Patent Application
20220041811
The present invention generally relates to methods of preparing silsesquioxane-silica hybrids. More particularly, it relates, inter alia, to one-pot synthetic methods are disclosed for synthesizing curable, antimicrobial silsesquioxane-silica hybrids and particles containing such hybrids.
Organically-modified silicates are organic-inorganic hybrid materials in which the organic moieties are covalently linked to the siloxane backbone (L. Nicole, L. Rozes, C. Sanchez, Adv. Mater., 2010, 22, 3208). Their rheological behavior may be modified by varying the precursor ratios, resulting in materials exhibiting rubbery or brittle characteristics (J. D. Mackenzie, Y. J. Chung, Y. Hu, J. Non-Cryst. Solids, 1992, 147-148, 271). Silsesquioxanes ([RSiO1.5]n) are specific examples of organically-modified silicates in which R is hydrogen or any organic group (e.g., alkyl, alkylene, aryl, etc.). Silsesquioxanes or silsesquioxane-silica hybrids are synthesized using a Stöber-like sol-gel route (W. Stöber, A. Fink, E. Bohn, J. Colloid Interface Sci., 1968, 26, 62), via hydrolytic condensation of trialkoxysilanes, bridged alkoxides or co-condensation between a tetra-alkoxysilane and a trialkoxysilane (F. Hoffmann, M. Cornelius, J. Morell, M. Fröba, Angew. Chem. Int. Ed., 2006, 45, 3216; H. Mori, Y. Miyamura, T. Endo, Langmuir, 2007, 23, 9014; E. Ruiz-Hitzky, P. Aranda, M. Darder, M. Ogawa, Chem. Soc. Rev., 2011, 40, 801). By controlling the organic-inorganic composition, as well as functionality of these hybrid materials, a wide variety of silicate-based hybrid materials may be produced for applications in the fields of catalysis (F. Hoffmann, M. Cornelius, J. Morell, M. Fröba, Angew. Chem. Int. Ed., 2006, 45, 3216), optical devices (C. Sanchez, B. Lebeau, F. Chaput, J. P. Boilot, Adv. Mater., 2003, 15, 1969), coating and polymer science (X. X. Zhang, B. B. Xia, H. P. Ye, Y. L. Zhang, B. Zhao, L. H. Yan, H. B. Lv, B. Jiang, J. Mater. Chem., 2012, 22, 13132; B. M. Novak, Adv. Mater., 1993, 5, 422).
The introduction of reactive functionalities to silsesquioxanes may be achieved via post-synthetic surface functionalization procedures (grafting), which are based upon chemical reaction of silica particles with coupling agents bearing organic functional groups. However, the limitations of the grafting method are that there are relatively few silanol groups available on the surface of the silica particles and the procedure is time-consuming. In addition, this method generally results in particles containing only one type of functional group.
Recently, efforts have been made to explore the ability of organosilanes with surfactant chain-bearing groups to self-direct the hydrolysis and condensation of alkoxysilane precursors into structures with mesoporous characteristics (G. Büchel, K. Klaus, K. K. Unger, A. Matsumoto, K. Tsutsumi, Adv. Mater., 1998, 10, 1036; E. Ruiz-Hitzky, S. Letaïef, V. Prévot, Adv. Mater., 2002, 14, 439; Y. Fujimoto, A. Shimojima, K. Kuroda, J. Mater. Chem., 2006, 16, 986; M. Choi, H. S. Cho, R. Sricastava, C. Venkatesan, D. H. Choi, R. Ryoo, Nat. Mater., 2006, 5, 718). Although the mechanisms of using surfactant silanes to facilitate formation of particles with tailored mesostructures (i.e., mesoporous, lamellar, and worm-like mesostrucutures) were well understood, little is known regarding the synthesis of mesostructured hybrid materials with dual functionalities.
Accordingly, there is a need for methods of preparing silsesquioxane-silica hybrids and for preparing particles containing these hybrids having mesoporous characteristics. The methods and compositions of the present invention are directed toward these, as well as other, important ends.
Direct synthesis, in which silica-based hybrid particles are generated by co-condensation of tetra-alkoxysilane with terminal trialkoxysilane, represents a more advantageous route, with the organic functionality distributed within the synthesized materials instead of the surface of the materials (A. Van Blaaderen, A. Vrij, J. Colloid Interface Sci., 1993, 156, 1; C. R. Silva, C. Airoldi, J Colloid Interface Sci., 1997, 195, 381; S. Chen, S. Hayakawa, Y. Shirosaka, E. Fujii, K. Kawabata, K. Tsuru, A. Osaka, J. Am. Ceram. Soc., 2009, 92, 2074; Y. Naka, Y. Komori, H. Yashitake, Colloids Surf. A. Physicochem. Eng. Aspects, 2010, 36, 162). In addition, the organic functionalities are more homogeneously distributed during the co-condensation process, when compared with materials that are produced by the grafting method. This is especially so in the case of fabricating mesoporous structures in which organic functionalization of the center of the pores through grafting method may be impaired as a result of the pore blocking effect if the organosilanes react preferentially at pore openings. It is generally believed that periodic mesoporous organsilica particulates that are produced via hydrolysis and condensation reactions of bridged organosilica precursors have a higher degree of homogeneity of the organic functionalities (F. Hoffmann, M. Cornelius, J. Morell, M. Fröba, Angew. Chem. Int. Ed., 2006, 45, 3216). Despite ample reports of such a method, the literature is sparse in the synthesis of silica-based hybrids containing dual functional groups.
