Source: http://www.google.com/patents/US7718737?dq=7,194,691
Timestamp: 2016-06-29 14:56:37
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Matched Legal Cases: ['Application No. 02819527', 'Application No. 02819527', 'Application No. 02819527', 'Application No, 10', 'Application No. 05742316', 'Application No. 02807196', 'Application No. 02807196', 'Application No. 582224', 'Application No. 582224']

Patent US7718737 - Rubber composition containing functionalized polymer nanoparticles - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsA polymer nanoparticle is provided. The nanoparticle includes an inner layer having alkenylbenzene monomer units. The nanoparticle further includes an outer layer having monomer units selected from conjugated dienes, alkylenes, alkenylbenzenes, and mixtures thereof. The nanoparticle has at least one...http://www.google.com/patents/US7718737?utm_source=gb-gplus-sharePatent US7718737 - Rubber composition containing functionalized polymer nanoparticlesAdvanced Patent SearchPublication numberUS7718737 B2Publication typeGrantApplication numberUS 10/791,177Publication dateMay 18, 2010Filing dateMar 2, 2004Priority dateMar 2, 2004Fee statusPaidAlso published asUS7897690, US20090156757, US20100016472Publication number10791177, 791177, US 7718737 B2, US 7718737B2, US-B2-7718737, US7718737 B2, US7718737B2InventorsXiaorong Wang, James E. Hall, Georg G. A. B�hm, Chenchy Jeffrey LinOriginal AssigneeBridgestone CorporationExport CitationBiBTeX, EndNote, RefManPatent Citations (242), Non-Patent Citations (273), Referenced by (13), Classifications (8), Legal Events (2) External Links: USPTO, USPTO Assignment, EspacenetRubber composition containing functionalized polymer nanoparticles
US 7718737 B2Abstract
A polymer nanoparticle is provided. The nanoparticle includes an inner layer having alkenylbenzene monomer units. The nanoparticle further includes an outer layer having monomer units selected from conjugated dienes, alkylenes, alkenylbenzenes, and mixtures thereof. The nanoparticle has at least one functional group associated with the outer layer. Applications of use as additives for rubber, including the rubber compositions, are also provided.
b. an outer layer including monomer units selected from the group consisting of conjugated diene, alkylene, alkenylbenzene, and mixtures thereof; and
c. at least one functional group associated with the outer layer;
wherein said nanoparticle has a mean average diameter of less than about 100 nm;
wherein said functional group is selected from the group consisting of maleic anhydride, amine, azo, carboxylic acid, epoxide, amino, and mixtures thereof;
provided that the functional group is not the product of an anionic initiator.
2. The nanoparticle of claim 1 wherein said nanoparticle is substantially monodisperse.
3. The nanoparticle of claim 1 wherein said conjugated dienes are selected from the group consisting of C4-C8 conjugated dienes and mixtures thereof.
4. The nanoparticle of claim 1 wherein said alkenylbenzene monomer units are selected from the group consisting of styrene, α-methyl styrene, 1-vinyl naphthalene, 2-vinyl naphthalene, 1-α-methyl vinyl naphthalene, 2-α-methyl vinyl naphthalene, vinyl toluene, methoxystyrene, t-butoxystyrene, and the like, as well as alkyl, cycloalkyl, aryl, alkaryl, and aralkyl derivatives thereof, in which the total number of carbon atoms in the combined hydrocarbon is not greater than 18, as well as any di- or tri-substituted aromatic hydrocarbons, and mixtures thereof.
5. The nanoparticle of claim 1 wherein said alkylene monomer units are formed by hydrogenating said conjugated diene monomer units.
6. The nanoparticle of claim 1 wherein said nanoparticles are crosslinked with a cross-linking agent.
7. The nanoparticle of claim 1 wherein said inner layer further includes conjugated diene monomer units.
8. The nanoparticle of claim 1, wherein the nanoparticle is formed by polymerizing alkenylbenzene monomer and conjugated diene monomer in a hydrocarbon solvent to form a diblock polymer;
forming micelles of said diblock polymer;
adding at least one crosslinking agent to the micelles to form crosslinked nanoparticles having an inner layer including alkenylbenzene monomer units and an outer layer including monomer units selected from the group consisting of alkenylbenzenes, conjugated dienes, and mixtures thereof; and
after forming micelles of the diblock polymer or after forming crosslinked nanoparticles, then combining said micelles or nanoparticles with at least one functional group to form functionalized nanoparticles.
9. The nanoparticle of claim 8 wherein the polymerizing step is performed in the presence of a lithium initiator.
10. The nanoparticle of claim 8 wherein said conjugated diene monomer units are selected from the group consisting of C4-C8 conjugated dienes and mixtures thereof.
11. The nanoparticle of claim 8 wherein said alkenylbenzene monomer units are selected from the group consisting of styrene, α-methyl styrene, 1-vinyl naphthalene, 2-vinyl naphthalene, 1-a-methyl vinyl naphthalene, 2-α-methyl vinyl naphthalene, vinyl toluene, methoxystyrene, t-butoxystyrene, and the like, as well as alkyl, cycloalkyl, aryl, alkaryl, and aralkyl derivatives thereof, in which the total number of carbon atoms in the combined hydrocarbon is not greater than 18, as well as any di- or tri-substituted aromatic hydrocarbons, and mixtures thereof.
