TW201343756A - Application of high toughness, low viscosity nano-molecular resin for reinforcing pothole patching materials in asphalt and concrete base pavement - Google Patents

Abstract

Described herein are methods of improving the durability of concrete by the infusion of the concrete with a low-viscosity oligomeric solution, and subsequent curing of the oligomeric solution to form a high toughness polymer. Also described herein are compositions containing concrete and high toughness polymers, and formed articles made from concrete and high toughness polymers. The methods and compositions are useful for improving the durability of concrete roads and structures, as well as the durability of repairs to concrete roads.

Description

Application of high-toughness and low-viscosity nano-molecular resin for reinforcing pothole repair materials on asphalt and concrete-based pavement Reference related application

The present application claims the benefit of U.S. Patent Application Serial No. 13/096,750, filed on Apr. 28, 2011, which is hereby incorporated by reference.

A research or development statement funded by the federal government

The invention of the present application was completed by the government under the auspices of the Ministry of Commerce-NIST, No. 70NANB10H019. The government certainly has rights to this invention.

Field of invention

The invention relates to the application of a high toughness and low viscosity nano molecular resin for reinforcing a pothole repairing material to a pavement based on asphalt and concrete.

Background of the invention

Damage to concrete structures such as roads, walkways, bridges, and even buildings is a long-term problem worldwide. Natural corrosion process The combination with contamination and/or overuse has a severe impact on the life of such structures.

Damage to the surface of concrete roads is caused by several reasons - freezing damage, post-finishing, coatings on the "capped" layer after the main cast sheet has been compacted and found to be low, or mechanical damage, caused by, for example, a vehicle. Concrete can have a high porosity content that allows moisture to enter the surface and when frozen, it creates tensile stress causing spalling and cracking of the surface. In addition, the concrete surface is peeled off by the use of deicers to remove ice and snow. Applying de-icing agents to a road covered with snow or ice causes rapid heat dissipation from the road surface. This melting of ice on the surface can cause freezing of any moisture that has been absorbed in the material, which can cause injury.

The occurrence of potholes on asphalt and concrete pavements has long been a problem for all transportation departments in the country and around the world. Over the years, improvements in materials, methods of repair and deployment, and support for dispensing systems have greatly helped to achieve more durable and economical repairs. However, the life of a patched pothole is usually calculated in days or months, not years. The cost of pothole repair is $1 million per year for city and state transportation and maintenance departments and federal units. In addition, the presence of potholes poses a significant safety risk to vehicles, structures, and pedestrians. An intrinsic reaction of a driver to steering away from a pothole often presents a danger to neighboring vehicles and pedestrians and can cause serious traffic disturbances.

Salt suggests that the main mechanism for forming potholes is different in different climates or environmental conditions, although the presence of water in the grassroots is a major cause of pothole formation. Potholes typically penetrate the cracks in the ground via moisture and water and accumulate on the basement of the road surface. In colder climates, subsequent freeze-thaw cycles push up the road At the same time, the traffic oppresses the road surface and the rupture of the road surface causes the material to disintegrate and form a pothole. Or, in warmer regions, the freeze-thaw cycle plays a less important role. In areas such as Florida, the combination of temperature and the effect of water on the integrity of the road material and under the ground reduces the integrity of the surface and causes its hazards. Furthermore, traffic, poor structures, aged concrete or a combination of these factors also play an important role in all regions. Therefore, by limiting the amount of water penetrating through road cracks or subsequent repairs, the adverse effects of moisture on road quality can be mitigated.

Salt believes that the failure or short life of pothole repair is due to the fracture of the precursor due to the low toughness of the repair material, low resistance to rutting and low strength. Moisture further assists in the removal of the anchoring agent in the repair material, followed by the repair material and the pavement substrate. Thus, the life of the pothole repair can be substantially improved by increasing the dynamic toughness and strength and removing the voids present in the repair mixture that provide a path for moisture penetration.

Similarly, buildings, bridges, and other concrete structures continue to be impacted by weathering processes that are primarily catalyzed by water. Exfoliation and breakage of water bridges and structures, exposed structural components such as steel beams and steel bars can further damage and even corrode concrete. Furthermore, acid rain not only causes unsightly discoloration of the exterior walls of the building, but also causes significant damage and deterioration of concrete buildings, bridges and other concrete surfaces because the acidic solution dissolves the calcium hydrate in the cement. Due to the vast and aging highway system in the United States, it is clear that there is a need to find a way to cost-effectively protect the roads and bridges that make up our infrastructure.

One method that has been used for asphalt concrete is polymer upgrading Green ("PMA"). PMA has become commonplace in road paving and roofing and accounts for 20% of all asphalt used today. Improvements in anti-rutting, thermal cracking, fatigue damage, peel performance and temperature sensitivity allow polymer upgrading fixers to replace asphalt in many paving applications, including hot mix, cold mix, chip seal, hot and cold Sew, repair, and slurry seal. PMA has been used wherever performance and durability are required. Asphalt specifiers have found that many Superpave grades (Superpave, which represents an excellent performance asphalt pavement, representing an improved, standardized system for designating, testing, and designing asphalt materials) require polymer modification to meet high temperature rutting and All the requirements for resistance to thermal cracking at low temperatures.

A typical design for a pit repair is to raise the surface above the road surface along the repaired perimeter and cover its material directly on the road surface. This can be done to prevent water intrusion. Furthermore, the area covered must be sufficiently thick so that no cracks can occur which can damage and misalign the patch. Although it is safer to make the repair flush with the road surface, this is impossible without a tight waterproof joint. It is expected that the production will be repaired, and it will not produce a bump in the shadow locomotive knight. It is further contemplated to have a repair material that will not be compacted by traffic, so it can be set at an expected height without fear of changing over time.

A typical implementation of asphalt repair is to wait long enough until the material is sufficiently cooled to be sufficiently hard to allow transportation. This can result in long stop times, which are devastating and expensive. It is advantageous to allow road excavation in a relatively short period of time without damaging the fast-curing thermoset.

A typical design implementation method is to temporarily repair the pothole repair material above the road surface and reduce it to the expected final height according to traffic. degree. This is difficult to estimate because how much time will be fixed and how much will be inaccurate. The climate is also an important change here, as the stability of asphalt repairs is getting faster and faster. It can be seen that a repair that is too high will result in an unsafe bump on the locomotive knight, and the repair that is too low can cause water accumulation. It is advantageous to have a repair material that does not change significantly after setting, to simplify the design, and to remove uncertainty.

Traditionally, polymers used for asphalt upgrading are typically thermoplastic polymers that can be added to a mixture of solids. Typically, the addition of this polymer involves the addition of a solid polymer, possibly after grinding to a pitch containing about 325 °F and shear mixing the vessel for a period of time to determine complete mixing. However, this is often a labor-intensive and capital-intensive process.