A modified Stöber route for synthesizing silsesquioxane-silica hybrid (SqSH) particles by hydrolytic co-condensation of tetraethoxysilane (TEOS) with two trialkoxysilanes: 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride (SiQAC) and 3-methacryloxypropyltrimethoxysilane (3-MPTS), in one embodiment, without the use of an additional surfactant. The alkylammonium chain from SiQAC is responsible for its antimicrobial potential (Ahlström B., Thompson R. A., Edebo L., APMIS, 1999, 107, 318), and serves as a structure-directing agent (i.e., surfactant silane) during the co-condensation process Q. Huo, D. I. Margolese, G. D. Stucky, Chem. Mater., 1996, 8, 1147). The dual roles of SiQAC as a surfactant silane and the contributor of the antimicrobial functionality eliminates the need for surfactant removal after synthesis, thereby avoiding the risk of destroying the other organic functionality (i.e., methacrylate groups from 3-MPTS, for example in one embodiment) during removal of surfactant by extractive or calcination methods. In this one-pot synthesis, the molar ratio of SiQAC and 3-MPTS was maintained at 1:1, while the molar ratio of TEOS varied from 1 to 32, resulting in silsesquioxane-silica hybrids (SqSHs) with overall molar ratios of 1:1:1, 1:2:1, 1:4:1, 1:8:1, 1:16:1 and 1:32:1. The sol-gel hydrolytic condensation product of TEOS was used as a comparative example (sol-gel silica).
Accordingly, in a first embodiment, the invention is directed to methods of preparing a silsesquioxane-silica hybrid, comprising:
hydrolytically co-condensing, in the presence of at least one (C1-C3)alcohol and a catalytic amount of an ammonium cation (NH4+), of a tetralkoxysilane of formula I:
with a trialkoxysilane of formula II:
and with a trialkoxysilane of formula III:
wherein said compound of formula II, said compound of formula I, and said compound of formula III are reacted in a molar ratio of about 1:1-32:1, respectively;
wherein:
each Ry is, independently, H, (C1-C8)alkyl, or trifluoro-substituted (C1-C8)alkyl.
In other embodiments, the invention is directed to the particles produced by the process. In certain embodiments, these particles have a substantially spherical morphology. In certain embodiments, these particles have a substantially ordered lamellar internal structure. In certain embodiments, these particles are mesoporous. In certain embodiments, these particles have the reacted residue of said trialkoxysilane of formula II and the reacted residue of said trialkoxysilane of formula III are substantially homogeneously distributed throughout said particle.
Other embodiments are directed to a plurality of particles, wherein each of said particles comprises:
a silsesquioxane-silica hybrid;
wherein each of said particles has a substantially spherical morphology;
wherein each of said particle has a substantially ordered lamellar internal structure;
wherein each of said particle is mesoporous; and
wherein the reacted residue of said trialkoxysilane of formula II and the reacted residue of said trialkoxysilane of formula III are substantially homogeneously distributed throughout each of said particle.
In yet other embodiments, the invention is directed to methods of preparing a polymer, comprising:
providing a plurality of particles described herein;
substantially fully hydrolyzing said particles to form a plurality of hydrolyzed particles; and
reacting said plurality of hydrolyzed particles with at least one co-monomer.
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention. In the drawings:
a to c show thermogravimetric analysis (TGA) of one embodiment of the invention and a comparative sol-gel silica at a rate of 10° C./min from ambient temperature to 1000° C. in atmospheric air. (a) Thermograms for SqSHs and sol-gel silica. The residual mass that remains after reaching at 700° C. is due to residual inorganic silica content. The weight percentage of remaining silica in SqSHs 1:1:1, 1:2:1, 1:4:1, 1:8:1, 1:16:1, 1:32:1 and comparative sol-gel silica are 22.7, 31.3, 38.7, 50.1, 58.7, 68.8, and 76.7 weight %, respectively. (b) Logarithmic regression model provides an excellent fit (R2=0.987; P<0.01) for the relation between the residual weight percentage and the molar ratio of tetraethoxysilane to a trialkoxysilane. (c) Derivative weight loss curves for SqSHs and sol-gel silica. For the peak below 100° C. (A), the highest was seen with sol-gel silica while the lowest peak was seen with SqSH 1:1:1. This indicates that there is more water molecules inside the sol-gel silica network. The overall peak intensity of the derivative weight plots increases with the increased composition of organosilane in SqSHs. The two peaks (B and C) from 200 to 420° C. indicate the decomposition of organic constituents (D. S. Bag, K. U. Rao, J. Appl. Poly. Sci. 2010, 115, 2352), representing two-stage decomposition of organic substances from SqSHs (W. Xie, Z. Gao, W.-P. Pan, D. Hunter, A. Singh, R. Vaia, Chem. Mater. 2001, 13, 2979). The peaks (D) above 600° C. are attributed to further condensation of the silanol groups in the bulk silicate network.
As employed above and throughout the disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings.
As used herein, the singular forms “a,” “an,” and “the” include the plural reference unless the context dearly indicates otherwise.
“Alkyl,” as used herein, refers to an optionally substituted, saturated straight, branched, or cyclic hydrocarbon having from about 1 to about 20 carbon atoms (and all combinations and subcombinations of ranges and specific numbers of carbon atoms therein), with from about 1 to about 8 carbon atoms or 1 to 6 carbon atoms (C1-C6) being preferred, and with from about 1 to about 4 carbon atoms. Alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, cyclopentyl, cyclopropyl, isopentyl, neopentyl, n-hexyl, isohexyl, cyclohexyl, cyclooctyl, adamantyl, 3-methylpentyl, 2,2-dimethylbutyl, and 2,3-dimethylbutyl. A branched alkyl group has at least 3 carbon atoms (e.g., an isopropyl group), and in various, embodiments, has up to 6 carbon atoms, i.e., a branched lower alkyl group. A branched alkyl group has at least 3 carbon atoms (e.g., an isopropyl group), and in various embodiments, has up to 6 carbon atoms, i.e., a branched lower alkyl group.
