Intumescent paint composition
By using a high concentration of Veova vinyl ester and vinyl acetate copolymer in intumescent coatings, the expansion performance and thermal stability of the coatings are improved, solving the problem of insufficient expansion in existing technologies and achieving efficient passive fire protection.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HEXION INC
- Filing Date
- 2024-11-21
- Publication Date
- 2026-06-19
AI Technical Summary
Existing intumescent coatings have shortcomings in terms of high-performance expansion properties, especially in water-based formulations where the amount of vinyl emulsion binder used is insufficient, resulting in a need to improve expansion and fire resistance.
A high-concentration copolymer of veova vinyl ester monomer and vinyl acetate is used as a binder, with the veova content in the copolymer ranging from 25% to 80% by weight. Combined with an acid donor, a carbon source and a foaming agent, an intumescent coating composition is formed.
It significantly improves the expansion performance and thermal stability of intumescent coatings, forming highly efficient heat-insulating carbonaceous foam and providing excellent passive fire protection.
Smart Images
Figure CN122249519A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates in particular to intumescent coatings based on intumescent emulsions, especially wherein the binder has a branched vinyl ester content between 25% and 80% by weight. Background Technology
[0002] Intumescent systems are a well-known and effective fire protection strategy. In particular, intumescent coatings offer relevant benefits such as ease of processing and application to a variety of materials, including plastics, textiles, metals, and wood, without altering their inherent properties. In the construction industry, intumescent coatings have gained particular relevance, especially for delaying the collapse of metal and wood structures, serving as passive protection to allow for the safe intervention of rescue teams and the necessary time for building evacuation.
[0003] When exposed to sufficiently high temperatures, intumescent coatings undergo significant expansion, forming insulating carbonaceous foam. Due to environmental concerns, the industry today focuses primarily on the development of waterborne formulations. Vinyl emulsion binders are particularly known for their high performance levels in waterborne intumescent coatings. Summary of the Invention
[0004] Overview of the Invention
[0005] Copolymers of vinyl acetate (VAM) and vinyl veova (which is a vinyl ester with a branched aliphatic structure) can be used as binders for paints. Monomer units available from Veova monomers impart hydrophobicity to the copolymer in addition to improved hydrolytic stability, adhesion, water resistance, and UV resistance. To the best of the inventors' knowledge, the content of units available from Veova monomers in copolymers used in intumescent paints to date is significantly less than 30% by weight.
[0006] Surprisingly, the inventors have found that a high concentration of Veova in the binder improves the swelling properties. The surprisingly good swelling properties imparted by using a high content of Veova, as observed by the inventors, have not yet been described. The inventors have discovered the swelling effectiveness (e.g., fire resistance and foam expansion upon heating) of copolymers containing a minimum and a maximum of 80% by weight of Veova in the polymer binder.
[0007] JTPimenta et al. (Effect of binder on performance of intumescentcoatings. J. Coat. Technol. Res. , 2016, 13(227-238) involved different types of waterborne resins (vinyl, acrylic, and styrene-acrylic) that were incorporated into intumescent paint formulations and tested for thermal degradation behavior, expansion thickness, and insulation. The correlation between the ratio of vinyl acetate to vinyl esters was not identified.
[0008] K.Kalafat et al. (Comparison of fire resistance of polymers in intumescentcoatings for steel structures. East.-Eur. J. Enterp. Technol. , 2020, 4 (45-54) discloses a study on the thermal degradation of flame-retardant intumescent coatings of ammonium polyphosphate / melamine / pentaerythritol / titanium dioxide / polymer compositions that can be used for fire protection of steel structures. The effects of polymers with different properties (ethylene-vinyl acetate, vinyl acetate tert-carbonate, styrene acrylate, and vinyltoluene acrylate) on the coke layer formation process and the flame-retardant effectiveness of the corresponding coatings were determined.
[0009] YC.Xia (Thermal Property of Waterborne Ultrathin Vac-veova Latex Intumescent Fire Retardant Coatings for Structural Steel. Materials Science and Engineering, 2017, 347-354) published a study on the thermal properties of intumescent coatings based on Vac-veova latex.
[0010] US Patent 2015 / 0291810 A1 discloses an intumescent coating composition and a coated metal substrate. The composition comprises: (a) a polymer binder; (b) an acid catalyst that efficiently forms polyphosphate upon thermal decomposition; (c) a solid carbon donor; (d) a liquid carbon donor in the form of one or more polyols that efficiently form phosphate esters upon contact with phosphoric acid; (e) an intumescent agent; (f) one or more pigments; (g) optionally, one or more other additives; and (h) a liquid carrier for the polymer binder. The ratio of components (b), (c), (e), and (f):(a) is at least 4:1 weight / weight. It further describes a coating composition in which the concentrations of components (b), (e), and (f) are in the range of 55-75% weight / weight solids.
[0011] However, there remains a commercial demand for expandable compositions with improved properties, including expansion properties.
[0012] The present invention therefore relates to an intumescent (preferably coating or paint) composition comprising...
[0013] (a) Polymer adhesive,
[0014] The polymer binder comprises one or more copolymers.
[0015] The one or more copolymers together comprise
[0016] i) Based on the total weight of the polymer binder, 0% to 75% by weight, preferably 2% to 75% by weight, preferably 4% to 75% by weight, more preferably 20% to 75% by weight, or 5% to 10% by weight of monomer units available from vinyl acetate, and
[0017] ii) Based on the total weight of the polymer binder, 25% to 80% by weight, preferably greater than 30% by weight and up to 80% by weight, of one or more types of monomer units available from the vinyl ester monomer represented by formula (1):
[0018]
[0019] R1, R2, and R3 are independently selected from the group consisting of: hydrogen and linear or branched unsubstituted C. 1-11 Alkyl groups, wherein the total number of carbon atoms in R1, R2 and R3 is in the range of 1 to 13;
[0020] And if the amount of monomer units available from vinyl acetate according to (i) is less than 20% by weight, then the polymer binder contains
[0021] iii) one or more, preferably two or more, additional types of monomer units available from the group consisting of ethylene, acrylates, methacrylates, acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinylamide, maleate esters and styrene, preferably acrylates, methacrylates and styrene,
[0022] Wherein the total amount of vinyl acetate according to (i) and one or more additional monomers reaches at least 20% by weight, preferably at least 50% by weight, and more preferably 70% by weight of the total weight of the polymer binder;
[0023] (b) Optionally, acid donor;
[0024] (c) Optionally, carbon source; and
[0025] (d) Optionally, a foaming agent.
[0026] The present invention further relates to a paint, preferably an emulsified paint, comprising or consisting of an intumescent coating composition as defined herein.
[0027] The present invention further relates to the use of one or more copolymers as defined herein or an intumescent coating composition as defined herein for use in intumescent coatings.
[0028] The present invention also relates to the preparation of an intumescent paint composition by applying (a) as defined herein to obtain the intumescent coating.
[0029] The present invention further relates to the preparation of an intumescent coating by applying an intumescent coating composition as defined herein to a surface and drying the intumescent coating composition.
[0030] The present invention further relates to coated articles comprising an intumescent coating obtained by applying and drying an intumescent coating composition as defined herein.
[0031] Detailed Description of the Invention
[0032] This invention relates to an intumescent paint composition comprising...
[0033] (a) Polymer adhesive,
[0034] The polymer binder comprises one or more copolymers.
[0035] The one or more copolymers together comprise
[0036] i) Based on the total weight of the polymer binder, 0% to 75% by weight, preferably 2% to 75% by weight, preferably 4% to 75% by weight, preferably 5% to 75% by weight, more preferably 10% to 75% by weight, even more preferably 15% to 75% by weight, further preferably 20% to 75% by weight or 5% to 10% by weight, or 0% to 65% by weight, or 0% to 55% by weight, or 0% to 45% by weight, or 0% to 35% by weight, or 0% to 25% by weight, or 0% to 15% by weight of monomer units available from vinyl acetate, and
[0037] ii) Based on the total weight of the polymer binder, 25% to 80% by weight of one or more types of monomer units available from the vinyl ester monomer represented by formula (1):
[0038]
[0039] R1, R2, and R3 are independently selected from the group consisting of: hydrogen and linear or branched unsubstituted C. 1-11 Alkyl groups, wherein the total number of carbon atoms in R1, R2 and R3 is in the range of 1 to 13;
[0040] (b) Optionally, acid donor;
[0041] (c) Optionally, carbon source; and
[0042] (d) Optionally, a foaming agent.