12. The nanoparticle of claim 8 wherein said functional group is selected from the group consisting of maleic anhydride, azo, epoxide and mixtures thereof.
13. The process of claim 8 wherein the nanoparticle is functionalized before it is crosslinked.
14. A nanoparticle comprising:
wherein said alkylene monomer units are formed by hydrogenating said conjugated diene monomer units;
wherein functional groups are located throughout the outer layer of the nanoparticle.
15. The nanoparticle of claim 14 wherein said functional group is complexed with a metal.
16. The nanoparticle of claim 1 wherein said functional group is complexed with a metal.
17. The nanoparticle of claim 1, wherein said functional group is selected from the group consisting of maleic anhydride, azo, epoxide, and mixtures thereof.
18. A nanoparticle comprising:
a. a cross-linked inner layer including alkenylbenzene monomer units,
wherein said functional group is polar;
19. The nanoparticle of claim 18 wherein said functional group is selected from the group consisting of maleic anhydride, azo, epoxide, and mixtures thereof.
20. The nanoparticle of claim 18 wherein said functional group is complexed with a metal.
21. The nanoparticle of claim 18 wherein the functional group is only associated with the outer layer after micelle formation or only after the inner layer of the nanoparticle is crosslinked.
22. The nanoparticle of claim 20 wherein the metal group is selected from the group consisting of: Cu, Ti, Fe, Cd, Ni, Pd, and mixtures thereof.
23. The nanoparticle of claim 14 wherein the functional group is associated with the outer layer only after micelle formation.
24. The nanoparticle of claim 18 provided that the functional group is not the product of an anionic initiator.
25. The nanoparticle of claim 1 wherein functional groups are located throughout the outer layer of the nanoparticle. Description
The present invention relates to polymer nanoparticles, methods for their preparation, and their use as, for example, additives for rubber and tire compositions. The invention advantageously provides mechanisms for surface modifications, functionalization, and general characteristic tailoring to improve performance in various host compositions.
A polymer nanoparticle is provided. The nanoparticle includes an inner layer having alkenylbenzene monomer units. The nanoparticle further includes an outer layer having monomer units selected from conjugated dienes, alkylenese, alkenylbenzenes, and mixtures thereof. The nanoparticle has at least one functional group associated with the outer layer.
A process for forming functionalized nanoparticles is also provided. The process includes polymerizing alkenylbenzene monomer and conjugated diene monomer in a hydrocarbon solvent to form a diblock polymer. After formation of the diblock polymer, micelles of the diblock polymer are formed. At least one crosslinking agent is added to the micelles to form crosslinked nanoparticles having a poly(alkenylbenzene) core and an outer poly(conjugated diene) layer from the micelles. The poly(conjugated dienee) layer is optionally hydrogenated to form nanoparticles containing a poly(alkenylbenzene) core and a polycrystalline outer layer. After formation, the nanoparticles are reacted with a compound including at least one functional group to form functionalized nanoparticles. The reaction may be carried out before or after hydrogenation.
According to a further embodiment, a polymer nanoparticle including a poly(alkynylbenzene) core, a copolymer outer layer and at least one functional group attached thereto is also provided. The copolymer outer layer includes at least an alkenylbenzene monomer unit and a conjugated diene monomer unit. The nanoparticle has a mean average diameter less than about 100 nm.
A process for forming a polymer nanoparticle with a copolymer outer layer and at least one functional group attached thereto is also provided. The process includes copolymerizing at least one alkenylbenzene monomer and at least one conjugated diene to form a random copolymer. After the polymerization is substantially completed, an additional charge of alkenylbenzene monomer is made and polymerized onto the copolymer chain ends to form a diblock copolymer. Micelles of the diblock copolymer are formed and at least one crosslinking agent is added to the polymerization mixture to form crosslinked nanoparticles. The nanoparticles have a mean average diameter less than about 100 nm. After formation, the nanoparticles are reacted with a compound including at least one functional group to form functionalized nanoparticles.
FIG. 1 is a graph depicting the dynamic modulus (G′) temperature dependence of rubber composition prepared in accordance with EXAMPLES 3, 4, and 5.
FIG. 2 is a graph depicting the G′ strain dependence of rubber particles prepared in accordance with EXAMPLES 3, 4, and 5.
FIG. 3 is a TEM photograph of polymer nanoparticles formed in accordance with EXAMPLE 6.
FIG. 4 is a TEM photograph of maleated polymer nanoparticles formed in accordance with EXAMPLE 7.
FIG. 5 is a TEM photograph of metallized polymer nanoparticles formed in accordance with EXAMPLE 13.
FIG. 6 is a TEM photograph of metal nanocomposites formed in accordance with EXAMPLE 13.