“Alkenyl,” as used herein, refers to an optionally substituted, singly unsaturated, straight, branched, or cyclic hydrocarbon having from about 2 to about 20 carbon atoms (and all combinations and subcombinations of ranges and specific numbers of carbon atoms therein), with from about 2 to about 8 carbon atoms or 2 to 6 carbon atoms (C2-C6) being preferred. Alkenyl groups include, but are not limited to, ethenyl (or vinyl), allyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, and octenyl.
“Alkylenyl,” as used herein, refer to the subsets of alkyl groups, as defined herein, including the same residues as alkyl but having two points of attachment within a chemical structure. Examples of (C1-C6)alkylenyl include methylenyl (—CH2—), ethylenyl (—CH2CH2—), propylenyl (—CH2CH2CH2—), and dimethylpropylenyl (—CH2C(CH3)2CH2—).
“Aryl,” as used herein, refers to an optionally substituted, mono-, di-, tri-, or other multicyclic aromatic ring system having from about 5 to about 50 carbon atoms (and all combinations and subcombinations of ranges and specific numbers of carbon atoms therein), with from about 6 to about 10 carbons (C6-C10) being preferred. Non-limiting examples include, for example, phenyl, naphthyl, anthracenyl, and phenanthrenyl.
As used herein, the terms “optionally substituted” or “substituted or unsubstituted” are intended to refer to the optional replacement of up to four hydrogen atoms with up to four independently selected substituent groups as defined herein. Unless otherwise specified, suitable substituent groups independently include hydroxyl, nitro, amino, imino, cyano, halo, thio, sulfonyl, aminocarbonyl, carbonylamino, carbonyl, oxo, guanidine, carboxyl, formyl, alkyl, perfluoroalkyl, alkylamino, dialkylamino, alkoxy, alkoxyalkyl, alkylcarbonyl, arylcarbonyl, alkylthio, aryl, heteroaryl, a heterocyclic ring, cycloalkyl, hydroxyalkyl, carboxyalkyl, haloalkyl, alkenyl, alkynyl, arylalkyl, aryloxy, heteroaryloxy, heteroarylalkyl, and the like. Substituent groups that have one or more available hydrogen atoms can in turn optionally bear further independently selected substituents, to a maximum of three levels of substitutions. For example, the term “optionally substituted alkyl” is intended to mean an alkyl group that can optionally have up to four of its hydrogen atoms replaced with substituent groups as defined above (i.e., a first level of substitution), wherein each of the substituent groups attached to the alkyl group can optionally have up to four of its hydrogen atoms replaced by substituent groups as defined above (i.e., a second level of substitution), and each of the substituent groups of the second level of substitution can optionally have up to four of its hydrogen atoms replaced by substituent groups as defined above (i.e., a third level of substitution).
“Mesoporous,” as used herein, refers to a material containing pores with diameters about 2 nm to about 50 nm.
“Polydispersity index,” as used herein, refers to the ratio of weight-average molecular weight to the number-average molecular weight (PDI=Mw/Mn).
“Molecular weight,” as used herein, unless otherwise indicated, refers to the weight average molecular weight of a polymer as measured by gel permeation chromatography (GPC) against a polyacrylic acid standard.
While the present invention is capable of being embodied in various forms, the description below of several embodiments is made with the understanding that the present disclosure is to be considered as an exemplification of the invention, and is not intended to limit the invention to the specific embodiments illustrated. Headings are provided for convenience only and are not to be construed to limit the invention in any manner. Embodiments illustrated under any heading may be combined with embodiments illustrate under any other heading.
The use of numerical values in the various quantitative values specified in this application, unless expressly indicated otherwise, are stated as approximations as though the minimum and maximum values within the stated ranges were both preceded by the word “about.” In this manner, slight variations from a stated value can be used to achieve substantially the same results as the stated value. Also, the disclosure of ranges is intended as a continuous range including every value between the minimum and maximum values recited as well as any ranges that can be formed by such values. Also disclosed herein are any and all ratios (and ranges of any such ratios) that can be formed by dividing a recited numeric value into any other recited numeric value. Accordingly, the skilled person will appreciate that many such ratios, ranges, and ranges of ratios can be unambiguously derived from the numerical values presented herein and in all instances such ratios, ranges, and ranges of ratios represent various embodiments of the present invention.
As used herein, the phrase “substantially” means have no more than about 10% difference between the target and actual level, preferably less than about 5% difference, more preferably, less than about 1% difference.
We have developed a facile method for synthesizing unique SqSH hybrid silica particles via a Stöber-like approach, with ordered lamellar structures with spherical morphology, without the use of additional surfactants. A scheme illustrating the influence of surfactant and formation of SqSH-silica hybrid nanospheres is shown in
Accordingly, in a first embodiment, the invention is directed to methods of preparing a silsesquioxane-silica hybrids comprising:
hydrolytically co-condensing, in the presence of at least one (C1-C3)alcohol and a catalytic amount of an ammonium cation (NH4+), of a tetralkoxysilane of formula I:
with a trialkoxysilane of formula II:
and with a trialkoxysilane of formula III:
wherein said compound of formula II, said compound of formula I, and said compound of formula III are reacted in a molar ratio of about 1:1-32:1, respectively;
wherein:
A1, A2, A3, and A4 are each independently selected from the group consisting of H, C1-C8alkyl, and trifluoro-substituted (C1-C8)alkyl;
Ra is independently a functional group comprising at least one curing group selected from the group consisting of acrylate, methacrylate, (C2-C8)alkenyl, glycidyloxy, epoxy, sulfonate, carboxylate, ester, amino, acrylamide, methacrylamide, isocyanato, amino acid, nucleic acid, and mercapto(C1-C6)alkyl;
Rb is independently
each Ry is, independently, H, (C1-C8)alkyl, or trifluoro-substituted (C1-C8)alkyl. The silsesquioxane-silica hybrid compounds that are formed may be linear, branched, or star-shaped with the residues of compound I forming the backbone and the residues of compounds of formula II and formula III terminally located on the compounds.
