Compositions containing methylene malonate monomers and polymers, their preparation and their use in flooring applications
阅读说明：本技术 含亚甲基丙二酸酯单体和聚合物的组合物、其制备及其在地板应用中的用途 (Compositions containing methylene malonate monomers and polymers, their preparation and their use in flooring applications ) 是由 孟磊 周圣中 S·希斯曼 H·勒克尔 于 2018-12-18 设计创作，主要内容包括：本发明涉及用于建筑领域中的包含亚甲基丙二酸酯单体和聚合物的组合物。特别地,本发明涉及包含至少一种亚甲基丙二酸酯单体(A)、至少一种聚合物(B)和至少一种酸稳定剂(C)以及含有至少一种碱速凝剂的组分II的双组分组合物,其制备方法,以及所述组合物作为涂料、特别是地板涂料的用途。(The present invention relates to compositions comprising methylene malonate monomers and polymers for use in the construction field. In particular, the present invention relates to a two-component composition comprising at least one methylene malonate monomer (a), at least one polymer (B) and at least one acid stabilizer (C) and component II comprising at least one base accelerator, a process for its preparation and the use of said composition as a coating, in particular a floor coating.)
1. A two-component composition comprising a component I and a component II comprising at least one base accelerator, wherein the component I comprises
(A) At least one methylene malonate monomer having the formula (I):
wherein R is1And R2Independently at each occurrence selected from C1-C30Alkyl radical, C2-C30-alkenyl, C3-C30-cycloalkyl, C2-C30-heterocyclyl radical, C2-C30-heterocyclyl- (C)1-C30Alkyl), C6-C30-aryl, C6-C30-aryl-C1-C30Alkyl radical, C2-C30-heteroaryl, C2-C30-heteroaryl-C1-C30-alkyl and C1-C30-alkoxy-C1-C30-alkyl, halo-C1-C30-alkyl, halo-C3-C30-cycloalkyl, each of said groups being optionally substituted, wherein the heteroatom is selected from N, O and S;
(B) at least one methylene malonate polymer having the formula (II):
wherein R is3And R4Independently at each occurrence selected from C1-C30Alkyl radical, C2-C30-alkenyl, C3-C30-cycloalkyl, C2-C30-heterocyclyl radical, C2-C30-heterocyclyl-C1-C30Alkyl radical, C6-C30-aryl, C6-C30-aryl- (C)1-C30Alkyl), C2-C30-heteroaryl, C2-C30-heteroaryl-C1-C30Alkyl radical, C1-C30-alkoxy-C1-C30-alkyl, halo-C1-C30-alkyl and halo-C3-C30-cycloalkyl, each of said groups being optionally substituted, wherein the heteroatom is selected from N, O and S;
n is an integer of 1 to 20;
R5if n is 1 or if n>1, then it is independently selected in each case from C1-C30Alkylene radical, C2-C30-alkenylene, C2-C30-alkynylene, C6-C30Arylene radical, C3-C30-cycloalkylene radical, C3-C30Cycloalkenylene radical, C3-C30-cycloalkynylene, C2-C30-heterocyclylene and C2-C30-a heteroarylene group, each of said groups being optionally substituted, wherein the heteroatom is selected from N, O and S, wherein R is5Optionally interrupted by a group selected from N, O and S; and
(C) at least one acid stabilizer;
wherein the amount of monomer (A) is from 0 to 40% by weight, preferably from 5 to 35% by weight, more preferably from 10 to 30% by weight, most preferably from 15 to 20% by weight, based in each case on the total weight of monomer (A) and polymer (B);
the amount of the acid stabilizer (C) is 0.1 to 500ppm, preferably 0.1 to 300ppm, more preferably 0.1 to 200 ppm; and is
The amount of component II is from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, more preferably from 0.1 to 2% by weight, based in each case on the total weight of components (I) and (II).
2. The two-component composition of claim 1, wherein the two-component composition comprises two separate packages of component I and component II that can be mixed on site to apply the composition.
3. Two-component composition according to claim 1 or 2, wherein R1And R2Independently at each occurrence selected from C1-C10Alkyl radical, C2-C10-alkenyl, C3-C10-cycloalkyl, C2-C10-heterocyclyl radical, C2-C10-heterocyclyl-C1-C10Alkyl radical, C3-C18-aryl, C3-C18-aryl-C1-C10Alkyl radical, 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 groups being optionally substituted with at least one group selected from: halogen, hydroxy, nitro, cyano, C1-C10Alkyl radical, C2-C10-alkenyl, C2-C10-alkynyl, C1-C10-alkoxy, C3-C10-cycloalkyl, C2-C10-heterocyclyl radical, C2-C10-heterocyclyl-C1-C10-alkyl, halo-C1-C10-alkyl, halo-C3-C10-cycloalkyl, C3-C18-aryl, C3-C18-aryl-C1-C10Alkyl radical, C2-C10-heteroaryl, C3-C10Cycloalkenyl radical and C3-C10-cycloalkynyl, wherein the heteroatom is selected from N, O and S;
R3and R4Independently at each occurrence selected from C1-C10Alkyl radical, C2-C10-alkenyl, C3-C10-cycloalkyl, C2-C10-heterocyclyl radical, C2-C10-heterocyclic radical-C1-C10Alkyl radical, C3-C18-aryl, C3-C18-aryl-C1-C10Alkyl radical, 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 groups being optionally substituted with at least one group selected from: halogen, hydroxy, nitro, cyano, C1-C10Alkyl radical, C2-C10-alkenyl, C2-C10-alkynyl, C1-C10-alkoxy, C3-C10-cycloalkyl, C2-C10-heterocyclyl radical, C2-C10-heterocyclyl-C1-C10-alkyl, halo-C1-C10-alkyl, halo-C3-C10-cycloalkyl, C3-C18-aryl, C3-C18-aryl-C1-C10Alkyl radical, C2-C10-heteroaryl, C3-C10Cycloalkenyl radical and C3-C10-cycloalkynyl, wherein the heteroatom is selected from N, O and S;
n is an integer of 1 to 15;
R5if n is 1 or if n>1, then it is independently selected in each case from C1-C10Alkylene radical, C2-C10-alkenylene, C2-C10-alkynylene, C3-C18Arylene radical, C3-C10-cycloalkylene radical, C3-C10Cycloalkenylene radical, C3-C10-cycloalkynylene, C2-C10-heterocyclylene and C2-C10-a heteroarylene group, each of said groups being optionally substituted with at least one group selected from: halogen, hydroxy, nitro, cyano, C1-C10Alkyl radical, C2-C10-alkenyl, C2-C10-alkynyl, C1-C10-alkoxy, C3-C10-cycloalkyl, C2-C10-heterocyclyl radical, C2-C10-heterocyclyl-C1-C10-alkyl, halo-C1-C10-alkyl, halo-C3-C10-cycloalkyl, C3-C18-aryl, C3-C18-aryl-C1-C10Alkyl radical, C2-C10-heteroaryl, C3-C10Cycloalkenyl radical and C3-C10-cycloalkynyl, wherein the heteroatom is selected from N, O and S, wherein R5Optionally interrupted by a group selected from N, O and S.