One exemplary functionalied polymer nanoparticle of the present invention is formed from diblock polymer chains having at least a poly(conjugated diene) block and a poly(alkenylbenzene) block. The poly(alkenylbenzene) blocks may be crosslinked to form the desired nanoparticles. After nanoparticle formation, the resultant nanoparticles are reacted with an organic compound to form functionalized nanoparticles. The functionalized nanoparticles preferably have at least one functional group associated with an outer layer or on an exterior of the nanoparticle. The funcationlzied nanoparticles have diameters—expressed as a mean average diameter—that are preferably less than about 100 nm, more preferably less than about 75 nm, and most preferably less than about 50 nm. The nanoparticles preferably are substantially monodisperse and uniform in shape. The dispersity is represented by the ratio of Mw to Mn, with a ratio of 1 being substantially monodisperse. The polymer nanoparticles of the present invention preferably have a dispersity less than about 1.3, more preferably less than about 1.2, and most preferably less than about 1.1. Moreover, the nanoparticles are preferably spherical, though shape defects are acceptable, provided the nanoparticles generally retain their discrete nature with little or no polymerization between particles.
The diblock polymer, preferably has Mw of about 5,000 to 200,000, more preferably between about 10,000 and 100,000. A typical diblock polymer will be comprised of 5 to 95% by weight conjugated diene and 5 to 95% by weight vinyl-substituted aromatic hydrocarbon, more preferably 20 to 80% by weight, and most preferably 50 to 60% by weight of each contributed monomer type.
A 1,2-microstructure controlling agent or randomizing modifier is optionally used to control the 1,2-microstructure in the conjugated diene contributed monomer units, such as 1,3-butadiene, of the nanoparticle. Suitable modifiers include hexamethylphosphoric acid triamide, N,N,N′,N-tetramethylethylene diamine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, 1,4-diazabicyclo [2.2.2] octane, diethyl ether, triethylamine, tri-n-butylamine, tri-n-butylphosphine, p-dioxane, 1,2-dimethoxy ethane, dimethyl ether, methyl ethyl ether, ethyl propyl ether, di-n-propyl ether, di-n-octyl ether, anisole, dibenzyl ether, diphenyl ether, dimethylethylamine, bis-oxalanyl propane, tri-n-propyl amine, trimethyl amine, triethyl amine, N,N-dimethyl aniline, N-ethylpiperidine, N-methyl-N-ethyl aniline, N-methylmorpholine, tetramethylenediamine, oligomeric oxolanyl propanes (OOPs), 2,2-bis-(4-methyl dioxane), and bistetrahydrofuryl propane. A mixture of one or more randomizing modifiers also can be used. The ratio of the modifier to the monomers can vary from a minimum as low as 0 to a maximum as great as about 4000 millimoles, preferably about 0.01 to 3000 millimoles, of modifier per hundred grams of monomer currently being charged into the reactor. As the modifier charge increases, the percentage of 1,2-microstructure (vinyl content) increases in the conjugated diene contributed monomer units in the outer layer of the polymer nanoparticle. The 1,2-microstructure content of the conjugated diene units is preferably between about 5 and 95%, more preferably between about 1 and 99%.
After micelle formation, or alternatively after crosslinking, the polydiene blocks may be functionalized to form a an outer layer funcationalized polymer nanoparticle. The functional group is preferably selected from the group consisting of maleimide, hydroxyl, carboxy, formyl, azocarboxy, epoxide, amino, and mixtures thereof.
Without being bound by theory, it is believed that a funcational group is added to the nanoparticle by reacting a compound including the desired functional group with the polydiene blocks of the nanoparticles.
The reaction is preferably carried out in a hydrocarbon solvent in an inert atmosphere at a temperature between about 100 and 250� C. Suitable solvents includes aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, nonane, decane, and the like, as well as alicyclic hydrocarbons, such as cyclohexane, methyl cyclopentane, cyclooctane, cycloheptane, cyclononane, cyclodecane, and the like. These hydrocarbons may be used individually or in combination. Of course, other known methods for conducting such reactions are contemplated.
In an alternative embodiment, an outer layer of the funcationalized polymer nanoparticle is a copolymer including at least one alkenylbenzene monomer unit and at least one conjugated diene monomer unit. The copolymer may be random or ordered. Accordingly, the outer layer may include an SBR rubber. Herein throughout, references to a poly (conjugated diene) outer layer are understood to include copolymers of the type described here.
The density of the poly (conjugated diene) outer layer of the nanoparticles may be controlled by manipulating the ratio of diblock to mono-block polymer chains. This ratio may be manipulated by altering the amount of initiator added during each step of the polymerization process. For example, a greater amount of initiator added during the polymerization of the conjugated diene monomer than added during the polymerization of the alkenylbenzene monomer would favor diblock formation over mono-block formation resulting in a high density outer layer. Conversely, a greater amount of initiator added during the polymerization of the alkenylbenzene monomer than added during the polymerization of the conjugated diene monomer would favor mono-block formation over diblock formation, resulting in a low density outer layer. The ratio of mono-blocks to diblocks can be from 1 to 99, preferably 10 to 90, more preferably 20 to 80.
