阅读说明：本技术 一种组合物、其制备方法和该组合物在建筑应用中的用途 (Composition, method for the production thereof and use of the composition in construction applications ) 是由 孟磊 周圣中 H·勒克尔 于 2018-12-19 设计创作，主要内容包括：本发明涉及一种可固化树脂组合物。更具体地,本发明涉及包括亚甲基丙二酸酯官能的反应性树脂的组合物,涉及其制备方法,并且涉及该组合物在建筑领域的用途。(The present invention relates to a curable resin composition. More particularly, the invention relates to a composition comprising a methylene malonate functional reactive resin, to a process for its preparation and to the use of this composition in the field of construction.)

1. A composition comprising

(A) At least one methylene malonate monomer of formula (I)

Wherein R is₁And R₂Independently selected in each case from C1-C30-alkyl, C2-C30-alkenyl, C3-C30-cycloalkyl, C2-C30-heterocyclyl, C2-C30-heterocyclyl-C1-C30-alkyl, C6-C30-aryl, C6-C30-aryl-C1-C30-alkyl, C2-C30-heteroaryl, C2-C30-heteroaryl-C1-C30-alkyl, C1-C30-alkoxy-C1-C30-alkyl, halo-C1-C30-alkyl, and halo-C3-C30-cycloalkyl, each of said radicals being optionally substituted, the heteroatom being selected from N, O and S;

(B) at least one methylene malonate polymer having the formula (II):

wherein R is₃And R₄Independently selected in each case from C1-C30-alkyl, C2-C30-alkenyl, C3-C30-cycloalkyl, C2-C30-heterocyclyl, C2-C30-heterocyclyl-C1-C30-alkyl, C6-C30-aryl, C6-C30-aryl-C1-C30-alkyl, C2-C30-heteroaryl, C2-C30-heteroaryl-C1-C30-alkyl, C1-C30-alkoxy-C1-C30-alkyl, halo-C1-C30-alkyl and halo-C3-C30-cycloalkyl, each of said radicals being optionally substituted, the heteroatoms being selected from N, O and S;

n is an integer from 1 to 20;

R₅if n is 1 or if n > 1, in each case independently selected from the group consisting of C1-C30-alkylene, C2-C30-alkenylene, C2-C30-alkynylene, C6-C30-arylene, C3-C30-cycloalkylene, C3-C30-cycloalkenylene, C3-C30-cycloalkynylene, C2-C30-heterocyclylene and C2-C30-heteroarylene, each of said radicals optionally being substituted, the heteroatom being selected from the group consisting of N, O and S, wherein R is₅Optionally interrupted by a radical selected from N, O and S; and

(C) at least one acidic stabilizer;

wherein the amount of the monomer (a) is 1 to 75 wt%, preferably 5 to 60 wt%, more preferably 10 to 55 wt%, and most preferably 10 to 30 wt%; and is

The amount of component (C) is from 0.1 to 1000ppm, preferably from 0.1 to 500ppm, and more preferably from 0.1 to 200ppm, in each case based on the total weight of the monomers (a) and the polymers (B).

2. The composition of claim 1, wherein R₁And R₂Independently selected in each case from C1-C10-alkyl, C2-C10-alkenyl, C3-C10-cycloalkyl, C2-C10-heterocyclyl, C2-C10-heterocyclyl-C1-C10-alkyl, C3-C18-aryl, C3-C18-aryl-C1-C10-alkyl, C2-C10-heteroaryl, C2-C10-heteroaryl-C1-C10-alkyl and C1-C10-alkoxy-C1-C10-alkyl, halo-C1-C10-alkyl and halo-C3-C10-cycloalkyl; each of said radicals being optionally substituted by at least one radical chosen from halogen, hydroxy, nitro, cyano, C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C10-alkoxy, C3-C10-cycloalkyl, C2-C10-heterocyclyl, C2-C10-heterocyclyl-C1-C10-alkyl, halo-C1-C10-alkyl, halo-C3-C10-cycloalkyl, C3-C18-aryl, C3-C18-aryl-C1-C10-alkyl, C2-C10-heteroaryl, C3-C10-cycloalkenyl and C3-C10-cycloalkynyl, the heteroatom being chosen from N, O and S;

R₃and R₄Independently selected in each case from C1-C10-alkyl, C2-C10-alkenyl, C3-C10-cycloalkyl, C2-C10-heterocyclyl, C2-C10-heterocyclyl-C1-C10-alkyl, C3-C18-aryl, C3-C18-aryl-C1-C10-alkyl, C2-C10-heteroaryl, C2-C10-heteroaryl-C1-C10-alkyl and C1-C10-alkoxy-C1-C10-alkyl, halo-C1-C10-alkyl and halo-C3-C10-cycloalkyl, each of said radicals optionally being selected from halogen, hydroxy, nitro, cyano, C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C10-alkoxy, C3-C10-cycloalkyl, C2-C10-heterocyclyl, C2-C10-heterocyclyl-C1-C10-alkyl, halo-C1-C10-alkyl, halo-C3-C10-cycloalkyl, C3-C18-aryl, C3-C18-aryl-C1-C10-alkyl, C2-C10-heteroaryl, C3-C10-cycloalkenyl and C3-C10-cycloalkynyl, the heteroatom being selected from N, O and S;

n is an integer from 1 to 15;