4. The two-component composition according to any of claims 1-3, wherein R1And R2Independently at each occurrence selected from C1-C6Alkyl radical, C2-C6-alkenyl, C3-C6-cycloalkyl, C3-C6-heterocyclyl radical, C3-C6-heterocyclyl-C1-C6Alkyl radical, C6-C8-aryl, C6-C8-aryl-C1-C6Alkyl radical, C3-C6-heteroaryl, C3-C6-heteroaryl-C1-C6Alkyl radical, C1-C6-alkoxy-C1-C6-alkyl, halo-C1-C10-alkyl and halo-C3-C10-cycloalkyl, each of said groups being optionally substituted with at least one group selected from: halogen, hydroxy, nitro, cyano, C1-C6Alkyl radical, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-heterocyclyl radical, C3-C6-heterocyclyl-C1-C6-alkyl, halo-C1-C6-alkyl, halo-C3-C6-cycloalkyl, C6-C8-aryl, C6-C8-aryl-C1-C6Alkyl radical, C3-C6-heteroaryl, C3-C6Cycloalkenyl radical and C3-C6-cycloalkynyl, wherein the heteroatom is selected from N, O and S;
R3and R4Independently at each occurrence selected from C1-C6Alkyl radical, C2-C6-alkenyl, C3-C6-cycloalkyl, C3-C6-heterocyclyl radical, C3-C6-heterocyclyl-C1-C6Alkyl radical, C6-C8-aryl, C6-C8-aryl-C1-C6Alkyl radical, C3-C6-heteroaryl, C3-C6-heteroaryl-C1-C6Alkyl radical, C1-C6-alkoxy-C1-C6-alkyl, halo-C1-C10-alkyl and halo-C3-C10-cycloalkyl, each of said groups being optionally substituted with at least one group selected from: halogen, hydroxy, nitro, cyano, C1-C6Alkyl radical, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-heterocyclyl radical, C3-C6-heterocyclyl-C1-C6-alkyl, halo-C1-C6-alkyl, halo-C3-C6-cycloalkyl, C6-C8-aryl, C6-C8-aryl-C1-C6Alkyl radical, C3-C6-heteroaryl, C3-C6Cycloalkenyl radical and C3-C6-cycloalkynyl, wherein the heteroatom is selected from N, O and S;
n is an integer of 1 to 10;
R5if n is 1 or if n>1, then in each case independently selected from C1-C6Alkylene radical, C2-C6-alkenylene, C2-C6-alkynylene, C6-C8Arylene radical, C3-C6-ACycloalkyl radical, C3-C6Cycloalkenylene radical, C3-C10-cycloalkynylene, C3-C6-heterocyclylene and C3-C6-a heteroarylene group, each of said groups being optionally substituted with at least one group selected from: halogen, hydroxy, nitro, cyano, C1-C6Alkyl radical, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-heterocyclyl radical, C3-C6-heterocyclyl-C1-C6-alkyl, halo-C1-C6-alkyl, halo-C3-C6-cycloalkyl, C6-C8-aryl, C6-C8-aryl-C1-C6Alkyl radical, C3-C6-heteroaryl, C3-C6Cycloalkenyl radical and C3-C6-cycloalkynyl, wherein the heteroatom is selected from N, O and S, wherein R5Optionally interrupted by a group selected from N, O and S.
5. The two-component composition of any of claims 1-4, wherein R1And R2Independently at each occurrence selected from C1-C6-an alkyl group;
R3and R4Independently at each occurrence selected from C1-C6-an alkyl group;
n is an integer of 1 to 8; and is
R5If n is 1 or if n>1, then it is independently selected in each case from C1-C6Alkylene and C6-C8-arylene, each of said groups optionally substituted with at least one C1-C6-alkyl substitution.
6. The two-component composition according to any one of claims 1 to 5, wherein the acid stabilizer (C) is selected from the group consisting of trifluoromethanesulfonic acid, chlorodifluoroacid, maleic acid, methanesulfonic acid, difluoroacetic acid, trichloroacetic acid, phosphoric acid, dichloroacetic acid, phenol, and mixtures thereof.
7. The two-component composition according to any one of claims 1 to 6, wherein the alkali accelerator is at least one selected from the group consisting of an alkali, an alkali precursor or an alkali enhancer.
8. Two-component composition according to claim 7, wherein the alkali accelerator is preferably at least one selected from the group consisting of: metal oxide, metal hydroxide, amine, guanidine, amide, piperidine, piperazine, morpholine, pyridine, halide, salt of a metal, ammonium, amine, wherein the anion in the salt is at least one selected from the group consisting of: halogen, acetate, chloroacetate, benzoate, fatty acid, alkene carboxylic acid, sulfur, carbonate, silicate, diketone, monocarboxylic acid, carboxylic acid-containing polymer.