Despite the advantages of adding polymers to asphalt to improve physical and mechanical properties, the polymers currently in use may not be able to optimize the performance of the asphalt. Moreover, the cost of adding the polymer to the asphalt in a sufficiently high amount to meet the expected specifications is prohibitively expensive. Therefore, the industry is looking forward to ways to promote the performance of polymer modifiers, such as the development of additional chemical agents. Many of these agents are known as crosslinkers and are believed to crosslink the polymer to the asphaltene component or crosslinked polymer of the asphalt and improve its properties. However, the incorporation of polymers and other components into the asphalt can cause a variety of problems that can jeopardize the necessary asphalt properties. Moreover, these methods are incompatible with the use of cement concrete. Accordingly, it is contemplated to develop techniques and methods for incorporating polymers into concrete that produce concrete having improved durability without compromising the necessary properties of the material.

Summary of invention

According to one embodiment, the present invention is directed to a method of increasing the durability of concrete and concrete structures by adding a polymer to a concrete structure. A low-viscosity, fast-curing oligomer solution containing a nanomolecular precursor is injected into the concrete and the monomer is polymerized into a polymer with high toughness to provide increased strength and durability of the concrete, as well as to provide surface degradation. A barrier to moisture and chemicals entering.

According to another embodiment, the present invention is directed to a method of increasing the durability of concrete and concrete structures by incorporating a thermoset polymer into the concrete structure. A low-viscosity, fast-curing oligomer solution containing a nanomolecular precursor is injected into the concrete and the monomer is polymerized into a thermosetting polymer with high toughness to provide increased strength of the concrete and to provide moisture that causes surface deterioration. A barrier to entry with chemicals. In certain embodiments, the thermoset polymer is a polymer formed by ring opening displacement polymerization. Specific examples include polydicyclopentadiene and polynorbornene.

According to another embodiment, the invention relates to a composition comprising concrete and a polymer formed by ring-opening displacement polymerization. The compositions of the embodiments of the present invention form highly durable materials that are resistant to moisture embedding and have improved resistance to weather or use degradation.

According to another embodiment, the invention relates to a shaped article comprising concrete and a polymer formed by ring-opening displacement polymerization. Shaped articles of embodiments of the present invention can be used, for example, in reinforcement of buildings or structures, such as buildings or bridges, as structures or barriers for reinforcing military or security areas, for highway concrete barriers, or for New or replacement profiles for roads.

Figure 1 is a schematic illustration of the infiltrated polyDCPD aggregate-asphalt mixture to form a hardened continuous web therein. Although this figure illustrates asphalt concrete and its repair materials, this method can also be used equivalently for cement concrete and its repairing depth materials.

Figure 2 is a two layer structure with selective strengthening and infiltration with an oligomer solution to a top layer having a depth less than the total thickness of the structure.

Detailed description of the preferred embodiment

SUMMARY In a first embodiment, the present invention comprises a method of increasing the strength and/or durability of concrete comprising injecting the concrete with an oligomer solution having a viscosity of less than about 200 cps and curing in less than about 24 hours. The oligomer solution comprises a nano molecular precursor, an optional solvent, an optional catalyst, an optional accelerator, and/or an optional initiator; and a cantilever beam having a notch The crash toughness is measured as a toughness polymer greater than 6.0 ft-lbs/in.

In another embodiment, the nano molecular precursor comprises an olefin, an ester, a urethane, an imine, a melamine, a urea formaldehyde, a decane, a phenol, a maleimide or an epoxide. In certain embodiments, the nano molecular precursor comprises a monocyclic olefin. In another embodiment, the nanomolecular precursor comprises a cyclic olefin that undergoes ring opening displacement polymerization ("ROMP"). In another embodiment, the nano molecular precursor comprises a five-, six-, seven-, eight-, nine-, ten- or n-membered cyclic olefin, which is bridged or unbridged, which may comprise two or two The above fusion ring is subjected to ring-opening displacement polymerization, wherein n is an integer such as in the range of 5 to 20, 5 to 15, or 5 to 10. In another embodiment, the nano molecular precursor comprises a mixture of monomers, dimers, trimers, and/or tetramers of ROMP-crossed cyclic olefins, and mixtures of two or more thereof are used. In order to control the reaction speed. In another embodiment, the nano molecular precursor comprises cyclopentadiene (ie, DCPD or C ₁₀ H ₁₂ ) or monomeric, dimeric, and/or trivalent of norbornene (ie, C ₇ H ₁₀ ). A mixture of polymers, and a mixture of two or more of these is used to control the reaction rate.

In another embodiment, the nanomolecular precursor comprises a combination of a monomer, dimer, and/or trimer of a cyclic olefin with one or more additional monomeric forms. In certain embodiments, the additional monomer comprises a monoester, an epoxide, and/or an olefin. In certain embodiments, the cyclic olefin comprises DCPD or norbornene. In certain embodiments, the cyclic olefin comprises DCPD. In certain embodiments, this additional monomer comprises butadiene or ethylene.

In another embodiment, the oligomer solution further comprises a solvent. In certain embodiments, the solvent is an anhydrous solvent, and in certain embodiments, the solvent is an organic solvent. In certain embodiments, the solvent is an olefin. Examples of alkenes include styrene, ethylene, and butadiene.

In certain embodiments, the oligomer solution further comprises a catalyst. In some embodiments, the catalyst is a ROMP catalyst. In certain embodiments, the catalyst is a ruthenium or molybdenum catalyst. In some embodiments, the catalyst is a Grubbs-type catalyst. In some embodiments, the catalyst is a Schrock-type catalyst. In some embodiments, the catalyst is a Piers-type catalyst. In a certain In some embodiments, the catalyst is a Hoveyda-type catalyst. In certain embodiments, the catalyst is a Hoveyda-Grubbs-type catalyst. In some embodiments, the catalyst is a "blackbox" catalyst. In certain embodiments, the catalyst is a titanocene catalyst.

In another embodiment, the oligomer solution further comprises an accelerator, a curing agent, an inhibitor, and/or an accelerator. In certain embodiments, additional additives may be present. Additional additives that may be included include, but are not limited to, processing aids, adhesive components, inorganic materials, fillers, and lubricants.