Functionalized nanoparticles produced in accordance with the present invention may be advantageously utilized in the formation of metal nanocomposites which can be advantageously added to rubber compositions. The formation of metal nanocomposites is preferably carried out by exposing functionalized nanoparticles to metals, preferably metals in solution. The metal is then capable of complexing with functional groups located throughout an outer layer of the funcationalized nanoparticle. The poly(conjugated diene) and/or polyalkylene layer may restrict the growth of the metal nanocomposites, thus providing size control of the metal nanocomposites. Metals contemplated for use in the present invention include those known in the art as useful in the form of nanocomposites, including but not limited to Cu, Ti, Fe, Cd, Ni, Pd, and mixtures thereof. The formation of the metal nanocomposites is preferably carried out at temperature of between about 0 and 100� C., more preferably between about 0 and 5� C. Preferred solvents useful in the formation include toluene, THF, water, alcohol, and mixtures thereof.
Hydrogenated functionalized nanoparticles prepared in accordance with the present invention may also find application in hard disk technology.
Serious damage to the magnetic disks, including loss of valuable information, can result by introducing gaseous and particulate contaminates into the disk drive assembly housing. To substantially prevent or reduce the introduction of gaseous and particulate contaminants into the disk drive housing, a flexible sealing gasket is disposed between the disk drive mounting base (support) plate and the disk drive assembly housing or cover plate. A sealing gasket is usually prepared by punching out a ring-shaped gasket from a sheet of cured elastomer. The elastomeric gasket obtained is usually attached to the base plate of the disk drive assembly mechanically, such as affixing the gasket with screws, or adhesives. The hydrogenated nanoparticles, when compounded with a polyalkylene and a rubber, demonstrate a tensile strength comparable to that necessary in hard disk drive compositions.
Funcationalized nanoparticles prepared in accordance with the present invention, whether hydrogenated or non-hydrogenated may also be blended with a variety of thermoplastic elastomers, such as SEPS, SEBS, EEBS, EEPE, polypropylene, polyethylene, and polystyrene. For example, nanoparticles with hydrogenated isoprene outer layers may be blended with a SEPS thermoplastic to improve tensile strength and thermostability. These blends of thermoplastic elastomer and maleated nanoparticles would typically be extended as known in the art. For example, suitable extenders include extender oils and low molecular weight compounds or components. Suitable extender oils include those well known in the art such as naphthenic, aromatic and paraffinic petroleum oils and silicone oils.
(1) Softening agents, namely aromatic naphthenic and parraffinic softening agents for rubbers or resins; (2) Plasticizers, namely plasticizers composed of esters including phthalic, mixed pthalic, aliphatic dibasic acid, glycol, fatty acid, phosphoric and stearic esters, epoxy plasticizers, other plasticizers for plastics, and phthalatc, adipatc, scbacatc, phosphatc, polycthcr and polyester plasticizers for NBR; (3) Tackifiers, namely coumarone resins, coumaroneindene resins, terpene phenol resins, petroleum hydrocarbons and rosin derivative; (4) Oligomers, namely crown ether, fluorine-containing oligomers, polybutenes, xylene resins, chlorinated rubber, polyethylene wax, petroleum resins, rosin ester rubber, polyalkylene glycol diacrylate, liquid rubber (polybutadiene, styrene/butadiene rubber, butadiene-acrylonitrile rubber, polychloroprene, etc.), silicone oligomers, and poly-α-olcfins; (5) Lubricants, namely hydrocarbon lubricants such as paraffin and wax, fatty acid lubricants such as higher fatty acid and hydroxy-fatty acid, fatty acid amide lubricants such as fatty acid amide and alkylene-bisfatty acid amide, ester lubricants such as fatty acid-lower alcohol ester, fatty acid-polyhydric alcohol ester and fatty acid-polyglycol ester, alcoholic lubricants such as fatty alcohol, polyhydric alcohol, polyglycol and polyglycerol, metallic soaps, and mixed lubricants; and, (6) Petroleum hydrocarbons, namely synthetic terpene resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, aliphatic or alicyclic petroleum resins, polymers of unsaturated hydrocarbons, and hydrogenated hydrocarbon resins. Other appropriate low-molecular weight organic materials include latexes, emulsions, liquid crystals, bituminous compositions, and phosphazenes. One or more of these materials may be used in as extenders.
One application for functionalized nanoparticle containing rubber compounds is in tire rubber formulations.
Preferred rubbers are conjugated diene polymers, copolymers, or terpolymers of conjugated diene monomers and monovinyl aromatic monomers, can be utilized as 100 parts of the rubber in the tread stock compound, or they can be blended with any conventionally employed treadstock rubber which includes natural rubber, synthetic rubber and blends thereof. Such rubbers are well known to those skilled in the art and include synthetic polyisoprene rubber, styrene-butadiene rubber (SBR), styrene-isoprene rubber, styrene-isoprene-butadiene rubber, butadiene-isoprene rubber, polybutadiene, butyl rubber, neoprene, acrylonitrile-butadiene rubber (NBR), silicone rubber, the fluoroelastomers, ethylene acrylic rubber, ethylene-propylene rubber, ethylene-propylene terpolymer (EPDM), ethylene vinyl acetate copolymer, epichrolohydrin rubber, chlorinated polyethylene-propylene rubbers, chlorosulfonated polyethylene rubber, hydrogenated nitrile rubber, tetrafluoroethylene-propylene rubber and mixtures thereof.
