least some of either said reinforcing filler or said non-reinforcing filler.
Further, the present invention also includes a pneumatic tire comprising tread stock vulcanized from the above second alternative compound made from the above second alternative process.
The second alternative process and vulcanizable compound are utilize the same preferences of process steps and ingredients as the first alternative process and vulcanizable compound, except as noted below.
As with the initial process and vulcanizable compound described above, the alkyl alkoxysilanes are selected from the group consisting of octyltriethoxy silane, octyltrimethyloxy silane, (3-glycidoxypropyl)trimethoxy silane, (3-glycidoxypropyl)triethoxy silane, hexyltrimethoxy silane, ethyltrimethyoxy silane, propyltriethoxy silane, phenyltrimethoxy silane, cyclohexyltrimethoxy silane, cyclohexyltriethyoxy silane, dimethyldimethyoxy silane, 3-chloropropyltriethoxy silane, methacroyltrimethoxy silane, and i-butyltriethoxy silane.
Preferably, for the second alternative vulcanizable silica-filled compound, the silica or carbon black-support processing aid is provided as a 50/50 mixture of processing aid to support.
The following examples amplify upon these embodiments.
Examples Testing of silica-filled vulcanizable elastomeric compounds was conducted to determine the effect silica-supported and carbon black-supported alkyl alkoxysilanes and polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated sugars as processing aids in the elastomeric stock formulations. The basic formulation. C-CC, of the elastomeric stock formulation is shown and described in Table I below.
The physical properties of the Example Nos. 1-6 and the control, C-DD, are shown and described in Table II, below. Example Nos. 2-6 indicated a Mooney viscosities (ML 1+4/100 C) comparable to the control, C-DD, with 3 phr of Si69 processing aid. Tensile properties of the cured elastomeric stocks, containing processing aids comprising octyl triethoxy silane and sorbitan oleate supported on silica are comparable to the tensile properties of the controi elastomeric stock formulation, C-DD, containing 3 phr of Si69 processing aid.
Curing at 171 C for 20 minutes was used to obtain the physical properties set forth below.
TABLE I
Basic Formulation of Elastomeric Stock (C-CC) Component Parts Oil 15 carbon black 35 silica VARIABLE
stearic acid 1.5 wax 1.0 process aid VARIABLE
antioxidant 0.95 sulfur 1.7 CBS 1.5 DPG 0.5 Zinc oxide 2.5 Table I Continued Final Elastomeric Stock Formulations Examples C-DD and 1-6 Example C-DD 1 2 3 4 5 6 46% SO on Silica" C 3.3 13 --- --- --- ---Table I Continued Final Elastomeric Stock Formulations Examples C-DD and 1-6 Example C-DD 1 2 3 4 5 6 47% OS on Silica --- 1.5 2.5 --- ---SO/3.8% OS on Silicac --- --- --- 32.9 --- --- ---5%
5% SO/3.8% OS on Silica --- --- --- --- 32.9 --- ---Sorbitan Oleate (SO) --- --- --- --- --- 1.65 1.65 Octyl triethoxysilane (OS) --- --- --- --- --- 1.25 1.25 a Flogard SP (712-090) b Flogard SP (712-091) c Flogard SP (712-097) d HiSil (712-098) Table II
Physical Properties of Elastomeric Formulations Example C-DD 1 2 3 4 5 6 Mooney Viscosity ML 1+4/100 C 77.6 132.4 75.2 77.9 80.8 64.6 72.9 T80 9.7 43.5 7.5 8.5 9.3 6.5 7.4 MDR Monsanto Cure at 165 C
ML 11.01 3.86 3.48 3.7 3.75 3.13 3.32 MH 35.37 20.42 19.39 19.67 20.28 18.89 19.1 ts2 2:36 2:08 2:16 2:26 2:16 2:22 2:24 tc90 17:06 13:55 l i: I4 10:37 11:14 10:41 10:02 tan 6 at MH -- 0.144 0.145 0.158 0.15 0.134 0.135 Ring Tensile at 24 C
50% Modulus,psi 221 256 230 1209 219 207 227 100% Modulus, psi 322 403 360 331 356 331 360 * comparative Table II
Physical Properties of Elastomeric Formulations Example C-DD 1 2 3 4 5 6 200% Modulus, psi 615 819 766 678 739 697 765 300% Modulus,psi 1008 1407 1338 1177 1279 1234 1335 Tensile Strength, psi 1852 2082 1899 1726 1959 1840 1886 % Elongation 474 400 386 392 407 395 381 Break energy, 4012 3762 3229 3013 3549 3156 3166 in-lbs/in' Ring Tensile at 100 C
50% Modulus,psi 189 229 208 212 196 193 190 100% Modulus, psi 263 350 323 312 303 296 300 200% Modulus, psi 518 685 654 632 607 614 604 300% Modulus,psi 869 1140 1107 1022 1025 1070 1023 Tensile Strength, psi 1299 1248 1227 1203 1075 1097 1 148 % Elongation 412 322 322 327 310 308 326 Break energy, 2496 1894 1837 1813 1557 1552 1761 in-lbs/in' Ring Tear at 171 C, psi 184.9 175.6 140.8 152.2 108.2 118.4 154 Wet Stanley 59/53 57/52 57/52 58/52 58/52 57/52 57/52 London(#/std) Shore A, at RT ---- 72 70 67 67 67 66 Shore A at 50 C ---- 67 67 65 67 66 65 Rheometrics at 7% Strain tan 6 at 24 C 0.193 0.195 0.169 0.173 0.175 0.166 0.180 o G' x 10-7 at 24 C 4.239 4.506 4.879 5.267 4.718 3.94 4.712 Table II
Physical Properties of Elastomeric Formulations Example C-DD 1 2 3 4 5 6 24 C G' x 10-' at 14.5% 3.006 3.138 3.261 3.01 3.127 2.856 3.422 tan S at 65 C 0.152 0.153 0.155 0.143 0.145 0.138 0.149 6 G' x 10-' at 65 C 2.689 3.779 5.667 3.939 4.554 4.172 3.836 50 C G' x 10-' at 14.5% 2.42 2.736 2.77 2.731 2.992 2.509 2.6 Mr, g/mol from 13680 10440 ---- 11320 ---- ---- ----Tensile Retraction Further testing of silica-filled vulcanizable elastomeric stock formulations was conducted to determine the effects of the silica and carbon black-supported processing aids on the physical properties and processability of the elastomeric formulations after six months of ambient storage.
The elastomeric stock formulations were prepared according to Table III, below, and the physical properties were evaluated after curing at 170 C for 20 minutes, followed by six months of ambient aging. The data for the physical properties and processability of the elastomeric formulations for the ambient aging study are shown in Table IV, below.