In another embodiment, the oligomer solution has no more than about 200 cps, 180 cps, 160 cps, 150 cps, 140 cps, 130 cps, 120 cps, 110 cps, 100 cps, 90 cps, 80 cps, 70 cps, 60 cps, 50 cps, 40 cps, 30 cps, or 20 cps. Viscosity. In another embodiment, the oligomer solution is less than about 12 hours, less than 10 hours, less 8 hours, less than 6 hours, less than 4 hours, less than 2 hours, less than 1 hour, less than 30 minutes, less than 15 minutes, less than Curing is carried out for 10 minutes, less than 5 minutes, less than 1 minute, less than 30 seconds, less than 1 second, or about 1 second or less. Furthermore, in another embodiment, the oligomer solution is at about 24 hours, 18 hours, 12 hours, 10 hours, 8 hours, 6 hours, 5 hours, 4 hours, 3 hours, 2 hours, 1 hour, Curing in 30 minutes, 15 minutes, 10 minutes, 5 minutes, 2 minutes, 1 minute, 30 seconds, 15 seconds, 10 seconds, 1 second, 0.5 seconds. In another embodiment, the oligomer solution is from about 1 minute to about 24 hours, from about 1 minute to about 12 hours, from about 1 minute to about 8 hours, from about 1 minute to about 6 hours, From about 1 minute to about 4 hours, from about 1 minute to about 2 hours, from about 1 minute to about 1 hour, from about 1 minute to about 30 minutes, from about 1 minute Minutes to about 15 minutes, from about 1 minute to about 10 minutes, from about 1 minute to about 5 minutes, from about 10 minutes to about 24 hours, from about 10 minutes to about 12 hours, from about 10 minutes to about 8 hours From about 10 minutes to about 6 hours, from about 10 minutes to about 4 hours, from about 10 minutes to about 2 hours, from about 10 minutes to about 1 hour, from about 10 minutes to about 30 minutes, from about 30 minutes Up to about 24 hours, from about 30 minutes to about 12 hours, from about 30 minutes to about 8 hours, from about 30 minutes to about 6 hours, from about 30 minutes to about 4 hours, from about 30 minutes to about 2 hours, From about 30 minutes to about 1 hour, from about 1 hour to about 24 hours, from about 1 hour to about 12 hours, from about 1 hour to about 8 hours, from about 1 hour to about 6 hours, from about 1 hour to About 4 hours, from about 1 hour to about 2 hours, from about 2 hours to about 24 hours, from about 2 hours to about 12 hours, from about 2 hours to about 8 hours, from about 2 hours to about 6 hours, or Curing from about 2 hours to about 4 hours.

In another embodiment, the polymer formed comprises a thermoset or thermoplastic polymer. In certain embodiments, the polymer formed comprises a thermoset polymer. In certain embodiments, the polymer formed comprises a thermoplastic polymer. In certain embodiments, the polymer comprises a copolymer or a composite. In certain embodiments, the copolymer or composite is a thermoset polymer. In certain embodiments, the copolymer or composite is a thermoplastic polymer. In certain embodiments, the polymer is a polyolefin, polyester, polyurethane, polyimine, poly(melamine-co-formaldehyde), poly(urea-formaldehyde), decane, diversified Phenol, poly(methyleneimine-decalamine), epoxide, or polydicyclopentadiene. In certain embodiments, the polymer is formed from a monocyclic olefin. In certain embodiments, the polymer is a A polymer formed from ROMP. In certain embodiments, the polymer is a polyDCPD. In certain embodiments, the polymer is polynorbornene.

In another embodiment, the polymer has a toughness of at least about 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, or 9.0 ft-lb/in as measured by a notched Izod impact ASTM D256. In certain embodiments, the polymer has a notched Izod impact ASTM D256 of from about 2.0 ft-lb/in to about 10.0 ft-lb/in, from about 3.0 ft-lb/in to about 10.0 ft. -lb/in, from about 4.0 ft-lb/in to about 10.0 ft-lb/in, from about 5.0 ft-lb/in to about 10.0 ft-lb/in, from about 6.0 ft-lb/in to about 10.0 Ft-lb/in, from about 7.0 ft-lb/in to about 10.0 ft-lb/in, from about 5.0 ft-lb/in to about 12.0 ft-lb/in, from about 6.0 ft-lb/in to about 12.0 ft-lb/in, from about 7.0 ft-lb/in to about 12.0 ft-lb/in, or from about 8.0 ft-lb/in to about 12.0 ft-lb/in.

In another embodiment, the concrete infused by the oligomer solution comprises asphalt concrete or cement concrete. In certain embodiments, the concrete is asphalt concrete. In certain embodiments, the concrete is cement concrete. In certain embodiments, the asphalt concrete comprises recycled material. In certain embodiments, the recycled material comprises automotive tires. In certain embodiments, the cement concrete comprises Portland cement, masonry cement, mortar cement, gypsum, calcium aluminate cement, hydratable alumina, hydratable alumina, colloidal oxidation Antimony, antimony oxide, magnesium oxide and may also include limestone, hydrated lime, volcanic ash, fly ash, granulated slag, metakaolin, rice husk ash, vermiculite, oil well combined mortar, or hydraulic cement fixing agent. In certain embodiments, the cement concrete comprises Portland cement, fly A combination of ash, slag cement or the like. In certain embodiments, the cement concrete comprises recycled material. In certain embodiments, the recycled material comprises recycled cement concrete.

In another embodiment, the concrete of the present invention is used to form a road or runway, a structural element or surface, a decorative element or surface, or a preform. In certain embodiments, the concrete used comprises cement concrete. In certain embodiments, the concrete used herein comprises asphalt concrete.

In another embodiment, the concrete of the present invention is used to repair a damaged surface. In certain embodiments, the damaged surface comprises a concrete surface. In certain embodiments, the damaged concrete surface comprises a cement concrete or asphalt concrete surface. In some embodiments, the damaged concrete surface comprises a road surface or a runway. In some embodiments, the damaged surface comprises a building or bridge surface. In some embodiments, the surface comprises a pothole or a crocodile crack. In certain embodiments, the repair material of the method of the present invention is approximately flush with the road surface rather than raised or overlapped, and the repair material is bonded to the road material and sealed against the ingress of water. In some embodiments, the material of the method of the present invention is used to set the appearance and height of the repair and is therefore not subject to subsequent traffic changes. In some embodiments, the material of the method of the present invention is used to set the shape and height of the repair, so that softening on a hot day does not cause traffic rutting. In certain embodiments, the material of the method of the present invention is for rapid curing so that the road can be opened for a short period of time.

In another embodiment, a method of improving the durability of concrete comprises adding the oligomer material to at least one precursor to the concrete. in In certain embodiments, the oligomer material is added to the aggregate followed by the oligomer/aggregate mixture asphalt or cement fixing agent. In certain embodiments, the oligomer material is added to a fixing agent, and then the fixing agent/oligomer mixture is combined with the aggregate. In certain embodiments, the oligomer material is added to the finished concrete mixture prior to settling.

In certain embodiments, the oligomer material replaces the anchor in the concrete.