Examples of reinforcing silica fillers which can be used in the vulcanizable elastomeric composition include wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, and the like. Other suitable fillers include aluminum silicate, magnesium silicate, and the like. Among these, precipitated amorphous wet-process, hydrated silicas are preferred. Silica can be employed in the amount of about one to about 100 parts per hundred parts of the elastomer, preferably in an amount of about 5 to 80 phr and, more preferably, in an amount of about 30 to about 80 phrs. The useful upper range is limited by the high viscosity imparted by fillers of this type. Some of the commercially available silica which can be used include, but are not limited to, HiSil� 190, HiSil� 210, HiSil� 215, HiSil� 233, HiSil� 243, and the like, produced by PPG Industries (Pittsburgh, Pa.). A number of useful commercial grades of different silicas are also available from DeGussa Corporation (e.g., VN2, VN3), Rhone Poulenc (e.g., Zeosil� 1165 MP), and J. M. Huber Corporation.
The rubber can be compounded with all forms of carbon black, optionally additionally with silica. The carbon black can be present in amounts ranging from about one to about 100 phr. The carbon blacks can include any of the commonly available, commercially-produced carbon blacks, but hose have a surface are of at least 20 m2/g and, or preferable, at least 35 m2/g up to 200 m2/g or higher are preferred. Among useful carbon blacks are furnace black, channel blacks, and lamp blacks. A mixture of two or more of the above blacks can be used in preparing the carbon black products of the invention. Typical suitable carbon black are N-110, N-220, N-339, N-330, N-352, N-550, N-660, as designated by ASTM D-1765-82a.
Specifically, the above-described functionalized nanoparticle containing rubber compounds are contemplated for use in rubber compounds used to make tire treads and side walls due to the enhanced reinforcement capabilities of the present nanoparticles. The higher dynamic modulus (G′) and its lower temperature dependence along with the lower hysteresis values ag high temperature leads to the improved cornering, handling, dry, snow, and wet traction, rolling resistance, dispersion, and aging properties of the resultant tire compositions. Improved aging properties, thermal aging (high temperature) or mechanical aging (static or dynamic deformation cycles), include retention of the G′ modulus, hysteresis, mechanical strengths, etc. Tin-functionalized nanoparticles are especially suited for use in tire compositions. Nanoparticles including a copolymer outer layer are also suitable for use in such tire compositions, because the longer copolymer chains in the outer layer leads to greater diffusion of the host rubber composition into the outer layer of the nanoparticle.
Similarly, the functionalized nanoparticles can be added into typical plastic materials, including polyethylene, polypropylene, polystyrene, polycarbonate, nylon, polyimides, etc. to for example, enhance impact strength, tensile strength and damping properties.
Of course, the present inventive functionalized nanoparticles are also suited to other presently existing applications for nanoparticles, including the medical field, e.g. drug delivery and blood applications, information technology, e.g. quantum computers and dots, aeronautical and space research, energy, e.g., oil refining, and lubricants.
Another application for such rubbers is in situations requiring superior damping properties, such as engine mounts and hoses (e.g. air conditioning hoses). Rubber compounds of high mechanical strength, super damping properties, strong resistance to creep are demanded in engine mount manufacturers. In engine mount, a rubber, because it sits most of its life in a packed and hot position require rubbers of very good characteristics. Utilizing the functionalized nanoparticles within selected rubber formulations can improve the characteristics of the rubber compounds.
The following examples are provided to help illustrate the present invention. The examples are not intended to limit the scope of the invention as defined by the appended claims.
Synthesis of PBD-PS Micelle Polymers
All of the polymers were prepared by anionic polymerization in hexane through three stages. In the first stage, butadiene (BD) and styrene (ST) were charged into the reactor which the polymerization was initiated with butyl lithium (BuLi) and the microstructure was controlled by adding oligomeric oxolanyl propane polar randomizer (OOPS). The polymer molecular weight (MW) was controlled by adjusting the ratio of the monomers and the level of imitator used. After nearly all of the monomers were consumed in the first stage, additional styrene was charged for polymerization for certain period of time to form the micelle PS core in the second stage. The 50 mL of the divinyl benzene (DVB) was charged into the reactor in the third stage to crosslink the micelle PS domain. The stoichiometry of the initiator, modifier, monomers, and DVB used to prepare these micelle polymers are detailed in Table 1. The polymerization temperature was maintained at 57� C. in all of the stages. All of these polymers were isolated by the addition of a mixture of acetone and isopropanol in a volume ratio of 95% to 5%. Tet-butyl-2 hydroxy toluene (BHT) was then added into the polymer as an antioxidant.