9. Two-component composition according to claim 8, wherein the base accelerator is preferably at least one selected from the group consisting of: dimethylethylamine, dimethylpropylamine, 2-ethylhexylamine, di- (2-ethylhexyl) amine, dibutylamine, dicyclohexylamine, ditridecylamine isomer mixture, N, N-dimethylisopropylamine, N-ethyldiisopropylamine, N, N-dimethylcyclohexylamine, N-octylamine, tributylamine, tridecylamine isomer mixture, tripropylamine, tri- (2-ethylhexyl) amine, triethylamine, trimethylamine, 2- (diisopropylamino) ethylamine, 3- (cyclohexylamino) propylamine, 3- (diethylamino) propylamine, 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane, isophoronediamine, di-N-2-ethylhexyl-amine, di-N-ethylhexylamine, di-N-octylamine, tri-butylamine, tridecylamine isomer mixture, tripropylamine, tri-2-ethylhexyl-amine, tri-ethylamine, triethylamine, tetramethyl-1, 6-hexanediamine, S-triazine, neopentanediamine (2, 2-dimethylpropane-1, 3-diamine), octamethylenediamine, diethylenetriamine, dipropylenetriamine, pentamethyldiethylenetriamine, N-bis- (3-aminopropyl) methylamine, N3-amine 3- (2-aminoethylamino) propylamine, N4-amine N, N' -bis- (3-aminopropyl) ethylenediamine, 4, 9-dioxadodecane-1, 12-diamine, bis- (2-methoxyethyl) amine, bis (2-dimethylaminoethyl) ether, polyetheramine D2000, polyetheramine D230, polyetheramine D400, polyetheramine T403, polyetheramine T5000, N-dimethylcyclohexylamine, n-methylmorpholine, 2,2 '-dimorpholinodiethylether, dimethylaminoethoxyethanol, bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, trimethylaminoethylethanolamine, tetramethyl-1, 6-hexanediamine, 1, 8-diazabicyclo-5, 4, 0-undecene-7, 2, 6-dimethylaniline, 2-phenylethylamine, 4,4' -diaminodiphenylmethane, aniline, benzylamine, tris (dimethylaminomethyl) phenol, 2-dimethylaminomethylphenol (DMP10), diethanol-p-toluidine, diisopropanol-p-toluidine, N- (2-hydroxyethyl) aniline, N-bis- (2-hydroxyethyl) aniline, N-dimethylaminoethoxyethanol, bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, trimethylaminoethylethanolamine, tetramethyl-1, 6-hexanediamine, 1, 8-diazabicyclo-5, 4, 0-unde, N-ethyl-N- (2-hydroxyethyl) aniline, o-toluidine, p-nitrotoluene, 3-dimethylaminopropan-1-ol, butyldiethanolamine, triisopropanolamine, dibutylethanolamine, diethylethanolamine, methyldiethanolamine, methyldiisopropanolamine, N, N-dimethylethanolamine S, N, N-dimethylisopropanolamine, dimethylethanolamine, 4- (2-hydroxyethyl) morpholine, N, N, N ', N' -tetrakis (2-hydroxyethyl) ethylenediamine, sodium acetate, potassium acetate, zinc acetate, copper acetate, magnesium acetate, aluminum acetate, sodium chloroacetate, potassium chloroacetate, copper chloroacetate, zinc chloroacetate, magnesium chloroacetate, aluminum chloroacetate, iron chloroacetate, acid salts of sodium, potassium, lithium, copper, iron and cobalt, sodium oxide, lithium, copper, iron and cobalt, Potassium oxide, calcium oxide, zinc oxide, copper oxide, magnesium oxide, aluminum oxide, iron oxide and ferrous oxide, sodium hydroxide, potassium hydroxide, zinc hydroxide, copper hydroxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, iron hydroxide and ferrous hydroxide, sodium silicate, potassium silicate, zinc silicate, copper silicate, magnesium silicate, iron silicate, aluminum silicate, lithium chloride and tetramethylguanidine.
10. The composition according to any one of claims 1-9, wherein the composition has an elongation (%), tensile strength (MPa), weight loss after 400 cycles of grinding (mg) related to abrasion resistance, and they satisfy the following relationship:
1.05<(2ER/[％]+TS/[Mpa])/AR[mg]<2.25.
where ER is an abbreviation for elongation, determined according to DIN53504, TS is an abbreviation for tensile strength, determined according to DIN53504, and AR is an abbreviation for weight loss (mg) after 400 cycles of grinding, related to abrasion resistance, determined according to ASTM D4060-07.
11. A mixture comprising the two-component composition according to any one of claims 1-10.
12. The mixture of claim 11, wherein the mixture is substantially free of any solvent.
13. A method of preparing the composition of any one of claims 1-12, comprising the steps of:
(1) mixing a monomer (a), a polymer (B) and an acid stabilizer (C) to obtain component I;
(2) component II was prepared.
14. Use of the two-component composition according to any one of claims 1-10 or the mixture according to claim 11 or 12 in floor coatings.
15. Use of a two-component composition according to claim 14, wherein the two-component composition or mixture is applied as a floor coating.
16. Use according to claim 14 or 15, wherein the two-component composition or mixture is applied on a substrate selected from the group consisting of concrete, wood, resin layers and stone.
17. Use according to claim 16, wherein the resin layer is selected from the group consisting of cement-based resin layers, epoxy-based resin layers, polyurethane-based resin layers, acrylate-based resin layers, polyethylene layers, polypropylene layers, polyvinyl chloride, rubber layers, asphalt layers and polymer-modified asphalt layers.
18. Use according to any one of claims 14 to 17, wherein the two-component composition or mixture is applied on a wet substrate.
19. Use according to any one of claims 14 to 18, wherein component I and component II are mixed and then applied to a substrate.
20. Use according to any one of claims 14 to 18, wherein component II is applied to the substrate first and then component I is applied to the substrate in a next step.
21. Use according to any one of claims 14-20, wherein the temperature for said use is from-30 ℃ to 60 ℃ and preferably from-20 ℃ to 40 ℃.
22. Use according to any one of claims 14-21, wherein the relative humidity for said use is from 1% to 99% and preferably from 5% to 95%.
Technical Field
The invention relates to a composition containing methylene malonate monomer and polymer, which is used in the field of construction. In particular, the present invention relates to a two-component composition comprising at least one methylene malonate monomer (a), at least one polymer (B) and at least one acid stabilizer (C) and component II comprising at least one base accelerator, a process for its preparation and the use of said composition as a coating, in particular as a floor coating.
Technical Field
Floor coatings are applied to substrates such as wood, concrete, stone, etc. to protect the substrate surface. To achieve this, a floor coating is required to have good mechanical properties such as tensile strength and abrasion resistance. In certain applications, for example in the chemical industry or in food processing plants, it is also required that the floor coatings are resistant to acids, bases and other solvents. And sometimes floor coatings are used to repair cracks or peeling, thus requiring strong adhesion of existing floor coatings. Furthermore, workability is also an important requirement for floor coatings.