In certain embodiments, the method of the invention comprises removing material from the pothole, followed by cleaning the pothole (typically with pressurized air or water or another solvent), optionally spraying the oligomer solution of the invention to the pit In the hole, filling the pothole with a concrete formula, optionally waiting for the concrete formulation to harden, spraying, pouring or coating the concrete formulation with sufficient oligomer solution to fill the voids in the material and/or prevent water from entering the concrete. And / or increase the durability of the repair. In some embodiments, the method includes forming a two-layer structure in a pothole. The two-layer structure may comprise a top layer or portion (eg, at a thickness of about 5 cm or less, such as about 4.5 cm or less, about 4 cm or less, or about 3.8 cm or less), which is an The polymer solution is infiltrated or strengthened with a resulting polymer to a porosity of about 5% or less (e.g., about 4% or less or about 3% or less) and comprises a bottom layer or portion (e.g., The same or different thickness), which is first deposited in the pothole and then substantially densified to a porosity of about 8% or less (eg, about 5% or less, about 4% or less, or about 3% or less) ). The viscosity and porosity of the oligomer solution can be adjusted to control the incorporation range of the oligomer solution, so the bottom layer may or may not be fortified by the resulting polymer. This two-layer structure (the top or part of which is selectively strengthened and the oligomer solution Infiltration into a depth less than the overall thickness of the structure has the advantage of reducing the use of polymeric materials, reducing the cost of pothole repair, and reducing the leakage of polymer reinforcement to the bottom or sides of the pothole. This top layer has the expected properties, including: (1) high toughness and prevention of cracking; (2) high strength to prevent rutting and prevent point loading; (3) impervious to water and prevent degradation and freeze/thaw; (4) Provides partial resin intrusion into the original road material to soften the rigid transition to the existing road material - this slows the crack at the interface; and (5) optionally has sand on the top surface, anti-slip, color matching road and joining resistance UV. The underlying features of the underlayer include: (1) providing road support to limit the bending load on the top layer; (2) cost-effective and less resin used; (3) accepting partial resin injection to have a softened interface with the top layer and Prevent cracks at the interface; and (4) provide a good rigidity fit and thermal expansion coefficient with the existing road bed.

In another embodiment, the method comprises selectively depositing an oligomer solution on a concrete area. The selective deposition may be applied to the concrete, such as a carriageway, bus route, truck route, or other area where heavy impact is required and additional durability is required before the concrete is deposited, spraying the oligomer material. The oligomer material is poured onto the concrete or poured onto the concrete.

In another embodiment, the invention comprises a composition comprising a polymer formed from ROMP and concrete. In certain embodiments, the concrete comprises asphalt concrete or cement concrete. In certain embodiments, the polymer formed from ROMP comprises a cyclic olefin. In certain embodiments, the polymer formed from ROMP comprises polyDCPD or polynorbornene. In some In an embodiment, the oligomer solution forming the polymer formed from ROMP comprises a nanomolecular precursor and has a viscosity of less than about 200 cps and cures in less than about 24 hours. In certain embodiments, the oligomeric solution forming the polymer formed from ROMP can optionally include a solvent, an optional catalyst, an optional accelerator, and/or an optional initiator. In certain embodiments, the composition further comprises an addition polymer. In certain embodiments, the addition polymer forms a copolymer or composite with the polymer formed via ROMP. In certain embodiments, the addition polymer is a polyester or epoxy. In certain embodiments, the addition polymer forms a cyclic olefin copolymer with a polymer formed via ROMP. In certain embodiments, the polymer formed from ROMP has a toughness greater than about 4.0, 5.0, 6.0, 7.0, 8.0, or 9.0 ft-lb/in as measured by a notched Izod impact ASTM D256. In certain embodiments, the polymer has a notched Izod impact ASTM D256 of from about 2.0 ft-lb/in to about 10.0 ft-lb/in, from about 3.0 ft-lb/in to about 10.0 ft. -lb/in, from about 4.0 ft-lb/in to about 10.0 ft-lb/in, from about 5.0 ft-lb/in to about 10.0 ft-lb/in, from about 6.0 ft-lb/in to about 10.0 Ft-lb/in, from about 7.0 ft-lb/in to about 10.0 ft-lb/in, from about 5.0 ft-lb/in to about 12.0 ft-lb/in, from about 6.0 ft-lb/in to about 12.0 ft-lb/in, from about 7.0 ft-lb/in to about 12.0 ft-lb/in or from about 8.0 ft-lb/in to about 12.0 ft-lb/in.

In another embodiment, the invention comprises a preform comprising a concrete injected with an oligomer solution having a viscosity of less than about 200 cps and cured in less than about 24 hours, the oligomer solution comprising a Molecular precursors and optional solvents, optional catalysts, optional additions a speeding agent and/or an optional initiator; and forming a polymer having a toughness greater than about 4.0, 5.0, 6.0, 7.0, 8.0, or 9.0 ft-lb/in as measured by a notched Izod impact ASTM D256.

In certain embodiments, the invention comprises a shaped article comprising concrete and a polymer formed from ROMP. In certain embodiments, the concrete comprises asphalt concrete or cement concrete. In certain embodiments, the shaped body comprises an assembly for a building or structural reinforcement, such as a building or bridge. In certain embodiments, the shaped body includes an assembly for reinforcing a structure or barrier of a military or security area. In certain embodiments, the shaped body comprises an assembly for a highway concrete barrier. In certain embodiments, the shaped body comprises an assembly for a new or replacement profile for a road.

In certain embodiments of the shaped body, the polymer formed from ROMP comprises a cyclic olefin. In certain embodiments, the polymer formed from ROMP comprises polyDCPD or polynorbornene. In certain embodiments, the oligomer solution forming the polymer formed from ROMP comprises a nanomolecular precursor and has a viscosity of less than about 200 cps and cures in less than about 24 hours. In certain embodiments, the oligomeric solution forming the polymer formed from ROMP can optionally include a solvent, an optional catalyst, an optional accelerator, and/or an optional initiator. In certain embodiments, the composition further comprises an addition polymer. In certain embodiments, the addition polymer forms a copolymer or composite with the polymer formed via ROMP. In certain embodiments, the addition polymer is a polyester or epoxy. In certain embodiments, the addition polymer forms a cyclic olefin copolymer with a polymer formed via ROMP. In some In an embodiment, the polymer formed from ROMP has a toughness greater than about 4.0, 5.0, 6.0, 7.0, 8.0, or 9.0 ft-lb/in as measured by a notched Izod impact ASTM D256. In certain embodiments, the polymer has a notched Izod impact ASTM D256 of from about 2.0 ft-lb/in to about 10.0 ft-lb/in, from about 3.0 ft-lb/in to about 10.0 ft. -lb/in, from about 4.0 ft-lb/in to about 10.0 ft-lb/in, from about 5.0 ft-lb/in to about 10.0 ft-lb/in, from about 6.0 ft-lb/in to about 10.0 Ft-lb/in, from about 7.0 ft-lb/in to about 10.0 ft-lb/in, from about 5.0 ft-lb/in to about 12.0 ft-lb/in, from about 6.0 ft-lb/in to about 12.0 ft-lb/in, from about 7.0 ft-lb/in to about 12.0 ft-lb/in or from about 8.0 ft-lb/in to about 12.0 ft-lb/in.

definition

The following definitions may be applied to describe certain aspects of certain embodiments related to the invention. These definitions can also be extended in this article.