[0043] Preferably, the present invention relates to an intumescent paint composition comprising...
[0044] (a) Polymer adhesive,
[0045] The polymer binder comprises one or more copolymers.
[0046] The one or more copolymers together comprise
[0047] i) Based on the total weight of the polymer binder, 0% to 75% by weight, preferably 2% to 75% by weight, preferably 4% to 75% by weight, preferably 5% to 75% by weight, more preferably 10% to 75% by weight, even more preferably 15% to 75% by weight, further preferably 20% to 75% by weight or 5% to 10% by weight, or 0% to 65% by weight or 0% to 55% by weight or 0% to 45% by weight or 0% to 35% by weight or 0% to 25% by weight or 0% to 15% by weight of monomer units available from vinyl acetate, and
[0048] ii) Based on the total weight of the polymer binder, 25% to 80% by weight, preferably greater than 30% by weight and up to 80% by weight, more preferably 35% to 80% by weight, or 45% to 80% by weight, or 55% to 80% by weight, or 65% to 80% by weight, of one or more types of monomer units available from the vinyl ester monomer represented by formula (1):
[0049]
[0050] R1, R2, and R3 are independently selected from the group consisting of: hydrogen and linear or branched unsubstituted C. 1-11 Alkyl groups, wherein the total number of carbon atoms in R1, R2 and R3 is in the range of 1 to 13;
[0051] And if the amount of monomer units available from vinyl acetate according to (i) is less than 20% by weight, then the polymer binder contains
[0052] iii) one or more, preferably two or more, additional types of monomer units available from the group consisting of ethylene, acrylates, methacrylates, acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinylamide, maleate esters and styrene, preferably acrylates, methacrylates and styrene,
[0053] Wherein the amount of vinyl acetate according to (i) and the amount of one or more additional monomers together reach at least 20% by weight, preferably at least 50% by weight, and more preferably 70% by weight of the total weight of the polymer binder;
[0054] (b) Optionally, acid donor;
[0055] (c) Optionally, carbon source; and
[0056] (d) Optionally, a foaming agent.
[0057] It has been found that intumescent paint compositions containing a polymer binder, such as the one described below, result in improved or at least comparable intumescent properties (relative to known commercial compositions), the polymer binder comprising vinyl acetate and high amounts (e.g., 25% to 80% by weight, preferably greater than 30% by weight and up to 80% by weight, more preferably 35% to 80% by weight) of one or more types of monomer units available from vinyl ester monomers represented by formula (1), such as VeoVa10, wherein vinyl acetate may be replaced by (meth)acrylate monomers, wherein preferably, vinyl acetate is not completely replaced by (meth)acrylate monomers.
[0058] One or more, preferably two or more, additional types of monomer units available from the group consisting of ethylene, acrylate, methacrylate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinylamide, maleate and styrene may be present in the copolymer containing vinyl acetate and / or the vinyl ester monomer of formula (1), or may be present in other copolymers or homopolymers.
[0059] In one embodiment, the one or more additional types of monomer units are present in the form of styrene polymers, acrylate polymers, and / or styrene-co-acrylate copolymers.
[0060] In embodiments where the polymer binder consists solely of copolymers, the intumescent paint composition contains no further polymers. In one embodiment, the polymer binder comprises at least 80% by weight, at least 90% by weight, or at least 95% by weight of copolymers, based on the total weight of all polymers in the composition. In one embodiment, the polymer binder / intumescent paint composition comprises at least 80% by weight, at least 90% by weight, or at least 95% by weight of copolymers, based on the total weight of all polymers in the composition.
[0061] As used herein, the term "intumescent coating" refers to a coating that expands upon heat exposure, increasing in volume and decreasing in density to form an insulating char that provides passive fire protection to a surface or object (e.g., structural elements of a building). Intumescent coatings expand up to 100 times their original thickness when exposed to heat, thus forming an insulating layer that protects the underlying coated structural elements and prevents the spread of flammable gases. In its broadest sense, the term "intumescent coating" refers to a coating whose thickness increases starting at temperatures of 250°C, 300°C, or 350°C, as determined by fire resistance testing according to DIN 4102 Part 8 or ISO 834.
[0062] As used herein, the term "expanding paint composition" refers to a composition suitable for forming an intumescent coating. More specifically, it refers to a mixture of components that, when combined, effectively impart intumescent properties to the coating thus formed. Here, the intumescent paint composition or intumescent coating preferably contains one or more, preferably all, of an acid donor, a carbon source, and a foaming agent as mandatory components.
[0063] As used herein, the term "binder" refers to a chemical material that represents the film-forming or coating component of the intumescent paint composition, wherein the binder binds together all the components typically combined in an emulsion or suspension prior to film or coating formation.
[0064] As used herein, the term "polymer binder" refers to a binder that comprises a polymer, preferably composed of polymers, and includes copolymers or mixtures of copolymers, and optionally further includes homopolymers. Preferably, all polymers present in the intumescent paint composition (i.e., any copolymers and homopolymers) are part of the polymer binder. Therefore, any organic polymers in the intumescent paint composition will be considered part of the polymer binder. The term "organic polymer" refers to the nature of the monomer unit, which is generally classified as an organic compound, and means that the main chain mainly contains carbon atoms (i.e., at least 50 mol%).
[0065] Preferably, at least one of the copolymers comprises monomer units available from the vinyl ester monomer represented by formula (1) according to ii) and monomer units available from vinyl acetate according to i), and optionally, one or more additional types of monomer units according to iii); or monomer units available from the vinyl ester monomer represented by formula (1) according to ii) and one or more additional types of monomer units according to iii), and optionally, monomer units available from vinyl acetate according to i). In one embodiment, the polymer binder comprises the aforementioned copolymer having at least 50% by weight or at least 75% by weight of the monomers according to i)-iii) of the total weight of the copolymer in the binder.
[0066] Preferably, all copolymers used contain vinyl acetate and one or more monomers of formula (1), preferably, the monomers of formula (1) are contained in at least 30% by weight.
[0067] As used herein, the term "polymer" should be understood to refer to a molecule containing a backbone (also known as the "main chain") of one or more different types of repeating units (the smallest building blocks of a molecule). A polymer can be a "homopolymer" when it has only one type of monomer unit, or a copolymer when it has two or more polymer units. The term "polymer" can refer to polymers with various architectures such as linear, branched, grafted, cyclic, or crosslinked. Furthermore, it should be understood that polymers / copolymers may contain residues from initiators, catalysts, and other elements that accompany the synthesis of such polymers, wherein these residues are understood to be not covalently bonded to the polymer / copolymer but are inseparably mixed. Moreover, these residues and other elements, although typically removed during post-polymerization purification, are typically mixed or blended with the polymer such that they generally remain with the polymer when transferred between containers or between solvents or dispersion media.
[0068] As used herein, the term "copolymer" refers to a polymer formed by the polymerization of at least two structurally different monomers. Therefore, the term "copolymer" also includes polymers formed by the polymerization of three or more structurally different monomers.
[0069] The term "monomer unit" refers to a structural portion of a polymer corresponding to a monomer that has been polymerized. "Monomer unit" is synonymous with other terms used in the art in a similar manner, such as "repeating unit," "repetition unit," "monomeric unit," etc.
[0070] As used herein, the term acrylate preferably refers to CH2=CHCO2R, and the term methacrylate preferably refers to CH2=C(CH3)-C(=O)OR, where R can be an organic group. For example, R can be a saturated linear or branched C1-C10 hydrocarbon. The acrylate monomers and methacrylate monomers used include acrylates and methacrylates, which are products of the reaction of olefinically unsaturated carboxylic acids with C1 to C20 alcohols. Examples of acrylate monomers and methacrylate monomers used include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, heptyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, nonyl methacrylate, decyl methacrylate, 2-propylheptyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate, norbornyl methacrylate, 4-tert-butylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, or mixtures thereof.