Current floor coatings are based primarily on epoxy, polyurethane, polyacrylate or unsaturated polyester. Each of them has its own drawbacks. The epoxy resin is slowly cured at low temperature such as 0 ℃. The monomer of polyurethane, i.e., isocyanate, is not environmentally friendly, and in addition, the high humidity environment used for its curing tends to cause foaming and foaming of the floor coating. In addition, the curing of polyacrylates is sensitive to oxygen, i.e. oxygen hinders the curing, which tends to make the surface of the floor coating oily or tacky.
Thus, there is still a need to provide a floor coating which is solvent-free, chemically resistant, cures rapidly over a wide temperature and humidity range and at the same time has good mechanical properties.
Disclosure of Invention
It is an object of the present invention to provide such a composition which does not have the above-mentioned disadvantages of the prior art as a floor coating. In particular, it is an object of the present invention to provide a novel composition wherein methylene malonate monomers and polymers thereof are mixed in specific proportions. Such compositions can undergo rapid cure with a small amount of alkali accelerator and can be applied under extreme conditions such as low temperature and high levels of humidity, and are thus suitable for use in flooring applications. The resulting cured product is essentially 100% solids, contains little Volatile Organic Compounds (VOC), and exhibits excellent properties in tensile strength as well as mechanical and chemical resistance, especially abrasion resistance.
Surprisingly, the inventors have found that the above object can be solved by a composition comprising a component I and a component II comprising at least one alkali accelerator, said component I comprising:
(A) at least one methylene malonate monomer of formula (I)
Wherein R is1And R2Independently at each occurrence selected from C1-C30Alkyl radical, C2-C30-alkenyl, C3-C30-cycloalkyl, C2-C30-heterocyclyl radical, C2-C30-heterocyclyl- (C)1-C30Alkyl), C6-C30-aryl, C6-C30-aryl-C1-C30Alkyl radical, C2-C30-heteroaryl, C2-C30-heteroaryl-C1-C30-alkyl and C1-C30-alkoxy-C1-C30-alkyl, halo-C1-C30-alkyl, halo-C3-C30-cycloalkyl, each of said groups being optionally substituted, wherein the heteroatom is selected from N, O and S;
(B) at least one methylene malonate polymer having the formula (II):
wherein R is3And R4Independently at each occurrence selected from C1-C30Alkyl radical, C2-C30-alkenyl, C3-C30-cycloalkyl, C2-C30-heterocyclyl radical, C2-C30-heterocyclyl-C1-C30Alkyl radical, C6-C30-aryl, C6-C30-aryl- (C)1-C30Alkyl), C2-C30-heteroaryl, C2-C30-heteroaryl-C1-C30Alkyl radical, C1-C30-alkoxy-C1-C30-alkyl, halo-C1-C30-alkyl and halo-C3-C30-cycloalkyl, each of said groups being optionally substituted, wherein the heteroatom is selected from N, O and S;
n is an integer of 1 to 20;
R5if n is 1 or if n>1, then in each case independently selected from C1-C30Alkylene radical, C2-C30-alkenylene, C2-C30-alkynylene, C6-C30Arylene radical, C3-C30-cycloalkylene radical, C3-C30Cycloalkenylene radical, C3-C30-cycloalkynylene, C2-C30-heterocyclylene and C2-C30-a heteroarylene group, each of said groups being optionally substituted, wherein the heteroatom isSelected from N, O and S, wherein R5Optionally interrupted by a group selected from N, O and S; and
(C) at least one acid stabilizer;
wherein the amount of component (a) is from 0 to 40% by weight, preferably from 5 to 35% by weight and more preferably from 10 to 30% by weight, and most preferably from 15 to 20% by weight, in each case based on the total weight of monomer (a) and polymer (B);
the amount of the acid stabilizer (C) is 0.1 to 500ppm, preferably 0.1 to 300ppm, more preferably 0.1 to 200 ppm; and is
The amount of component II is from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, more preferably from 0.1 to 2% by weight, based in each case on the total weight of the monomers (A) and the polymers (B).
In another aspect, the present invention relates to a mixture comprising the two-component composition of the present invention.
The two-component composition may be prepared by a process comprising the steps of:
(1) mixing a monomer (A), a polymer (B) and an acid stabilizer (C) to obtain a component I; and
(2) component II was prepared.
Surprisingly, it has been found that the two-component composition according to the invention can be cured even at low temperatures below 0 ℃ and high levels of humidity. The cured coatings thus obtained have both resistance to water, solvents and abrasion and high chemical and mechanical strength and are therefore suitable as floor coatings for use in the construction sector.
Thus, in a still further aspect, the present invention relates to the use of the composition or mixture according to the invention as a coating material, in particular as a floor coating.
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 mean a range of numbers that one of skill in the art would consider equivalent to the recited value if performing the same function or result.
As used herein, the term "methylene malonate" refers to a compound having the core formula-O-C (O) -C (═ CH)2) -C (O) -O-.
As used herein, the term "two-component" relates 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 in two separate packages that can be mixed on site at the time of application.
As used herein, the term "RH" is equal to "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 absent" as in "substantially absent solvent" applies to a reaction mixture that contains less than 1 weight percent of a particular component as compared to the total reaction mixture. In certain embodiments, "substantially absent" refers to less than 0.7 wt.%, less than 0.5 wt.%, less than 0.4 wt.%, less than 0.3 wt.%, less than 0.2 wt.%, or less than 0.1 wt.% of a particular component as compared to the total reaction mixture. In certain embodiments, "substantially absent" refers to less than 1.0 vol.%, less than 0.7 vol.%, less than 0.5 vol.%, less than 0.4 vol.%, less than 0.3 vol.%, less than 0.2 vol.%, or less than 0.1 vol.% of a particular component, as compared to the total reaction mixture.
As used herein, the term "stable," e.g., in the context of a "stable" monomer of the invention or a composition comprising the monomer, means that the monomer of the invention (or a composition thereof) does not substantially polymerize over time, does not substantially harden, gel, thicken or otherwise increase in viscosity over time, and/or does not substantially exhibit minimal loss of cure speed (i.e., maintain cure speed) over time, as compared to an unstable similar composition.
