Polymeric propanedioate and cyanoacrylate based concrete surface sealers

Abstract

A sealing method is provided comprising providing a substrate having a plurality of holes, placing a polymerizable composition on a surface of the substrate, the polymerizable composition comprising a monofunctional, difunctional or multifunctional methylene malonate or cyanoacrylate, and initiating a polymerization reaction, wherein the polymerization is initiated by an initiator or a latent activator.

Description

Technical Field

[0001] This invention relates to surface sealing compositions, and more specifically, to sealing compositions for sealing concrete surfaces. Background Technology

[0002] Concrete and other similar materials are frequently used in the construction industry. However, concrete is easily damaged by many processes, including the expansion of corrosion products from the reinforcing steel, freezing of internal moisture, flame or radiant heat, aggregate expansion, seawater effects, bacterial corrosion, leaching, water erosion, and other physical and chemical damage. Therefore, it is desirable to provide a concrete coating that can prevent one or more of these problems.

[0003] U.S. patents with patent numbers 8,609,885, 8,884,051 and 9,181,365, and U.S. patent applications with publication numbers 2014 / 1329980 and 2015 / 0056879 are related to this invention and are incorporated herein by reference for all purposes.

[0004] Despite the above teachings, there is still a need for a fast-polymerizing concrete sealant composition that can be easily integrated into the construction process. Summary of the Invention

[0005] This invention satisfies one or more of the above-mentioned needs and relates to a sealing method comprising providing a substrate having a plurality of pores, placing a polymerizable composition on the surface of the substrate, the polymerizable composition comprising a monofunctional, bifunctional, or multifunctional methylene malonate or cyanoacrylate, and initiating polymerization of the composition. Polymerization can be initiated by an initiator or a latent activator.

[0006] The substrate may be selected from concrete, plaster, brick, or combinations thereof. The composition may contain additives to increase the glass transition temperature of the composition. The method may include sealing the plurality of pores with the composition to prevent liquid from accumulating in one or more of the pores. The polymerization may occur within hours, one hour, or even 30 minutes after initiation. The polymerized composition may be substantially transparent. The polymerization may be anionic. The composition may be selected from diethyl methylene malonate (DEMM), dimethyl methylene malonate (DMMM), di-n-propyl malonate, diisopropyl methylene malonate, dibenzyl methylene malonate, methylene β-ketoester, methylene β-diketone, methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, n-butyl cyanoacrylate, 2-octyl cyanoacrylate, and combinations thereof. The glass transition temperature of the composition is at least about 50°C.

[0007] The composition may include a malonic acid ester component and a cyanoacrylate component. The composition may be free of any cyanoacrylate component. The composition may be free of any malonic acid ester component. The composition may increase the hydrophobicity of the substrate by at least about 5%, at least about 10%, at least about 15%, or even at least about 20%. The composition may reduce the water absorption of the substrate by at least about 5%, at least about 10%, at least about 15%, or even at least about 20%. The composition may include pyrolytic silica, polymethyl methacrylate (PMMA), sulfonated polymers, carboxylated polymers, polymer fibers, surface-modified silica, or combinations thereof.

[0008] The method may include rolling, brushing, or spraying the composition onto a substrate. The method may also include mixing the composition into the substrate prior to curing the substrate.

[0009] The composition may be substantially free of any curing agent. The composition can polymerize under ultraviolet light. The composition can polymerize under heat. The composition can polymerize at ambient temperature without additional stimulation, but polymerization can be accelerated by applying stimulation.

[0010] The present invention also provides the application of the method of any one of the preceding claims in sealed concrete. Detailed Implementation

[0011] The explanations and descriptions provided herein are intended to familiarize others skilled in the art with the invention, its principles, and practical applications. The specific embodiments of the invention described above are not intended to be exhaustive or limiting. The scope of the invention should be determined by referring to the appended claims and the full scope of their equivalents. All disclosures in articles and references, including patent applications and publications, are incorporated herein by reference for all purposes. Other combinations may also be obtained from the claims and are incorporated herein by reference.

[0012] This application claims priority to U.S. Provisional Application No. 62 / 396,600, filed September 19, 2016, the contents of which are incorporated herein by reference for all purposes.