TABLE III
Basic Formulation of Elastomeric Stock (C-CC) Component Parts Oil 15 carbon black 35 si{ica VARIABLE
stearic acid 1.5 TABLE III
Basic Formulation of Elastomeric Stock (C-CC) Component Parts wax 1.0 process aid VARIABLE
antioxidant 0.95 sulfur 1.7 CBS 1.5 DPG 0.5 Table III Continued Final Elastomeric Stock Formulations Examples 7-12 Example 7 8 9 10 11 12 46% SO on Sitica' 3.3 3.3 --- ---47% --- ---OS on Silica -- 2.5 --- --- --- ---5% SO/3.8% OS on Silica` - --- 32.9 --- --- ---5% SO/3.8% OS on Silica --- --- --- 32.9 --- ---Sorbitan Oleate (SO) --- --- --- --- 1.65 1.65 Octyl triethoxysitane (OS) 1.25 --- --- --- 1.25 1.25 Table IV
Physical Properties of Elastomeric Formulations After Ambient aging for 6 months Example 7 8 9 10 11 12 Mooney Viscosity ML 1+4/100 C 77 80.8 78.9 78.9 74.8 78.1 MDR Monsanto Cure at 165 C
ML 2.97 3.62 3.5 3.69 3.29 3.47 MH 16.12 19.65 19.02 19.62 18.72 16.49 ts2 2:52 2:42 3:04 3:05 2:49 2:54 tc90 14:27 10:47 9:37 9:11 9:41 14:00 tan S at MH 0.2 0.093 0.102 0.103 0.091 0.189 Ring Tensile at 24 C
50% Modulus,psi 181 159 172 166 171 165 100% Modulus, psi 333 286 316 296 310 294 200% Modulus, psi 778 676 754 691 740 696 300% Modulus,psi 1415 1242 1389 1273 1375 1288 Tensile Strength, psi 2551 2233 2442 2298 2548 2438 % Elongation 448 445 441 447 454 461 Breakes4735 4088 4521 4235 4731 4605 in-lbs/in' Ring Tensile at 100 C
50% Modulus,psi 131 131 146 153 146 139 100% Modulus, psi 244 240 267 274 266 250 200% Modulus. psi 541 532 596 596 590 546 Table IV
Physical Properties of Elastomeric Formulations After Ambient aging for 6 months Example 7 8 9 10 11 12 300% Modulus, psi 973 963 1073 1076 1069 982 Tensile Strength, psi 1285 1400 1356 1433 1430 1396 % Elongation 367 394 356 369 371 388 Break energy, 2024 2353 2069 2266 2270 2330 in-lbs/in 2 New Lambourn at 179 181 157 147 158 149 65%, g lost New Lambourn at 0.145 0.148 0.1456 0.1506 0.1454 0.1481 65%, INDEX
Ring Tear at 171 C, 0.97 0.95 0.96 0.93 0.96 0.95 psi Wet Stanley 53/48.5 57/48.5 53/48.5 53/48.5 56/48.5 53/48.5 London(#/std) Shore A, at RT 66.4 67 67.7 67.5 65.8 64.1 Shore A at 50 C 63.6 64.3 64.8 64.9 63.9 64.1 Rheometrics at 7% Strain Tan S at 24 C 0.1779 0.169 0.181 0.1843 0.159 0.1724 24 C G' x 10' at 7% 0.628 0.605 0.657 0.739 0.491 0.577 S G' x 10" at 24 C 4.772 4.224 5.233 5.909 3.13 4.087 24CG'x10' at 14.5% 2.652 2.779 2.779 3.009 2.48 2.572 tan S at 50 C
0.15 0.1391 0.1524 0.1544 0.1417 0.1412 50 C G' x 10' at 7% 0.462 0.441 0.482 0.521 0.38 0.401 S G' x 10-" at 50 C
3.648 3.374 3.941 4.428 2.829 2.995 50 C G' x 10' at 14.5% 2.417 2.536 2.477 2.644 2.151 2.281 It is apparent from the data contained in Table IV, that elastomeric formulations containing a silica-supported or carbon black-supported processing aid selected from the group consisting of an alkyl alkoxysilane, fatty acid ester of hydrogenated or non-hydrogenated C5 and C6 sugars, e.g., sorbitan, and ethoxylated derivatives of fatty acid esters of these sugars provide physical properties, after six months of ambient aging, comparable to the control elastomeric formulation containing 3 phr of Si69 as a processing aid (C-DD).
Thus, it should be evident that the process of the present invention is useful in improving the processability of formulations of diene polymer elastomers containing silica filler by reducing the viscosity of silica-filled elastomeric vulcanizable compounds. It is further demonstrated that the present invention provides vulcanizable silica-filled elastomeric compounds having enhanced physical properties. Practice of the present invention allows a reduction of Si69 which is added to vulcanizable rubber compositions containing silica fillers. The reduction can be effected by the addition of the processing aids described herein, mineral and non-mineral fillers as well as combinations of more than one.
Thus, it should be evident that the process of the present invention is useful in improving the processability of formulations of diene polymer elastomers containing silica filler by reducing the viscosity of silica-filled elastomeric vulcanizable compounds. It is further demonstrated that the present invention provides vulcanizable silica-filled elastomeric compounds having enhanced physical properties. Practice of the present invention allows a reduction of Si69 which is added to vulcanizable rubber compositions containing silica fillers. The reduction can be effected by the addition of the processing aids described herein, mineral and non-mineral fillers as well as combinations of more than one.
Claims (14)
1. A process for the preparation of a silica-filled, vulcanized elastomeric compound comprising:
.cndot. (a)mixing ~ (1) 100 parts by weight of an elastomer;
~ (2) from 5 to 100 parts by weight of a reinforcing filler selected from the group consisting of silica filler or mixtures thereof with carbon black, per 100 parts of said elastomer, wherein the silica filler has a BET surface area of 150 to 220m2/g;
~ (3) from 0.1 to 150 percent by weight, based on said silica filler, of a combination of an alkylalkoxysilane and an additional processing aid selected from the group consisting of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars, polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars and mixtures thereof;
~ (4) optionally from 0 to 40 parts by weight of a non-reinforcing filler, per 100 parts elastomer;
~ (5) optionally from 0 to 20 percent by weight of bis[(triethoxysilyl)-propyl]tetrasulfide, based upon the weight of said silica filler; and ~ (6) a cure agent;
wherein said alkylalkoxysilane and said additional processing aid are first mixed with and supported on at least some of either said silica reinforcing filler or said non-reinforcing filler prior to mixing with said elastomer, and wherein the minimal amount for the alkylalkoxysilane and said additional processing aid is about one part by weight; and .cndot. (b) effecting vulcanization.