As used herein, the term "shelf-life", e.g. as in the case of compositions of the invention having an improved "shelf-life", refers to a given period of time for which the compositions of the invention will be stable, e.g. 1 month, 6 months or even 1 year or more.
As used herein, the term "additive" refers to additives included in a formulated system to enhance its physical or chemical properties and provide a desired result, including, but not limited to, dyes, pigments, toughening agents, impact modifiers, rheology modifiers, plasticizers, thixotropic agents, natural or synthetic rubbers, fillers, reinforcing agents, thickeners, opacifiers, inhibitors, fluorescers or other marking agents, thermal degradation reducers, heat resistance imparting agents, defoamers, surfactants, wetting agents, 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 can be converted to a base upon acting thereon in some manner (e.g., application of heat, chemical reaction, or UV activation).
As used herein, the term "base enhancer" refers to an agent that can act in some manner to improve or enhance the basicity of the agent.
As used herein, the terms "halogen atom", "halogen", "halo-" or "Hal-" are understood to mean a fluorine, chlorine, bromine or iodine atom.
As used herein, the term "alkyl", by itself or in combination with other terms such as haloalkyl, is understood to mean a radical of a saturated aliphatic hydrocarbon group and may be branched or unbranched, such as 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 other terms such as haloalkenyl, is understood to mean a straight or branched chain group having at least one double bond, such as 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 other terms such as haloalkynyl, is understood to mean a straight or branched chain group having at least one triple bond, such as ethynyl, propynyl or propargyl, or isomers thereof.
As used herein, the term "cycloalkyl", by itself or in combination with other terms, is understood to mean a fused or non-fused, saturated, monocyclic or polycyclic hydrocarbon ring, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, or isomers thereof.
As used herein, the term "alkoxy", by itself or in combination with other terms such as haloalkoxy, is understood to mean a straight or branched chain saturated group having the 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 other terms such as arylalkyl, is understood to include fused or non-fused aryl groups such as phenyl or naphthyl, wherein phenyl is optionally substituted with 1-5 groups and naphthyl is optionally substituted with 1-7 groups.
As used herein, the term "hetero-" is understood to mean a saturated or unsaturated group interrupted by at least one heteroatom selected from oxygen (O), nitrogen (N) and sulfur (S).
As used herein, the term "a-to B-membered hetero-", for example "3-to 6-membered hetero-", is understood to mean a fused or non-fused, saturated or unsaturated, mono-or polycyclic group which, in addition to carbon atoms, comprises 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. According to the invention, the hetero radical is preferably a 5-to 30-membered hetero radical, most preferably a 6-to 18-membered hetero radical, especially a 6-to 12-membered hetero radical, and especially a 6-to 8-membered hetero radical.
As used herein, the term "heterocyclyl" is understood to include aliphatic or aromatic heterocyclyl 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 is not exceeded in the present case, 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" refers to optional substitution with the indicated group, radical or moiety. Unless otherwise stated, an optionally substituted group may be mono-or polysubstituted, wherein in the case of polysubstitution the substituents may be the same or different.
As used herein, a halogen-substituted group, such as haloalkyl, is monohalogenated or polyhalogenated, up to the maximum number of substituents possible. 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 prefix "ene" means that the group has two covalent bonds that can be attached to other groups, e.g., -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 percent" unless otherwise indicated.
The radical definitions or explanations given above in general terms or in preferred ranges apply to the end products and correspondingly to the starting materials and intermediates. These radical definitions may be combined with one another as desired, i.e. including combinations between the general definitions and/or the individual preferred ranges 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 and 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 component I comprising
1. Two-component composition comprising a component I and a component II containing at least one base accelerator, said component I comprising
(A) At least one methylene malonate monomer of formula (I)
Wherein R is1And R2Independently at each occurrence selected from C1-C30Alkyl radical, C2-C30-alkenyl, C3-C30-cycloalkyl, C2-C30-heterocyclyl radical, C2-C30-heterocyclyl- (C)1-C30Alkyl), C6-C30-aryl, C6-C30-aryl-C1-C30Alkyl radical, C2-C30-heteroaryl, C2-C30-heteroaryl-C1-C30-alkyl and C1-C30-alkoxy-C1-C30-alkyl, halo-C1-C30-alkyl, halo-C3-C30-cycloalkyl, each of said groups being optionally substituted, wherein the heteroatom is selected from N, O and S;
(B) at least one methylene malonate polymer having the formula (II)
Wherein R is3And R4Independently at each occurrence selected from C1-C30Alkyl radical, C2-C30-alkenyl, C3-C30-cycloalkyl, C2-C30-heterocyclyl radical, C2-C30-heterocyclyl-C1-C30Alkyl radical, C6-C30-aryl, C6-C30-aryl- (C)1-C30Alkyl), C2-C30-heteroaryl, C2-C30-heteroaryl-C1-C30Alkyl radical, C1-C30-alkoxy-C1-C30-alkyl, halo-C1-C30-alkyl and halo-C3-C30-cycloalkyl, each of said groups being optionally substituted, wherein the heteroatom is selected from N, O and S;
n is an integer of 1 to 20;
R5if n is 1 or if n>1, then it is independently selected in each case from C1-C30Alkylene radical, C2-C30-alkenylene, C2-C30-alkynylene, C6-C30Arylene radical, C3-C30-cycloalkylene radical, C3-C30Cycloalkenylene radical, C3-C30-cycloalkynylene, C2-C30-heterocyclylene and C2-C30-a heteroarylene group, each of said groups being optionally substituted, and wherein the heteroatom is selected from N, O and S, wherein R is5Optionally interrupted by a group selected from N, O and S; and
(C) at least one acid stabilizer;
wherein the amount of monomer (A) is from 0 to 40% by weight, preferably from 5 to 35% by weight, more preferably from 10 to 30% by weight, most preferably from 15 to 20% by weight, based in each case on the total weight of monomer (A) and polymer (B);
the amount of the acid stabilizer (C) is 0.1 to 500ppm, preferably 0.1 to 300ppm, more preferably 0.1 to 200 ppm; and is
The amount of component II is from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, more preferably from 0.1 to 2% by weight, based in each case on the total weight of the monomers (A) and the polymers (B).