R₅if n is 1 or if n > 1, in each case independently from C1-C10-alkylene, C2-C10-alkenylene, C2-C10-alkynylene, C3-C18-arylene, C3-C10-cycloalkylene, C3-C10-cycloalkenylene, C3-C10-cycloalkynylene, C2-C18-C10-heterocyclylene and C-C-heteroarylene, each of which is optionally substituted with at least one radical selected from the group consisting of halogen, hydroxy, nitro, cyano, C-C-alkyl, C-C-alkenyl, C-C-alkynyl, C-C-alkoxy, C-C-cycloalkyl, C-C-heterocyclyl-C-alkyl, halo-C-C-cycloalkyl, C-C-aryl-C-alkyl, C-C-heteroaryl, C-C-cycloalkenyl and C-C-cycloalkynyl, the heteroatom is selected from N, O and S, wherein R₅Optionally interrupted by a radical selected from N, O and S; and

3. the composition of claim 1 or 2, wherein R₁And R₂Independently selected in each case from C1-C6-alkyl, C2-C6-alkenyl, C3-C6-cycloalkyl, C3-C6-heterocyclyl, C3-C6-heterocyclyl-C1-C6-alkyl, C6-C8-aryl, C6-C8-aryl-C1-C6-alkyl, C3-C6-heteroaryl, C3-C6-heteroaryl-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkyl, halo-C1-C10-alkyl and halo-C3-C10-cycloalkyl, each of said radicals optionally being selected from halogen, hydroxy, nitro, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-heterocyclyl, C3-C6-heterocyclyl-C1-C6-alkyl, halo-C1-C6-alkyl, halo-C3-C6-cycloalkyl, C6-C8-aryl, C6-C8-aryl-C1-C6-alkyl, C3-C6-heteroaryl, C3-C6-cycloalkenyl and C3-C6-cycloalkynyl, the heteroatom being selected from N, O and S;

R₃and R₄Independently selected in each case from C1-C6-alkyl, C2-C6-alkenyl, C3-C6-cycloalkyl, C3-C6-heterocyclyl, C3-C6-heterocyclyl-C1-C6-alkyl, C6-C8-aryl, C6-C8-aryl-C1-C6-alkyl, C3-C6-heteroaryl, C3-C6-heteroaryl-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkyl, halo-C1-C10-alkyl and halo-C3-C10-cycloalkyl, each of said radicals optionally being selected from halogen, hydroxy, nitro, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-heterocyclyl, C3-C6-heterocyclyl-C1-C6-alkyl, halo-C1-C6-alkyl, halo-C3-C6-cycloalkyl,C6-C8-aryl, C6-C8-aryl-C1-C6-alkyl, C3-C6-heteroaryl, C3-C6-cycloalkenyl and C3-C6-cycloalkynyl, with the heteroatom selected from N, O and S;

n is an integer from 1 to 10;

R₅if n is 1 or if n > 1, in each case independently from C1-C6-alkylene, C2-C6-alkenylene, C2-C6-alkynylene, C6-C8-arylene, C3-C6-cycloalkylene, C3-C6-cycloalkenylene, C3-C10-cycloalkynylene, C3-C6-heterocyclylene and C3-C6-heteroarylene, each of which is optionally substituted by a group selected from halogen, hydroxy, nitro, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-heterocyclyl, C3-C6-heterocyclyl-C6-C6-alkyl-6-C6-alkyl, halo-C1-C6-alkyl, halo-C3-C6-cycloalkyl, C6-C8-aryl, C6-C8-aryl-C1-C6-alkyl, C3-C6-heteroaryl, C3-C6-cycloalkenyl and C3-C6-cycloalkynyl, with the heteroatom being selected from N, O and S, wherein R is₅Optionally interrupted by a radical selected from N, O and S; and

4. the composition of any one of claims 1 to 3, wherein R₁And R₂Independently at each occurrence, is selected from C1-C6-alkyl;

R₃and R₄Independently at each occurrence, is selected from C1-C6-alkyl;

n is an integer from 1 to 8; and is

R₅If n is 1 or if n > 1, in each case independently selected from C1-C6-alkylene and C6-C8-arylene, each of said radicals optionally being substituted by at least one C1-C6-alkyl group.