.cndot. (a)mixing ~ (1) 100 parts by weight of an elastomer;
~ (2) from 5 to 100 parts by weight of a reinforcing filler selected from the group consisting of silica filler or mixtures thereof with carbon black, per 100 parts of said elastomer, wherein the silica filler has a BET surface area of 150 to 220m2/g;
~ (3) from 0.1 to 150 percent by weight, based on said silica filler, of a combination of an alkylalkoxysilane and an additional processing aid selected from the group consisting of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars, polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars and mixtures thereof;
~ (4) optionally from 0 to 40 parts by weight of a non-reinforcing filler, per 100 parts elastomer;
~ (5) optionally from 0 to 20 percent by weight of bis[(triethoxysilyl)-propyl]tetrasulfide, based upon the weight of said silica filler; and ~ (6) a cure agent;
wherein said alkylalkoxysilane and said additional processing aid are first mixed with and supported on at least some of either said silica reinforcing filler or said non-reinforcing filler prior to mixing with said elastomer, and wherein the minimal amount for the alkylalkoxysilane and said additional processing aid is about one part by weight; and .cndot. (b) effecting vulcanization.
2. The process of claim 1, wherein the alkylalkoxysilane is represented by the formula (R1)2Si(OR2)2 or R1Si(OR2)3, wherein each R1 independently is selected from the group consisting of C1 to C18 aliphatic and C5 to C12 cycloaliphatic;
and wherein the alkoxygroups are the same or are different, each R2 independently containing from one to 6 carbon atoms.
and wherein the alkoxygroups are the same or are different, each R2 independently containing from one to 6 carbon atoms.
3. The process of claim 2, wherein the alkylalkoxysilane is selected from the group consisting of octyltriethoxy silane, octyltrimethoxy silane, (3-glycidoxypropyl)trimethoxy silane, (3-glycidoxypropyl)triethoxy silane, hexyltrimethoxy silane, ethyltrimethoxy silane, propyltriethoxy silane, cyclohexyltrimethoxy silane, cyclohexyltriethoxy silane, dimethyldimethoxy silane, 3-chloropropyltriethoxy silane and i-butyltriethoxy silane.
4. The process of any one of claims 1 to 3, wherein the elatomer is a diene monomer homopolymer or a copolymer of at least one diene and at least one monomer selected from the group consisting of monovinyl aromatic monomers and triene monomers.
5. The process of any one of claims 1 to 4, wherein the process further includes mixing insoluble sulfur prior to vulcanizing.
6. The process of any one of claims 1 to 5, wherein the elastomer is styrene-butadiene rubber.
7. The process of any one of claims 1 to 6, wherein the elastomer is a copolymer of styrene-butadiene rubber and butyl rubber.
8. The process of any one of claims 1 to 7, wherein the elastomer further contains natural rubber.
9. The process of any one of claims 1 to 8, wherein the fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars are selected from the group consisting of sorbitan monooleate, sorbitan diolate, sorbitan trioleate, sorbitan sesquioleate, sorbitan laurate, sorbitan palmitate and sorbitan stearate, and wherein the polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars are selected from the group consisting of POE (20) sorbitan stearate; POE (20) sorbitan oleate; POE (20) sorbitan trioleate;
POE (20) sorbitan sesquioleate; POE (20) sorbitan laurate and POE (20) sorbitan palmitate.
POE (20) sorbitan sesquioleate; POE (20) sorbitan laurate and POE (20) sorbitan palmitate.
10. The process of any one of claims 1 to 9, wherein the additional processing aid is a mixture of at least one fatty acid ester of hydrogenated and non-hydrogenated C5 and C6 sugars and at least one polyoxyethylene derivative of a fatty acid ester of hydrogenated and non-hydrogenated C5 and C6 sugars.
11. The process of any one of claims 1 to 10, wherein the amount of said carbon black reinforcing filler ranges from 0 to 50 parts by weight, per 100 parts by weight of elastomer, and the amount of said reinforcing silic filler ranges from 1 to 100 parts, per 100 parts of elastomer, with the priviso that where carbon black is 0, at least 30 phr of silica is employed.
12. A compound obtained from a process of any one of claims 1 to 11.
13. A pneumatic tire comprising tread stock vulcanized from a compound of claim 12.
14. A pneumatic tire comprising tread stock obtained from a process of any one of claims 1 to 11.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/203,438 | 1998-12-01 | ||
US09/203,438 US6384117B1 (en) | 1997-07-11 | 1998-12-01 | Processability of silica-filled rubber stocks |
PCT/US1999/027890 WO2000032684A1 (en) | 1998-12-01 | 1999-11-24 | Improved processability of silica-filled rubber stocks |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2353503A1 CA2353503A1 (en) | 2000-06-08 |
CA2353503C true CA2353503C (en) | 2009-03-17 |
Family
ID=22754023
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002353503A Expired - Fee Related CA2353503C (en) | 1998-12-01 | 1999-11-24 | Improved processability of silica-filled rubber stocks |
Country Status (6)
Country | Link |
---|---|
US (3) | US6384117B1 (en) |
EP (1) | EP1135433B1 (en) |
JP (1) | JP2002531617A (en) |
CA (1) | CA2353503C (en) |
DE (1) | DE69925861T2 (en) |
WO (1) | WO2000032684A1 (en) |
Families Citing this family (90)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4676587B2 (en) * | 2000-02-28 | 2011-04-27 | 住友ゴム工業株式会社 | Rubber composition |
DE60116716T2 (en) * | 2000-07-28 | 2006-08-10 | Sumitomo Rubber Industries Ltd., Kobe | Katschuk composition for tire treads and tires with tread therefrom |
US6313210B1 (en) * | 2000-07-31 | 2001-11-06 | Bridgestone Coporation | Silica-reinforced rubber compounds containing moisture stabilized polymers |
US6608145B1 (en) | 2000-10-13 | 2003-08-19 | Bridgestone Corporation | Silica-reinforced rubber compounded with an organosilane tetrasulfide silica coupling agent at high mixing temperature |