In a preferred embodiment of the invention, R1And R2Independently at each occurrence selected from C1-C10Alkyl radical, C2-C10-alkenyl, C3-C10-cycloalkyl, C2-C10-heterocyclyl radical, C2-C10-heterocyclyl-C1-C10Alkyl radical, C3-C18-aryl, C3-C18-aryl-C1-C10Alkyl radical, 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 groups being optionally substituted, wherein the heteroatom is selected from N, O and S.
Preferably, R1And R2Independently at each occurrence selected from C1-C6Alkyl radical, C2-C6-alkenyl, C3-C6-cycloalkyl, C3-C6-heterocyclyl radical, C3-C6-heterocyclyl-C1-C6Alkyl radical, C6-C8-aryl, C6-C8-aryl-C1-C6Alkyl radical, C3-C6-heteroaryl, C3-C6-heteroaryl-C1-C6Alkyl radical, C1-C6-alkoxy-C1-C6-alkyl, halo-C1-C10-alkyl and halo-C3-C10-cycloalkyl, each of said groups being optionally substituted, wherein the heteroatom is selected from N, O and S.
More preferably, R1And R2Independently at each occurrence selected from C1-C6Alkyl radicals, such as the methyl, ethyl, n-propyl or isopropyl radical, the n-butyl radical,Isobutyl, tert-butyl or 2-butyl, pentyl such as n-pentyl and isopentyl, hexyl such as n-hexyl, isohexyl and 1, 3-dimethylbutyl.
More preferably, R1And R2Independently at each occurrence, selected from straight chain C1-C6Alkyl radicals, such as the methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl radical.
In a preferred embodiment of the invention, R3And R4Independently at each occurrence selected from C1-C10Alkyl radical, C2-C10-alkenyl, C3-C10-cycloalkyl, C2-C10-heterocyclyl radical, C2-C10-heterocyclyl-C1-C10Alkyl radical, C3-C18-aryl, C3-C18-aryl-C1-C10Alkyl radical, 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 groups being optionally substituted, wherein the heteroatom is selected from N, O and S.
Preferably, R3And R4Independently at each occurrence selected from C1-C6Alkyl radical, C2-C6-alkenyl, C3-C6-cycloalkyl, C3-C6-heterocyclyl radical, C3-C6-heterocyclyl-C1-C6Alkyl radical, C6-C8-aryl, C6-C8-aryl-C1-C6Alkyl radical, C3-C6-heteroaryl, C3-C6-heteroaryl-C1-C6Alkyl radical, C1-C6-alkoxy-C1-C6-alkyl, halo-C1-C10-alkyl and halo-C3-C10-cycloalkyl, each of said groups being optionally substituted, wherein the heteroatom is selected from N, O and S.
More preferably, R3And R4Independently at each occurrence selected from C1-C6Alkyl, such as methyl, ethyl, n-or isopropyl, n-, isobutyl, tert-butyl or 2-butyl, pentyl, such as n-and isopentyl, hexyl, such as n-hexyl, isohexyl and 1, 3-dimethylbutyl.
More preferably, R3And R4Independently at each occurrence, selected from straight chain C1-C6Alkyl radicals, such as the methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl radical.
In a preferred embodiment of the invention, R1、R2、R3And R4The same is true.
In a preferred embodiment of the invention, n is preferably from 1 to 15, more preferably from 1 to 10, more preferably from 1 to 8, especially preferably from 2 to 8, most preferably from 3 to 6.
In a preferred embodiment of the invention, R5If n is 1 or if n>1, then it is independently selected in each case from C1-C10Alkylene radical, C2-C10-alkenylene, C2-C10-alkynylene, C3-C18Arylene radical, C3-C10-cycloalkylene radical, C3-C10Cycloalkenylene radical, C3-C10-cycloalkynylene, C2-C10-heterocyclylene and C2-C10-a heteroarylene group, each of said groups being optionally substituted, wherein the heteroatom is selected from N, O and S, wherein R is5Optionally interrupted by a group selected from N, O and S; and is
Preferably, R5If n is 1 or if n>1, then it is independently selected in each case from C1-C6Alkylene radical, C2-C6-alkenylene, C2-C6-alkynylene, C6-C8Arylene radical, C3-C6-cycloalkylene radical, C3-C6Cycloalkenylene radical, C3-C10-cycloalkynylene, C3-C6-heterocyclylene and C3-C6-a heteroarylene group, each of said groups being optionally substituted, wherein the heteroatom is selected from N, O and S, wherein R is5Optionally interrupted by a group selected from N, O and S; and is
More preferably, R5If n is 1 or if n>1, then it is independently selected in each case from C1-C6Alkylene and C6-C8-arylene, each of said groups optionally substituted with at least one C1-C6-alkyl substitution.
Most preferably, R5If n is 1 or if n>1, which is in each case independently selected from propylene, pentylene and phenylene, each of said groups being optionally substituted with methyl.
In particular, R5May be a phenylene group. It may be attached to other groups of the main chain in its ortho, meta or para position, preferably in the para position, i.e.
In a preferred embodiment of the present invention, the group may be further substituted with a substituent. Possible substituents may be selected from halogen, hydroxy, nitro, cyano, C1-C10Alkyl radical, C2-C10-alkenyl, C2-C10-alkynyl, C1-C10-alkoxy, C3-C10-cycloalkyl, C2-C10-heterocyclyl radical, C2-C10-heterocyclyl-C1-C10-alkyl, halo-C1-C10-alkyl, halo-C3-C10-cycloalkyl, C3-C18-aryl, C3-C18-aryl-C1-C10Alkyl radical, C2-C10-heteroaryl, C3-C10Cycloalkenyl radical and C3-C10-cycloalkynyl, wherein the heteroatom is selected from N, O and S.
Preferably, the substituents may be selected from halogen, hydroxy, nitro, cyano, C1-C6Alkyl radical, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-heterocyclyl radical, C3-C6-heterocyclyl-C1-C6-alkyl, halo-C1-C6-alkyl, halo-C3-C6-cycloalkyl, C6-C8-aryl, C6-C8-aryl-C1-C6Alkyl radical, C3-C6-heteroaryl, C3-C6Cycloalkenyl radical and C3-C6-cycloalkynyl, wherein the heteroatom is selected from N, O and S.
