HIGHLY DISPERSIBLE ANTI-MICROBIAL AND ADHESION AGENTS
Compositions of matter having anti-microbial properties and/or adhesion properties. The compositions of matter are be highly dispersible in aqueous solutions. The presence of a large number of silanols on the molecules of the compositions creates a solubility or disperseability for these molecules in aqueous solutions that is not otherwise obtainable.
The present application claims the benefit to U.S. Non-provisional patent application Ser. No. 15/872,516, filed on Jan. 16, 2018, published as U.S. 2018/0134733 A1 and claiming benefit to U.S. Non-provisional patent application Ser. No. 15/082,026, filed on Mar. 28, 2016, now U.S. Pat. No. 9,902,744 B2, which are incorporated herein by reference in their entirety.
FIELD OF THE DISCLOSUREThe present disclosure relates to compositions of matter having anti-microbial and/or adhesion properties.
BACKGROUND OF THE DISCLOSUREThis invention deals with compositions of matter that have anti-microbial properties and/or adhesion properties and are highly dispersible in aqueous solutions. The presence of a large number of silanols on the molecules of this invention creates a solubility or disperseability of these molecules in aqueous solutions that is not obtainable from prior art anti-microbial monomers. The inventor herein is not aware of any like molecules in the prior art.
SUMMARY OF THE DISCLOSUREWhat is disclosed and claimed herein is a composition of matter having the average general formula:
wherein the average molar ratio of x:y:z is 0.25-3:4:0.25-3, with the proviso that there is present at least one RSi-unit and at least one R′Si unit and W is independently selected from the group consisting essentially of Si, Ti, and Zr, and A1, wherein R is a cure functionality based on the chemistry selected from the group consisting of glycidoxy, amino, acrylamide, methacrylamide, acrylate, methacrylate, C2-C8 alkenyl, mercapto, ester, isocyanato, epoxycyclohexyl, carboxylic acid, and O
wherein p has a value of from 1 to 6 and R3 is selected from the group consisting of hydroxyl and alkoxy groups having 1 to 4 carbon atoms.
wherein R2 is independently selected from the group consisting of hydroxyl groups,
wherein s has a value of about 1 to 5 and y has a value of 4 wherein R1 is selected from the group consisting of:
i. a sulfonium salt of the formula:
Si(R5)2CdH2dS+(R4)2X−,
wherein R4 is independently an alkyl group or aralkyl group wherein there is a total of less than 60 carbon atoms in the molecule, and R5 is independently selected from the group consisting of hydroxyl groups,
wherein d is an integer of 1 or greater, and X− is a water soluble monovalent anion;
ii. an isothiuronium salt of the formula:
Si(R5)2dCdH2dS+C(NH2)2X−,
wherein R5 is independently selected from the group consisting of hydroxyl groups,
wherein d is an integer of 1 or greater, and X− is a water soluble monovalent anion;
iii. a phosphonium salt of the formula:
Si(R5)2CdH2dP+(R6)3X−,
wherein R6 is independently selected from an alkyl group or aralkyl group wherein there is a total of less than 60 carbon atoms in the molecule, R5 is independently selected from the group consisting of hydroxyl groups,
wherein d is an integer of 1 or greater, and X− is a water soluble monovalent anion, and
iv. an amine of the formula:
Si(R5)2CdH2dN(H)(CdH2d)NH2
wherein R5 is independently selected from the group consisting of hydroxyl groups,
wherein d is an integer of 1 or greater, and wherein (WOy) is derived from W(OR7)4 wherein (OR7) is independently selected from the group consisting of:
-
- a.—OCH3,
- b.—OCH2CH3,
- c.—OCH(CH3)2,
- d.—O(CH2)3CH3,
- e.—OCH2CH(CH3)2,
- f.—O(2-ethylhexyl),
- g. acetoxy, and,
- h. oximo.