[0071] It should be noted that not all hydrogen atoms are shown in the chemical formula throughout the application. Furthermore, any atom in the general formula can be substituted with any of its isotopes. That is, any hydrogen atom can be substituted with deuterium (D).
[0072] Furthermore, any carbon atom in the disclosed and / or claimed compounds may be present in any of its isotopes (preferably) 13 C) (Partial or complete) substitution. Furthermore, any nitrogen atom in the disclosed and / or claimed compounds may be replaced. 15 N is (partially or completely) substituted. Furthermore, any oxygen atom in the disclosed and / or claimed compounds may be... 17 O (partially or completely) substituted. Furthermore, any phosphorus atom in the disclosed and / or claimed compounds may be... 31 P (partial or complete) replacement.
[0073] The term "linear C" 1-11 "Alkyl" refers to a straight-chain saturated hydrocarbon group having 1-11 carbon atoms. Linear C 1-11 Alkyl groups include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl.
[0074] The term "branching C" 1-11 "Alkyl" refers to a branched saturated hydrocarbon group having 1-11 carbon atoms. Branched C1-11 Alkyl groups include, for example, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-methyloctyl, 2-methyloctyl, 3-methyloctyl, 4-methylheptyl, 4-methylheptyl -Methyloctyl, 5-methyloctyl, 6-methyloctyl and 7-methyloctyl, 1-ethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 1-ethylheptyl, 2-ethylheptyl, 3-ethylheptyl, 4-ethylheptyl and 5-ethylheptyl, 1-propylbutyl, 1-propylpentyl, 2-propylpentyl, 1-propylhexyl, or 2-propylhexyl and 3-propylhexyl.
[0075] As used herein, the term "substituted" in relation to groups such as alkyl groups refers to groups in which one or more hydrogen atoms are replaced by different atoms or groups such as halogens (e.g., Cl, Br, I, F), amines (primary, secondary, tertiary), sulfates, phosphates, ethers, esters, OH, SH, CF3, CN, C 1-4 Heteroalkyl, C 6-14 Aryl and C 4-12 Substitution with heteroaryl groups, etc.
[0076] As used herein, the term "unsubstituted" in relation to groups such as alkyl groups refers to groups in which no hydrogen is replaced by different atoms or groups such as halogens (e.g., Cl, Br, I, F), amines (primary, secondary, tertiary), sulfates, phosphates, ethers, esters, OH, SH, CF3, CN, C 1-4 Heteroalkyl, C 6-14 Aryl and C 4-12 Substitution with heteroaryl groups, etc.
[0077] As used herein, the term "acid donor" refers to a compound that effectively forms an acid upon thermal decomposition. This acid can react with other components in the intumescent coating / paint composition. The acid donor as used herein may also be referred to as an acid donor catalyst, acid catalyst, acid donor, acid-forming compound, acid donor agent, carbonization accelerator, or acid (catalyst) source, as used in the prior art. Acid donors are typically inorganic acids or substances that release acid at 100-250°C.
[0078] As used herein, the term "carbon source" refers to a compound that reacts effectively with an acid formed from the acid donor to form the carbon source and an ester of the acid formed from the acid donor. The carbon source used herein may also be referred to as a coking agent or coking agent, as used in the prior art. The carbon source used herein is a polyol (or polyhydroxy compound), i.e., an organic hydroxyl-containing compound with a high carbon content. During the reaction of the carbon source with the acid formed from the acid donor, carbonaceous coke can be formed, preferably wherein the carbonaceous coke is a foamed carbon matrix. The carbon source and the ester of the acid formed from the acid donor can decompose to form a foamed carbon matrix.
[0079] As used herein, the term "foaming agent" refers to a compound that effectively releases gas upon thermal decomposition to achieve foaming of the carbon matrix and to expand the carbon still attached to the substrate. The foaming agent used herein may also be referred to as a foaming agent, porophore, or expanding agent, as used in the prior art.
[0080] The polymeric adhesive may contain at least one copolymer. Such a copolymer contains a different composition from the monomer units defined in the claims.
[0081] The polymer binder may comprise a mixture of at least two different copolymers, wherein the at least two different copolymers comprise monomer unit compositions that are different from the monomer unit compositions defined in the claims, but the average monomer unit composition is consistent with the monomer unit composition defined in the claims.
[0082] As referred to herein, “total weight of the polymer binder” takes into account the weight of all organic polymers that are part of the intumescent paint composition. Any polymers in the intumescent paint composition and in the intumescent coating are part of the polymer binder.
[0083] According to the invention, the total content of all copolymers in the composition, preferably all polymers of vinyl acetate-derived / obtainable or derivatable / derived monomer units, and one or more types of vinyl ester monomers of formula (1) is decisive for the expansion properties. For example, this means that in order to obtain the desired total content of one or more types of vinyl ester monomers of formula (1) in all copolymers, the use of a copolymer with a low content can be compensated by using a copolymer with a high content.
[0084] For example, the polymer adhesive may contain or consist of the following items:
[0085] - 15% by weight of a monomer unit available from vinyl acetate and 85% by weight of one or more types of vinyl ester monomer units available from one or more types of vinyl ester monomers represented by formula (1), and
[0086] - A first copolymer comprising 85% by weight of monomer units available from vinyl acetate and 15% by weight of one or more types of vinyl ester monomer units available from one or more types of vinyl ester monomers represented by formula (1),
[0087] Each of them does not comply with the claims when used alone, but does when used in a mixture that provides the total monomer content as defined in the claims.
[0088] Both alternatives (a single copolymer or a mixture of at least two copolymers) effectively impart advantageous and particular swelling behavior to the intumescent paint compositions of the present invention.
[0089] When the claims are satisfied by using a vinyl acetate homopolymer with a homopolymer of monomer units available from the vinyl ester monomer represented by formula (1) in a blend, the vinyl acetate homopolymer is expected to hydrolyze particularly quickly compared to similar blends using copolymers containing these monomer units. The vinyl acetate units are only protected from hydrolysis when the monomer units available from the vinyl ester monomer represented by formula (1) are copolymerized with vinyl acetate, resulting in a random distribution of the monomer units available from the vinyl ester monomer represented by formula (1) throughout the polymer chain. Therefore, the use of the copolymers defined herein is advantageous compared to similar homopolymer blends.
[0090] The relative molar percentage of either the monomer unit obtainable from vinyl acetate or the vinyl ester monomer unit obtainable from one or more types of vinyl ester monomers represented by formula (1) can be determined by proton nuclear magnetic resonance (NMR). 1 Quantification was performed using ¹H-NMR, taking into account the relative areas of the peaks corresponding to the shifts of their -CH3 groups. An example of this quantification is provided by, for instance, XQWu et al. (Miniemulsion and macroemulsion copolymerization of vinyl acetate with vinyl versatate). J. Appl. Polym. Sci. ,2002, 85 , 2219 – 2229).
[0091] The vinyl acetate-derived monomer unit according to the claim can be obtained by copolymerization of at least vinyl acetate and one or more other types of monomers (e.g., vinyl ester monomers represented by formula (1)).
[0092] The structure of vinyl acetate before polymerization is shown in the following formula:
[0093] .
[0094] The structure of the monomeric unit obtained / obtained or derived / derived from vinyl acetate is shown in the following formula:
[0095]
[0096] The dashed lines represent bonds within the polymer backbone, i.e., bonds with adjacent monomer units.
[0097] The structure of the vinyl ester monomer unit of one or more types represented by formula (1) that is available / obtainable or derivatable / derived is shown in the following formula:
[0098]
[0099] Where R1, R2, and R3 are defined as in this paper,
[0100] The dashed lines represent bonds within the polymer backbone, i.e., bonds with adjacent monomer units.
[0101] The structure of a copolymer comprising monomer units available from vinyl acetate and one or more types of vinyl ester monomer units available from vinyl ester monomers represented by formula (1) is shown in the following formula:
[0102]
[0103] Where R1, R2, and R3 are defined as in this paper,
[0104] Where n is the weight fraction or degree of polymerization of the monomer units available / obtainable or derivatable / derived from vinyl acetate.