US6433065B1 (en) | 2000-10-13 | 2002-08-13 | Bridgestone Corporation | Silica-reinforced rubber compounded with mercaptosilanes and alkyl alkoxysilanes |
US7041745B2 (en) * | 2002-04-17 | 2006-05-09 | Bridgestone Corporation | Addition of polar polymer to improve tear strength and processing of silica filled rubber |
US7183358B2 (en) * | 2002-07-25 | 2007-02-27 | Wacker Polymer Systems Gmbh & Co. Kg | Hydrophobically modified polymers |
JP4522947B2 (en) | 2002-10-30 | 2010-08-11 | 株式会社ブリヂストン | Method of using sulfur-containing initiators for anionic polymerization of monomers |
ES2268210T5 (en) † | 2003-05-02 | 2010-05-19 | Evonik Degussa Gmbh | ORGANOSILAN MOTHER BLEND. |
JP4493314B2 (en) * | 2003-10-08 | 2010-06-30 | 住友ゴム工業株式会社 | Rubber composition for tire |
US7259204B2 (en) * | 2004-03-01 | 2007-08-21 | Bridgestone Corporation | Tire compositions comprising surface-modified silica |
JP2007534833A (en) | 2004-04-27 | 2007-11-29 | 株式会社ブリヂストン | Method for producing tire composition having improved silica reinforcement performance |
CN101107294B (en) | 2005-01-14 | 2011-05-25 | 株式会社普利司通 | Functionalized polymers and improved tires therefrom |
ES2624856T3 (en) | 2005-03-24 | 2017-07-17 | Bridgestone Corporation | Silica-reinforced rubber compound with low emission of volatile organic compounds (VOCs) |
US20060223917A1 (en) * | 2005-04-05 | 2006-10-05 | Bridgestone Corporation | Method of optimizing a tire tread compound, and a tire tread compound made by said method |
JP2006306947A (en) * | 2005-04-27 | 2006-11-09 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire tread and pneumatic tire |
US20060252869A1 (en) * | 2005-05-09 | 2006-11-09 | Ashland Inc. | Synergistic filler compositions and low density sheet molding compounds therefrom |
US20070037908A1 (en) * | 2005-08-09 | 2007-02-15 | Wolfgang Pille-Wolf | Rubber compositions containing improved tackifiers |
US7635729B2 (en) * | 2005-09-29 | 2009-12-22 | Raymond Lee Nip | Zinc oxide coated particles, compositions containing the same, and methods for making the same |
ATE530593T1 (en) * | 2006-05-30 | 2011-11-15 | Borealis Tech Oy | USE OF A SILICON COMPOUND AS A PROCESSING AID AND AS A SURFACE SMOOTHING ADDITIVE IN A POLYOLEFIN COMPOSITION CONTAINING CROSS-LINKABLE POLYOLEFIN WITH SILANE GROUPS AND A SILANOL CONDENSATION CATALYST |
ES2374415T3 (en) * | 2006-05-30 | 2012-02-16 | Borealis Technology Oy | A COMPOUND THAT CONTAINS SILICON AS A PROCESSING ASSISTANCE FOR POLYOLEFIN COMPOSITIONS THAT INCLUDE INTERRUPTABLE POLYOLEFINS WITH HYDROLYABLE SILANO GROUPS. |
CN101501109B (en) * | 2006-07-14 | 2012-05-30 | 耐克国际有限公司 | Rubber compositions with activated sulfur cure |
US7858690B2 (en) | 2006-10-06 | 2010-12-28 | Bridgestone Corporation | Functional coupling agents and polymers prepared therewith |
ZA200711158B (en) | 2006-12-28 | 2009-03-25 | Bridgestone Corp | A method for producing functionalized cis-1,4-polydienes having high cis-1,4-linkage content and high functionality |
US8372925B2 (en) | 2007-04-10 | 2013-02-12 | Bridgestone Corporation | Nickel-based catalyst composition |
US8324329B2 (en) | 2007-08-07 | 2012-12-04 | Bridgestone Corporation | Process for producing functionalized polymers |
US7879958B2 (en) | 2007-08-07 | 2011-02-01 | Bridgestone Corporation | Polyhydroxy compounds as polymerization quenching agents |
US8314189B2 (en) | 2007-10-12 | 2012-11-20 | Bridgestone Corporation | Polymers functionalized with heterocyclic nitrile compounds |
US7988903B2 (en) * | 2008-07-02 | 2011-08-02 | Zeon Chemicals L.P. | Fast curing vulcanizable multi-part elastomer composition, and process for blending, injection molding and curing of elastomer composition |
US8735487B2 (en) * | 2008-07-03 | 2014-05-27 | Bridgestone Corporation | Tire components with improved heat transfer |
EP2303951B1 (en) * | 2008-07-24 | 2018-03-07 | Industrias Negromex, S.a. De C.v. | Processes for making silane, hydrophobated silica, silica masterbatch and rubber products |
US8329297B2 (en) | 2008-12-01 | 2012-12-11 | Bridgestone Corporation | Rubber compositions containing non-sulfur silica coupling agents bound to diene rubbers |
US20110077325A1 (en) | 2009-09-30 | 2011-03-31 | Bridgestone Corporation | Functionalized polymers and methods for their manufacture |
KR101762461B1 (en) | 2009-10-14 | 2017-07-27 | 가부시키가이샤 브리지스톤 | Processes for preparation of cyclic acyclic diene copolymer and rubber composition |
KR101140246B1 (en) * | 2009-12-21 | 2012-05-02 | 한국타이어 주식회사 | Rubber composition for tire tread and tire manufactured by the same |
US8338544B2 (en) | 2009-12-21 | 2012-12-25 | Bridgestone Corporation | Polymers functionalized with polyoxime compounds and methods for their manufacture |
KR101830872B1 (en) | 2009-12-22 | 2018-02-26 | 가부시키가이샤 브리지스톤 | Improved vinyl modifier composition and processes for utilizing such composition |
WO2011082098A1 (en) | 2009-12-30 | 2011-07-07 | The Rockefeller University | Lysine and arginine methyltransferase inhibitors for treating cancer |
JP5551796B2 (en) | 2009-12-31 | 2014-07-16 | 株式会社ブリヂストン | Aminosilane initiators and functionalized polymers prepared therefrom |
JP5599901B2 (en) | 2010-01-22 | 2014-10-01 | 株式会社ブリヂストン | Polymers functionalized with nitrile compounds containing protected amino groups |
JP5859545B2 (en) | 2010-08-31 | 2016-02-10 | 株式会社ブリヂストン | Rubber composition comprising filler and ketoxime or ketoximosilane |
CN105646754B (en) | 2010-09-23 | 2018-08-07 | 株式会社普利司通 | Method for producing polydiene |
EP2452951A1 (en) | 2010-11-16 | 2012-05-16 | LANXESS Deutschland GmbH | Carbinol-terminated polymers containing silane |
EP2452981A1 (en) | 2010-11-16 | 2012-05-16 | LANXESS Deutschland GmbH | Trialkylsilyloxy-terminated polymers |
EP2452952A1 (en) | 2010-11-16 | 2012-05-16 | LANXESS Deutschland GmbH | Carbinol-terminated polymers containing ether |
US8748531B2 (en) | 2010-12-10 | 2014-06-10 | Bridgestone Corporation | Polymers functionalized with oxime compounds containing an acyl group |