5. The composition of any one of claims 1 to 4, wherein the acidic stabilizer is selected from sulfuric acid (H)₂SO₄) At least one of trifluoromethanesulfonic acid (TFA), monochlorodifluoroacid, maleic acid, methanesulfonic acid (MSA), p-toluenesulfonic acid (p-TSA), difluoroacetic acid, trichloroacetic acid, phosphoric acid, dichloroacetic acid.

6. A mixture comprising the composition of any one of claims 1 to 5.

7. The mixture of claim 6, wherein the mixture is substantially free of any solvent.

8. A process for preparing the composition according to any one of claims 1 to 5, comprising the step of mixing the monomer (A), the polymer (B) and the acidic stabilizer (C).

9. Use of a composition according to any one of claims 1 to 5 or a mixture according to claims 6 to 7 as a coating material.

10. The use of claim 9, wherein the composition or the mixture is used in construction applications.

11. The use of claim 10, wherein the construction application is selected from the group consisting of flooring, waterproofing, wall painting, and underground construction applications.

12. The use of any one of claims 9 to 11, wherein the composition or the mixture is applied to an alkaline substrate.

13. Use of the composition of claim 12, wherein the alkaline substrate is selected from one or more of concrete, alkaline rock material, alkaline ore fines and metal.

14. Use of a composition according to any one of claims 9 to 13, wherein the composition or the mixture is applied to a wet substrate.

15. Use of a composition according to any one of claims 9 to 14, wherein the temperature for said use is from-30 ℃ to 60 ℃, and preferably from-20 ℃ to 40 ℃.

16. Use of a composition as claimed in any one of claims 9 to 15, wherein the relative humidity for said use is from 1% to 99%, and preferably from 5% to 95%.

Technical Field

The present invention relates to a curable resin composition. More particularly, the invention relates to a composition comprising a methylene malonate functional reactive resin, to a process for its preparation and to the use of this composition in the field of construction.

Background

Building cladding is widely used in applications including, but not limited to: floors in industrial and commercial buildings, anchors (anchoring) in tunnels and mines, consolidated rock (consolidating rock), slag and coal in tunnels and mines, and waterproofing in roofs, basements, balconies, bridges, dams, river locks, rock walls, sea freight ports, docks, parking lots, ponds, sewers (sewages), tunnels, mines, and subway and railway tracks.

Substrates for building cladding, such as concrete or stone, generally have a porous surface where tiny pores hold air and enable permeability of moisture, certain chemicals and coatings. Therefore, a primer is required before the next coat is applied, and primer is even more important for thick coatings such as self-leveling (self-leveling). The primer is a thin coating that adheres sufficiently to the porous surface and thereby penetrates the substrate to render the substrate surface water impermeable. The tiny pores are filled with primer and the trapped air is released into the atmosphere. Thus, imperfections in the coating, such as bubbles or pores, are avoided and the primer forms a barrier between the substrate and moisture, certain chemicals and the coating. On the one hand, the substrate is protected by the primer, since moisture and certain compounds cause deterioration. And on the other hand the substrate absorbs little coating and therefore no waste occurs.

Current primers are primarily based on epoxy, urethane, polyester and acrylate resins. One big disadvantage of epoxy-based and urethane-based primers is their long curing time, especially at low temperatures or at high humidity. And the acrylate-based primer has a problem of strong odor. Another disadvantage of current primers is that the solvents used, such as xylene-based or toluene-based chemicals, are hazardous to health. And an additional disadvantage of current primers is that they are typically two-pack products (two-pack products) and require strict proportions to obtain a mixture for applying the coating, which adds further complexity to the operator.

Accordingly, there remains a need to provide a primer for use in various construction applications that is solvent free, easy to handle, fast curing over a wide range of temperatures and humidity, and, at the same time, has desirable properties including good mechanical and chemical properties.

Disclosure of Invention

It is an object of the present invention to provide a composition which does not have the above-mentioned drawbacks in the art. In particular, it is an object of the present invention to provide novel compositions wherein methylene malonate monomers and compounds thereof are mixed in a certain ratio. Such compositions can be anionically polymerized with substrates that are basic in nature, such as concrete and alkaline stone surfaces, and are excellent in curability and form cured products that are excellent in adhesion, acid/base resistance, solvent resistance, and the like. The resulting cured product is essentially a 100% solids composite with few Volatile Organic Compounds (VOCs). The curable resin composition of the present invention can be effectively used as a coating in building applications, such as for flooring, waterproofing, wall painting, and underground construction applications.