In certain embodiments, said (C1-C3)alcohol is methanol, ethanol, propanol (n-propanol or isopropanol), or mixtures thereof. In certain embodiments, the (C1-C3)alcohol is ethanol.
In certain embodiments, said ammonium cation (NH4+) is derived from ammonium hydroxide, ammonium carbonate, ammonium chloride, ammonium nitrate, aqueous ammonia, or a mixture thereof. In certain embodiments, said ammonium cation (NH4+) is derived from ammonium hydroxide.
In certain embodiments, each Ry is, independently, Ry is, independently, H, methyl, ethyl, or propyl. In certain embodiments, each Ry is H. In certain embodiments, each Ry is methyl.
In certain embodiments, said siloxane of formula I is tetra(C1-C6)alkoxysilane. In certain embodiments, said siloxane of formula I is tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetrapropoxysilane (TPOS), or a mixture thereof. In certain embodiments, said siloxane of formula I is tetraethoxysilane (TEOS).
In certain embodiments, Ra is acrylate, methacrylate, or vinyl, preferably methacrylate. In certain embodiments, Ra is methacryloxypropyl.
In certain embodiments, said trialkoxysilane of formula II is 3-methacryloxypropyl trimethoxysilane (3-MPTS).
In certain embodiments, Ry is H or (C1-C2)alkyl. Ethyl is preferred for certain dental and medical applications. In certain embodiments, Ry is H.
In certain embodiments, Rb is independently —(C3-C6 alkylenyl)-(dimethyl)-(C6-C22alkyl) quaternary ammonium chloride or —(C3-C6 alkylenyl)-(methyl)-(phenyl)-(C6-C22alkyl) quaternary ammonium chloride. In certain embodiments, Rb is —(C3-C6)alkylenyl-dimethyl-(C18alkyl) quaternary ammonium chloride, especially Rb is —(C3 alkylenyl)-(dimethyl)-(C18alkyl) quaternary ammonium chloride, such Aegis 5700 or 5772 commercially available from Aegis or Rb is —(C3-C6)alkylenyl-methyl-phenyl-(C6-C22alkyl) quaternary ammonium chloride, which may be prepared by N-alkylation of N-hexylaniline in a two-step process where N-hexylanlysis is reacted with 3-chloropropyl)triethoxysilane to yield a tertiary amine which then is further quarternized in the second step by reacting with iodomethane, such as described in Saif, et al., Langmuir, 2009, 25, 377-379.
In certain embodiments, Rb is
In certain embodiments, Rc is methyl.
In certain embodiments, Rd is methyl.
In certain embodiments, Re is octadecyl.
In certain embodiments, X⊖ is Cl−.
In certain embodiments, said trialkoxysilane of formula III is 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride (SiQAC).
In certain embodiments, said method is conducted substantially free of a separate surfactant other than said compound of formula II.
In certain embodiments, said compound of formula II, said compound of formula I, and said compound of formula III are reacted in a molar ratio selected from the group consisting of 1:1:1, 1:2:1, 1:4:1, 1:8:1, 1:16:1, 1:32:1, and mixtures thereof, respectively.
In other embodiments, the invention is directed to the particles produced by the process. In certain embodiments, these particles have a substantially spherical morphology. In certain embodiments, these particles have a substantially ordered lamellar internal structure. In certain embodiments, these particles are mesoporous. In certain embodiments, these particles have the reacted residue of said trialkoxysilane of formula II and the reacted residue of said trialkoxysilane of formula III are substantially homogeneously distributed throughout said particle.
Other embodiments are directed to a plurality of particles, wherein each of said particles comprises:
a silsesquioxane-silica hybrid;
wherein each of said particles has a substantially spherical morphology;
wherein each of said particle has a substantially ordered lamellar internal structure;
wherein each of said particle is mesoporous; and
wherein the reacted residue of said trialkoxysilane of formula II and the reacted residue of said trialkoxysilane of formula III are substantially homogeneously distributed throughout each of said particle.
In certain embodiments, said plurality of particles has an average particle size of about 50 nm to about 2000 nm, preferably about 250 nm to about 1000 nm. In certain embodiments, said plurality of particles has a polydispersity index of about 1 to about 20. In certain embodiments, the Mw is about 20,000 to about 200,000.
In yet other embodiments, the invention is directed to methods of preparing a polymer, comprising:
providing a plurality of particles described herein;
substantially fully hydrolyzing said particles to form a plurality of hydrolyzed particles; and
reacting said plurality of hydrolyzed particles with at least one co-monomer.
In another embodiment, the invention is directed to kits, comprising:
a plurality of particles described herein;
at least one polymerization initiator;
optionally, at least one synergist;
optionally, at least one filler; and
optionally, at least one co-monomer.
In other embodiments, the invention is directed to compositions, comprising:
at least one filler;
a plurality of particles described herein;
In other embodiments, the compositions, further comprise:
at least one natural rubber, synthetic rubber, or a combination thereof.
In another embodiment, the compositions, further comprise:
at least one first polymer selected from the group consisting of thermoplastic polymer, thermosetting polymer, and mixtures thereof.
In yet other embodiments, the invention is directed to polymeric articles, comprising:
said compositions described herein, said particles described herein or a polymerized residue of said particles described herein.
In further embodiments, the invention is directed to coating materials, comprising:
said compositions described herein, said particles described herein or a polymerized residue of said particles described herein.
In other embodiments, the invention is directed to compositions comprising:
the polymerized residue of said particles described herein.
In another embodiment, the invention is directed to toothpastes, comprising:
said compositions described herein or said particles described herein.
In other embodiments, the invention is directed to mouthwashes,
comprising:
said compositions described herein or said particles described herein.
In yet other embodiments, the invention is directed to contact lenses, comprising:
said compositions described herein, said particles described herein or a polymerized residue of said particles described herein.
In other embodiments, the invention is directed to the products produced by the processes and methods described herein.