CN107236061B (en) | 2010-12-30 | 2020-08-07 | 株式会社普利司通 | Aminosilane initiators and functionalized polymers prepared therefrom |
WO2012092551A1 (en) | 2010-12-31 | 2012-07-05 | Bridgestone Corporation | Bulk polymerization of conjugated dienes using a nickel-based catalyst system |
CN103339157B (en) | 2010-12-31 | 2015-09-09 | 株式会社普利司通 | Use the conjugated diolefine mass polymerization based on the catalyst system of nickel |
WO2012135451A2 (en) | 2011-03-29 | 2012-10-04 | Bridgestone Corporation | Polymers functionalized with a carboxylic or thiocarboxylic ester containing a silylated amino group |
US8993683B2 (en) | 2011-08-31 | 2015-03-31 | Bridgestone Corporation | Polymers functionalized with lactones or thiolactones containing a protected amino group |
RU2605552C2 (en) | 2011-11-17 | 2016-12-20 | Бриджстоун Корпорейшн | Method of producing polydienes |
KR101956957B1 (en) | 2011-11-18 | 2019-03-11 | 가부시키가이샤 브리지스톤 | Method for producing polydienes and polydiene copolymers with reduced cold flow |
CN104093751B (en) | 2011-12-09 | 2017-05-31 | 株式会社普利司通 | The method for preparing the polydiene and polydiene copolymer with the cold flow for reducing |
TWI585115B (en) | 2011-12-15 | 2017-06-01 | 普利司通股份有限公司 | Stabilized multi-valent anionic polymerization initiators and methods for preparing the same |
CN104220466B (en) | 2012-03-14 | 2016-09-21 | 株式会社普利司通 | For the method preparing polydiene |
EP2662392A1 (en) | 2012-05-09 | 2013-11-13 | LANXESS Deutschland GmbH | Carbinol-terminated polymers containing allylamine |
EP2662406A1 (en) | 2012-05-09 | 2013-11-13 | LANXESS Deutschland GmbH | Carbinol-terminated polymers containing amine |
US9469706B2 (en) | 2012-06-08 | 2016-10-18 | Bridgestone Corporation | Polymers functionalized with unsaturated heterocycles containing a protected amino group |
DE102012110121A1 (en) * | 2012-10-24 | 2014-04-24 | Continental Reifen Deutschland Gmbh | Rubber compound and pneumatic vehicle tires |
CN105026448B (en) | 2012-11-09 | 2017-10-17 | 株式会社普利司通 | The purposes of bio-based styrene |
WO2014100342A1 (en) | 2012-12-20 | 2014-06-26 | W. R. Grace & Co.-Conn. | Container sealant composition |
US9663637B2 (en) | 2012-12-31 | 2017-05-30 | Bridgestone Corporation | Polymers functionalized with unsaturated heterocycles containing an azolinyl group |
US9127092B2 (en) | 2012-12-31 | 2015-09-08 | Bridgestone Corporation | Method for producing polydienes and polydiene copolymers with reduced cold flow |
US9315599B2 (en) | 2013-01-02 | 2016-04-19 | Bridgestone Corporation | Functionalized polymers |
US9850328B2 (en) | 2013-03-15 | 2017-12-26 | Bridgestone Corporation | Polymers functionalized with heterocyclic imines |
US10590208B2 (en) | 2013-10-02 | 2020-03-17 | Bridgestone Corporation | Polymers functionalized with imine compounds containing a cyano group |
US10035908B1 (en) | 2013-12-03 | 2018-07-31 | Bridgestone Corporation | Process for preparing blends of trans-1,4-polybutadiene and syndiotactic 1,2-polybutadiene |
US9982115B2 (en) | 2013-12-03 | 2018-05-29 | Bridgestone Corporation | Process for preparing blends of cis-1,4-polybutadiene and syndiotactic 1,2-polybutadiene |
WO2015089356A2 (en) | 2013-12-12 | 2015-06-18 | Firestone Polymers, Llc | Method for producing polymeric compositions including functionalized polymers |
PL3010856T3 (en) | 2014-03-07 | 2019-04-30 | Ind Negromex S A De C V | Silica masterbatch made with emulsion and solution rubber |
US10030083B2 (en) | 2014-05-15 | 2018-07-24 | Bridgestone Corporation | Polymers functionalized with protected oxime compounds containing a cyano group |
US10526475B2 (en) * | 2014-09-24 | 2020-01-07 | Bridgestone Americas Tire Operations, Llc | Silica-containing rubber compositions containing specified coupling agents and related methods |
EP3204429B1 (en) | 2014-10-07 | 2018-09-05 | Bridgestone Corporation | Method for producing polydienes and polydiene copolymers with reduced cold flow |
WO2016081300A1 (en) | 2014-11-17 | 2016-05-26 | Bridgestone Corporation | Bulk polymerization of polyisoprene with preformed catalyst |
US10683381B2 (en) | 2014-12-23 | 2020-06-16 | Bridgestone Americas Tire Operations, Llc | Actinic radiation curable polymeric mixtures, cured polymeric mixtures and related processes |
WO2016123376A1 (en) | 2015-01-28 | 2016-08-04 | Bridgestone Corporation | End-functionalized polydienes |
JP6164261B2 (en) * | 2015-03-04 | 2017-07-19 | 横浜ゴム株式会社 | Rubber composition and pneumatic tire using the same |
JP6244033B2 (en) * | 2015-03-05 | 2017-12-06 | 株式会社ブリヂストン | Rubber composition and tire |
WO2016147089A1 (en) * | 2015-03-13 | 2016-09-22 | Bridgestone Corporation | Method to prepare rubber compounds containing silicon dioxide for the production of tyres |
US10370460B1 (en) | 2015-05-20 | 2019-08-06 | Bridgestone Corporation | Process for producing functionalized polymers |
US10077323B2 (en) | 2015-07-24 | 2018-09-18 | Bridgestone Corporation | Polymers functionalized with imine compounds containing a protected thiol group |
WO2017201397A1 (en) | 2016-05-19 | 2017-11-23 | Bridgestone Corporation | Process for producing functionalized polymers |
US11059920B2 (en) | 2016-07-29 | 2021-07-13 | Bridgestone Corporation | Process for producing high cis-1,4-polydiene with lanthanide-based catalyst compositions |
CA3032778C (en) | 2016-08-31 | 2021-11-02 | Dynasol Elastomeros, S.A. De C.V. | Processes for making masterbatches of rubber and silica |
WO2018045291A1 (en) | 2016-09-02 | 2018-03-08 | Bridgestone Corporation | Production of cis-1,4-polydienes with multiple silane functional groups prepared by in-situ hydrosilylation of polymer cement |
US11111979B2 (en) | 2016-09-17 | 2021-09-07 | Firestone Industrial Products Company, Llc | Elastomeric articles with improved fire protection properties |
WO2018089635A1 (en) | 2016-11-09 | 2018-05-17 | Bridgestone Corporation | High cis-1,4 block copolymers of polybutadiene and polyisoprene |