In a preferred embodiment of the invention, the composition has an elongation (%), tensile strength (MPa), weight loss after 400 cycles of grinding (mg) related to abrasion resistance, and they satisfy the following relationship:
1.05<(2ER/[％]+TS/[Mpa])/AR[mg]<2.25。
where ER is an abbreviation for elongation, determined according to DIN53504, TS is an abbreviation for tensile strength, determined according to DIN53504, and AR is an abbreviation for weight loss (mg) after 400 cycles of grinding, related to abrasion resistance, determined according to ASTM D4060-07. Hereinafter, the abbreviations "ER", "TS" and "AR" have the same meaning.
More preferably, the following relationship is satisfied: 1.15< (2 ER/[% ] + TS/[ MPa ])/AR [ mg ] <1.85 and most preferably, the following relationship is satisfied:
1.25<(2ER/[％]+TS/[Mpa])/AR[mg]<1.75。
unexpectedly, the present inventors have discovered that suitable amounts of monomers and components of the polymer or composition result in an excellent balance of properties desired for building materials, such as workability, physical and chemical resistance, tensile strength, abrasion resistance, and the like.
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 acid stabilizer.
The present invention contemplates any suitable acid stabilizer known in the art, including, for example, sulfuric acid (H)2SO4) Acids such as trifluoromethanesulfonic acid (TFA), chlorodifluoroacid, maleic acid, methanesulfonic acid (MSA), p-toluenesulfonic acid (p-TSA), difluoroacetic acid, trichloroacetic acid, phosphoric acid, and dichloroacetic acid. The acid stabilizer may include any material that can be added to the monomer or polymer component to extend the shelf life, e.g., up to, e.g., 1 year or more. Such acid stabilizers may have a pKa 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.
For each of these acidic stabilizing materials, the acid stabilizer may be present in the following amounts: 0.1-500ppm, preferably 0.5-400, more preferably 1-300ppm, very more preferably 5-250ppm, and very more preferably 10-200ppm, and still more preferably 30-180, and most preferably 50-150 ppm.
According to one embodiment of the invention, the composition may further comprise a base accelerator.
According to a preferred embodiment of the invention, the alkali accelerator is in the form of an alkali, an alkali precursor or an alkali enhancer. Preferably, the alkali accelerator is at least one selected from the group consisting of: metal oxide, metal hydroxide, amine, guanidine, amide, piperidine, piperazine, morpholine, pyridine, halide, salt of a metal, ammonium, amine, wherein the anion in the salt is at least one selected from the group consisting of: halogen, acetate, chloroacetate, benzoate, fatty acid, alkene carboxylic acid, sulfur, carbonate, silicate, diketone, monocarboxylic acid, carboxylic acid-containing polymer.
And more preferably, the alkali accelerator is at least one selected from the group consisting of: dimethylethylamine, dimethylpropylamine, 2-ethylhexylamine, di- (2-ethylhexyl) amine, dibutylamine, dicyclohexylamine, ditridecylamine isomer mixtures, N-dimethylisopropylamine, N-ethyldiisopropylamine, N-dimethylcyclohexylamine, N-octylamine, tributylamine, tridecylamine isomer mixtures, tripropylamine, tris- (2-ethylhexyl) amine, triethylamine, trimethylamine, 2- (diisopropylamino) ethylamine, 3- (cyclohexylamino) propylamine, 3- (diethylamino) propylamine, 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane, isophoronediamine, mixtures of ditridecylamine isomers, mixtures of bis-, Tetramethyl-1, 6-hexanediamine, S-triazine, neopentanediamine (2, 2-dimethylpropane-1, 3-diamine), octamethylenediamine, diethylenetriamine, dipropylenetriamine, pentamethyldiethylenetriamine, N, N-bis- (3-aminopropyl) methylamine, N3-amine 3- (2-aminoethylamino) propylamine, N4-amine N, N' -bis- (3-aminopropyl) ethylenediamine, 4, 9-dioxadodecane-1, 12-diamine, bis- (2-methoxyethyl) amine, bis (2-dimethylaminoethyl) ether, polyetheramine D2000, polyetheramine D230, polyetheramine D400, polyetheramine T403, polyetheramine T5000, N, N-dimethylcyclohexylamine, n-methylmorpholine, 2,2 '-dimorpholinodiethylether, dimethylaminoethoxyethanol, bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, trimethylaminoethylethanolamine, tetramethyl-1, 6-hexanediamine, 1, 8-diazabicyclo-5, 4, 0-undecene-7, 2, 6-dimethylaniline, 2-phenylethylamine, 4,4' -diaminodiphenylmethane, aniline, benzylamine, tris (dimethylaminomethyl) phenol, 2-dimethylaminomethylphenol (DMP10), diethanol-p-toluidine, diisopropanol-p-toluidine, N- (2-hydroxyethyl) aniline, N-bis- (2-hydroxyethyl) aniline, N-dimethylaminoethoxyethanol, bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, trimethylaminoethylethanolamine, tetramethyl-1, 6-hexanediamine, 1, 8-diazabicyclo-5, 4, 0-unde, N-ethyl-N- (2-hydroxyethyl) aniline, o-toluidine, p-nitrotoluene, 3-dimethylaminopropan-1-ol, butyldiethanolamine, triisopropanolamine, dibutylethanolamine, diethylethanolamine, methyldiethanolamine, methyldiisopropanolamine, N, N-dimethylethanolamine S, N, N-dimethylisopropanolamine, dimethylethanolamine, 4- (2-hydroxyethyl) morpholine, N, N, N ', N' -tetrakis (2-hydroxyethyl) ethylenediamine, sodium acetate, potassium acetate, zinc acetate, copper acetate, magnesium acetate, aluminum acetate, sodium chloroacetate, potassium chloroacetate, copper chloroacetate, zinc chloroacetate, magnesium chloroacetate, aluminum chloroacetate, iron chloroacetate, acid salts of sodium, potassium, lithium, copper, iron and cobalt, sodium oxide, lithium, copper, iron and cobalt, Potassium oxide, calcium oxide, zinc oxide, copper oxide, magnesium oxide, aluminum oxide, iron oxide and ferrous oxide, sodium hydroxide, potassium hydroxide, zinc hydroxide, copper hydroxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, iron hydroxide and ferrous hydroxide, sodium silicate, potassium silicate, zinc silicate, copper silicate, magnesium silicate, iron silicate, aluminum silicate, lithium chloride and tetramethylguanidine.