Surprisingly, the inventors have found that the above-mentioned drawbacks can be solved by a composition comprising:

(A) at least one methylene malonate monomer of formula (I)

Wherein R is₁And R₂Independently selected in each case from C1-C30-alkyl, C2-C30-alkenyl, C3-C30-cycloalkyl, C2-C30-heterocyclyl, C2-C30-heterocyclyl-C1-C30-alkyl, C6-C30-aryl, C6-C30-aryl-C1-C30-alkyl, C2-C30-heteroaryl, C2-C30-heteroaryl-C1-C30-alkyl, C1-C30-alkoxy-C1-C30-alkyl, halo-C1-C30-alkyl and halo-C3-C30-cycloalkyl, each of said radicals being optionally substituted, the heteroatoms being selected from N, O and S;

(B) at least one methylene malonate polymer having the formula (II):

wherein R is₃And R₄Independently selected in each case from C1-C30-alkyl, C2-C30-alkenyl, C3-C30-cycloalkyl, C2-C30-heterocyclyl, C2-C30-heterocyclyl-C1-C30-alkyl, C6-C30-aryl, C6-C30-aryl-C1-C30-alkyl, C2-C30-heteroaryl, C2-C30-heteroaryl-C1-C30-alkyl, C1-C30-alkoxy-C1-C30-alkyl, halo-C1-C30-alkyl and halo-C3-C30-cycloalkyl, each of said radicals being optionally substituted, the heteroatoms being selected from N, O and S;

n is an integer from 1 to 20;

R₅if n is 1 or if n > 1, in each case independently selected from the group consisting of C1-C30-alkylene, C2-C30-alkenylene, C2-C30-alkynylene, C6-C30-arylene, C3-C30-cycloalkylene, C3-C30-cycloalkenylene, C3-C30-cycloalkynylene, C2-C30-heterocyclylene and C2-C30-heteroarylene, each of said radicals optionally being substituted, the heteroatom being selected from the group consisting of N, O and S, wherein R is₅Optionally interrupted by a radical selected from N, O and S; and

(C) at least one acidic stabilizer;

wherein the amount of monomer (a) is 1 to 75 wt%, preferably 5 to 60 wt%, more preferably 10 to 55 wt%, and most preferably 10 to 30 wt%;

the amount of acidic stabilizer (C), based in each case on the total weight of the monomers (a) and the polymers (B), is from 0.1 to 1000ppm, preferably from 0.1 to 500ppm and more preferably from 0.1 to 200 ppm.

The composition is prepared by a process comprising the steps of:

mixing the monomer (A), the polymer (B) and the acidic stabilizer (C).

It has been unexpectedly found that compositions according to the present invention can be formulated without the need for additional catalysts/initiators applied to the concrete or stone surface, allowing for rapid curing. The cured product seals the porous surface very well and its adhesion on the surface is very good. The cured product also exhibits excellent mechanical properties and is resistant to solvent, acid, and base conditions.

In a further aspect, the present invention relates to the use of the composition according to the invention as a coating material.

Detailed Description

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. As used herein, the following terms have the meanings assigned to them hereinafter, unless otherwise specified.

As used herein, the articles "a" and "an" refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. For example, "an element" means one element or more than one element.

As used herein, the term "about" is understood to refer to a range of numbers where a person of skill in the art would consider equivalent to the number listed in the context of achieving the same function or result.

As used herein, the term "methylene malonate" refers to a compound having the general core formula-O-C (O) -C (═ CH)₂) -C (O) -O-.

As used herein, the term "two-component" refers to a composition comprising two components, each of which may also be a mixture of several compounds. The two components may be blended together if desired. And the two components may also be two separate packages that can be mixed on site for use.

As used herein, the term "RH" is equal to "Relative Humidity (Relative Humidity)", and refers to the ratio of the partial vapor pressure of water to the saturated vapor pressure of water at a given temperature.

As used herein, the term "substantially free of" in "substantially free of solvent" means that the reaction mixture includes less than 1% by weight of the particular component relative to the total reaction mixture. In certain embodiments, "substantially free" means less than 0.7%, less than 0.5%, less than 0.4%, less than 0.3%, less than 0.2%, or less than 0.1% of a particular component by weight of the total reaction mixture. In certain other embodiments, "substantially free" means that the specified component is less than 1.0%, less than 0.7%, less than 0.5%, less than 0.4%, less than 0.3%, less than 0.2%, or less than 0.1% by volume of the total reaction mixture.

As used herein, the term "stabilized", for example, in the context of the "stabilized" monomer of the invention or a composition comprising the monomer, means that the monomer of the invention (or a composition thereof) tends to be substantially non-polymeric over time, not substantially harden, gel-form, thicken, or otherwise increase in viscosity over time, and/or to exhibit substantially minimal loss in cure speed over time (i.e., cure speed is maintained) as compared to an unstabilized, similar composition.

As used herein, the term "shelf life", e.g., in the context of the compositions of the present invention having improved "shelf life", means that the compositions of the present invention are stabilized for a given period of time, e.g., 1 month, 6 months, or even 1 year or more.