WO2018221665A1 (en) * | 2017-05-31 | 2018-12-06 | 国立大学法人大阪大学 | Layered product and method for producing same |
EP3409505B1 (en) | 2017-06-02 | 2020-07-15 | Bridgestone Americas Tire Operations, LLC | Adhesive systems for preparing composites of rubber and polar thermosets |
Family Cites Families (110)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE864605C (en) | 1942-05-12 | 1953-01-26 | Krenzler Fa Emil | Kloeppel, especially for wire mesh machines |
CH299373A (en) | 1942-11-13 | 1954-06-15 | Degussa | Process for the production of moldings from elastomers. |
DE824131C (en) | 1950-02-09 | 1951-12-10 | Otto Meyer | Plansifter with several sieve boxes one above the other with insert frames |
US3627723A (en) | 1968-12-26 | 1971-12-14 | Du Pont | Filler loaded elastomeric compositions having improved extrudability and physical properties |
US3664403A (en) | 1969-07-07 | 1972-05-23 | Ppg Industries Inc | A vulcanized rubber comprising a siliceous pigment, a rubber and an organic coupling agent having an active olefinic linkage |
US3717600A (en) | 1971-01-13 | 1973-02-20 | Merck & Co Inc | Magnesium oxide dispersions |
US4076550A (en) | 1971-08-17 | 1978-02-28 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Reinforcing additive |
US3873489A (en) | 1971-08-17 | 1975-03-25 | Degussa | Rubber compositions containing silica and an organosilane |
US3978103A (en) | 1971-08-17 | 1976-08-31 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Sulfur containing organosilicon compounds |
US3884285A (en) | 1971-10-08 | 1975-05-20 | Ppg Industries Inc | Abrasion-resistant rubber compositions |
US3881536A (en) | 1972-08-31 | 1975-05-06 | Ppg Industries Inc | Rubber vulcanizates |
US3768537A (en) | 1972-11-09 | 1973-10-30 | Ppg Industries Inc | Tire |
US3923712A (en) | 1973-04-25 | 1975-12-02 | Basic Inc | Metal oxide paste dispersions and use as curing agents |
US4029513A (en) | 1973-07-03 | 1977-06-14 | Philadephia Quartz Company | Surface treated silica |
US3938574A (en) | 1973-10-11 | 1976-02-17 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Vulcanizable rubber mixture for tire treads having improved skid resistance |
CA1046681A (en) | 1974-06-25 | 1979-01-16 | Union Carbide Corporation | Mercapto-silane coupler-inorganic powder mixtures |
DE2536674C3 (en) | 1975-08-18 | 1979-09-27 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Crosslinkable mixtures based on rubber, organosilanes and silicate fillers |
DE2837117A1 (en) | 1977-08-30 | 1979-03-15 | Shinetsu Chemical Co | RUBBER ASSEMBLY |
US4179537A (en) | 1978-01-04 | 1979-12-18 | Rykowski John J | Silane coupling agents |
JPS54110250A (en) | 1978-02-17 | 1979-08-29 | Bridgestone Corp | Vulcanizable rubber composition having improved sulfur blooming |
JPS5752416Y2 (en) | 1978-03-09 | 1982-11-15 | ||
US4937104A (en) | 1979-05-31 | 1990-06-26 | Huels Aktiengesellschaft | Process for imparting hydrophobicity to mineral substrates |
US4433013A (en) | 1979-05-31 | 1984-02-21 | Dynamit Nobel Aktiengesellschaft | Process for imparting hydrophobicity to mineral substrates |
DE2933346C2 (en) | 1979-08-17 | 1982-07-01 | Degussa Ag, 6000 Frankfurt | Silane / filler preparations, processes for their production and application of the same |
US4436847A (en) | 1982-05-27 | 1984-03-13 | Ppg Industries, Inc. | Rubber compositions |
US4474908A (en) | 1982-05-27 | 1984-10-02 | Ppg Industries, Inc. | Rubber compositions |
US4431755A (en) | 1982-07-16 | 1984-02-14 | Standard Oil Company (Indiana) | Rubber composition comprising phyllosilicate minerals, silanes, and quaternary ammonium salts |
CA1183628A (en) | 1982-09-01 | 1985-03-05 | Erhardt Fischer | Silica-polymer mixtures |
US4623414A (en) | 1983-01-24 | 1986-11-18 | Sws Silicones Corporation | Process for preparing an aqueous undertread adhesive composition |
US4463120A (en) | 1983-01-24 | 1984-07-31 | Sws Silicones Corporation | Process for preparing an aqueous adhesive composition |
JPS60250078A (en) | 1984-05-28 | 1985-12-10 | Bridgestone Corp | Adhesive for rubber |
WO1988005448A1 (en) | 1987-01-14 | 1988-07-28 | Bridgestone Corporation | Tire |
US4906680A (en) | 1987-04-14 | 1990-03-06 | Bridgestone Corporation | Rubber composition and steel cord-rubber composite body |
US5317051A (en) | 1988-08-22 | 1994-05-31 | Nippon Petrochemicals Co., Ltd. | Surface whitening preventing flame-retardant olefin polymer composition |
US5057601A (en) | 1989-11-06 | 1991-10-15 | Olin Corporation | Process for producing a gel-free coagulated rubber with low ethylenic unsaturation |
DE69119125T3 (en) | 1990-03-02 | 2001-01-11 | Bridgestone Corp | tire |
DE4023537A1 (en) | 1990-07-25 | 1992-01-30 | Degussa | CHEMICALLY MODIFIED ROUGS WITH ORGANOSILICIUM COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
US5178676A (en) | 1990-10-31 | 1993-01-12 | J. M. Huber Corporation | Surfactant treated clays useful as anti-tack agents for uncured rubber compounds |
FR2673187B1 (en) | 1991-02-25 | 1994-07-01 | Michelin & Cie | RUBBER COMPOSITION AND TIRE COVERS BASED ON SAID COMPOSITION. |
US5227431A (en) | 1991-04-12 | 1993-07-13 | Bridgestone/Firestone, Inc. | Diene polymers and copolymers jumped by partial crosslinking and terminated with a substituted imine |
US5552473A (en) | 1992-10-02 | 1996-09-03 | Bridgestone Corporation | Functionalized polymer and rubber compositions produced from solubilized anionic polymerization initiators |
EP0599643B1 (en) | 1992-11-26 | 1996-05-15 | Sumitomo Rubber Industries Ltd. | Rubber compositions of tyre tread |
DE4308311C2 (en) | 1993-03-16 | 1995-04-06 | Degussa | Use of precipitated silicas with high spec. Surface for improving the transparency and brightness properties of vulcanizable, light rubber mixtures, rubber mixtures containing the precipitated silicas and their production |
US5426136A (en) | 1993-03-24 | 1995-06-20 | Ppg Industries, Inc. | Particulate amorphous silica associated with thin polymeric film |