Stiochimetry of the initiator, modifier, monomers,
and DVB employed for polymerization Process.
butadiene in
Synthesis of Maleated Functionalized PBD-PS Micelle Polymers (M-PBD-PS)
Sixty grams of maleic anhydride in 300 ml of DTDP oil under the continuous purge of nitrogen gas were heated to 170� C. 500 mL of the hexane solution that contained 10% of the product from Example 1, PBD-PS, was slowly added into the maleic anhydride solution in two hours. After the completion of the addition of PBD-PS, it was heated to 180� C. for 30 minutes before dropping into toluene solvent and isolated with isopropanol. 2.8 wt % of maleic anhydride was found covalently bonded to the PBD layer of the M-PBD-PS nanoparticles, as confirmed by 13C NMR analysis. The maleated nanoparticles are not soluble in hexane.
The characterization of these polymers include Mw, molecular weight distribution (MWD), polymer microstructure, and Tg are displayed in Table 2.
Characterization data of nanoparticles from Examples 1 and 2
SBR-Duradiene 715
Mw of the polymer
1,026,960
Mw of single PS in
micelle core
Cis BR %
Trans BR %
Compounding of PBD-PS and M-PBD-PS Nanoparticles
Three stocks of rubber compounds were prepared using the formulation and mixing conditions shown in Tables 3 and 4. Seventy phr of SBR Duradiene 715 and thirty parts of polybutadiene were used to prepare example 3, the control. An addition 10 phr of PBD-PS or M-PBD-PS was added to example 3 to form examples 4 and 5. The composition of the polymers used for each of the examples is listed in Table 5. The final stock was sheeted and then was subsequently molded at 171� C. for 15 minutes.
Formulation used to prepare rubber compounds of Examples 3-5
Silica (HiSil 190)
Disulfide silane
Antioxidant [N-(1,3-dimethlybutyl)-N′-phenyl-p-
phenylene-diamine]
Accelerator [N-cyclohexyl-2-benzothiasole-
sulfenaimde]
The mixing conditions used to prepare
the rubber compounds of Examples 3-5
Charging polymers and nanoparticles
(where included)
Charging silica and all pigments
Charging remilled stock and silane
SBR, BR, PBD-PS and M-PBD-PS used to prepare examples 3-5
SBR-phr
BR-phr
PBD-PS phr
M-PBD-PS phr
The processing of the rubber compound was evaluated by examining the compound Mooney and scorch data along with the curing characteristic data. The Mooney viscosity and the curing characteristics of the uncured stocks are shown in Table 6. Mooney viscosity measurements were conducted at 130� C. using a large rotor. The Mooney viscosity data was recorded as the torque when rotor has rotated for 4 minutes. The sample was preheated at 130� C. for 1 minute before the rotor starts. T5 is the time required to increase 5 Mooney units during the Mooney-scorch measurement. It is used as an index to predict how fast the compound viscosity will rise during processing such as extrusion processing. TS2 and T90 are the time when torque rises to 2% and 90% of the total increase during curing characterization experiment at 171� C. They are used to predict the speed of the viscosity build-up (TS2) and the curing rate during the curing process.
Mooney scorch and curing characteristics
T5 scorch @
ML1+4 @
The Scorch T5, TS2, and curing characteristics of examples 4-5 were found to be comparable to the control (example 3). With the exception of the higher compound Mooney found for example 3, it is apparent that addition of ABR-PS polymer in rubber compounds will not affect the processing. The higher Mooney in silica compound can be adjusted by use of processing aids or shielding agents. Therefore, it is not expected to encounter apparent processing problems with these stocks containing nanoparticles.
Tensile Mechanical Properties:
The tensile mechanical properties of Examples 3-5 are listed in Table 7. The tensile mechanical properties were measured using the standard procedure described in ASTM-D 412 at 25� C. The tensile test specimens are round rings with a dimension of 0.05 inches in width and 0.075 inches in thickness. A specific gauge length of 2.54 cm is used for the tensile test.
Improvements in the tensile mechanical properties, including elongation at break (10%) and tensile toughness (15%), by addition of nanoparticles are evident. However, at an elevated temperature of 100� C., the improved mechanical properties found in PBD-PS examples at room temperature are not reproducible (as seen in Table 8, below). By replacing the PBD-PS nanoparticles with M-PBD-PS, better mechanical properties were obtained, as shown in Table 8.
Tensile mechanical properties at 100� C.
The superior elevated temperature mechanical properties were also confirmed by the tensile mechanical properties obtained from dumbbell shape samples (Table 9).