[0013] This invention proposes coating porous substrates with monomer compositions. The monomer composition can be a one-component material that polymerizes immediately at room temperature or at a later specified time. The monomer composition is likely to polymerize at room temperature without the addition of any initiator or stimuli. However, an initiator or stimuli can also be used to induce polymerization of the composition. The polymerization time of the composition can be varied to suit specific needs. In other words, the composition can be applied as a coating to a second material, providing sufficient open time for coating without polymerization, and the composition will not polymerize before contact with a stimuli or surface. Therefore, the open time of the application process can be extended by several minutes or even an hour without concern about premature polymerization. It is also possible that polymerization of the composition will only be initiated upon contact with certain substrates.

[0014] The composition provides one or more of the following benefits: It can form a non-sticky surface. It can polymerize at room temperature without the need for additional initiators or irritants. It can polymerize in less than one hour, making it suitable for construction environments.

[0015] The composition can be applied directly to concrete or other porous materials. Polymerization can occur within 60 minutes of application, or even within 30 minutes. The composition can also be polymerized via electropolymerization, mechanically initiated polymerization, dual-curing polymerization, thermally initiated polymerization, coordination polymerization, or nucleophilic polymerization. The composition can undergo solution polymerization or emulsion polymerization. The composition can also undergo random copolymerization or block copolymerization.

[0016] The composition may contain additives to impart toughness, increase the glass transition temperature, or increase the viscosity of the composition. To give the adhesive composition sufficient viscosity to be applied to the desired location without significant dripping, a viscosity modifier may be added. The viscosity modifier may be selected from one or more fillers, including pyrolytic silica, polymethyl methacrylate (PMMA), sulfonated polymers, carboxylated polymers, polymer fibers, surface-modified silica, and combinations thereof.

[0017] The substrate can be any porous substrate (e.g., it can have multiple pores). The substrate may be selected from concrete, plaster, brick, or combinations thereof. The composition can have the effect of sealing multiple pores to prevent liquid from accumulating in one or more of the pores. This sealing can improve the hydrophobicity of the substrate and also reduce the amount of water absorbed by the substrate. The composition can further be used as a corrosion inhibitor.

[0018] The composition can be specifically configured to polymerize rapidly depending on the chosen application. Not only is the composition capable of rapid polymerization, but polymerization can also occur faster or slower by adding or removing stimuli, allowing for on-demand polymerization. Polymerization can occur within 2 hours, 1 hour, or even 30 minutes after initiation. After polymerization, the composition is substantially transparent, leaving the substrate surface unaffected. Alternatively, the composition may include pigments to provide the desired substrate coloring.

[0019] The composition can be rolled, brushed, or sprayed onto the substrate. The composition can be mixed into the substrate before curing.

[0020] Unlike many coatings, the composition may be free of a curing agent. The inherent properties of malonate or cyanoacrylate can promote polymerization without the need for additional chemical components to initiate it. The composition may also polymerize upon exposure to selected stimuli. The composition can polymerize upon application of ultraviolet light. The composition can polymerize upon heating. The composition can polymerize at ambient temperature without additional stimuli, but polymerization can be accelerated by adding stimuli.

[0021] The compositions described herein can be used on construction sites to coat any porous building materials that may be damaged by moisture, corrosion, salt, or other materials that may enter and / or damage the pores in the substrate.

[0022] As used herein, unless otherwise stated, any component of the invention may be excluded from a class (list); and / or any component of the Markush group may be excluded from the group.

[0023] Unless otherwise stated, any numerical value described herein includes all values ​​from lower to higher values ​​in increments of one unit, provided that there is an interval of at least two units between any lower and any higher value. As an example, if the amount, property, or process variable of a component is mentioned, such as temperature, pressure, time, etc., and is, for example, 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, this means that intermediate range values, such as 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc., are all within the teachings of this specification. Similarly, individual intermediate values ​​are also within the teachings. For values ​​less than 1, one unit is considered as 0.0001, 0.001, 0.01, or 0.1, as appropriate. These are merely examples to illustrate that all possible combinations of numerical values ​​between the listed minimum and maximum values ​​should be considered as expressly stated in a similar manner in this application. It can be seen that quantities expressed as "parts by weight" herein also consider the same range expressed as weight percentages. Therefore, in similar expressions such as “at least 'x' parts by weight of the resulting composition”, the range of “x” representing the same amount as a weight percentage of the resulting composition is also considered.

[0024] Unless otherwise stated, all ranges include all numbers between the endpoints. When combining ranges, use "about" or "approximately" to apply to both ends of the range. Therefore, "about 20 to 30" is intended to encompass "about 20 to about 30," including at least the specified endpoints.