The singular articles "a", "an", and "the" Thus, for example, reference to an item may include a plurality of items unless clearly indicated in the article. When the words "a" or "an" and "comprising" are used in the specification, they mean "one", but also by "one or more", At least one and one or more meanings. The word "about" is used to mean all values in the range unless otherwise specified. For example, about 1, 2, or 3 is equal to about 1, about 2, or about 3, and more includes from about 1-3, from about 1-2, and from about 2-3.

The term oligomer solution as used herein refers to a nanomolecular precursor and optional catalysts, initiators, inhibitors, solvents, accelerators, Combinations of curing agents or combinations thereof, and may further include other monomers, dimers, trimers or oligomers that may be polymerized by any method, or may include additional thermosetting or thermoplastic polymers. Preferably, the oligomer solution comprises the nanomolecular precursor, the catalyst and an optional inhibitor.

As used herein, the term "concrete" is used to describe a hardened mixture of a fixing agent and an aggregate. In the case of cement concrete, the hardened mixture is typically formed via a chemical reaction of a fixing agent with water in the presence of aggregates. Asphalt concrete contains asphalt as a combination of a fixing agent and an aggregate to form a thermoplastic composition. The structural surface as used herein describes a concrete surface that is accessible to the interior of the concrete from which the oligomer solution is accessible, wherein the surface is part of a building, concrete body, road or similar component of the structure or load bearing assembly. The decorative surface used herein describes a concrete surface that is easily accessible to the oligo-polymer solution, wherein the surface is a component of a building, concrete body, road, or the like that is primarily used for decoration, aesthetics, and/or non-functionality. Part of it.

Fixing agents include cements such as Portland cement, masonry cement, mortar cement, and/or gypsum, calcium aluminate cement, hydratable aluminum oxide, hydratable alumina, colloidal cerium oxide, cerium oxide, oxidation Magnesium may also include limestone, hydrated lime, pozzolans such as fly ash and/or granulated slag, metakaolin, rice husk ash, and vermiculite or other materials generally included in the cement, and may also describe slurries, Mud, mortar, grouting agents such as oil wells combined with mortar and hydraulic cement fixing agent. Further, in the example of asphalt cement, the fixing agent is asphalt.

Aggregates in concrete play a dual role as a fill Filling and affecting the properties of concrete materials. Changes in the size, maximum size, basis weight and moisture content of the aggregates can alter the properties and properties of the concrete. Aggregates contain, for example, from 60% to 80% of typical cement concrete mixtures, which are selected for durability and are suitably controlled for optimum efficiency to produce consistent concrete strength, processability, modification and durability. . Aggregates as used herein may include any material that is practical to meet the requirements for use, and may include sand, gravel or gravel, recycled materials, and polymers.

A nanomolecular precursor as referred to herein refers to a discrete molecule that can then be reacted to form a polymer of an embodiment of the invention. The nanomolecular precursors of the embodiments of the invention include monomers, dimers, trimers, or oligomers, or combinations thereof. The nanomolecular precursor has about 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, 40 nm or less, 30 nm or more along its longest dimension. Less, 20 nm or less, 10 nm or less, 5 nm or less, 4 nm or less, 3 nm or less, 2 nm or less, 1.5 nm or less, 1.2 nm or less, 1 nm or less, 0.8 Nm or less, or 0.6 nm or less, and a molecular length reduced to about 0.4 nm or less. Alternatively, or in combination, the nanomolecular precursor has about 0.4 nm to 100 nm, 0.4-90 nm, 0.4-80 nm, 0.4-70 nm, 0.4-60 nm, 0.4-50 nm, 0.4-40 nm, 0.4-30 nm along its longest dimension, Molecular length of 0.4-20 nm, 0.4-10 nm, 0.4-5 nm, 0.4-4 nm, 0.4-3 nm, 0.4-2 nm, 0.4-1.5 nm, 0.4-1.2 nm or 0.4-1 nm. Preferably, the nanomolecular precursor is a cyclic olefin via ROMP. Preferably, the nanomolecular precursor comprises monomers, dimers, trimers and/or oligomers of cyclic olefins via ROMP. More preferably, the cyclic olefin is a monomer, a dimer and/or a trimer of cyclopentadiene or is a norbornene. More preferably, the monomer, dimer and/or trimer of the cycloolefin cyclopentadiene. Dicyclopentadiene as referred to herein means a compound C ₁₀ H ₁₂ and a temperature-dependent combination of DCPD and its monomeric cyclopentadiene.

The cyclic olefins of the embodiments of the invention may be combined with other monomers to form complexes and/or copolymers. As used herein, "cycloalkene" includes monocyclic compounds as well as polycyclic (bridged and unbridged), homocyclic and heterocyclic compounds. For example, DCPD can be used in composites to modify traditional unsaturated polyesters. In such modified polyester resins, this DCPD maleic acid reacts and results in a higher _Tg and a faster development of acceptable hardness. DCPD has a low viscosity, thus allowing a reduction in the total amount of styrene, resulting in a decrease in volatilization and divergence of the polymer. DCPD also improves the curing of the resin under an oxygen atmosphere, thus helping to create a crack-free surface.

DCPD can also be used for the formation of epoxy composites. DCPD polymerizes on the backbone and the epoxy group is still at the cross-linking end. Significant improvement of DCPD added epoxy resin T _g, 22% at a concentration of up to 160. deg.] C to 180 [deg.] C and at 28% concentration. Another modification of the formation of pure DCPD monomers is the copolymer between DCPD and butadiene. This gives a significant increase in toughness for a tough polymer. A similar copolymer can be formed between DCPD and ethylene. DCPD/butadiene and DCPD/ethylene copolymers refer to cyclic olefin copolymers (COCs) and, unlike DCPD alone, are thermoplastic.

As used herein, a ROMP polymer refers to a polymer that undergoes ring opening displacement polymerization. A variant of the ROMP olefin displacement reaction. This reaction Strained cyclic olefins are used to produce stereoregular and monodisperse polymers and co-polymers. This reaction driving force is the ring strain released in the cyclic olefin (for example, norbornene or cyclopentadiene). The addition of a substituent in the monomer and the choice of solvent can alter the molecular weight of the polymer produced.

The mechanism of the ROMP reaction involves an alkylidene-based catalyst and is similar to the mechanism of olefin substitution and two important modifications. First, when the reaction involves a cyclic olefin, the resulting "new" olefin remains attached to the catalyst as part of a growing polymer chain. The second difference is that the driving force of the ROMP reaction is the release of the ring strain. Therefore, the aforementioned second step is substantially irreversible. Olefins such as cyclohexene or benzene have less or no ring strain and are not polymerizable because there is no thermodynamic preference for polymers and monomers. The strained cyclic olefin has sufficient ring strain to make this process possible. Monomers based on norbornene derivatives are particularly popular because they are readily synthesized by Diels-Alder reaction with cyclopentadiene.