TABLE 9 Tensile mechanical properties at 100� C. obtained from tensile test on dumbbell-shaped samples M50 M300 Strength, Tb Elongation at Toughness Example (Mpa) (Mpa) (Mpa) break, Eb, % (Mpa) 3 (control) 1.94 7.72 8.09 315 13.93 4 1.85 6.89 8.01 355 15.71 5 1.92 6.82 8.35 379 17.71 Dynamic Mechanical Storage Modules (G′)
The dynamic viscoelastic storage modulus (G′) of the cured stocks in shown in FIGS. 1 and 2, where data from FIG. 1 was obtained from temperature sweep experiments (TS) and data from FIG. 2 was obtained from 50� C. strain sweeps. Temperature sweep experiments were conducted with a frequency of 31.4 rad/sec using 0.5% strain for temperatures ranging from −100� C. to 100� C. A frequency of 3.14 rad/sec was used for strain sweep which is conducted at 50� C. with strain sweeping from 0.25% to 14.75%.
Improvements of G′ at over a range of measured temperatures and applied strain levels of examples with M-PBD-PS over the PBD-PS and control examples are seen in FIGS. 1 and 2.
The wear resistance of the test samples was evaluated by weighing the amount of wear using the Lambourn test. The wearing index was obtained from the ratio of the weighty loss of the control to that of the tested sample. Samples with higher wear indices have better wear resistance properties. Samples used for Lambourn test are circular donuts with the following approximate dimensions: 0.9 and 1.9 inches in inside and outside diameter, and 0.195 inches in thickness. Test specimens are placed on an axle and run at a slip ratio of 65% against a driven abrasive surface.
The degraded abrasion resistance found in the PBD-PS added example can be improved by to the control level by replacing it with the M-PBD-PS. This can clearly be seen in the abrasion resistance data shown in Table 10.
A 7.5 L polymerization reactor was used for the preparation. The reactor was first charged with 517 g of hexane, followed by 1.0 kg butadiene/hexane blend (22.0 wt % of butadiene). The reactor was then heated to 57� C. After the temperature stabilized, the reactor was first charged with 2.5 mL of 1.6 M OOPS. The polymerization was initiated with 5.0 mL of a 1.68 M solution of butyl lithium in hexane. The batch temperature was maintained at 57� C. for the duration of the polymerization. After 2 hours (when the reaction was finished), the reactor was charged with 680 g of styrene/hexane blend (33 wt % of styrene). After additional two-hour reaction, the reactor was charged with 1.8 kg of Hexane. After another additional 20 minutes, the reactor was charged with 50 mL of divinyl benzene. The temperature was maintained at 57� C. for two-hours, and a small amount of the product was taken for GPC analysis. The GPC analysis of the product showed that the micelle polymer had a number average molecular weight of 1,027,000. The polydispersity of the molecular weight was 1.11. The conversion of the reaction is about 100%. The NMR analysis showed that the product contains 50% of butadiene and 50% of styrene. The polybutadiene contains 22% cis, 18% trans and 60% vinyl structures. The product was dropped into isopropanol, precipitated, and drum dried. TEM analysis (FIG. 3) showed nano-sized particles.
A 2000 mL three-neck round-bottom flask was used for the preparation. The middle neck was connected with a mechanical string motor. The left neck was used to charge various materials. The right neck was open for N2 purging and thermometer placing. To the flask, 300 mL of DTDP oil (C. P. Hall) and 60 g of maleic anhydride (Aldrich) were charged. The flask was placed into a silicon oil bath and heated to 170� C. After temperature was stabilized, 500 mL of the hexane solution containing 10% of the product from Example 6 was added in droplet fashion into the flask. The charging speed was very slow and the process took about 2 hrs. After charging, the flask was maintained at 180� C. for half hour. The product was dropped into toluene and precipitated via addition of isopropenol. The product was washed five times with isopropenol. TEM analysis (FIG. 4) showed nano-sized particles. 13C NMR analysis shows that the BR shell of particles contains about 2.8 wt % covalently bonded maleic anhydride. The product was insoluble in hexane.
A) 0.5 g of the products from example 7 was added into 15 g THF solvent. After vigorous stirring for half hour, the maleated particles were dissolved. The solution was completely transparent.
B) 0.5 g of the products from example 7 was added into 15 g toluene solvent. After vigorous stirring for half hour, the maleated particles were dissolved. The solution was completely transparent.
The bottle B was then charged with 1.5 mL of solution from bottle C. The resulting solution was placed in a vacuum oven at 50� C. Further drying of the product under vacuum yielded a polymer micelle-Cu complex film. The film is dark blue, but transparent to light. In addition, the resulting film is insoluble in toluene, indicating that a new polymer complex was formed.
A bottle was charged with 1.5 mL of solution from bottle C. The resulting solution was dark blue color. H2S gas was bubbled through the solution to fully convert the Cu ions to CuS. The solution was purged with N2 to remove excess H2S. The resulting solution was dark colored, with no evidence of macroscopic precipitation of CuS from the solution. This indicated the CuS particles formed are nano-scaled. The resulting solution was placed in a vacuum oven at 50� C. Further drying of the product under vacuum yielded a polymer micelle-CuS nanocomposite film. The materials was black, but transparent to light.