As used herein, the term "additive" refers to an additive included in a formulated system to enhance its physical or chemical properties and provide a desired result. Such additives include, but are not limited to, dyes, pigments, toughening agents, impact modifiers, rheology modifiers, plasticizers, thixotropic agents, natural or synthetic rubbers, fillers, reinforcing agents, thickeners, opacifying agents (opaciffers), inhibitors, fluorescent or other markers, thermal degradation reducers, thermal resistance imparting agents, surfactants, wetting agents, defoamers, dispersants, flow or slip aids, biocides, and stabilizers.

As used herein, the term "base" refers to a component having at least one electronegative group capable of initiating anionic polymerization.

As used herein, the term "base precursor" refers to a component that is convertible to a base by the action of some means, such as the application of heat, a chemical reaction, or UV activation.

As used herein, the term "base enhancer" refers to an agent that is capable of acting in some manner to improve or enhance the basicity of the agent.

As used herein, the terms "halogen atom", "halogen", "halo-" or "halo-" are understood to mean a fluorine, chlorine, bromine, or iodine atom.

As used herein, the term "alkyl", by itself or in combination with another term, such as haloalkyl, is understood to mean an radical of a saturated aliphatic hydrocarbon group and may be branched or unbranched, for example, methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl, or isomers thereof.

As used herein, the term "alkenyl", by itself or in combination with another term, such as haloalkenyl, is understood to mean a straight-chain or branched radical having at least one double bond, such as, for example, vinyl, allyl, propenyl, butenyl, butadienyl, pentenyl, pentadienyl, hexenyl, or hexadienyl, or isomers thereof.

As used herein, the term "alkynyl", by itself or in combination with another term, such as haloalkynyl, is understood to mean a straight or branched radical having at least one triple bond, such as ethynyl, propynyl or propargyl, or an isomer thereof.

As used herein, the term "cycloalkyl", by itself or in combination with another term, is understood to mean a fused or non-fused, saturated, mono-or polycyclic hydrocarbon ring, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, or isomers thereof.

As used herein, the term "alkoxy", by itself or in combination with another term, such as haloalkoxy, is understood to mean a linear or branched, saturated group having the general formula-O-alkyl, wherein the term "alkyl" is as defined above, such as methoxy, ethoxy, propoxy, butoxy, pentoxy or hexoxy, or isomers thereof.

As used herein, the term "aryl", by itself or in combination with another term, such as arylalkyl, is understood to include fused or non-fused aryl groups, such as phenyl or naphthyl, wherein phenyl is optionally substituted with 1 to 5 groups and naphthyl is optionally substituted with 1 to 7 groups.

As used herein, the term "hetero-" is understood to mean a saturated or unsaturated radical of atoms interrupted by at least one heteroatom selected from oxygen (O), nitrogen (N) and sulfur (S).

As used herein, the term "a-to B-hetero-", for example "3-to 6-hetero-", is understood to mean a fused or non-fused, saturated or unsaturated, monocyclic or polycyclic radical comprising, in addition to carbon atoms, at least one heteroatom selected from oxygen (O), nitrogen (N) and sulfur (S), with the proviso that the sum of the number of carbon atoms and the number of heteroatoms is in the range a to B. The heterogroups according to the invention are preferably 5-to 30-heterogroups, most preferably 6-to 18-heterogroups, especially 6-to 12-heterogroups, and in particular 6-to 8-heterogroups.

As used herein, the term "heterocyclyl" is understood to include aliphatic or aromatic heterocyclic groups, such as heterocyclylalkyl or heterocyclylalkenyl.

The term "substituted" means that one or more hydrogens on the designated atom is replaced with a selection from the indicated group, provided that the designated atom's normal valency under existing conditions is not exceeded, and that the substitution results in a stable compound. Combinations of substituents and/or variables are permissible only if such combinations result in stable compounds.

The term "optionally substituted" means optional substitution with a given group, radical or moiety. Unless otherwise stated, an optionally substituted radical may be mono-or polysubstituted, wherein the substituents in the case of polysubstitution may be identical or different.

As used herein, a halogen-substituted radical, such as a haloalkyl group, is monohalogenated or polyhalogenated up to the maximum number of possible substituents. In the case of polyhalogenation, the halogen atoms can be identical or different. In this case, halogen is fluorine, chlorine, bromine or iodine.

As used herein, a group with the suffix "-ene" represents a group with a double covalent bond that can be attached to other radicals, such as-CH₂CH(CH₃)CH₂- (isobutylidene),(phenylene), and in the case of phenylene, the covalent bond can be in the ortho, meta, or para position.

All percentages (%) are "weight percentages" unless otherwise indicated.

The radical definitions or explanations given above in general or in preferred ranges apply to the end products and correspondingly to the starting materials and intermediate products. These radical definitions may be combined with each other as desired, i.e. including combinations between the respective ranges of the general definitions and/or preferences and/or embodiments.