[0025] All publicly available information in articles and references, including patent applications and publications, is incorporated herein by reference for all purposes. The term “consistently of” shall include the indicated element, ingredient, component, or step, as well as other elements, components, or steps that do not materially affect the essential and novel features of the combination. The terms “comprising” or “including” used to describe combinations of elements, ingredients, components, or steps of the invention also cover embodiments consisting of or substantially consisting of said elements, ingredients, components, or steps.

[0026] Multiple elements, components, components, or steps may be provided through a single integrated element, ingredient, component, or step. Alternatively, a single integrated element, ingredient, component, or step may be divided into multiple separate elements, ingredients, components, or steps. The use of "a" or "an" to describe an element, ingredient, component, or step is not intended to exclude additional elements, ingredients, components, or steps.

[0027] It should be understood that the above description is intended to be illustrative and not restrictive. Many embodiments and applications, in addition to the examples provided, will be apparent to those skilled in the art upon reading the above description. Therefore, the scope of the invention should not be determined by reference to the above description, but rather by reference to the appended claims and the full scope of their equivalents. All disclosures in articles and references, including patent applications and publications, are incorporated herein by reference for all purposes. The omission of any aspect of the subject matter disclosed herein in the following claims does not constitute a disclaimer of liability for such subject matter, nor should it be considered that the inventors do not consider such subject matter to be part of the disclosed inventive subject matter.

Claims

1. A sealing method, comprising: A substrate having multiple pores is provided, the substrate being selected from concrete, plaster, or a combination thereof; A polymerizable composition is placed on the surface of the substrate, the polymerizable composition comprising monofunctional, difunctional, or polyfunctional methylene malonate and cyanoacrylate; Initiate polymerization of the composition; The method further includes mixing the polymerizable composition into the substrate before curing the substrate. The polymerization is initiated by using an initiator or a latent activator, wherein the composition contains additives to increase the glass transition temperature of the composition; The glass transition temperature of the composition is at least 50°C.

2. The method of claim 1, further comprising sealing the plurality of orifices with the composition to prevent liquid from accumulating in one or more of the plurality of orifices.

3. The method according to claim 1 or 2, wherein the polymerization occurs within 2 hours after initiation.

4. The method according to claim 1 or 2, wherein the polymerization occurs within 1 hour after initiation.

5. The method according to claim 1 or 2, wherein the polymerization occurs within 30 minutes after initiation.

6. The method according to claim 1 or 2, wherein the composition is substantially transparent after polymerization.

7. The method according to claim 1 or 2, wherein the polymerization is anionic polymerization.

8. The method according to claim 1 or 2, wherein the methylene malonate is selected from diethyl methylene malonate, dimethyl methylene malonate, di-n-propyl methylene malonate, diisopropyl methylene malonate, dibenzyl methylene malonate, and combinations thereof, and the cyanoacrylate is selected from methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, n-butyl cyanoacrylate, 2-octyl cyanoacrylate, and combinations thereof.

9. The method according to claim 1 or 2, wherein the composition increases the hydrophobicity of the substrate by at least 5%.

10. The method according to claim 1 or 2, wherein the composition increases the hydrophobicity of the substrate by at least 10%.

11. The method according to claim 1 or 2, wherein the composition increases the hydrophobicity of the substrate by at least 15%.

12. The method according to claim 1 or 2, wherein the composition increases the hydrophobicity of the substrate by at least 20%.

13. The method according to claim 1 or 2, wherein the composition reduces the water absorption rate of the substrate by at least 5%.

14. The method according to claim 1 or 2, wherein the composition reduces the water absorption rate of the substrate by at least 10%.

15. The method according to claim 1 or 2, wherein the composition reduces the water absorption rate of the substrate by at least 15%.

16. The method according to claim 1 or 2, wherein the composition reduces the water absorption rate of the substrate by at least 20%.

17. The method according to claim 1 or 2, wherein the composition comprises pyrolytic silica, polymethyl methacrylate, sulfonated polymer, carboxylated polymer, polymer fiber, surface-modified silica, or a combination thereof.

18. The method according to claim 1 or 2, comprising rolling, brushing or spraying the composition onto the substrate.

19. The method according to claim 1 or 2, wherein the composition does not contain any curing agent.

20. The method according to claim 1 or 2, wherein the composition is polymerized when ultraviolet light is applied.

21. The method according to claim 1 or 2, wherein the composition polymerizes upon heating.

22. The method according to claim 1 or 2, wherein the composition polymerizes at ambient temperature without additional stimulation, but applying stimulation may cause it to polymerize more quickly.

23. The application of the method according to any one of claims 1-22 in sealed concrete.