Another embodiment of this invention is a water solution of said compositions described herein, said particles described herein or a polymerized residue of said particles described herein.
Still another embodiment of this invention is a water-alcohol solution of said compositions described herein, said particles described herein or a polymerized residue of said particles described herein.
Yet another embodiment is the use of the material described herein as fillers for adhesive (primer) and the use of the material described herein in commercial adhesives used in dentistry.
Still another embodiment is the use of a material described herein as an additive (filler) to dental compositions for adhesion of the dental composition to a tooth. Other embodiments include the use of a material described herein as fillers for plastic bags, polyethylene films, toothpastes, and any other application requiring a filler polymer, especially one that is antimicrobial.
In addition, the materials of this invention can act as tooth desensitizers when placed on a tooth, and still further, this material can be added to filler material for teeth, especially filling materials such as siloxanes, glass ionomers, methacrylates, and silver amalgams.
In still other embodiments, the materials of the invention may be used in contact lenses as the primary material or as a secondary material.
In certain embodiments, the compositions described herein further comprise at least one natural rubber, synthetic rubber, or a combination thereof. In certain other embodiments, the compositions further comprise at least one first polymer selected from the group consisting of thermoplastic polymer, thermosetting polymer, and mixtures thereof.
In certain embodiments, the compositions comprising said compositions described herein, said particles described herein or a polymerized residue of said particles described herein, further comprise at least one first polymer selected from the group consisting of thermoplastic polymer, thermosetting polymer, and mixtures thereof.
Suitable thermoplastic polymers for use in the compositions of the invention include, but are not limited to, polyethylene, polypropylene, polyvinyl chloride, polyester, acrylic, methacrylic, or a copolymer or mixture thereof.
Suitable thermosetting polymers for use in the compositions of the invention include, but are not limited to, epoxy, polyester, alkyd, diallyl phthalate, melamine, polybutadiene, phenolic, silicone, urea, urethane, imide, or a mixture thereof.
In certain embodiments, the compositions described herein, the particles described herein or a polymerized residue of the particles described herein are in the form of a powder. In certain embodiments, the compositions of the invention are in the form of a master batch. A “master batch,” as used herein, is a product in which additives are dispersed (usually well dispersed) in a carrier material that is compatible with the main polymer or plastic in which it will be let down and may be supplied in a granule, a pellet, or a powder form. In certain embodiments, the compositions of the invention further comprise a second polymer that is the same or different from the first polymer.
In certain embodiments, the compositions described herein, the particles described herein or a polymerized residue of the particles described herein, with or without filler, further comprise at least one first polymer wherein said first polymer is:
In certain embodiments, the compositions described herein, the particles described herein or a polymerized residue of the particles described herein and filler further comprise at least one thermoplastic polymer, thermosetting polymer, or a combination thereof. Suitable thermoplastic polymers include, but are not limited to, polyethylene, polypropylene, polyvinyl chloride, polyesters, and the like, copolymers and mixtures thereof.
In certain embodiments, the compositions described herein, the particles described herein or a polymerized residue of the particles described herein, with or without filler, are useful as polymeric articles, such as film, sheet, container, foam container, bottle, crate, plastic parts, toys, pipe, foam insulation, panel, plastic lumber, or the like. In certain embodiments, the polymeric article is prepared by blown film, cast film, extrusion (such as profile extrusion, sheet extrusion, and foam extrusion), roto-molding, injection molding, blow molding, foamed, coating, or a combination thereof or the like.
In certain embodiments, the compositions described herein, the particles described herein or a polymerized residue of the particles described herein, with or without filler, are useful as toothpaste, mouthwash, contact lenses (for example in heat curable systems with HEMA and a small amount of ethyleneglycol methacrylate), artificial nails and adhesives therefor, and the like.
The compositions described herein, the particles described herein or a polymerized residue of the particles described herein may be used to increase the contact angle (and hence increase the surface energy) of compositions into which they are incorporated. Thus, the compounds of the invention are useful in methods of increasing the printability and/or dyeability of a polymeric composition. For example, this would lead to better print quality and permitting use of environmentally-friendly water-based inks in the place of solvent-based inks. Such methods comprise incorporating said compositions described herein, said particles described herein or a polymerized residue of said particles described herein into a polymeric composition, either as a separate component or as a residue in the polymer itself (by polymerizing with at least one co-monomer).
The compositions described herein, the particles described herein or a polymerized residue of the particles described herein may be used to increase the hydrophilicity, improve antistatic properties, and reduce surface resistivity (by attracting water) of the compositions into which they are incorporated. Such methods comprise incorporating the compositions described herein, the particles described herein or a polymerized residue of the particles described herein into a polymeric composition, either as a separate component or as a residue in the polymer itself (by polymerizing with at least one co-co-monomer).
The present invention is further defined in the following Examples, in which all parts and percentages are by weight, unless otherwise stated. It should be understood that these examples, while indicating preferred embodiments of the invention, are given by way of illustration only and are not to be construed as limiting in any manner. From the above discussion and these examples, one skilled in the art can ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.
Chemicals and reagents: Tetraethoxysilane (TEOS), 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride (SiQAC), 3-methacryloxypropyltrimethoxysilane (3-MPTS), ammonium hydroxide solution (28-30% NH3), triethylene glycol dimethacrylate (TEGDMA), ethyl(4-dimethylamino)benzoate (EDMAB) and camphorquinone (CQ) were purchased from Sigma-Aldrich (St Louis, Minn., USA) and used without further purification. The SiQAC was supplied at 72 weight % in methanol. 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (bis-GMA) was a gift from Esstech, Inc. (Essington, Pa., USA).