[0105] Where m is the weight fraction or degree of polymerization of one or more types of vinyl ester monomer units available / obtainable or derivatable / derived from one or more types of vinyl ester monomers represented by formula (1). Of course, the copolymer may comprise a sequence of one or more monomer units. The typical weight-average molecular weight of the copolymer is between 20,000 and 2,000,000 Daltons, preferably between 100,000 and 1,000,000 Daltons, measured using gel permeation chromatography.
[0106] Although vinyl acetate-based polymers are widely used in the field of polymer adhesives, they are known to have low durability. One or more types of vinyl ester monomer units of the obtained / obtained or derivatized / derived from formula (1) compensate for the low durability of vinyl acetate-based adhesives. Since the total carbon number of R1, R2, and R3 is in the range of 1 to 13, preferably in the range of 6 to 11, more preferably in the range of 6 to 9, the one or more types of vinyl ester monomer units of the obtained / obtained or derivatized / derived from formula (1) improve hydrophobicity, impart a high level of branching, and thereby improve the stability of the corresponding copolymers. Copolymers containing one or more types of vinyl ester monomer units of the obtained / obtained or derivatized / derived from formula (1) used as adhesives also protect additives sensitive to moisture and acids (e.g., ammonium polyphosphate (APP) or pentaerythritol (PER)).
[0107] Moreover, the vinyl ester monomer units of one or more types obtainable from vinyl ester monomers represented by one or more types of formula (1) exhibit specific thermal degradation mechanisms, which improve the coking of the corresponding intumescent coatings. More specifically, the corresponding copolymers decompose in a two-step process (i-chain stripping process-deacetylation-accompanied by chain scission reaction leading to polyene formation, and ii-its chain scission), while acrylic and styrene-acrylic resins are known to decompose directly into volatile monomers mainly through chain scission mechanisms [JT Pimenta et al., Effect of binder on performance of intumescent coatings]. J. Coat. Technol. Res. , 2016, 13 , 227 – 238; K.Kalafat et al., Comparison of fire resistance of polymers in intumescentcoatings for steel structures. East.-Eur. J. Enterp. Technol. , 2020, 4 [45-54.]. Furthermore, the vinyl acetate binder has a lower thermal decomposition temperature compared to both acrylic and styrene-acrylic resins. As a result, the styrene-acrylic binder exhibits different elastic behavior when melamine begins to decompose into gaseous products, which hinders uniform foam expansion in both acrylic and styrene-acrylic systems. This makes the copolymers of the present invention particularly superior to acrylic systems.
[0108] Furthermore, when the target is that the total carbon number of R1, R2, and R3 is in the range of 1 to 13, it is possible to achieve controlled polymerization via emulsion polymerization to produce copolymers with the target molecular weight or degree of polymerization and the target monomer composition. Here, for example, it is known that emulsion polymerization using monomer units from one or more types of vinyl ester monomers represented by formula (1) but with a total carbon number of 14 or higher for R1, R2, and R3 can hinder the controlled polymerization process.
[0109] Typically, monomer units that are available / obtainable or derivatable from vinyl acetate are simply referred to as "vinyl acetate," for example, as in poly(vinyl acetate).
[0110] Typically, the vinyl ester monomer unit of one or more types that is available / obtainable or derivatizable / derived from the vinyl ester monomer represented by formula (1) may be simply referred to as "vinyl ester of branched acid".
[0111] Suitable vinyl esters for use with vinyl ester monomer units available from one or more types of vinyl ester monomers represented by formula (1) include those derived from branched acids, such as neopentanoic acid, 2-ethylhexanoic acid, neocarboxylic acids (also known as VERSATIC ACID™, from Hexion Inc.), wherein the total number of carbon atoms in R1, R2, and R3 is 7, 8, 9, and 10. Examples of these vinyl ester monomers include vinyl pentanoate, vinyl 2-ethylhexanoate, vinyl decanoate, and vinyl nonanoate, and combinations thereof. Commercial examples of these vinyl ester monomers include Veova 9, Veova 10, and combinations thereof, commercially available from Hexion Inc. of Columbus, Ohio, and vinyl laurate, commercially available from Wacker Chemie AG or others.
[0112] In one embodiment, the total number of carbon atoms in R1, R2, and R3 is in the range of 6 to 11.
[0113] In one implementation, the total number of carbon atoms in R1, R2, and R3 is in the range of 6 to 9.
[0114] In one implementation, the total number of carbon atoms in R1, R2, and R3 is in the range of 6 to 8.
[0115] In one implementation, the total number of carbon atoms in R1, R2, and R3 is in the range of 7 to 8.
[0116] In one embodiment, one of R1, R2, and R3 is methyl.
[0117] In one embodiment, one or two of R1, R2, and R3 are hydrogen, or one of R1, R2, and R3 is hydrogen; preferably, none of R1, R2, and R3 are hydrogen.
[0118] In one embodiment, the total number of carbon atoms in R1 and R2 is 6 or 7, and R3 is a methyl group.
[0119] In one embodiment, the total number of carbon atoms in R1 and R2 is 6 or 7, and R3 is a methyl group.
[0120] In one embodiment, R1 and R2 have a total of 6 carbon atoms, and R3 is a methyl group.
[0121] In one embodiment, R1 and R2 have a total of 7 carbon atoms, and R3 is a methyl group.
[0122] In one embodiment, R1 has 4 carbon atoms, R2 has 2 carbon atoms, and R3 is H.
[0123] In one embodiment, one or more types of vinyl ester monomers represented by formula (1) are selected from the group consisting of vinyl decanoate and vinyl nonanoate.
[0124] In one embodiment, one or more types of vinyl ester monomers represented by formula (1) are vinyl neodecanoate.
[0125] In one embodiment, the intumescent paint composition comprises
[0126] (b) Optionally, acid donor;
[0127] (c) Optionally, carbon source; and
[0128] (d) Optionally, a foaming agent.
[0129] The intumescent paint composition may contain solvents and additives (such as pigments).
[0130] In one embodiment, the intumescent paint composition optionally includes the acid donor.
[0131] In one embodiment, the intumescent paint composition optionally includes the carbon source.
[0132] In one embodiment, the intumescent paint composition optionally includes the foaming agent.
[0133] In one embodiment, the intumescent paint composition further comprises
[0134] (e) Optional, water.
[0135] The acid formed during the thermal decomposition of the acid donor can be phosphoric acid, more preferably polyphosphoric acid.
[0136] The thermal decomposition temperature of the acid donor can be 100°C or higher.
[0137] The reaction between the carbon source and the acid formed from the acid donor can occur at temperatures of 200°C or higher, or 300°C or higher.
[0138] The carbonaceous char may contain the carbon source and the acid ester formed from the acid donor, as well as the decomposition products of the carbon source and the acid ester formed from the acid donor.
[0139] The temperature of the gas released during the thermal decomposition of the foaming agent can be 280°C to 380°C or higher.
[0140] According to a preferred embodiment of the invention, one or more of the copolymers, preferably each of the copolymers comprises
[0141] i) Based on the total weight of the copolymer, 2% to 98% by weight of monomer units available from vinyl acetate, and
[0142] ii) Based on the total weight of the copolymer, 2% to 98% by weight of one or more types of monomer units available from the vinyl ester monomer represented by formula (1).
[0143] According to a preferred embodiment of the invention, the composition of the invention is in the form of an aqueous emulsion or dispersion; preferably containing 15% to 75% by weight of water, more preferably containing 40% to 60% by weight of water, and particularly preferably containing 50% by weight of water, based on the total weight of the composition.
[0144] The terms "aqueous emulsion" or "aqueous dispersion" refer to an emulsion or dispersion containing water as the main continuous (carrier) phase. More specifically, the term is intended to refer to an emulsion or dispersion in which one or more copolymers of the present invention are dispersed in the form of (solid or liquid) particles or droplets within an aqueous phase forming the continuous phase of the emulsion / dispersion, wherein at least 50% by weight of the solvent is water based on the total weight of the solvent in the emulsion / dispersion.
[0145] This polymer binder can be dispersed or emulsified in an aqueous medium. The carrier for this aqueous (polymer) emulsion can be water.
