Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2000-09-21
2003-01-28
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C205S159000, C525S331900
Reexamination Certificate
active
06512040
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to a carbon black modified by a two step process in which carbon black is initially treated with functional monomers by an electropolymerization process to form a functionalized carbon black having an initial polymer attached to, of grafted to, the carbon black following which
(A) at least one diene monomer, or
(B) living anionic catalysis prepared polymer, is introduced to the functionalized carbon black to continue the polymerization, starting from a living end of the initially formed polymer, and thereby form an extended diene-based polymer. By the addition of the diene monomer or the live anionic polymer to form the associated extended diene-based polymer, it is contemplated that the modified carbon black is rendered more compatible with diene-based elastomers. Such modified carbon black may be used, for example, as reinforcement for component(s) of various articles of manufacture, including tires. Accordingly, an article of manufacture is provided, such as for example a tire, having at least one component of a rubber composition which contains such modified carbon black.
BACKGROUND OF THE INVENTION
Preparation of a modified carbon black by an electropolymerization process may be accomplished, for example, by providing a suspension of carbon black particles and/or carbon black fibers in a suitable solvent and causing electropolymerization of functional monomers onto the surface of such carbon black
Exemplary of such process is seen in WO 99/02614 and WO 99/20697 patent publications.
However, it is contemplated herein that, where it is intended that such modified carbon blacks be used to reinforce various diene-based elastomers, such carbon blacks can be further modified to enhanced their usefulness for blending with diene-based elastomers.
In the description of this invention, the term “phr” where used herein, and according to conventional practice, refers to “parts of a respective material per 100 parts by weight of rubber, or elastomer”.
The terms “rubber” and “elastomer” if used herein, may be used interchangeably, unless otherwise prescribed. The terms “rubber composition”, “compounded rubber” and “rubber compound”, if used herein, are used interchangeably to refer to “rubber which has been blended or mixed with various ingredients and materials” and such terms are well known to those having skill in the rubber mixing or rubber compounding art.
SUMMARY AND PRACTICE OF THE INVENTION
In accordance with this invention, an electropolymerization surface modified carbon black is prepared by a method which comprises the steps of treating carbon black particles and/or carbon black fibers by:
(A) Forming a functional polymer by electropolymerization onto the surface of carbon black selected from at least one of carbon black particles and carbon black fibers by treating a dispersion of said carbon black particles and/or carbon black fibers in a combination of a monomer and solvent by introducing a negatively charged cathode and a positively charged anode individually to said dispersion with an electrical potential said cathode and anode to cause an electropolymerization of said monomer to form a living polymer (ionic or radicalar) on the surface of said carbon black particles and/or fibers, wherein said monomer and solvent combination is selected from;
(1) combination of monomer “X” and solvent selected from acrylic and methacrylic solvents, or
(2) monomer “Y” and aprotic solvent, followed by
(B) introducing at least one polymerizable monomer to the living ends of said functional polymer formed on the surface of said carbon black particles and/or carbon black fibers of step (A) in said solvent solution and polymerizing said polymerizable monomer thereon in the presence of an anionic catalyst, and preferably in the presence of an anionic polymerization randomizing modifier, to form an elastomeric extension to said functional polymer carbon black particles and/or functionalized carbon black fibers, or
(C) quenching a living, anionic catalysis organic solution prepared elastomer by introducing said functionalized carbon black particles and/or functionalized carbon black fibers of said step (A) to said living elastomer, wherein said living elastomer is prepared by polymerizing at least one polymerizable monomer in the presence of an anionic catalyst, and preferably in the presence of an anionic catalyst modifier, to thereby form an elastomeric extension to said functionalized carbon black particles and/or said functionalized carbon black fibers, and
(D) recovering said treated carbon black particles and/or carbon black fibers;
wherein said solvent for said electropolymerization contains an electrolyte for providing a suitable electrical conductivity for the organic solvent solution for the electric current to effectively flow between said anode and said cathode;
wherein said polymerizable monomers for said step (B) and step (C) are selected from at least one of
(1) isoprene and 1,3-butadiene, and
(2) a combination of at least one of isoprene and 1,3-butadiene together with at least one of styrene and alphamethyl styrene, preferably styrene;
wherein said anionic catalysis prepared elastomer is preferably selected from cis 1,4-polybutadiene, cis 1,4-polyisoprene, isoprene/butadiene copolymer and styrene/isoprene/butadiene terpolymer,
wherein said combination of monomer “X” and solvent is a combination selected from acrylonitrile/acetonitrile, acrylonitrile/propylene carbonate, acrylonitrile/dimethylformamide, acrylonitrile/dimethacrylamide, acrylonitrile/pyridine, ethylacrylate/dimethylformamide, acrylonitrile/dimethacrylamide, ethylacrylate/pyridine, silyated-2-hydroxyethylmethacrylate/dimethylformamide, methylmethacrylate/dimethylformamide, glycidylmethacyrlate/dimethylformamide, n-butylacrylate/dimethylformamide, ter-butylacrylate/dimethylformamide, allylmethacrylate/dimethylformamide, pyrrole/dimethylformamide, thiophene/dimethylformamide and vinylpiridine/dimethylformamide; and
wherein said combination of monomer “Y” and solvent is a combination selected from acrylonitrile/acetonitrile, acrylonitrile/dimethylacetamide, acrylonitrile/N,N′-dimethylformamide, acrylonitrile/pyridine, ethylacrylate/N,N′dimethylformamide, ethylacrylate/pyridine, trimethylsiloxyethylmethacrylate/N,N′dimethylformamide, methylmethacrylate/N,N′dimethylformamide, ter-butylacrylate/N,N′dimethyhlformamide, glycidylmethacrylate/N,N′dimethyhlformamide, n-butylacrylate/N,N′dimethylformamide, allylmethacrylate/N,N′dimethylformamide, pyrrole/dimethylformamide, thiophene/dimethylformamide and vinylpiridine/dimethylformamide.
It is to be appreciated that, for said electropolymerization of monomers onto the surface of said carbon black particles and/or carbon black fibers, the electrolysis bath also typically contain an electrolyte for a purpose of providing a suitable electrical conductivity for the organic solvent solution to enable the electric current to effectively flow from one electrode to the other and to cause the electrochemical reaction to proceed (electrical current flow between the aforesaid anode and cathode, as the case may be). A typical example of an electrolyte is tetraethyl ammonium perchlorate.
In practice, said anionic catalysis prepared elastomers can be prepared by polymerizing said polymerizable monomer(s) in an organic solvent in the presence of an anionic catalyst such as, for example, a butyl lithium catalyst, for which an anionic polymerization modifier is used for randomizing the prepared elastomer such as, for example, tetranethylene diamine (TMEDA) which is understood to be a typical modifier, for example, for butyl lithium catalysis of 1,3-butadiene to from a relatively randomized cis 1,4-polybutadiene.
Significant aspects of two step procedure for the invention is that in addition to
(A) first forming a functionalized carbon black by forming what is considered herein to be a significant covalent linkage between an electropolymerization formed first polymer and the carbon black particles and/
Agostini Giorgio
Edme Materne Thierry Florent
Lee Rip A
The Goodyear Tire & Rubber Company
Wu David W.
Young, Jr. Henry C.
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