It is to be understood that the invention may assume various alternative orientations and step sequences, except where expressly specified to the contrary. It is also understood that the specific devices and processes illustrated in the attached drawings, and described in the specification are simply exemplary embodiments of the inventive concepts disclosed and defined herein. Hence, specific dimensions, directions, steps, or other physical characteristics relating to the various embodiments disclosed are not to be considered as limiting, unless expressly stated otherwise.
The present disclosure relates to compositions of matter and methods of making the same. It is within the scope of this disclosure and as a non-limiting example, the compositions of matter described herein may have anti-microbial and/or adhesion properties. As a result, it is within the scope of this disclosure and as a non-limiting example that the compositions of matter described herein may be useful in killing and/or reducing the number of bacteria, viruses, algae, mildew, and/or mold that may exist on an item.
One method for providing the materials of this invention comprises providing the components:
wherein the molar ratio of x:y:z is 0.25-3:4:0.25-3, p and q are each independently have a value of 2 or less, and co-hydrolyzing the components in the presence of a stoichiometric amount of water, and a catalyst for hydrolysis and condensation.
By careful, controlled hydrolysis of the precursor monomers, one can obtain these materials at very low molecular weights providing a large number of silanols on the molecules, the detail of which can be found infra in the specification, and in the examples.
The materials have the average general formula:
which is derived by the hydrolysis of the silane precursors
in conjunction with the orthosilicate, or orthotitanate, orthozirconate, or orthoaluminate, having the general formula
{W(OR″′)4}y,
wherein the molar ratio of x:y:z is 0.25-3:4:0.25-3.
This hydrolysis is carried out using a stoichiometric or near stoichiometric amounts of water and a catalyst for hydrolysis and condensation. Stoichiometric amounts of water, or, an amount of water greater than stoichiometric, results in low molecular weight materials, which is one of the objectives of the method in this invention. Caution should be noted for the use of substantially lesser amounts of water as that will result in a residual amount of alkoxy in the material which is undesirable for purposes of this invention.
It is believed by the inventors herein that the key to this invention is the use of the molecule {W(OR″′)4}y as the third component of this invention. W in the case of this invention is independently selected from the group consisting of Si, Ti, Zr, and A1. Preferred for this invention is Si and Ti and most preferred is Si.
The (OR″′) group is selected from the group consisting of —OCH3, —OCH2CH3, —OCH(CH3)2, —O(CH2)2CH3, —OCH2CH(CH3)2, —O(2-ethylhexyl), acetoxy, and, oximo. Preferred for this invention are the groups —OCH3, —OCH2CH3, and —OCH(CH3) and most preferred are the —OCH3and —OCH2CH3groups. Preferred orthosilicates and orthotitanates for this invention are Si(OCH2CH3)4and Ti(—OCH(CH3)2)4.
Stoichiometry is based on the number of hydrolysable groups on the combined components. The reaction is carried out in the presence of base or acid, with acid being the preferred catalyst. The acid catalysts are preferred to be HC1,phosphoric, and acetic acids, with HC1 and phosphoric acids being most preferred.
Bases that are useable herein are amines, NaOH, KOH and the like and preferred for this invention is NaOH. The hydrolysis reaction is carried out by combining the components in a predetermined ratio and then adding acidic or basic water to the components at a controlled rate to form silanols from the alkoxy moieties. For some end use applications of the inventive materials, a slightly higher molecular weight (higher number of silanol reactive groups) is preferred and in this case, the silicate component is treated for a short period of time by acidic or basic water to cause the silicate component to hydrolyze and condense before the other components are added.
By the preferred means, the following reaction sequence is achieved:
No heat is used in this reaction as higher temperatures (in excess of about 150° C.) may result in a gelation of the reaction mixture. There is a small exotherm from the hydrolysis reaction but the heat is not sufficient to provide problems with the resultant product. No solvents are required in this reaction, but it is within the scope of this invention to utilize solvents. It should be noted that the byproduct of the hydrolysis reaction is alcohol. Typically, the products of this reaction do not need filtration.