[0146] In one embodiment of the invention, the aqueous emulsion further comprises
[0147] Pigments, preferably titanium dioxide; and / or
[0148] The filler material is preferably selected from the group consisting of: glass fiber, mineral fiber, kaolin, talc, alumina, aluminum hydroxide, magnesium hydroxide, precipitated silica, silicate, hollow microspheres, and crushed cellulose; and / or
[0149] Dispersant; and / or
[0150] Thickener; and / or
[0151] Solvent / coalescing agent; and / or
[0152] Wetting agents; and / or
[0153] Preservatives, preferably biocidal preservatives; and / or
[0154] One or more other additives.
[0155] As used herein, the term "pigment" includes compounds that provide color or opacity to a composition.
[0156] As used herein, the term "filler" is understood to refer to a substance that is substantially insoluble in the application medium (e.g., the intumescent paint composition according to the invention) and is particularly used to increase one or more of volume, color, and opacity.
[0157] As used herein, the term "dispersant" refers to a reagent that stabilizes dispersed particles or droplets, ensuring their stability within the dispersion or emulsion, and effectively preventing or at least minimizing their reaggregation. This enables the achievement of desired viscosities in the resulting dispersion or emulsion, as this allows for good handling of flowable systems (and even at high concentrations) in practice.
[0158] The term "thickener" as used in this article refers to a compound that increases the viscosity of a composition.
[0159] The term "solvent" or "coalescing agent" in this article refers to a slow-evaporating solvent that fuses polymer particles into a continuous film under ambient conditions.
[0160] The term "wetting agent" refers to a surfactant that has wetting properties, and further refers to an excipient that reduces the surface tension of water or other liquids.
[0161] The term "preservative" refers to a substance that protects a composition from the growth of microorganisms, especially bacteria or fungi.
[0162] The term "additive" refers to an additive included in a composition to enhance its physical or chemical properties and provide desired results.
[0163] According to a preferred embodiment of the invention, the one or more copolymers comprise 25% to 75% by weight, preferably 25% to 65% by weight, or 35% to 65% by weight, or 40% to 60% by weight of the monomer units available from vinyl acetate, based on the total weight of the polymer binder, preferably based on the total weight of the one or more copolymers.
[0164] According to a preferred embodiment of the invention, the one or more copolymers comprise monomer units available from the vinyl ester monomer represented by formula (1) in the range of 30% to 80% by weight, preferably 30% to 70% by weight, more preferably 40% to 70% by weight, or 40% to 60% by weight, based on the total weight of the one or more copolymers.
[0165] In one embodiment of the invention, the one or more copolymers comprise monomer units available from the vinyl ester monomer represented by formula (1) in the range of 25% to 75% by weight, preferably 35% to 75% by weight, more preferably 35% to 65% by weight, or 40% to 60% by weight, based on the total weight of the one or more copolymers.
[0166] According to a preferred embodiment of the present invention, the total number of carbon atoms in R1, R2 and R3 is in the range of 6 to 11.
[0167] According to a preferred embodiment of the invention, one or more of the one or more copolymers, preferably all of them, effectively release the acid represented by Formula 2 upon thermal decomposition:
[0168]
[0169] Where R1, R2, and R3 are defined as in this paper,
[0170] The preferred temperature for thermal decomposition is 200°C or higher, 250°C or higher, or 300°C or higher.
[0171] The term "thermal decomposition" as used herein refers to the decomposition or chemical breakdown of a substance or compound that can be caused by heat. The one or more copolymers of the present invention exhibit a specific thermal degradation mechanism during the aforementioned thermal decomposition process (i-chain stripping process-deacetylation-accompanied by chain scission reaction leading to polyene formation, and ii-chain scission). In particular, during the thermal decomposition or thermal degradation mechanism, the bonds in the monomer units of the one or more types of vinyl ester monomers represented by formula (1) are weakened, which in a further process leads to the release of the acid represented by formula 2.
[0172] According to a preferred embodiment of the invention, the polymer binder / composition, in addition to the copolymer, further comprises:
[0173] iii) Based on the total weight of the polymer binder (all polymers), 0% to 20% by weight, or 0% to 10% by weight, or 0% to 5% by weight of monomer units other than those available from vinyl acetate and those available from the vinyl ester monomer represented by formula (1). In one embodiment, the monomer units other than those available from vinyl acetate and those available from the vinyl ester monomer represented by formula (1) are selected from the group consisting of ethylene, acrylate, methacrylate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinylamide, and styrene, preferably ethylene. Preferably, all copolymers used comprise vinyl acetate and one or more monomers of formula (1), preferably, the monomers of formula (1) are contained in at least 30% by weight. Alternatively, the polymer binder comprises at least 80% by weight, or at least 90% by weight, or at least 95% by weight of copolymers. More preferably, the copolymer consists of monomer units available from vinyl acetate and monomer units available from the vinyl ester monomer represented by formula (1).
[0174] Therefore, in one embodiment, the present invention relates to an intumescent paint composition comprising...
[0175] (a) Polymer adhesive,
[0176] The polymer binder comprises one or more copolymers.
[0177] The one or more copolymers collectively comprise the following items, and preferably, the one or more copolymers consist of the following items:
[0178] i) Based on the total weight of the polymer binder, 20% to 75% by weight, and
[0179] ii) Based on the total weight of the polymer binder, 25% to 80% by weight of one or more types of monomer units available from the vinyl ester monomer represented by formula (1):
[0180]
[0181] R1, R2, and R3 are independently selected from the group consisting of: hydrogen and linear or branched unsubstituted C. 1-11 Alkyl groups, wherein the total number of carbon atoms in R1, R2 and R3 is in the range of 1 to 13;
[0182] The polymer binder comprises, in total, 0% to 20% by weight, or 0% to 10% by weight, or 0% to 5% by weight, monomer units other than those available from vinyl acetate and from the vinyl ester monomer represented by formula (1), based on the total weight of the polymer binder, and wherein
[0183] In this polymer binder, the only monomer units other than those available from vinyl acetate and from the vinyl ester monomers represented by formula (1) are selected from the group consisting of: ethylene, acrylate, methacrylate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinylamide, and styrene, preferably ethylene.
[0184] (b) Acid donor;
[0185] (c) Carbon source; and
[0186] (d) A foaming agent, preferably wherein components (a)-(d) are further defined as in other paragraphs herein.
[0187] Therefore, in one embodiment, the present invention relates to an intumescent paint composition comprising...
[0188] (a) Polymer adhesive,
[0189] The polymer binder comprises one or more copolymers.
[0190] The one or more copolymers collectively comprise the following items, and preferably, the one or more copolymers consist of the following items:
[0191] i) Based on the total weight of the polymer binder, 20% to 75% by weight, and
[0192] ii) Based on the total weight of the polymer binder, 25% to 80% by weight of one or more types of monomer units available from the vinyl ester monomer represented by formula (1):
[0193]
[0194] R1, R2, and R3 are independently selected from the group consisting of: hydrogen and linear or branched unsubstituted C. 1-11 Alkyl groups, wherein the total number of carbon atoms in R1, R2 and R3 is in the range of 1 to 13;
[0195] The polymer binder comprises, in total, 0% to 20% by weight, or 0% to 10% by weight, or 0% to 5% by weight, monomer units other than those available from vinyl acetate and from the vinyl ester monomer represented by formula (1), based on the total weight of the polymer binder.
[0196] (b) Acid donor;
[0197] (c) Carbon source; and
[0198] (d) A foaming agent, preferably wherein components (a)-(d) are further defined as in other paragraphs herein.
[0199] Therefore, in one embodiment, the present invention relates to an intumescent paint composition comprising...
[0200] (a) Polymer adhesive,
[0201] The polymer binder comprises, preferably consists of, at least 80% by weight, or at least 90% by weight, or at least 95% by weight of one or more copolymers, based on the total weight of the polymer binder.
[0202] The one or more copolymers collectively comprise the following items, and preferably, the one or more copolymers consist of the following items:
[0203] i) based on the total weight of the one or more copolymers, 20% to 75% by weight, and
[0204] ii) Based on the total weight of the one or more copolymers, 25% to 80% by weight of one or more monomer units of one or more types obtained from the vinyl ester monomer represented by formula (1):
[0205]
[0206] R1, R2, and R3 are independently selected from the group consisting of: hydrogen and linear or branched unsubstituted C. 1-11 Alkyl groups, wherein the total number of carbon atoms in R1, R2, and R3 is in the range of 1 to 13; and
[0207] Based on the total weight of the polymer binder, 0% to 20% by weight, or 0% to 10% by weight, or 0% to 5% by weight of a polymer or copolymer comprising, preferably, monomer units other than monomer units available from vinyl acetate and from the vinyl ester monomer represented by formula (1), and wherein
[0208] In this polymer binder, the only monomer units other than those available from vinyl acetate and from the vinyl ester monomers represented by formula (1) are selected from the group consisting of: ethylene, acrylate, methacrylate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinylamide, and styrene, preferably ethylene.