Unless otherwise indicated, temperature refers to room temperature and pressure refers to ambient pressure.

Unless otherwise indicated, solvents refer to all organic or inorganic solvents known to those skilled in the art and do not include any type of monomer molecule.

In one aspect, the present invention provides a composition comprising

(A) At least one methylene malonate monomer of formula (I)

Wherein R is₁And R₂Independently selected in each case from C1-C30-alkyl, C2-C30-alkenyl, C3-C30-cycloalkyl, C2-C30-heterocyclyl, C2-C30-heterocyclyl- (C1-C30-alkyl), C6-C30-aryl, C6-C30-aryl-C1-C30-alkyl, C2-C30-heteroaryl, C2-C30-heteroaryl-C1-C30-alkyl, and C1-C30-alkoxy-C1-C30-alkyl, halo-C1-C30-alkyl, and halo-C3-C30-cycloalkyl, each of said radicals being optionally substituted, the heteroatom being selected from N, O and S;

(B) at least one methylene malonate polymer having the formula (II)

Wherein R is₃And R₄Independently selected in each case from C1-C30-alkyl, C2-C30-alkenyl, C3-C30-cycloalkyl, C2-C30-heterocyclyl, C2-C30-heterocyclyl-C1-C30-alkyl, C6-C30-aryl, C6-C30-aryl- (C1-C30-alkyl), C2-C30-heteroaryl, C2-C30-heteroaryl-C1-C30-alkyl, C1-C30-alkoxy-C1-C30-alkyl, halo-C1-C30-alkyl and halo-C3-C30-cycloalkyl, each of said radicals being optionally substituted, the heteroatoms being selected from N, O and S;

n is an integer from 1 to 20;

R₅if n is 1 or if n > 1, in each case independently selected from the group consisting of C1-C30-alkylene, C2-C30-alkenylene, C2-C30-alkynylene, C6-C30-arylene, C3-C30-cycloalkylene, C3-C30-cycloalkenylene, C3-C30-cycloalkynylene, C2-C30-heterocyclylene and C2-C30-heteroarylene, each of said radicals optionally being substituted, the heteroatom being selected from the group consisting of N, O and S, wherein R is₅Optionally interrupted by a group selected from N, O and S; and

(C) at least one acidic stabilizer;

wherein the amount of monomer (a) is 1 to 75 wt%, preferably 5 to 60 wt%, more preferably 10 to 55 wt%, and most preferably 10 to 30 wt%; and is

The amount of acidic stabilizer (C) is from 0.1 to 1000ppm, preferably from 0.1 to 500ppm and more preferably from 0.1 to 200ppm, in each case based on the total weight of monomer (A) and polymer (B).

In a preferred embodiment of the invention, R₁And R₂Independently selected in each case from C1-C10-alkyl, C2-C10-alkenyl, C3-C10-cycloalkyl, C2-C10-heterocyclyl (hetercyclyl), C2-C10-heterocyclyl-C1-C10-alkyl, C3-C18-aryl, C3-C18-aryl-C1-C10-alkyl, C2-C10-heteroaryl, C2-C10-heteroaryl-C1-C10-alkyl and C1-C10-alkoxy-C1-C10-alkyl, halo-C1-C10-alkyl and halo-C3-C10-cycloalkyl; each of the radicals is optionally substituted and the heteroatom is selected from N, O and S.

Preferably, R₁And R₂Independently selected in each occurrence from C1-C6-alkyl, C2-C6-alkenyl, C6-C6-cycloalkyl, C6-C6-heterocyclyl-C6-C6-alkyl, C6-C6-aryl-C6-alkyl, C6-C6-heteroaryl-C6-C6-alkyl, C6-C6-alkoxy-C6-C6-alkyl, halo-C6-C6-alkyl, and halo-C6-C6-cycloalkyl; each of said radicals being optionally substituted and the heteroatom being selected from N, O and S;

more preferably, R₁And R₂Independently selected in each case from C1-C6-alkyl, such as methyl, ethyl, n-propyl or isopropyl, n-butyl, isobutyl, tert-butyl or 2-butyl, pentyl, such as n-pentyl and isopentyl, hexyl, such as n-hexyl, isohexyl and 1, 3-dimethylbutyl;

according to a still further preferred embodiment of the invention, wherein R₁And R₂Independently selected in each case from C1-C6-alkyl radicals, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl.

In a preferred embodiment of the invention, R₃And R₄Independently selected in each case from C1-C10-alkyl, C2-C10-alkenyl, C3-C10-cycloalkyl,C2-C10-heterocyclyl, C2-C10-heterocyclyl-C1-C10-alkyl, C3-C18-aryl, C3-C18-aryl-C1-C10-alkyl, C2-C10-heteroaryl, C2-C10-heteroaryl-C1-C10-alkyl, and C1-C10-alkoxy-C1-C10-alkyl, halo-C1-C10-alkyl, and halo-C3-C10-cycloalkyl; each of the radicals is optionally substituted and the heteroatom is selected from N, O and S.