The molar ratio of SiQAC and 3-MPTS was maintained at 1:1, while the molar ratio of TEOS varied from 1 to 32, resulting in silsesquioxane-silica hybrids (SqSHs) with overall molar ratios of 1:1:1, 1:2:1, 1:4:1, 1:8:1, 1:16:1 and 1:32:1 (
Attenuated total reflection-Fourier transform infrared (FTIR) spectroscopy
Infrared spectra were recorded between 4,000-400 cm−1 using a Fourier-transform infrared spectrometer (Nicolet 6700, Thermo Scientific, Waltham, Mass., USA) with an attenuated total reflection (ATR) set up at a resolution of 4 cm−1 and averaging 32 scans per spectrum.
The structures of SqSHs and sol-gel silica were characterized by 29Si solid-state NMR at ambient temperature using a 270 MHz spectrometer (JEOL, Tokyo, Japan) equipped with a 7 mm Magic Angle Spinning (MAS) probe. Spectra were acquired in the 1H→29Si cross polarization (CP) mode, using a MAS frequency of 4 kHz, with a 45 degree pulse angle of 5 psec. The 1H Larmor frequency for 29Si was 53.76 MHz. Chemical shifts were referenced to external tetramethylsilane (TMS) at 0 ppm.
TGA was performed with a Q500 thormogravimetric analyzer (TA Instruments, New Castle, Del., USA). Approximately 40 mg of dried particles (SqSHs or sol-gel silica) was placed in individual platinum pans and heated at a rate of 10° C./min to 1000° C. in atmospheric air. The data were analyzed using the Universal Analysis 2000 software (TA Instruments) and expressed as weight vs temperature as well as derivative weight vs temperature.
X-ray diffraction (Rigaku America, Woodlands, Tex., USA) of the non-sintered particles was performed using Ni-filtered Cu Kα radiation (30 KeV, 20 mA), in the 20 range of 1-30°, with a scan rate of 4°/min, and a sampling interval of 0.02°. The determination of d-spacing values was based on Bragg-Brentano geometry.
Dried particles sputter-coated with gold/palladium were examined using a field emission-scanning electron microscope (XL-30 FEG; Philips, Eindhoven, The Netherlands) operating at 10-15 kV. Dried particles were embedded in epoxy resin and cut into 70-90 nm thick sections. Unstained sections were examined using a JSM-1230 transmission electron microscope (JEOL, Tokyo, Japan) at 110 kV. Selected area electron diffraction (SAED) was performed to identify the crystallinity of the SqSH particles.
Elemental analysis of representative SqSH 1:8:1 and 1:32:1 was performed on unstained thin sections prepared previously for TEM using a Tecnai G2 STEM (FEI, Hillsboro, Oreg., USA) at 200 kV. Spectrum acquisition and elemental mapping were conducted using an Oxford Instruments INCA x-sight detector. Images were collected with a Gatan 1K×1K CCD camera. Elemental mappings were acquired with the FEI TIA software using a spot dwell time of 300 msec. As each 250×250 pixel mapping required 7 hours to complete, drift correction was performed after every 30 images.
Cold-polymerized epoxy resin with embedded SqSH or sol-gel silica particles was sectioned with a water-cooled diamond-impregnated blasé to expose the particles along the flat resin surface. Mechanical properties of the specimens were evaluated by quasi-static indentation using a nanoindenter (Hysitron Tribinderter 900, Minneapolis, Minn., USA) with a 100 nm radius cono-spherical diamond tip indenter. A standard trapezoidal profile was used including a maximum load of 100 mN, indentation hold time of 5 sec, and loading and unloading rates of 20 mN/sec. An initial offset load of 10 mN was used for identifying contact and initialize the indentation process. The load-displacement curves generated for the individual indentations were corrected for the offset force. Six indentations were performed to characterize the mechanical behavior of each SqSH or sol-gel silica control (N=6). Reduced modulus and hardness (in GPa) were calculated based on the Oliver-Pharr method for nanoindentation testing (W. C. Oliver, G. M. Pharr, J. Mater. Res., 1992, 7, 1564). Data were analyzed using one-way ANOVA with Tukey's multiple comparison at α=0.05.
A bis-GMA/TEGDMA light-polymerizable resin blend (composition: 70 weight % bis-GMA, 28.5 weight % TEGDMA, 1 weight % EDMAB and 0.5 weight % CQ) was used to mix with 50 weight % SqSH particles in a centrifugal mixing device at 3200 rpm for 60 seconds (DAC 150 Speedmixer; FlackTek Inc., Landrum, S.C., USA). Bis-GMA/TEGDMA resin without any SqSH was used as control. Polymerization of these resins was achieved by photocuring with visible light in the wavelength range of 410-500 nm. With a Teflon mold and Mylar sheets covering both sides, polymerized resin disks (6±0.1 mm diameter, 1 t 0.1 mm thick) were fabricated.
Streptococcus mutans ATCC 35668 (ATCC, Manassas, Va., USA) and Actinomyces naeslundii ATCC 12104 were cultured in Brain Heart Infusion (BHI) broth (Difco, Becton-Dickinson and Co., Sparks, Md., USA), supplemented with 50 mM sucrose (pH 7.2). Candida albicans ATCC 90028 was cultured in Yeast Nitrogen Base (YNB; Difco) supplemented with 50 mM glucose (pH 7.2). Harvested cells were re-suspended in 100 mL of the respective growth medium, and adjusted to a concentration of 107 CFU/mL before use. Each microbe was used individually for the formation of single-species biofilms on salivary pellicle-coated resin disks inside an oral biofilm reactor. After the formation of biofilms on acrylic surfaces, half of the disks from each group were transferred carefully into separate microtubes containing 4 mL of phosphate buffered saline (PBS; 0.01 mM, pH 7.3), avoiding any disturbances to the biofilms. Fifty mL of 1 mg/mL solution of 2,3-bis-(2-methoxy-4-nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxanilide (XTT; Sigma-Aldrich) was then added to each microtube, together with 4 μL of 1 mM menadione (Sigma-Aldrich). The solutions were mixed gently, covered with aluminum foil, and incubated for 5 hours at 37° C. After incubation, the solution was transferred to a new microtube and centrifuged at 4000 rpm for 10 minutes at 4° C. The supernatant was placed in a 96-well plate and read at 492 nm using a spectrophotometer (Victor, R & D systems, Minnesota, USA).