[0209] (b) Acid donor;
[0210] (c) Carbon source; and
[0211] (d) Foaming agent;
[0212] Preferably, components (a)-(d) are further defined as described in other paragraphs herein.
[0213] Therefore, in one embodiment, the present invention relates to an intumescent paint composition comprising...
[0214] (a) Polymer adhesive,
[0215] The polymer binder comprises a copolymer, preferably composed of a copolymer, wherein the copolymer comprises the following items in total, and preferably, the copolymer comprises the following items:
[0216] i) Based on the total weight of the copolymer, 20% to 75% by weight, and
[0217] ii) Based on the total weight of the copolymer, 25% to 80% by weight of one or more types of monomer units available from the vinyl ester monomer represented by formula (1):
[0218]
[0219] R1, R2, and R3 are independently selected from the group consisting of: hydrogen and linear or branched unsubstituted C. 1-11 Alkyl groups, wherein the total number of carbon atoms in R1, R2, and R3 is in the range of 1 to 13; and
[0220] (b) Acid donor;
[0221] (c) Carbon source; and
[0222] (d) Foaming agent,
[0223] Preferably, components (a)-(d) are further defined as described in other paragraphs herein.
[0224] Monomer units available from monomers selected from the group consisting of ethylene, acrylates, methacrylates, acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinylamide, and styrene, preferably ethylene, may be included in the polymer binder, for example, via addition of a polymer (homopolymer or copolymer) containing said monomer units to one or more copolymers consisting of monomer units available from vinyl acetate and one or more types of monomer units available from vinyl ester monomers represented by formula (1). Furthermore, for example, a terpolymer consisting of said monomer units and monomer units available from vinyl acetate and one or more types of monomer units available from vinyl ester monomers represented by formula (1) is conceivable.
[0225] According to a preferred embodiment of the invention, the polymeric adhesive is present in an amount of 5% to 40% by weight, preferably 5% to 30% by weight, more preferably 5% to 25% by weight, based on the total weight of the composition.
[0226] In one embodiment, the polymeric binder is present in an amount of 10% to 30% by weight, based on the total weight of the composition.
[0227] According to a preferred embodiment of the present invention, the one or more copolymers have
[0228] The glass transition temperature is 0 to 40°C, measured using differential scanning calorimetry; and / or
[0229] The minimum film-forming temperature is 0 to 30°C, as measured by the instrument according to the minimum film-forming temperature; and / or
[0230] The total residual monomers in the emulsion obtained after synthesis via emulsion polymerization are less than 1000 ppm, or less than 500 ppm, as measured by gas chromatography.
[0231] In one embodiment, the polymeric adhesive comprises, preferably, the following:
[0232] A copolymer, wherein the copolymer comprises, preferably, the copolymer consists of, the following:
[0233] i) Based on the total weight of the copolymer, 20% to 75% by weight, and
[0234] ii) Based on the total weight of the copolymer, 25% to 80% by weight of one or more types of monomer units available from the vinyl ester monomer represented by formula (1):
[0235]
[0236] R1, R2, and R3 are independently selected from the group consisting of: hydrogen and linear or branched unsubstituted C. 1-11 Alkyl groups, wherein the total number of carbon atoms in R1, R2 and R3 is in the range of 1 to 13;
[0237] Wherein the copolymer has
[0238] The glass transition temperature is 0 to 40°C, measured using differential scanning calorimetry; and / or
[0239] The minimum film-forming temperature is 0 to 30°C, as measured by the instrument according to the minimum film-forming temperature; and / or
[0240] The total residual monomers in the emulsion obtained after synthesis via emulsion polymerization are less than 1000 ppm, or less than 500 ppm, as measured by gas chromatography.
[0241] The glass transition temperature of one or more copolymers can be measured using differential scanning calorimetry, taking into account the midpoint, while heating at 10°C / min.
[0242] Compared to the compositions or emulsions of the present invention, prior art emulsions, such as commercial waterborne emulsions for intumescent coatings based on vinyl decanoate, vinyl nonanoate, and combinations thereof, typically have higher residual monomer (i.e., vinyl decanoate and / or vinyl nonanoate) content.
[0243] In one embodiment of the invention, the acid donor comprises or consists of one or more compounds selected from the group consisting of: orthophosphoric acid; esters of orthophosphoric acid; salts of orthophosphoric acid, such as ammonium phosphate, ammonium phosphate, and amide phosphate; and polyphosphoric acid; esters of polyphosphoric acid; and salts of polyphosphoric acid.
[0244] Preferably, the acid donor comprises one or more compounds selected from the group consisting of: ammonium polyphosphate, trichloroethyl phosphate, trichloropropyl phosphate, melamine pyrophosphate, and triphenyl phosphate.
[0245] More preferably, the acid donor comprises or consists of ammonium polyphosphate and optionally one or more compounds selected from the group consisting of ammonium phosphate and polyphosphate.
[0246] The acid donor may alternatively or additionally contain a salt of sulfuric acid, including p-nitroalanine disulfate, ammonium sulfate; or a salt of boric acid, including alkali metal borates, such as sodium borate or potassium borate.
[0247] In one embodiment of the invention, the acid donor is present in an amount of 5% to 50% by weight, or 10% to 30% by weight, or 5% to 30% by weight, or 10% to 25% by weight, or 5% to 25% by weight, based on the total weight of the composition.
[0248] In one embodiment of the invention, the carbon source comprises one or more compounds selected from the group consisting of: polyols, preferably selected from the group consisting of: mono-, di-, and tripentaerythritols or mixtures thereof; linear liquid polyols having 2-5 carbon atoms (e.g., glycerol and triethylene glycol); sorbitol; resorcinol; trimethylol melamine; phenol-formaldehyde; phenols; glucose; maltose; mannitol; polyvinyl alcohol; cellulose; dextrin and starch; polyfunctional alcohols; proteins;
[0249] More preferably, the carbon source comprises pentaerythritol and optionally one or more other polyols. Other hydroxyl-containing components may include certain oils or compounds with more complex structures.
[0250] In one embodiment of the invention, the carbon source is present in an amount of 5% to 20% by weight, or 5% to 10% by weight, or 5% to 8% by weight, based on the total weight of the composition.
[0251] In one embodiment of the invention, the foaming agent comprises or consists of one or more compounds selected from the group consisting of organic amines, amides and chlorinated paraffins;
[0252] Preferably, the foaming agent comprises one or more compounds selected from the group consisting of: urea, butylurea, dicyandiamide, casein, hexamethylenetetramine, guanidine, sulfonamide, polyamide and aminoformaldehyde oligomers, melamine and its derivatives, preferably melamine phosphate, melamine cyanurate, melamine borate, melamine polyphosphate and chlorinated paraffin;
[0253] Particularly preferably, the foaming agent comprises or is composed of melamine and optionally one or more other foaming agents, such as one or more other foaming agents selected from the group consisting of urea, butylurea, dicyandiamide, casein, hexamethylenetetramine, guanidine, sulfonamide, polyamide and aminoformaldehyde oligomers, melamine and its derivatives, preferably melamine phosphate, melamine cyanurate, melamine borate, melamine polyphosphate and chlorinated paraffin.
[0254] In one embodiment of the invention, the foaming agent is present in an amount of 5% to 20% by weight, based on the total weight of the composition.
[0255] In one embodiment of the present invention, the weight ratio of the polymer binder to the acid donor to the carbon source to the foaming agent is 1.0-2.5: 2.5-3.5: 0.5-1.5: 0.5-1.5.
[0256] The present invention also relates to paints or coatings, preferably emulsified paints, which comprise (e.g., at least 10% by weight, or at least 50% by weight, or at least 80% by weight) an intumescent paint composition as defined herein or consist of an intumescent paint composition as defined herein.