The polymers produced in the ROMP reaction typically have a very narrow range of molecular weights, some of which are difficult to achieve via standard polymerization methods such as free radical polymerization. This degree of polydispersity (weight average MW divided by number average MW) is typically in the range of 1.03 to 1.10. Such molecular weight distributions are narrow to the extent that this polymer can be referred to as a single dispersion.

An important feature of this mechanism is that the ROMP system is a typical living polymerization catalyst. For example, 100 equivalents of ornidene are polymerized and the second monomer is added after the first consumption. ROMP is a preferred method of making diblock and triblock co-polymers and allows for the properties of a customizable material. This technique only has a perfect ratio of initial chain action and chain growth. It is possible to balance. Therefore, it is not uncommon for a particular functional monomer to try several different catalysts, solvents, concentrations, temperatures, etc. to achieve the best results.

Solvent as used herein refers to an aqueous or non-aqueous solution that can be added to the oligomer solution to achieve the desired viscosity and/or other desirable properties. Preferably, the solvent is an anhydrous, organic solvent.

The catalyst used herein is a substance that can modify and increase a reaction rate without being consumed in the process. Catalysts of embodiments of the invention include those which form a polymer having the claimed principles. The catalyst includes a ROMP catalyst.

For certain embodiments, the catalyst of the present invention is a ROMP catalyst. ROMP catalysts include Grubbs-type catalyst, Schrock-type catalyst, Piers-type catalyst, Hoveyda-type catalyst, Hoveyda-Grubbs-type catalyst, "blackbox" catalyst, and ferrocene Catalyst. "Black box" catalyst refers to a heterogeneous catalyst comprising a high valence transition metal halide, an oxide or an oxo-halide and an alkylated co-catalyst such as an alkyl zinc or an aluminum alkyl. Examples include WCl ₆ /SnMe ₄ and Re ₂ O ₇ Al ₂ O ₃ . Titanocene-type catalyst means that Cp ₂ TiCl ₂ reacts with divalent AlMe ₃ to produce Cp ₂ Ti(μ-Cl)(μ-CH ₂ )AlMe ₂ , also known as Tebbe reagent (Cp=ferrocene) ;Me=methyl). This reagent is functionally equivalent to "Cp ₂ Ti=CH ₂ " in the presence of a strong base such as pyridine. These Ti-based catalysts typically have little or no catalyst-like activity or carbonyl functionality tolerance, but such Ti complexes are stoichiometrically similar to ketones, aldehydes, and other carbonyls (Wittig -like) react to form the corresponding methylene derivative. Although such catalysts are very reactive, they typically have low tolerance to functional groups because of their Lewis acid nature.

For certain embodiments, the catalyst of the embodiments of the present invention is an air and moisture stabilized ROMP catalyst. Catalysts that satisfy these conditions include Grubbs-type catalysts and ruthenium and ruthenium catalysts.

As used herein, accelerator refers to a compound that is added to an oligomer solution to increase the rate of polymerization or cure. As used herein, an inhibitor refers to a compound that is added to an oligomer solution to reduce the rate of polymerization or cure.

As used herein, a starter refers to a compound that decomposes into a free radical in the presence of a monomer to initiate a free radical polymerization process. The initiator can be used in combination with free radical addition polymerization.

Viscosity as used herein is a measure of the resistance of a fluid to deformation induced by shear or tensile stress, and relates to the dynamic viscosity of a fluid. In other words, viscosity describes the resistance of a fluid to flow and can be considered as a measure of fluid friction. Viscosity is measured in a variety of types of viscometers and rheological measurements and is measured in centipoise (cP).

Maturation or curing as used herein refers to the toughening or hardening of a polymeric material via polymerization or monomeric and/or crosslinking of a polymer chain substantially directed by a chemical additive, ultraviolet light, electron beam or heat. Typically, during the curing process, the resin viscosity initially drops as heat is applied, begins to increase through a maximum flow area and increases the average length and amount of cross-linking between the component oligomers due to chemical reactions. This process continues until a 3-dimensional network of oligomer chains is produced - this stage is called gelation. In the processability of the resin, this is an important watershed: before the gelation, the system is relatively fluid, after which the fluidity is limited, the microstructure of the resin and composite material is fixed and produces stricter for further curing. The diffusion limit.

The curing agent of the examples of the present invention is a substance or a mixture of substances added to the composition to promote or control the curing reaction. It can be reactive or catalytic. A reactive curing agent or hardener is typically used in an amount greater than the catalyst, and is actually incorporated into the resulting polymer. The accelerator of the embodiments of the present invention increases the reactivity of the curing system (shorter gelation time and faster curing).

Thermosets as used herein are irreversibly cured polymeric materials. The thermosetting polymer is a softly solid or or viscous prepolymer that is irreversibly altered by curing to a poorly soluble, insoluble polymer network. Curing can be induced by heat, or a suitable irradiation, or a combination of two or more of these. A cured thermoset polymer is referred to as a thermoset.

Thermoplastics as used herein are polymers that are converted to a liquid state upon heating to a sufficiently high temperature and freeze to a glassy state when sufficiently cooled. Most of the thermoplastics are high molecular weight polymers whose chains are via weak van der Waals (polyethylene); stronger dipole-dipole interfabrication and hydrogen bonding (nylon); or even the stacking of aromatic rings ( Polystyrene) composition. Thermoplastic polymers differ from thermoset polymers in that they are remeltable and remolded. Many thermoplastic materials are addition polymers; for example, ethylene chain growth polymers such as polyethylene and polypropylene.

The toughness as used herein is an energy measurement of a sample that can be absorbed without fracture or other deformation. Various methods have been developed to quantify the toughness or impact resistance of polymers. There are two types of toughness - balance toughness and impact toughness. The reason why balance toughness is so named is because the speed of the tensile test is usually slow enough to be considered as an equilibrium condition. Under these conditions, the toughness is the area under the stress-strain curve with respect to the integration of the curve describing the stress strain. area. In general, the toughness of a material is more important under dynamic conditions because a force is suddenly applied. Therefore, impact toughness is defined as the energy absorbed through the material under a sudden impact. Impact toughness depends on the internal deformability of the material. Several test measurements have been developed to measure the impact toughness of a material. These include the Charpy impact test (ASTMD-6110), the Izod impact test (ASTMD-256), the tensile impact test (ASTM-1822), and the drop impact test (ASTMD-5628). The cantilever beam crash test uses a specimen attached to one end to impact the single swing arm of the specimen at the unsupported end, with a notch on the same side of the specimen and the specimen being clamped directly under the concavity.

The shaped article used herein is a concrete product that is described as being cast in a mold made at the factory. Alternative words include squat objects or preformed items. The advantages of shaped articles are better quality control and mass production that cannot be achieved in the field. Examples include concrete or precast concrete walls, barriers, blocks, columns, beams, sections, bridge assemblies, railway sleepers, junction boxes, grille air intakes, culverts, swimming pools or partial swimming pools, foundations, security or shelters, hidden Nests, modular enclosures, enclosure components (ie, structural or artistic components that are integrated into a house or apartment structure), featured products, architectural forms, or sculptures.