As mentioned Supra, it is possible to enhance the molecular weight and thereby increase the amount of silanol functionality on the molecule by first mildly hydrolyzing the ortho precursor and then adding the remainder of the components.
Thus, a molecule having the following average formula may be obtained:
One can also provide a material having the formula:
by hydrolyzing the components (CH3O)3Si(CH2)3OOC(CH3)C═CH2,1Si(OCH2CH3)4 and 2 (CH3O)3Si(R5)2CdH2dP+(R6)3C1−.
A preferred material is:
The materials are liquids as prepared. In some cases, if preferred, the by-produced alcohols and any residual water can be removed to provide a solid material, and in some cases the solid material may be hard and appear to be almost crystalline and in some cases, the material may be waxy or paste-like.
These compositions of matter have anti-microbial properties and adhesion properties and are highly dispersible in aqueous solutions. The presence of a large number of silanols on the molecules of this invention creates a solubility or disperseability of these molecules in aqueous solutions that is not obtainable from prior art anti-microbial monomers. The materials of this invention are also suitable for providing adhesion in combination with ionomers, especially glass ionomers.
EXAMPLES
The tetraethylorthosilicate or tetrabutyltitanate were placed in a 40 ml vial with a magnetic stirring bar. The functional trialkoxy-silane was added and allowed to mix for 30 minutes. Water, adjusted with KOH to pH 10 or HC1 to pH 2, was added dropwise with agitation. This was allowed to hydrolyze for 60 minutes and 24 hours after which the solution was evaluated for appearance. All weights are in grams. Compound molecular weights were used to calculate the moles and molar ratios of each component.
The purpose of this study was to evaluate the effectiveness of test materials labeled #1 and #8, in killing or reducing Escherichia coli (E. coli). The standard pour plate count test method was used to evaluate Percent Reduction of Colony Forming Units (CFU).
Study DesignThe E.coli (lot number 168756) was purchased from Quanti-Cult™ and is derived from original ATCC® stock cultures. They are received dehydrated. A viable streak plate was colonized from this culture. One colony was transferred to 5 ml of sterile Tryptic Soy Broth (lot # A3303) and incubated overnight.
Anti-microbial activity is determined by comparing results from the test sample to simultaneously run controls or from the T0. The concentration of the suspension is determined using serial dilution and plate counts to determine the amount of Colony Forming Units (CFU's)/ml of suspension.
The materials tested in this study are described in the Purpose section of this report. Sterile 0.3 mM KH2PO4 buffer was inoculated to a concentration of ˜1.0-3.0×105CFU/ml. A T0 plate originated from the inoculated buffer for quantification and prepared 1:100 dilution to insure that viable inoculum was applied in the test system. The test materials were formulated in 20×150 ml test tubes. Aliquots of 0.3 grams of each of the materials (#1 and #8) were added to sterile test tubes. Five ml of Tryptic Soy Broth was added to each tube and the tubes inoculated with 1×105 CFU, E. coli. The materials were incubated for 48 hours. To of the inoculums was 9.6×104 CFU/ml. One milliliter aliquots of the test article inoculums were added to Petri dishes, Plate Count Agar added and swirled and the plates were incubated at 35° C. overnight.
ResultsThe results show 16 CFU/ml for material #1 or >99.9% reduction and material #8 had 0 CFU/ml (no growth) or 100% reduction.