Preferably, R₃And R₄Independently selected in each occurrence from C1-C6-alkyl, C2-C6-alkenyl, C6-C6-cycloalkyl, C6-C6-heterocyclyl-C6-C6-alkyl, C6-C6-aryl-C6-alkyl, C6-C6-heteroaryl-C6-C6-alkyl, C6-C6-alkoxy-C6-C6-alkyl, halo-C6-C6-alkyl, and halo-C6-C6-cycloalkyl; each of the radicals is optionally substituted and the heteroatom is selected from N, O and S.

More preferably, R₃And R₄Independently selected in each case from C1-C6-alkyl, for example methyl, ethyl, n-propyl or isopropyl, n-butyl, isobutyl, tert-butyl or 2-butyl, pentyl, for example n-pentyl and isopentyl, hexyl, for example n-hexyl, isohexyl and 1, 3-dimethylbutyl.

According to a still further preferred embodiment of the invention, wherein R₃And R₄Independently selected in each case from C1-C6-alkyl radicals, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl.

In a preferred embodiment of the invention, R₁、R₂、R₃And R₄Are the same.

Preferably, n is an integer from 1 to 15, more preferably from 1 to 10, more preferably from 1 to 8, most preferably from 2 to 8, and especially from 3 to 6.

In a preferred embodiment of the invention, R₅If n is 1 or if n > 1, in each case independently selected from the group consisting of C1-C10-alkylene, C2-C10-alkenylene, C2-C10-alkynylene, C3-C18-arylene, C3-C10-cycloalkylene, C3-C10-cycloalkenylene, C3-C10-cycloalkynylene, C2-C10-heterocyclylene and C2-C10-heteroarylene, each of said radicals optionally being substituted, the heteroatom being selected from the group consisting of N, O and S, wherein R is₅Optionally interrupted by a radical selected from N, O and S; and is

Preferably, R₅If n is 1 or if n > 1, in each case independently from C1-C6-alkylene, C2-C6-alkenylene, C2-C6-alkynylene, C6-C8-arylene, C3-C6-cycloalkylene, C3-C6-cycloalkenylene, C3-C10-cycloalkynylene, C3-C6-heterocyclylene and C3-C6-heteroarylene; each of said radicals being optionally substituted and the heteroatom being selected from N, O and S, wherein R is₅Optionally interrupted by a radical selected from N, O and S.

More preferably, R₅Independently selected in each case from C1-C6-alkylene and C6-C8-arylene, if n ═ 1 or if n > 1; each of said radicals being optionally substituted by at least one C1-C6-alkyl group.

Most preferably, R₅Independently selected in each case from propylene, pentylene and phenylene if n ═ 1 or if n > 1; each of the radicals is optionally substituted with methyl.

In a preferred embodiment of the present invention, the radical is further substituted with a substituent. Possible substituents are selected from the group consisting of halogen, hydroxy, nitro, cyano, C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C10-alkoxy, C3-C10-cycloalkyl, C2-C10-heterocyclyl, C2-C10-heterocyclyl-C1-C10-alkyl, halo-C1-C10-alkyl, halo-C3-C10-cycloalkyl, C3-C18-aryl, C3-C18-aryl-C1-C10-alkyl, C2-C10-heteroaryl, C3-C10-cycloalkenyl and C3-C10-cycloalkynyl, the heteroatom being selected from the group consisting of N, O and S.

Preferably, the substituents are selected from halogen, hydroxy, nitro, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-heterocyclyl, C3-C6-heterocyclyl-C1-C6-alkyl, halo-C1-C6-alkyl, halo-C3-C6-cycloalkyl, C6-C8-aryl, C6-C8-aryl-C1-C6-alkyl, C3-C6-heteroaryl, C3-C6-cycloalkenyl and C3-C6-cycloalkynyl, the heteroatom being selected from N, O and S.

In each case, the compositions of the present invention should include one or more compounds to extend shelf life. In certain embodiments, the composition is formulated such that the composition is stable for at least 6 months and preferably for at least one year. The compound includes an acidic stabilizer.

The acidic stabilizer is preferably selected from sulfuric acid (H)₂SO₄) One or more of trifluoromethanesulfonic acid (TFA), chlorodifluoroacid (chlorodifluoroacid), maleic acid, methanesulfonic acid (MSA), p-toluenesulfonic acid (p-TSA), difluoroacetic acid, trichloroacetic acid, phosphoric acid, dichloroacetic acid. Such acidic stabilizers have a pKa value in the range of, for example, from about-15 to about 5, or from about-15 to about 3, or from about-15 to about 1, or from about-2 to about 2, or from about 2 to about 5, or from about 3 to about 5.