CA2104537A1 (en) | 1993-06-18 | 1994-12-19 | Paul Harry Sandstrom | Silica reinforced rubber composition |
CA2104529A1 (en) | 1993-06-18 | 1994-12-19 | Paul Harry Sandstrom | Tire with silica reinforced tread |
EP0641824B1 (en) | 1993-09-01 | 1999-12-01 | Sumitomo Rubber Industries Ltd. | Rubber composition for tyre treads |
CA2118778A1 (en) | 1993-09-20 | 1995-03-21 | Jean-Claude Joseph Marie Kihn | Tire with silica reinforced tread |
WO1995017458A1 (en) | 1993-12-20 | 1995-06-29 | Ppg Industries, Inc. | Tire tread composition comprising highly reinforcing silica |
ES2245339T3 (en) | 1993-12-29 | 2006-01-01 | Bridgestone Corporation | POLYMERS AND COPOLYMERS OF DIES WITH AN ALCOXISILAN GROUP. |
AT406683B (en) | 1994-04-14 | 2000-07-25 | Semperit Ag | RUBBER BLEND |
US5591794A (en) | 1994-04-19 | 1997-01-07 | Sumitomo Rubber Industries, Ltd. | Rubber composition for tire tread |
ES2116748T3 (en) | 1994-04-20 | 1998-07-16 | Dow Chemical Co | SUBSTANTIALLY LINEAR ETHYLENE POLYMERS, RETICULABLE WITH SILANE AND ITS USES. |
US5422403A (en) | 1994-08-11 | 1995-06-06 | The Goodyear Tire & Rubber Company | Coupled styrene-isoprene-butadiene rubber |
EP0733673B1 (en) | 1994-10-11 | 2000-01-05 | Bridgestone Corporation | Rubber composition improved in static-charge buildup and pneumatic tire made therefrom |
JP2788212B2 (en) | 1994-11-11 | 1998-08-20 | 横浜ゴム株式会社 | Surface-treated carbon black and rubber composition using the same |
US5521309A (en) | 1994-12-23 | 1996-05-28 | Bridgestone Corporation | Tertiary-amino allyl-or xylyl-lithium initiators and method of preparing same |
ES2151635T3 (en) | 1995-01-13 | 2001-01-01 | Bridgestone Corp | PROCESS FOR THE PREPARATION OF PNEUMATIC COVERS. |
US5574109A (en) | 1995-02-01 | 1996-11-12 | Bridgestone Corporation | Aminoalkyllithium compounds containing cyclic amines and polymers therefrom |
IT1274257B (en) | 1995-02-24 | 1997-07-15 | Pirelli | PROCEDURE FOR THE PRODUCTION OF A VULCANIZABLE RUBBER MIXTURE WITH SILICA-BASED REINFORCING CHARGE |
US5674932A (en) | 1995-03-14 | 1997-10-07 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and use in tires |
US5580919A (en) | 1995-03-14 | 1996-12-03 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and use in tires |
US5569697A (en) | 1995-05-08 | 1996-10-29 | Uniroyal Chemical Company, Inc. | Tire tread composition |
DE19519364A1 (en) | 1995-05-26 | 1996-11-28 | Degussa | Mixtures of organosilane compounds, their use in vulcanizable rubber mixtures and molding compositions and the associated mixtures |
US5686523A (en) | 1995-05-26 | 1997-11-11 | Osi Specialties, Inc. | Aqueous curable silane/polymer compositions |
US5872178A (en) | 1995-06-05 | 1999-02-16 | The Goodyear Tire & Rubber Company | Tire with coated silica reinforced rubber tread |
CA2160333A1 (en) | 1995-06-07 | 1996-12-08 | Joseph Kevin Hubbell | Tire with silica reinforced tread |
US5610227A (en) | 1995-06-07 | 1997-03-11 | Bridgestone/Firestone, Inc. | Lithium amino magnesiate polymerization initiators and elastomers having reduced hysteresis |
CA2160324C (en) | 1995-06-07 | 2007-05-01 | Joseph Kevin Hubbell | Tire having silica reinforced tread |
ES2116199B1 (en) | 1995-07-17 | 1999-04-01 | Repsol Quimica Sa | PROCEDURE FOR THE PREPARATION OF USEFUL 1,3-BUTADIENE AND STYRENE COPOLYMERS FOR THE MANUFACTURE OF TIRES WITH LOW ROLLING RESISTANCE AND 1,3-BUTADIENE AND STYRENE COPOLYMERS, SO OBTAINED, |
AT405285B (en) | 1995-09-07 | 1999-06-25 | Semperit Ag | RUBBER BLEND |
US5616655A (en) | 1995-09-11 | 1997-04-01 | The Goodyear Tire & Rubber Company | Sulfur vulcanizable rubber containing sodium thiosulfate pentahydrate |
JPH0987426A (en) | 1995-09-20 | 1997-03-31 | Bridgestone Corp | Production of rubber composition |
CA2168697A1 (en) | 1995-09-22 | 1997-03-23 | Jean-Paul Lambotte | Tire with tread having silica reinforcement |
US5883179A (en) | 1995-10-25 | 1999-03-16 | The Yokohama Rubber Co., Ltd. | Rubber composition comprising carbon black surface treated with silica |
CA2194638A1 (en) | 1996-03-06 | 1997-09-06 | Giorgio Agostini | Asymmetrical siloxy compounds |
CA2197832A1 (en) | 1996-03-07 | 1997-09-07 | Rene Jean Zimmer | Na, k and li salts of siloxy compounds |
US5914364A (en) | 1996-03-11 | 1999-06-22 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
US5780538A (en) | 1996-03-11 | 1998-07-14 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
US5719207A (en) | 1996-03-18 | 1998-02-17 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
US5659056A (en) | 1996-04-10 | 1997-08-19 | Bridgestone Corporation | Stabilization of siloxane terminated polymers |
CA2198663A1 (en) | 1996-06-21 | 1997-12-22 | Richard Robinson Smith | Silica-filled rubber composition containing two different carbon blacks and tire with tread made therefrom |
CA2208712A1 (en) | 1996-08-15 | 1998-02-15 | The Goodyear Tire & Rubber Company | Silica-filled rubber compositions and the processing thereof |
US5708053A (en) | 1996-08-15 | 1998-01-13 | The Goodyear Tire & Rubber Company | Silica-filled rubber compositions and the processing thereof |
US5898047A (en) | 1996-09-23 | 1999-04-27 | The Goodyear Tire & Rubber Company | Tire with outer carbon black reinforced rubber strip for static reduction |
JP3685572B2 (en) | 1996-12-17 | 2005-08-17 | 住友ゴム工業株式会社 | Rubber composition for tire tread |
US5763388A (en) | 1996-12-18 | 1998-06-09 | Dsm Copolymer, Inc. | Process for producing improved silica-reinforced masterbatch of polymers prepared in latex form |
US5777013A (en) | 1997-01-24 | 1998-07-07 | Arizona Chemical Company | Dispersion and adhesion of silica in elastomeric materials |
US5886074A (en) | 1997-03-04 | 1999-03-23 | The Goodyear Tire & Rubber Company | Rubber compositions containing o-salicylsalicyclic acid |
US5916981A (en) | 1997-03-24 | 1999-06-29 | Dow Corning Corporation | Silicone pressure sensitive adhesive compositions |
US5872171A (en) | 1997-04-10 | 1999-02-16 | Bridgestone/Firestone, Inc. | Silica containing tire compositions for suppression of static charge accumulation |