Claims
1. A method of reducing the number of one or more micro-organisms, said method comprising:
- i. providing one or more micro-organisms;
- ii. treating said one or more micro-organisms provided with a composition having the average formula:
- wherein the average molar ratio of x:y:z is 0.25-3:4:0.25-3, with the proviso that there is present at least one RSi-unit and at least one R′Si unit;
- wherein W is independently selected from the group consisting essentially of Si, Ti, and Zr, and Al;
- wherein R is a cure functionality based on the chemistry selected from the group consisting of glycidoxy, amino, acrylamide, methacrylamide, acrylate, methacrylate, C2-C8alkenyl, mercapto, ester, isocyanato, epoxycyclohexyl, carboxylic acid, and
- wherein p has a value of from 1 to 6;
- wherein R3 is selected from the group consisting of hydroxyl and alkoxy
- groups having 1 to 4 carbon atoms;
- wherein R2 is independently selected from the group consisting of hydroxyl groups,
- wherein s has a value of about 1 to 5;
- wherein y has a value of 4;
- wherein R1 is selected from the group consisting of:
- a. a sulfonium salt of the formula: Si(R5)2CdH2dS+(R4)2X−
- wherein R4 is independently an alkyl group or aralkyl group
- wherein there is a total of less than 60 carbon atoms in the molecule, R5 is independently selected from the group consisting of hydroxyl groups,
- wherein d is an integer of 1 or greater, and
- wherein X− is a water soluble monovalent anion;
- b. an isothiuronium salt of the formula: Si(R5)2CdH2dS+C(NH2)2X−,
- wherein R5 is independently selected from the group consisting of hydroxyl groups,
- wherein d is an integer of 1 or greater, and
- wherein X− is a water soluble monovalent anion;
- c. a phosphonium salt of the formula: Si(R5)2CdH2dP+(R6)3X−
- wherein R6 is independently selected from an alkyl group or aralkyl group wherein there is a total of less than 60 carbon atoms in the molecule, R5 is independently selected from the group consisting of hydroxyl groups,
- wherein d is an integer of 1 or greater, and
- wherein X− is a water soluble monovalent anion; and
- d. an amine of the formula: Si(R5)2CdH2dN(H)(CdH2d)NH2
- wherein R5 is independently selected from the group consisting of hydroxyl groups,
- wherein d is an integer of 1 or greater; and
- wherein (WOy) is derived from W(OR7)4where (OR7) is independently selected from the group consisting of:
- A.—OCH3,
- B.—OCH2CH3,
- C.—OCH(CH3)2,
- D.—O(CH2)3CH3,
- E.—OCH2CH(CH3)2,
- F.—O(2-ethylhexyl),
- G. acetoxy, and
- H. oximo.
2. The method of claim 1, wherein said composition has anti-microbial and/or adhesion properties.
3. The method of claim 1, wherein said one or more micro-organisms are one or more bacteria.
4. The method of claim 1, wherein said one or more bacteria are Escherichia coli (E. coli).
5. The method of claim 1, wherein said one or more micro-organisms are one or more viruses.
6. The method of claim 1, wherein said one or more micro-organisms are one or more algae.
7. The method of claim 1, wherein said one or more micro-organisms are one or more mildews.
8. The method of claim 1, wherein said one or more micro-organisms are one or more molds.
9. The method of claim 1, further comprising the step of providing said composition with one or more ionomers.
10. The method of claim 9, wherein said one or more ionomers are one or more glass ionomers.
11. The method of claim 9, wherein said one or more ionomers are one or more modified glass ionomers.
12. The method of claim 9, further comprising the step of applying said composition to a surface or substrate.
13. The method of claim 1, further comprising adding said composition into an aqueous solution.
14. The method of claim 13, wherein said composition is soluble and dispersible within said aqueous solution.
15. The method of claim 14, wherein said solubility and disperseability of said composition within said aqueous solution is due to a large number of silanols.
16. The method of claim 1, wherein said method providing said composition is performed without the addition of heat to reduce gelation of said composition.
17. The method of claim 1, wherein said composition is a gel or a liquid.
18. The method of claim 1, further comprising the step of removing an amount of water from said composition to provide a substantially solid material.
19. The method of claim 18, wherein said solid material composition is substantially crystalline, substantially waxy, or substantially paste-like.
20. The method of claim 1, further comprising the step of providing a catalyst for hydrolysis and condensation of said composition.
Type: Application
Filed: Apr 3, 2020
Publication Date: Jul 23, 2020
Inventor: John D. Blizzard (Bay City, MI)
Application Number: 16/839,678