A 2000 mL three-neck round-bottom flask was used for the preparation. The middle neck was connected with a mechanical string motor. The left neck was used to charge various materials. The right neck was opened to N2 purging and the thermometer placing. 200 mL of DTDP oil (from C. P. Hall) and 70 g of diisopropyl azocarboxylate (from Aldrich) were charged to the flask. The flask was placed into a silicon oil bath and heated to 90� C. After the temperature stabilized, 660 g of the toluene solution containing 10% of the product from Example 6 was added in droplet fashion into the flask. The charging speed was slow, over about 2 hrs. After charging, the flask was heated to 100� C. and held at that temperature for two hours. The flask was then heated to 110� C. and held at that temperature for another two hours. Finally, the flask was heated to between 120� C. and 125� C. and held at that temperature for three hours.
The product was dropped into hexane, and a light-yellow product precipitated from the hexane solution. The product was washed five times with hexane. GPC analysis of the product, using polystyrene/THF as the standard, showed that the polymer had a number average molecular weight (Mn) of 857,900. The polydispersity of the molecular weight was 1.09. 13C NMR analysis C═O and styrene showed that the product contained about 86.7 parts of chemically bonded diisopropyl azocarboxylate over one hundred parts (by weight) of the polymer of example 6. The product was soluble in methanol, ethanol, isopropanol, THF, chloroform, and toluene, but not soluble in hexane and cyclohexane.
Preparation of Nano-Sized Copper Sulfide (Cus) Particles
Three 40 mL bottles were charged according to the following descriptions. The bottles were then named as bottle D, E, and F respectfully. The material inside those bottles was named accordingly as material D, E, and F.
D) 0.5 g of the products from example 10 was added into 15 g toluene solvent. After vigorous stirring for half hour, the azocarboxylated particles were dissolved resulting in a transparent solution.
Bottle D was charged with 1.5 mL of solution from bottle E. The resulting solution was dark blue color. H2S gas (Aldrich) was bubbled through the solution to fully convert the Cu ions to CuS. The solution was purged with N2 to remove excess H2S. The resulting solution is dark colored, with no macroscopic precipitation of CuS from the solution for a period of one month, indicating formation of nanoscale CuS particles complexed to the nanoparticles of Example 10. The resulting solution was placed in a vacuum oven at 50� C. Further drying of the product under vacuum yielded a polymer micelle-CuS nanocomposite film. The film was black, but transparent to light.
Bottle F was then charged with 1.5 mL of solution from bottle E. The resulting solution was dark blue color. H2S gas was then bubbled through the solution to fully convert the Cu ions to CuS. The solution was purged with N2 to remove excess H2S. The resulting solution showed macroscopic precipitation of CuS from the solution immediately during the process.
The transmission electron microscopy (TEM) analysis was taken on the solution in bottle D after the H2S treatment. The solution was further diluted with the toluene solvent to about 10−5 wt %. A drop of the diluted solution was then coated on a graphed copper micro-grid. After the solvent was evaporized, the screen was examined by TEM. The results showed that the polymer synthesized is a particle-like material and the average particle size was about 40 nm (FIG. 5). The CuS nano particles existed inside of each polymer particle and the average particle size of CuS crystals was 5 to 10 nm (FIG. 6). It is noted that the two pictures were taken at the same position, but the focus depths were different.
Example 14. A 2000 mL three-neck round-bottom flask was used for the preparation. 740 g of the toluene solution containing 10% of the product from Example 6 and 100 g of diisopropyl azocarboxylate (from Aldrich) were added to the flask together. The flask was purged with N2 for 0.5 hours. The flask was then heated to 115� C. and held at that temperature for seven hours. The product was dropped into hexane, and a light-yellow product was precipitated. The product was washed five times with hexane. GPC analysis of the product, using polystyrene/THF as the standard, showed that the polymer had a Mn of 858,200. The polydispersity of the nanoparticles was 1.10 13C NMR analysis showed the product contained about 121 parts of covalently bonded diisopropyl azocarboxylate over one hundred parts (by weight) of the polymers of Example 6. The product was soluble in methanol, ethanol, isopropanol, THF, chloroform, and toluene, but was insoluble in hexane and cyclohexane.
Preparation of Nano-Sized Cadmium Sulfide (Cds) Particles
G) 0.5 g of the products from example 14 was added to 15 g toluene solvent. After vigorous stirring for half hour, the azocarboxylated particles were dissolved, and the solution was completely transparent.
Bottle G was charged with 1.5 mL of solution from bottle H. H2S gas was bubbled through the solution to fully convert the Cd ions to CdS. The solution was purged with N2 to remove excess of H2S. The resulting solution was yellow, with no macroscopic precipitation of CdS from the solution for a period of one month, indicating formation of nano-scaled CdS particles complexed to the nanoparticles of Example H. The resulting solution was placed in a vacuum oven at 50� C. Further drying of the product under vacuum yielded to a polymer nanocomposite film. The film was yellow colored, but transparent to light.
Bottle I was charged with 1.5 mL of solution from bottle H. H2S gas was bubbled through the solution to fully convert the Cd ions to CdS. The solution was purged with N2 to remove excess H2S. The resulting solution showed macroscopic precipitation of the yellow CdS from the solution immediately during the process.
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