The amount of the acidic stabilizer is 0.1 to 500ppm, preferably 0.1 to 300ppm and more preferably 0.1 to 200ppm, based on the total weight of component (a) and component (B).

According to one embodiment of the invention, the composition is substantially free of any solvent.

According to one embodiment of the invention, the composition further comprises an additive. In certain embodiments of the invention, the additive is at least one selected from the group consisting of plasticizers, thixotropic agents, adhesion promoters, antioxidants, light stabilizers, UV stabilizers, fillers, cements, limestone, surfactants, wetting agents, viscosity modifiers, extenders, dispersants, antiblocking agents, air release agents (airriease agents), anti-sagging agents (anti-fogging agents), anti-agglomerating agents (anti-parting agents), matting agents, flatting agents, waxes, anti-mar additive (anti-mar additive), anti-scratch additive (anti-scratch additive), antifoaming agents, colorants, fibers, polymer powders, mesh (mesh), crumb (chip), hollow spheres, and inert resins. In a preferred embodiment of the present invention, the additive is at least one selected from the group consisting of plasticizers, thixotropic agents, adhesion promoters, antioxidants, light stabilizers, UV stabilizers, fillers, surfactants, wetting agents, viscosity modifiers, dispersants, degassing agents, anti-sagging agents, anti-agglomerating agents, antifoaming agents, colorants, fibers, polymer powders, meshes, crumbles, hollow spheres, and inert resins.

In a preferred embodiment, the additive is selected from at least plasticizers, thixotropic agents, adhesion promoters, antioxidants, light stabilizers, UV stabilizers, fillers, cement, limestone, surfactants, wetting agents, viscosity modifiers, dispersants, air release agents, anti-sagging agents, anti-agglomerating agents, defoamers, colorants, fibers, polymer powders, meshes, crumbles, hollow spheres, and inert resins.

The above additives are commercially available to those skilled in the art. The above formulation additives, if any, are present in amounts commonly used in the art.

The composition according to the invention is obtained by a process comprising the step of mixing the monomer (a), the polymer (B) and the acidic stabilizer (C). The mixing used in the process is carried out by means conventional in the art in a unit suitable for mixing, for example by stirring or agitation at room temperature.

In a preferred embodiment, the process for preparing the composition according to the invention comprises: a) mixing monomer (a) and polymer (B) in the amounts as described hereinbefore; b) adding an acidic stabilizer (C) to the mixture obtained from step (a).

According to a particular aspect of the invention, the monomer (a) having formula (I) can be prepared by a person skilled in the art by means of the following steps: (a) reacting a malonate ester (malonic acid ester) with a source of formaldehyde, optionally in the presence of an acidic or basic base promoter, and optionally in the presence of an acidic or non-acidic solvent, to form a reaction composition (reaction complex); (b) contacting the reaction composition or a portion thereof with an energy transfer means to produce a vapor phase comprising a methylene malonate monomer; and (c) separating the methylene malonate monomer from the vapor phase.

According to an embodiment of the present invention, the person skilled in the art can prepare the polymer (B) having formula (II) by means of the following steps: an appropriate amount of starting material (e.g., DEMM) and an appropriate amount of OH-containing linking group (e.g., diol) are mixed and reacted in the presence of a catalyst (e.g., Novazym 435), and the resulting mixture is stirred and heated at a temperature for a period of time while the alcohol produced is removed by evaporation. Subsequently, the reaction mixture is cooled and stabilized with a small amount of an acid stabilizer, and then filtered to obtain a crude residue, which is purified on column chromatography to obtain the desired product.

In a further aspect, the present invention relates to the use of the composition according to the invention as a coating for floor, water, wall paints and underground construction applications applied on alkaline substrates.

The application of the present invention is carried out in a manner conventional in the art. In a preferred embodiment, the mixture comprising the monomer (A) and the polymer (B) is mixed with the acidic stabilizer (C) and additives such as fillers and UV stabilizers, applied to a substrate, and, after a while, a substantially 100% solids product is obtained.

In the present invention, the coating is carried out in a manner known to the person skilled in the art, for example by brushing, spraying or roller coating. It is to be noted that the coating manner used in the present invention depends on the workability (workability) of the composition, and specifically, the roll coating requires a long gel time, while the spray coating requires a short gel time.

In an embodiment of the invention, the alkaline substrate comprises concrete, alkaline stone, alkaline ore powder, metal. Examples of the alkaline stone include limestone, andesite, basalt and the like.

In an embodiment of the invention, the composition or mixture is applied to a wet substrate.

In an embodiment of the invention, the temperature used for this purpose is from-30 ℃ to 60 ℃, preferably from-20 ℃ to 40 ℃.

In an embodiment of the invention, the relative humidity for this purpose is from 1% to 99%, preferably from 5% to 95%.