The rest of the disks from each group were placed carefully in separate microtubes containing 1 mL of PBS and vortexed (Maxi Mix vortex mixer, Thermo Scientific, Waltham, Mass., USA) for 2 min at high speed to detach the biofilm. Ten-fold serial dilutions were generated in PBS (0.01 mM, pH 7.3), and each dilution was plated (50 μL aliquots) onto Sabouraud Dextrose Agar plates for C. albicans, and Brain Heart Infusion agar plates for S. mutans and A. naeslundii. The plates were incubated at 37° C. for 48 hours in an aerobic chamber for C. albicans and anaerobic chamber for S. mutans and A. naeslundii. After incubation, the colony forming counts (CFU) per resin disk were counted manually. Data were analyzed using one-way ANOVA with Tukey's multiple comparison at α=0.05.
The cytotoxicity of SqSHs and sol-gel silica was investigated using a mouse fibroblast cell line (L-929). The growth medium for L-929 consisted of Dulbecco's Modified Eagle's Medium (DMEM, Lonza, Wakersville, Md., USA) and 10% fetal bovine serum (Gibco; Invitrogen Corp., Carlsbad, Calif., USA), supplemented with 2 mM L-glutamine, 100 U/mL penicillin, and 100 μg/mL streptomycin. The cells were plated in a 96-well plate at a density of 5000 cells/cm2, in 200 μL of the growth medium, and incubated at 37° C. in a humidified 5% CO2 atmosphere. After 24 hours, pre-confluent cells were washed twice with serum or antibiotics free DMEM and further incubated in DMEM containing SqSH or silica particles at different concentrations. Cells incubated in growth medium without particles were used as the blank control.
The final SqSH or silica dispersions in DMEM were prepared immediately before use by serial dilution (i.e., 2, 5, 25, 125, 625, and 3125 folds) of the stock suspension (ca. 883 μg/mL) with intense vortexing.
Succinic dehydrogenase (SDH) activity of the cells was determined using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. The retrieved cells were incubated in MTT-succinate solution for 60 min and fixed with Tris-formalin. The formazan product was dissolved in-situ using DMSO and absorbance was recorded using a microplate reader at 562 nm. Results were determined as a percentage of mean control values. The half-maximal inhibitory concentration (IC50) was defined as the concentration of SqSH or silica particles leading to a 50% reduction in L-929 cell viability A. M. Chen, M. Zhang, D. Wei, D. Stueber, O. Taratula, T. Minko, H. He, Small, 2009, 5, 2673). It was determined by linear regression analysis of the logarithmic derivative of particle concentration vs reduction of cell viability using SPSS 16.0 (SPSS Inc., Chicago, Ill., USA).
An issue that confronts silane-based co-condensation reactions is homocondensation of the trialkoxysilanes (H. Yoshitake, New J. Chem., 2005, 29, 1107). Thus, the reaction products of the sol-gel reactions were subjected to multiple washings in ethanol prior to analyses to remove unreacted reagents. Attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy validates the presence both the methacrylate group at 1690-1714 cm−1 (C═O), 1637 cm−1 (C═C), 1305 cm−1 (C—CO—O), 1295 cm−1 (C—CO—O) (S. K. Medda, D. Kundu, G. De, J. Non-Cryst. Solids, 2003, 318, 149), 815 cm−1 (C═C)) and the alkylammonium chain (1373 cm−1 (C—N)(S. Köytepe, T. Seckin, N. Kivrilcim, H. 1. Adigüzel, J. Inorgnomet. Polym., 2008, 18, 222) in the sol-gel reaction products (
Using 29Si cross polarization-magic angle spinning nuclear magnetic resonance spectroscopy (CP-MAS NMR), two different units were delineated from the NMR spectrum, providing information on the connectivity of the silica network (C. Bonhomme, C. Coelho, N. Baccile, C. Gervais, T. Azaïs, F. Babonneau, Acc. Chem. Res., 2007, 40, 738): Tn:RSKOH)(3−n)(OSi)n, and Qn:Si(OH)(4−n)(OSi)n (
By changing the feed ratios of TEOS to the trialkoxysilanes, ordered structures with variable d spacing within the spherical particles could be discerned by XRD and electron microscopy. The SiQAC molecule contains a long hydrophobic alkyl chain linked to the silicon atom by a Si—C bond, which is chemically stable under hydrolytic conditions. It becomes amphiphilic when silanol groups are formed during hydrolysis (A. Shimojima, K. Kuroda, Chem. Rec., 2006, 6, 53). Based on this amphiphilic assembly mechanism, lamellar mesostructures may be produced inside the hybrid silica particles within two hours using the Stöber route with a strong base (ammonium hydroxide) as catalyst. Small angle powder X-ray diffraction (XRD) patterns of the SqSH 1-n-1 hybrids (n=2, 8, 16, and 32) show diffraction peaks corresponding to the d spacing value of 2.9±0.1 nm (
Sol-gel silica particles synthesized by the hydrolysis and condensation reactions of TEOS alone in the present study are monodisperse (˜200 nm in diameter; data not shown), whereas the SqSH particles are slightly larger (ca. 250-1000 nm), and polydisperse, as revealed by scanning electron microscopy (SEM) (
The presence of silicon, oxygen, nitrogen, carbon within SqSH 1:8:1 and SqSH 1:32:1 particles was confirmed using scanning transmission electron microscopy-energy dispersed X-ray analysis (STEM-EDX;
Silsesquioxane-silica hybrids with different organic/inorganic compositions and variable structures should be modifiable in terms of mechanical and biological properties. The mechanical properties of SqSHs can be tuned by altering the TEOS molar feed ratio, so that particles with higher silica content can be produced. Nanoindentation performed on SqSH particles and sol-gel silica using the method reported by Oliver and Pharr (W. C. Oliver, G. M. Pharr, J. Mater. Res., 1992, 7, 1564) revealed correlations between increases in reduced modulus and hardness, with increasing feed ratios of TEOS to the trialkoxysilane (