Also, as used herein, the terms "preferably", "preferably" and "preferably" mean that the embodiments of the invention provide particular advantages in the particular circumstances. However, other embodiments may be preferred under the same or other circumstances. In addition, the listing of one or more preferred embodiments does not imply that other embodiments are not useful and are not intended to exclude other embodiments.

discuss

Embodiments of the invention are used to enhance the strength and/or durability of concrete under any conditions. A special application is the pit repair application that is rarely mentioned so far. The life of a patched pothole is calculated in days or months, not years. The pothole repair material can be viewed as a structural composite that typically includes discrete aggregates in the continuous phase of the asphalt after compaction. Therefore, the short life of the repaired potholes on the asphalt pavement can be described in a sequence of failures: weak bonding between asphalt and aggregates; presence of interconnected voids in the asphalt-aggregate mixture; moisture Or water seeps into the repaired area and embeds the asphalt-aggregate mixture through the interconnected voids and weakens (peeles) the bond between the bitumen and the aggregate; the initial burst of the repaired area due to traffic pressure and the passage between the bitumen and the aggregate The voids are interspersed with the bonding interface; the weakly bonded aggregates are pulled out of the asphalt phase by the surface and edges of the top-overlapping or non-overlapping repair mixture due to compression, shear and tensile stress exerted by the traffic load on the repaired area. Dispersion; the development of small cracks and the formation of wide cracks; and then the repair of the separation of the material from the initial pit or the whole block; and finally, the failure of the repaired area causes further damage to the original edge of the road and produces more Big potholes.

In view of the aforementioned failure sequence of the bitumen-aggregate composite and concrete-aggregate composite repair material for potholes, it is necessary to develop a strong bonding material for the aggregate-asphalt mixture, or aggregates and other continuous phase substrates. material. Because of these conditions, the road continues to perform and leads to specific steps in the repair of the pothole repair. The following properties are important to the material that will extend the life of the pothole repair:

1. Compaction (throw-and-roll) and vibration compaction (semi-permanent) , spray injection) asphalt-aggregate mixture voids.

2. Reduce the continuous, interconnected voids within the aggregate composite mixture to increase the strength of the repair material and prevent water/moisture injection through the thickness of the repair material.

3. Strengthening the continuous phase of the aggregate composite by substituting or promoting the soft asphalt continuous phase and increasing its strength and fracture toughness.

4. This "subsequent" material shall have one or more of the following properties:

a. Compatible with asphalt.

b. Low viscosity for penetration into asphalt-aggregate mixtures.

c. Controlled cure time (hardening time) for on-site requirements.

d. Adjustable viscosity for penetration depth control.

e. High resistance to cracking with energy absorption without cracking.

f. High pressure strain, shear and tensile strength.

g. Resistance to moisture and water.

h. Moderate extension.

i. The potential to have a fixative for aggregates. If necessary, change the viscosity.

j. It can also be applied as a joint material in the edge repair of potholes.

k. Non-toxic and environmentally friendly.

l. UV and ozone resistant.

Based on the foregoing, the described embodiments of the invention not only refer to the defined principles, but are further applicable to all concrete applications and provide new and increased durability to the repaired concrete. Embodiments of the present invention can be applied as a method of repairing pavement holes. This method roughly uses a low-viscosity oligo The polymer solution is infiltrated or injected into the concrete. This oligomer solution then allows curing to a polymer with high toughness. The oligomer solution comprises a nanomolecular precursor and additional optional components such as a catalyst, an initiator, an accelerator, an inhibitor, a curing agent, a solvent, and the like. Preferably, the nano molecular precursor is a cyclic olefin, and more preferably, the nano molecular precursor is a cyclic olefin undergoing ROMP. Cyclic olefins undergoing ROMP are expected because of their tendency to have very low viscosities, cure by controlled media and oligomer solutions, and form incredible ductile polymers but sustain their use in general road use. Durability of the temperature range. More preferably, the ROMP polymer is a polyDCPD, optionally in combination with a cyclopentadiene trimer. PolyDCPD is about 25% less dense than epoxy resin but more tough, especially at low temperatures. In addition, as a dimer, very small rings (about 7 Å) are easily trapped with each other, resulting in very low viscosity; about water. The DCPD and cyclopentadiene trimers can be cured via a ROMP catalyst and can be thermally cured at room temperature for a few seconds up to 24 hours by the amount of inhibitor and cyclopentadiene trimer. Moreover, the addition of a substituent in the monomer and the choice of solvent can change the molecular weight of the polymer produced.

The ROMP method is quite useful because it forms a regular polymer with a regular double bond amount. The resulting product can be partially or fully hydrogenated or functionalized to a more complex compound. Furthermore, the copolymer, the block copolymer and the polymer formed by the ROMP-formation, such as polyDCPD, and/or other ROMP-formed polymers, may be reacted by other types of polymers. Complex. The advantage of a block or mixed copolymer or composite is that it allows for the formation of the polymer Another degree of control.

Moreover, for certain embodiments, the strength and/or durability of the concrete can be improved based on commercially available ROMP-catalyzed polymers. Some examples of polymers produced by ROMP catalysis are Vestenamer® or trans-polyoctene, which are metathesis polymers of cyclooctene; Norsorex® or polynorbornene; and Telene® and Metton®, which are in the original A polydicyclopentadiene catalyst produced in a side reaction of the polymerization of borneol. The lanthanide catalyst produced by Materia Corporation can be used as a ROMP catalyst in certain embodiments.

The method of the embodiments of the present invention allows the oligomer solution to be quickly and completely injected into the concrete and then reacted. This depth of penetration is a function of the pore space of the concrete and the viscosity of the oligomer solution. In the case of asphalt concrete, injection by all materials is possible. While not being bound by a particular theory, in asphalt concrete, the solidified polymer acts similarly to a cage, filling the pores in the asphalt and bonding the pores together. This is advantageous in pothole repair because it allows the filling material to be "linked" to the old road surface substantially via the polymer cage. Another embodiment is the use of a cyclic olefin that diffuses into the old road material as well as the void repair material, which are combined and sealed to prevent water from penetrating therebetween.

In the case of cement concrete, the depth of immersion depends on the gap of the holes in the material, but is typically at least a few millimeters. This immersion depth is sufficient to provide significant additional toughness and improved concrete durability through the prevention of water embedding into the concrete. Although not limited by any particular theory, the salty polymer forms a cage-like form that joins the holes in the concrete and seals the surface. A particular embodiment of the invention is the use of a cyclic olefin that undergoes ROMP, Such as DCPD, to improve the durability of aggregate-asphalt pothole repair materials or any aggregates that use continuous fixing agents, including cement.