US5723531A (en) | 1997-04-30 | 1998-03-03 | The Goodyear Tire & Rubber Company | Rubber composition and tire having tread thereof |
US6228908B1 (en) | 1997-07-11 | 2001-05-08 | Bridgestone Corporation | Diene polymers and copolymers incorporating partial coupling and terminals formed from hydrocarboxysilane compounds |
US6525118B2 (en) | 1997-07-11 | 2003-02-25 | Bridgestone Corporation | Processability of silica-filled rubber stocks with reduced hysteresis |
US6008295A (en) | 1997-07-11 | 1999-12-28 | Bridgestone Corporation | Diene polymers and copolymers incorporating partial coupling and terminals formed from hydrocarboxysilane compounds |
US5866650A (en) | 1997-07-11 | 1999-02-02 | Bridgestone Corporation | Composition of cyclic amine-initiated elastomers and amorphous silica and process for the production thereof |
US6252007B1 (en) | 1997-07-11 | 2001-06-26 | Bridgestone Corporation | Elastomers having a reduced hysteresis via interaction of polymer with silica surfaces |
US5872176A (en) | 1997-07-11 | 1999-02-16 | Bridgestone Corporation | Addition of salts to improve the interaction of silica with rubber |
US6221943B1 (en) | 1997-07-11 | 2001-04-24 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
US5916961A (en) | 1997-07-11 | 1999-06-29 | Bridgestone Corporation | Amine-initiated elastomers having hysteresis reducing interaction with silica |
US6080809A (en) | 1997-07-30 | 2000-06-27 | Bridgestone/Firestone, Inc. | Kaolin clay in silica tread compounds technical field |
GB9721528D0 (en) | 1997-10-11 | 1997-12-10 | Wms Pvcu Hardware Limited | A device for fastening an openable window or door member to a frame |
US6053226A (en) | 1998-03-13 | 2000-04-25 | The Goodyear Tire & Rubber Company | Rubber composition reinforced with silica and tire with tread thereof |
US6046266A (en) | 1998-09-24 | 2000-04-04 | The Goodyear Tire & Rubber Company | Tire with silica reinforced tread and/or sidewall components |
KR200286123Y1 (en) * | 2002-05-30 | 2002-08-22 | 하나 마이크론(주) | flash memory apparatus with single body type rotary cover |
US20040212966A1 (en) * | 2002-12-02 | 2004-10-28 | Fisher Ken Scott | Integral computer connector cover |
KR100560645B1 (en) * | 2002-12-17 | 2006-03-16 | 삼성전자주식회사 | USB flash memory device displaying memory using information |
US20040215966A1 (en) * | 2003-04-28 | 2004-10-28 | Rainbow Technologies, Inc. | Bending USB token |
US6816121B1 (en) * | 2003-06-18 | 2004-11-09 | Benq Corporation | Motorized rotatable wireless antenna |
US20050181634A1 (en) * | 2004-02-12 | 2005-08-18 | International Business Machines Corp. | Personal device embedded synch connector |
-
1998
- 1998-12-01 US US09/203,438 patent/US6384117B1/en not_active Expired - Fee Related
-
1999
- 1999-11-24 JP JP2000585321A patent/JP2002531617A/en active Pending
- 1999-11-24 DE DE69925861T patent/DE69925861T2/en not_active Expired - Lifetime
- 1999-11-24 WO PCT/US1999/027890 patent/WO2000032684A1/en active IP Right Grant
- 1999-11-24 CA CA002353503A patent/CA2353503C/en not_active Expired - Fee Related
- 1999-11-24 EP EP99965889A patent/EP1135433B1/en not_active Expired - Lifetime
-
2000
- 2000-11-28 US US09/723,674 patent/US6342552B1/en not_active Expired - Lifetime
-
2002
- 2002-03-11 US US10/095,604 patent/US6790889B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
US6790889B2 (en) | 2004-09-14 |
CA2353503A1 (en) | 2000-06-08 |
EP1135433A1 (en) | 2001-09-26 |
DE69925861D1 (en) | 2005-07-21 |
DE69925861T2 (en) | 2006-05-11 |
EP1135433B1 (en) | 2005-06-15 |
US6342552B1 (en) | 2002-01-29 |
WO2000032684A1 (en) | 2000-06-08 |
US6384117B1 (en) | 2002-05-07 |
JP2002531617A (en) | 2002-09-24 |
US20030022972A1 (en) | 2003-01-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2353503C (en) | Improved processability of silica-filled rubber stocks | |
US6608145B1 (en) | Silica-reinforced rubber compounded with an organosilane tetrasulfide silica coupling agent at high mixing temperature | |
EP1326913B1 (en) | Silica-reinforced rubber compounded with mercaptosilanes and alkyl alkoxysilanes | |
EP1282659B1 (en) | Improved processability of silica-reinforced rubber containing an amide compound | |
US8084517B2 (en) | Addition of polar polymer to improve tear strength and processing of silica filled rubber | |
EP1329478B1 (en) | Rubber composition | |
US9752008B2 (en) | Esters of cyclohexane polycarboxylic acids as plasticizers in rubber compounds | |
JPH10506673A (en) | Tire / tread composition | |
US7897661B2 (en) | Polymerized (substituted imidazolium) liquid ionomers for improved handling properties in silica-reinforced rubber compounds | |
WO2001088028A1 (en) | Improved processability of silica-reinforced rubber containing a monofunctional alkyl tin compound | |
EP3592789B1 (en) | Coupled polymer products, methods of making and compositions containing | |
KR101142550B1 (en) | Rubber composition for tire tread and tire manufactured by using the same | |
US7432318B2 (en) | Rubber composition for a tire and pneumatic tire using the same | |
KR20120014449A (en) | Tread rubber composition and tire manufactured by using the same | |
KR101016370B1 (en) | Tire tread rubber composition | |
KR100841179B1 (en) | Tire tread rubber composition reinforced with surface-modified silica having abrasion resistance | |
KR20060136059A (en) | Tire tread rubber composition having an improved wear resistance | |
KR20070000089A (en) | Tire tread rubber composition having an improved wear resistance | |
KR100510946B1 (en) | Rubber composition for tire tread | |
KR100570266B1 (en) | Silica and Silane Coupling Reinforced Silica Tread Compound | |
JPH11181159A (en) | Rubber composition | |
EP4169980A1 (en) | Rubber compositions | |
KR100871280B1 (en) | Rubber compositions for tire tread | |
KR101311253B1 (en) | Tread rubber composition and tire manufactured by using the same | |
KR100815007B1 (en) | Tire tread rubber composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKLA | Lapsed |