Because SqSHs bearing methacryloxy functional groups can be co-polymerized with methacrylate resin in the presence of certain catalysts (e.g. photoinitiator and tertiary amine accelerator), SqSHs with different TEOS-trialkoxysilanes molar feed ratios are added into a resin blend consisting of 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (bis-GMA) and triethylene glycol dimethacrylate (TEGDMA), with camphorquinone (CO) and ethyl(4-dimethylamino)benzoate (EDMAB) as the photoinitiator and accelerator, respectively. Incorporation of the SqSH organic-inorganic hybrid particles into the methacrylate resin blend results in a series of antimicrobial resin composites that may be used for restoring teeth and preventing recurrent decay caused by colonization of bacterial biofilms around the margins of the tooth fillings. Three SqSH-containing resin composites (SqSH 1:8:1, 1:16:1 and 1:32:1) were chosen in the present study due to their relatively high reduced modulus and hardness, when compared to sol-gel silica, which are desirable properties for preparing restorative resin composites. Previous studies have demonstrated that incorporation of SiQAC-derived sol-gel reaction products confers resinous materials with antimicrobial activities against bacteria and fungi (S.-q.Gong, L.-n. Niu, Kemp L. K., C. K. Y. Yiu, H. Ryou, Y.-p. Qi, J. D. Blizzard, S. Nikonov, M. G. Brakkett, R. L. W. Messer, C. D. Wu, J. Mao, L. B. Brister, F. A. Rueggeberg, D. D. Arola, D. H. Pashley, F. R. Tay, Acta Biomater., 2012, 8, 3270; S. Q. Gong, J. Epasinghe, F. A. Rueggeberg, L. N. Niu, D. Mettenberg, C. K. Y. Yiu, J. D. Blizzard, C. D. Wu, J. Mao, C. L. Drisko, D. H. Pashley, F. R. Tay, PLoS One, 2012, 7, e42355; S. Q. Gong, D. J. Epasinghe, B. Zhou, L. N. Niu, K. A. Kimmerling, F. A. Rueggeberg, C. K. Y. Yiu, J. Mao, D. H. Pashley, F. R. Tay, Acta Biomater., 2013, 9, 6964). The antimicrobial potentials of SqSH-containing methacrylate resins against Streptococcus mutans, Actinomyces naeslundii, and Candida albicans were confirmed using 2,3-bis-(2-methoxy-4-nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxanilide (XTT) and Colony Forming Unit (CFU) assays (
Because materials that possess antimicrobial properties against bacteria or fungi may be toxic to mammalian cells, we performed 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay on a mouse fibroblast cell line (L929) to examine the effects of increasing molar feed ratios of SIQAC on the cytotoxicity of SqSHs (
Mesoporous antimicrobial SqSH particles with spherical morphology and lamellar structures may also be used as absorbents or carriers for loading bioactive agents, such as growth factors, catalysts, metal ions, and photoactive molecules, to achieve other functions. Other alkoxysilanes with different organofunctional moieties (e.g., acrylate, methacrylate, (C2-C8)alkenyl, glycidyloxy, epoxy, sulfonate, carboxylate, ester, amino, acrylamide, methacrylamide, isocyanato, amino acid, nucleic acid, mercapto(C1-C6)alkyl, and the like) may be used in lieu of 3-MPTS, enabling these hybrid particles to satisfy different product requirements. The versatile functionality of these hybrid materials will expand the range of their applications in various fields. For example, antimicrobial SqSH particles containing acrylate functionalities may be incorporated into acrylate-based paints; antimicrobial SqSH particles containing vinyl functionalities may be blended with polypropylene via an extruder to produce antimicrobial food wraps for the food industry.
A facile method has been developed for synthesizing unique SqSH hybrid silica particles via a Stöber-like approach, with ordered lamellar structures with spherical morphology, without the use of additional surfactants. The one-pot synthesis approach leads to the development of unique and useful antimicrobial hybrid silica particles with quaternary ammonium groups distributed within the entire particles, and therefore, non-leaching antimicrobial activities, as opposed to a grafting procedure, where thus type of functionality is present only along the particle surface. Moreover, antimicrobial activities are present irrespective of the degree of mesoscopic order of the hybrid silica particles. This synthesis approach may be further expanded by replacing the curing functionality with other organofunctional moieties, thereby enabling the antimicrobial hybrid particles with tunable mechanical properties to be incorporated into different polymers/copolymers for a wide range of commercial applications. Likewise, this synthesis approach may be further expanded by replacing the antimicrobial functionality with other organofunctional moieties, thereby enabling the antimicrobial hybrid particles with tunable biological properties to be incorporated into different polymers/copolymers for a wide range of commercial applications.
When ranges are used herein for physical properties, such as molecular weight, or chemical properties, such as chemical formulae, all combinations, and subcombinations of ranges specific embodiments therein are intended to be included.
The disclosures of each patent, patent application, and publication cited or described in this document are hereby incorporated herein by reference, in their entirety.
Those skilled in the art will appreciate that numerous changes and modifications can be made to the preferred embodiments of the invention and that such changes and modifications can be made without departing from the spirit of the invention. It is, therefore, intended that the appended claims cover all such equivalent variations as fall within the true spirit and scope of the invention.
| Number | Date | Country | |
|---|---|---|---|
| 61959177 | Aug 2013 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16241078 | Jan 2019 | US |
| Child | 17240409 | US | |
| Parent | 14907799 | Jan 2016 | US |
| Child | 16241078 | US |