The polymers formed in the examples of the invention advantageously carry out the following:

1. A pure aggregate that penetrates into the aggregate-asphalt mixture or a low-viscosity liquid (oligomer solution). This aggregate-asphalt mixture still contains high vol% interconnected voids prior to compaction or even after roller compaction. After the oligomer solution has penetrated, matured, and solidified, the mixture through which it has passed has pores formed along the discontinuous aggregate to form a continuous web (ie, a mechanical cage). The cage-shaped web of this structure mechanically envelops the aggregates and prevents the aggregates from spreading out of the asphalt under traffic pressure.

2. Form a continuous mechanical cage network that prevents moisture/water from penetrating into the thickness of the repair material and slowing down the harmful peeling on the fixation.

3. Forming with aggregates is stronger than between asphalt and aggregates. (If a polymer is used as a single fixative or fixative and part of the aggregate).

4. In the face of multiple traffic pressures, aggregates that reduce the main components of the traffic force are pulled out.

5. Distribute and shift the load more evenly and efficiently between aggregates.

6. Because of the one-way thermoset polymerization, it is subjected to high climatic temperatures without significant damage such as asphalt.

7. Can be applied on asphalt or concrete roads on site or in the field. Potholes and cracks of different sizes.

8. Can be applied as an edge sealing material for pothole repair. The oligomer solution can also penetrate the sidewalls and base layers of the surrounding pavement due to its low viscosity. This provides the anchoring force of the repair material to the original road surface.

9. Replace water to prevent erosion of concrete. PolyDCPDs typically do not undergo phase changes and have negligible shrinkage at lower temperatures.

10. It is catalyzed to exhibit a strong exotherm that can be used with minimal heating (eg, using a propane torch at the center of the installed repair material) to create a chain reaction and cure the entire repair material.

A schematic of the penetration of the DCPD resin into the aggregate-asphalt composite is shown in FIG. It shows that the solidified cage network of DCPD polymer holds the aggregates by connecting the pores in the filled aggregate mixture. The DCPD polymer viscosity can be adjusted to achieve the desired depth and cure to a hardened state during the control time.

The oligomer solution concentration can be used in any percentage of the repair material mixture and can be used in any existing and future pothole repair process, including but not limited to:

1. Throw-and-go and throw-and-roll methods

2. Spray injection

3. Roll-roll edge sealing

4. Semi-permanent

5. Quick repair method for cement pits

6. Similar types of closures for crocodile cracks or road discontinuities

7. Pavement surface coverage

The oligomer solution can be applied via spray to the surface or side of any of the aforementioned repair methods. It can also be used with prepolymers of aggregates, which may or may not have asphalt or other type of fixing agent.

Although specific conditions and principles have been described herein, it is understood that such conditions and principles may be applied to the embodiments of the invention, and such conditions and principles may be relaxed or modified for use in other embodiments of the invention.

While the invention has been described with reference to the specific embodiments thereof, it will be understood by those skilled in the art that the various modifications and equivalents can be substituted without departing from the spirit and scope of the invention as defined by the appended claims. In addition, many modifications may be made to adapt a particular condition, material, composition, method, or process of the invention to the purpose of the invention. All such modifications are intended to fall within the scope of the appended claims. In particular, although the method disclosed herein has been described as being specifically described in a particular order, it is understood that such operations may be combined, decomposed or recombined to form an equivalent method without departing from the teachings of the invention. Therefore, the order and group of operations are not limiting of the invention unless specifically indicated herein. Finally, all references cited in this specification are incorporated by reference in their entirety.

Claims (23)

A method for repairing a concrete structure, comprising: forming a bottom layer at a discontinuity of the concrete structure; forming a top layer on the bottom layer; injecting at least the top layer with an oligomer solution, the oligomer solution comprising: a molecular precursor; wherein the oligomer solution: (i) has a viscosity of not more than 100 cps; and (ii) is cured in less than 2 hours; and a thermosetting polymer is formed from the oligomer solution, wherein the thermosetting polymerization The material has a toughness greater than 6.0 ft-lbs/in as measured by a notched Izod impact ASTM D256. The method of claim 1, wherein the nano molecular precursor comprises a monocyclic olefin. The method of claim 2, wherein the nano molecular precursor comprises dicyclopentadiene or norbornene. The method of claim 2, wherein the nano molecular precursor comprises a trimer of a cyclic olefin. The method of claim 2, wherein the nano molecular precursor comprises a mixture of a monomer, a dimer, a trimer, and a tetramer of a cyclic olefin. The method of claim 1, wherein the oligomer solution comprises an open-loop displacement polymerization catalyst. The method of claim 6, wherein the ring-opening displacement polymerization catalyst is a Grubbs catalyst. The method of claim 1, wherein the thermosetting polymer is formed by ring-opening displacement polymerization, and the thermosetting polymer comprises polydicyclopentadiene or polynorbornene. The method of claim 1, wherein the concrete structure is a road surface, the discontinuity of the concrete structure is a pothole, and at least one of the top layer and the bottom layer is formed by a pothole repairing material. The method of claim 9, wherein the pothole repair material comprises at least a mixture of asphalt and aggregate. The method of claim 9, further comprising compacting at least the bottom layer to control the depth of the oligomer solution injection. The method of claim 11, wherein the bottom layer is compacted to a porosity of 8% or less. The method of claim 11, wherein the compacting is performed such that the top surface of the top layer is substantially flush with the top surface of the road. The method of claim 9, wherein the injecting comprises injecting the oligomer layer into the top layer, so that the top layer is strengthened via the thermosetting polymer to a porosity of 5% or less. The method of claim 9, wherein the top layer has a thickness of 5 cm or less. The method of claim 9, wherein the pothole repairing material comprises Aggregates, and forming the thermoset polymer comprises forming a network of the thermoset polymer extending through pores interconnected between the aggregates. The method of claim 1, wherein the injecting comprises implanting the oligomer solution to a depth less than a total thickness of the top layer and the bottom layer. The method of claim 1, wherein the thermoset polymer provides moisture impermeable embedding at the edges of the discontinuities of the concrete structure. An object for pothole repair, comprising: (a) a two-layer structure, wherein the double-layer structure is constructed for being placed in a pothole of a road surface, and the double-layer structure comprises a bottom layer and a top layer on the bottom layer; and (b) a thermosetting polymer; wherein the thermosetting polymer is selectively implanted into the top layer to enhance the moisture barrier of the top layer; wherein the thermosetting polymer has: a cantilever beam collision with a notched ASTM D256 The toughness is measured to be greater than about 6.0 ft-lbs/in. The article of claim 19, wherein the top layer comprises an aggregate reinforced with the thermosetting polymer to a porosity of 5% or less. The article of claim 19, wherein the bottom layer comprises aggregates compacted to a porosity of 8% or less. The article of claim 19, wherein the double layer structure has a thickness such that a top surface of the double layer structure is substantially flush with a top surface of the road surface. The article of claim 19, wherein the thermoset polymer is injected to a depth less than a total thickness of the bilayer structure.