[0257] The term "paint" is used to refer to a material that can be applied to the surface of an object using any suitable application method (non-limiting examples of which include brushing, spraying, vapor deposition, spin coating, roller coating, and wiping) to provide a desired decorative finish and / or functional finish to the surface. Compared to intumescent paint compositions, this paint may contain additional solvents and additives (e.g., pigments).
[0258] The term "emulsion paint" refers to an aqueous emulsion comprising the composition of the present invention (including the polymer binder). The polymer binder can be used as a film-forming component. As used herein, emulsion paint may also be referred to as latex paint, as used in the prior art.
[0259] The present invention also relates to the use of one or more copolymers as defined herein or intumescent paint compositions as defined herein for use in intumescent coatings.
[0260] The present invention also relates to the preparation of an intumescent paint composition by combining / applying (a), (optional) (b), (optional) (c) and (optional) (d) as defined herein to obtain the intumescent coating.
[0261] The intumescent paint composition can be prepared by combining and homogenizing (e.g., stirring) the components using mixing equipment or, more commonly, equipment used for homogenization (e.g., a double-jacketed high-speed mixer). Cooling of the reactor in which homogenization takes place can be applied during homogenization. Additional additives that can be added during this process include water (e.g., demineralized water), thickeners, wetting agents, dispersants, biocidal preservatives, and pigments (preferably titanium dioxide). For example, these components, except for binders and coalescing agents, can be combined and homogenized in a first step, followed by a second step in which binders and coalescing agents are added last; subsequently, in a further third step, an additional solvent, namely water, can be added.
[0262] The present invention also relates to an intumescent coating obtained by applying an intumescent paint composition as defined herein to a surface and drying the intumescent paint composition.
[0263] An intumescent coating was applied to a steel plate that had already been primed. The coated plate was then allowed to dry at room temperature for 2 weeks. The dry film thickness was 1 mm.
[0264] The present invention also relates to coated articles comprising an intumescent coating obtained by applying and drying an intumescent paint composition as defined herein.
[0265] The term "coated article" refers to an article comprising a substrate coated with one or more layers comprising an intumescent coating formed by the intumescent paint composition. Preferred articles may be metal and wood structures or materials, such as plastics, textiles, metals, and wood, wherein the intumescent coating does not alter their inherent properties.
[0266] According to a preferred embodiment of the invention, in the intumescent coating of the coated article,
[0267] Based on the total weight of the coating, the polymeric adhesive is present in an amount of 5% to 30% by weight; and / or
[0268] Based on the total weight of the coating, the acid donor is present in an amount of 10% to 40% by weight; and / or
[0269] Based on the total weight of the coating, the carbon source is present in an amount of 5% to 20% by weight; and / or
[0270] The foaming agent is present in an amount of 5% to 20% by weight, based on the total weight of the coating. Attached Figure Description
[0271] Figure 1 : Figure 1 A photograph of the intumescent coating 1 after heat exposure is shown.
[0272] Figure 2 : Figure 2 A photograph of the intumescent coating 2 after heat exposure is shown.
[0273] Figure 3 : Figure 3 A photograph of the intumescent coating 3 after heat exposure is shown.
[0274] Figure 4 : Figure 4 A photograph of the intumescent coating 4 after heat exposure is shown.
[0275] Figure 5 : Figure 5 A photograph of the intumescent coating 5 after heat exposure is shown.
[0276] Figure 6 : Figure 6 A photograph of the intumescent coating 7 after heat exposure is shown. Detailed Implementation
[0277] Example
[0278] 1. Synthesis of polymer binders via emulsion polymerization
[0279] The emulsion polymerization of vinyl acetate is extensively described in H. Yildirim Erbil's book "Vinyl Acetate Emulsion Polymerization and Copolymerization with Acrylic Monomers".
[0280] A semi-continuous method was used to synthesize polymer binders for further use in intumescent coatings. Polymerization was carried out in a 3L double-jacketed reactor equipped with a mechanical stirrer, a temperature control system, an inlet for feeding the pre-emulsion, an inlet for feeding the initiator solution, and a reflux condenser.
[0281] The initial reactor charge was prepared by mixing the components in the order shown in Tables 1 and 2. Hydroxyethyl cellulose should be added to the reactor at room temperature under good mixing. The reactor was then heated at 76°C under nitrogen.
[0282] The preemulsion was prepared in the listed order under good mixing. Nitrogen gas was stopped at 60°C, and 10% by weight of the preemulsion was added to the reactor. The temperature was then raised to 76°C. When reflux stopped and the temperature stabilized at 76°C, the remaining preemulsion and initiator solution were continuously added in separate lines over 3 hours and 3 hours and 15 minutes, respectively, while maintaining the temperature at 76°C.
[0283] After the initiator solution is complete, raise the temperature to 80°C and maintain it for another 30 minutes.
[0284] The temperature was then cooled to 55°C, and the monomer conversion accelerator was fed through two separate pipelines for 90 minutes.
[0285] The latex is then cooled to below 35°C. A biocidal agent is added, and the latex is filtered into a suitable container.
[0286] Examples 1, 2 and 3 relate to vinyl acetate homopolymers, vinyl acetate-VeoVa 10 copolymers having 30% by weight of VeoVa 10, or vinyl acetate-VeoVa 10 copolymers having 50% by weight of VeoVa 10, respectively.
[0287] Table 1: Emulsion formulations of comparative examples.
[0288]
[0289] Anionic surfactant: Rhodacal® DS 10 (from Solvay); Sulfosuccinate anionic surfactant: Aerosol A 102 (from Solvay), for example; Buffer: Sodium bicarbonate; Reactive surfactant: Reasoap SR10 (from Adeka); Initiator: Potassium persulfate; Hydroxyethyl cellulose: Cellosize® QP300 (from Dow), for example; Nonionic emulsifier: Abex® 2535 (from Solvay); Crosslinking agent: Silquest A-174 NT (from Momentive); Oxidizing agent: Tert-butyl hydroperoxide (70% aqueous solution); Reducing agent: Bruggolite® FF6M (from Bruggeman); Biocide: Acticide® MV (from Thor).
[0290] Table 2: Emulsion formulations of the examples.
[0291]
[0292] Sulfosuccinate anionic surfactants: for example, Aerosol A 102 (from Solvay).
[0293] 2. Characterization of polymer binders
[0294] Table 3: Properties of dried polymer binder films.
[0295]
[0296] As can be seen from Comparative Examples 1 and 3, and Examples 1 and 2, the hydrophobic properties (characterized by water contact angle and water stain resistance measured on a dry polymer film) increase with increasing VeoVa 10 content in the polymer binder or copolymer. The addition of butyl acrylate (Comparative Example 2) resulted in a lower water contact angle, and the hydrolysis resistance remained poor compared to the addition of the same level of VeoVa (Comparative Example 3, which provided much higher water resistance and hydrolysis resistance).
[0297] Furthermore, when copolymerized with vinyl acetate, VeoVa 10 provides excellent hydrolytic resistance. The best hydrolytic resistance was achieved using the highest concentration of VeoVa 10.
[0298] 3. Formulation of intumescent coatings
[0299] Intumescent coatings are produced based on corresponding intumescent paint formulations, which are prepared in a double-jacketed high-speed mixer according to the method described below, while containing a polymer binder or a contrast binder according to the invention.
[0300] Table 4 illustrates the composition of expandable paint formulations.
[0301] Table 4: Expansion-type paint formulations.
[0302]
[0303] Thickener: Polysaccharide (e.g., Deuteron® VT 819, from Deuteron); Wetting & Dispersing Additive: Disperbyk® 190, from Byk; Biocide: Acticide® MV, from Thor; Titanium Dioxide: Kronos® 2300, from Kronos; Carbon Source: Pentaerythritol (e.g., Charmor® PM40, from Perstorp); Foaming Agent: Melamine; Acid Donor: Ammonium Polyphosphate (e.g., Exolit® AP 422, from Clariant); Coagulant: 2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate (e.g., Texanol®, from Eastman).