According to a preferred embodiment of the invention, the required amount of alkali accelerator may be present in the following amounts: from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, more preferably from 0.1 to 2% by weight, most preferably from 0.5 to 1% by weight, based in each case on the total weight of the monomers (A) and polymers (B).
According to one embodiment of the invention, the mixture comprises the two-component composition of the invention.
According to one embodiment of the invention, the mixture comprising the composition of the invention is substantially free of any solvent.
According to one embodiment of the invention, the mixture comprising the composition of the invention may also comprise other additives.
In certain embodiments of the invention, the other additive may be at least one selected from the group consisting of: plasticizers, thixotropic agents, adhesion promoters, antioxidants, light stabilizers, UV stabilizers, fillers, cement, limestone, surfactants, wetting agents, viscosity modifiers, extenders, dispersants, antiblocking agents, degassing agents, anti-sagging agents, anti-settling agents, flatting agents, levelling agents, waxes, mar-resistant additives, scratch-resistant additives, defoamers or inert resins. In a preferred embodiment of the present invention, the additive may be at least one selected from the group consisting of: plasticizers, thixotropic agents, adhesion promoters, antioxidants, light stabilizers, UV stabilizers, fillers, cement, limestone, surfactants, wetting agents, viscosity modifiers, dispersants, degassing agents, anti-sagging agents, anti-settling agents, defoamers, colorants, fibers, polymer powders, networks, chips, 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 conventionally used in the art.
In other embodiments of the present invention, the mixture containing the composition of the present invention may further include colorants including, but not limited to, organic pigments, organometallic pigments, mineral-based pigments, carbon pigments, titanium pigments, azo compounds, quinacridone compounds, phthalocyanine compounds, cadmium pigments, chromium pigments, cobalt pigments, copper pigments, iron pigments, clay pigments, lead pigments, mercury pigments, titanium pigments, aluminum pigments, manganese pigments, ultramarine pigments, zinc pigments, arsenic pigments, tin pigments, iron oxide pigments, antimony pigments, barium pigments, biological pigments, dyes, photochromic, conductive and liquid crystalline polymer pigments, piezochromic pigments, goniochromatic (goniochromatic) pigments, silver pigments, pyrrolopyrroledione (diketopyrroloole), benzimidazolone (benzimidazolone), isoindoline, isoindolinone, radio-opacifying agents (radio-opaque), and the like.
The above colorants are commercially available to those skilled in the art. The above colorants, if any, are present in amounts conventionally used in the art.
The definitions and explanations regarding the compositions also apply to the method and the use according to the invention.
The composition according to the invention can be obtained by a process comprising the following steps:
(1) mixing a monomer (a), a polymer (B) and an acid stabilizer (C) to obtain component I;
(2) component II was prepared.
In a preferred embodiment, the process for preparing the composition of the invention comprises a) mixing monomer (a) and polymer (B) in the amounts described above; b) adding an acid stabilizer (C) to the mixture obtained from step (a); and c) adding an alkali accelerator and other additives to the mixture obtained from step (b).
The mixing used in the method is carried out by means conventional in the art in an apparatus suitable for mixing, for example, by stirring or agitation at room temperature.
According to a particular aspect of the invention, the methylene malonate monomer having formula (I) or (II) can be prepared by a person skilled in the art by means of the following steps: (a) reacting a malonate with a source of formaldehyde, optionally in the presence of an acidic catalyst or a basic catalyst, and optionally in the presence of an acidic solvent or a non-acidic solvent, to form a reaction mixture; (b) contacting the reaction mixture or a portion thereof with an energy transfer device to produce a vapor phase comprising a methylene malonate monomer; (c) separating the methylene malonate monomer from the gas phase.
According to one embodiment of the present invention, the polymer (B) having formula (II) can be prepared by one skilled in the art 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 then stirred and heated at a temperature and for a period of time while removing the alcohol produced by evaporation. Subsequently, the reaction mixture was cooled and stabilized with a small amount of an acid stabilizer, and then filtered to obtain the desired product.
In one aspect, the present invention relates to the use of the composition according to the invention as a coating, in particular a floor coating.
The two-component composition or mixture is applied to a substrate selected from the group consisting of concrete, wood, resin layers, and stone, and the resin layer is selected from the group consisting of cement-based resin layers, epoxy-based resin layers, polyurethane-based resin layers, acrylate-based resin layers, polyethylene layers, polypropylene layers, polyvinyl chloride, rubber layers, asphalt layers, and polymer-modified asphalt layers.
Component I and component II are mixed and then applied to the substrate, or component II is first applied to the substrate and then component I is applied to the substrate in the next step.
The temperature at the time of use is-30 ℃ to 60 ℃ and preferably-20 ℃ to 40 ℃. And the relative humidity at the time of use is 1% to 99% and preferably 5% to 95%.
The compositions of the present invention may be applied in a manner conventional in the art. In a preferred embodiment, the monomers (a) and polymers (B) are mixed with the acid stabilizer (C) and additives such as fillers or UV stabilizers to give the finished formulation, then an alkali accelerator such as triethylamine is added to the system and the mixture is applied to the substrate. In a further preferred embodiment, monomer (a) and polymer (B) are first placed in a suitable container and acid stabilizer (C) is added to the container, thereby obtaining a finished (ready-made) formulation; subsequently, the alkali accelerator is coated on the floor substrate and the finished formulation is then applied on the coated substrate.
In the present invention, the coating or application can be carried out in a manner known to the person skilled in the art, for example by brushing, spraying or rolling. Notably, the manner of coating or application used in the present invention depends on the ease of composition; in particular, for roll coating, a long gel time is required, and for spray coating, a short gel time is required.
In an embodiment of the invention, the floor substrate to be coated comprises concrete, wood, a resin layer and a cement-based resin layer. In a preferred embodiment, the resin layer includes a cement-based resin layer, an epoxy-based resin layer, a polyurethane-based resin layer, an acrylate-based resin layer, a polyethylene layer, a polypropylene layer, polyvinyl chloride, a rubber layer, an asphalt layer, and a polymer-modified asphalt layer.
In an embodiment of the invention, the two-component composition or mixture is applied to a wet substrate.
In an embodiment of the invention, the temperature for said use is from-30 ℃ to 60 ℃, preferably from-20 ℃ to 40 ℃.
In an embodiment of the invention, the relative humidity for said use is from 1% to 99%, preferably from 5% to 95%.
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