[0304] Paint preparation procedure: Mix components 1 to 4 under gentle stirring for 5 minutes. Add pigments and expanding additives 5 to 8. Gradually increase the stirring speed to 700-1200 rpm and maintain this for 30 minutes while cooling the reactor. Add the emulsion (component 9) of the respective polymer binder of the comparative example and the example, and water, under gentle stirring, and stir at 600 rpm for 10 minutes. Finally, add the solvent and continue stirring for another 10 minutes.
[0305] The polymer binder from Comparative Example 1 was formulated into an intumescent paint using the paint formulation shown in Table 4 to obtain an intumescent coating 6.
[0306] The polymer binders from Examples 1 and 2 were formulated into intumescent paints using the paint formulations shown in Table 4 to obtain intumescent coatings 7 and 8, respectively.
[0307] The polymer binders from Comparative Examples 1, 2 and 3 were formulated into intumescent paints using proprietary formulations (not specified herein) to obtain intumescent coatings 1, 2 and 3.
[0308] The polymer binders from Examples 1 and 2 have been formulated into intumescent paints using the proprietary formulations to obtain intumescent coatings 4 and 5.
[0309] The polymer binder from Comparative Example 4 was formulated into an intumescent paint using the paint formulation shown in Table 4 to obtain an intumescent coating 9 (monomer share: 100% by weight of acrylate).
[0310] The polymer binders from Comparative Examples 4 and 5 were blended and formulated into an intumescent paint using the paint formulations shown in Table 4 to obtain an intumescent coating 10. The blending ratios were calculated to obtain 30% by weight of VeoVa 10 (monomer share: 30% by weight of VeoVa 10 and 70% by weight of acrylate) in the final polymer composition.
[0311] The polymer binders from Comparative Examples 4 and 3 were blended and formulated into an intumescent paint using the paint formulations shown in Table 4 to obtain an intumescent coating 11. The blending ratios were calculated to obtain 30% by weight of VeoVa 10 in the final polymer composition (monomer proportions: 30% by weight of VeoVa 10, 62.5% by weight of acrylate and 7.5% by weight of vinyl acetate).
[0312] Table 5: List of Intumescent Paints
[0313]
[0314] 4. Characterization of Intumescent Coatings
[0315] Table 6: Performance of intumescent coating examples 1, 2, 3, 4 and 5.
[0316]
[0317] As can be seen from the intumescent coatings 1, 3, 4 and 5 (Table 5) with increasing amounts of VeoVa 10, the more VeoVa 10 in the polymer binder, the higher the fire resistance of the intumescent coating.
[0318] Introducing VeoVa 10 into vinyl acetate-based polymer binders enables excellent fire resistance of intumescent coatings. Compared to butyl acrylate used as a comonomer at the same level (15 wt%, intumescent coatings 2 and 3), the introduction of VeoVa 10 improves the intumescent properties, while butyl acrylate reduces the fire resistance.
[0319] The results in Table 6 show that intumescent coating 4 (30% by weight of VeoVa) and intumescent coating 5 (50% by weight of VeoVa) performed better than the coatings in the comparative examples.
[0320] also, Figures 1 to 6 A photograph of the intumescent coating after heat exposure is shown. From Figure 6 It can be seen that expansion was also observed in the intumescent coating 7.
[0321] Table 7: Performance of intumescent coating examples 9, 10 and 11.
[0322]
[0323] Place the coated Q-plate vertically and bring the torch flame into contact with the intumescent coating. Run the test for 3 minutes, then turn off the flame. Manually measure the thickness of the formed coke.
[0324] The results in Table 7 show that intumescent coatings 9 and 10 exhibit very limited coke development due to the absence of vinyl acetate. In intumescent coating 11, the introduction of vinyl acetate, thanks to the polymer binder of Example 3, results in improved coke expansion.
[0325] List of cited references
[0326]
Claims
1. An intumescent paint composition, the composition comprising polymer adhesives The polymer binder comprises one or more copolymers. The one or more copolymers together comprise i) Based on the total weight of the polymer binder, 0% to 75% by weight of monomer units available from vinyl acetate, and ii) Based on the total weight of the polymer binder, 25% to 80% by weight of one or more types of monomer units available from the vinyl ester monomer represented by formula (1): R1, R2, and R3 are independently selected from the group consisting of: hydrogen and linear or branched unsubstituted C. 1-11 Alkyl groups, wherein the total number of carbon atoms in R1, R2 and R3 is in the range of 1 to 13; And if the amount of monomer units available from vinyl acetate according to (i) is less than 20% by weight, then the polymer binder contains iii) One or more additional types of monomer units available from the group consisting of ethylene, acrylates, methacrylates, acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinylamide, maleate and styrene. The amount of vinyl acetate according to (i) and the amount of one or more additional types of monomer units according to (iii) together reach at least 20% by weight of the total weight of the polymer binder.
2. An intumescent paint composition comprising A) polymer adhesives The polymer binder comprises one or more copolymers. Wherein the one or more copolymers comprise a total of i) Based on the total weight of the polymer binder, 2% to 75% by weight, preferably 4% to 75% by weight, more preferably 20% to 75% by weight of monomer units available from vinyl acetate, and ii) Based on the total weight of the polymer binder, 25% to 80% by weight of one or more types of monomer units available from the vinyl ester monomer represented by formula (1): R1, R2, and R3 are independently selected from the group consisting of: hydrogen and linear or branched unsubstituted C. 1-11 Alkyl groups, wherein the total number of carbon atoms in R1, R2, and R3 is in the range of 1 to 13; or B) polymer adhesives The polymer binder comprises one or more copolymers. Wherein the one or more copolymers comprise a total of i) Based on the total weight of the polymer binder, 2% to 75% by weight, preferably 5% to 75% by weight, 2% to 75% by weight, more preferably 10% to 75% by weight, even more preferably 15% to 75% by weight, 20% to 75% by weight of monomer units available from vinyl acetate. ii) Based on the total weight of the polymer binder, 25% to 80% by weight of one or more monomer units of one type available from the vinyl ester monomer represented by formula (1) above, and if the amount of monomer units available from vinyl acetate according to (i) is less than 20% by weight, the polymer binder contains iii) one or more, preferably two or more, additional types of monomer units available from the group consisting of ethylene, acrylate, methacrylate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinylamide, maleate and styrene, preferably acrylate and styrene, wherein the amount of vinyl acetate according to (i) and the amount of one or more additional monomers together reach at least 20% by weight of the total weight of the polymer binder.
3. The composition according to claim 1, wherein one or more of the copolymers, preferably each of the copolymers comprises i) Based on the total weight of the copolymer, 2% to 98% by weight of monomer units available from vinyl acetate, and ii) Based on the total weight of the copolymer, 2% to 98% by weight of one or more types of monomer units available from the vinyl ester monomer represented by formula (1).
4. The composition according to claim 1 or 2, wherein it is in the form of an aqueous emulsion or dispersion; preferably containing 15% to 75% by weight of water based on the total weight of the composition.
5. The composition according to any one of the preceding claims, wherein the one or more copolymers comprise up to 65% by weight, or in the range of 25% to 75% by weight, preferably 25% to 65% by weight, or 35% to 65% by weight, or 40% to 60% by weight, the monomer units available from vinyl acetate, based on the total weight of the polymer binder, preferably based on the total weight of the one or more copolymers.
6. The composition according to any one of the preceding claims, wherein the one or more copolymers comprise 30% to 80% by weight, or 31% to up to 80% by weight, preferably 30% to 70% by weight, or 31% to 70% by weight, more preferably or 40% to 70% by weight, or 40% to 60% by weight, of the vinyl ester monomers represented by formula (1), based on the total weight of the one or more copolymers.
7. The composition according to any one of the preceding claims, wherein the total number of carbon atoms in R1, R2 and R3 is in the range of 6 to 11; and / or one or more of the one or more copolymers, preferably all of them, effectively release the acid represented by Formula 2 upon thermal decomposition: Wherein R1, R2, and R3 are as defined in claim 1 or 2. The preferred temperature for thermal decomposition is 200°C or higher, 250°C or higher, or 300°C or higher.
8. The composition according to any one of the preceding claims, wherein the composition further comprises one or more selected from the group consisting of an acid donor, a carbon source, and a blowing agent.
9. The composition according to any one of the preceding claims, wherein the one or more copolymers have The glass transition temperature is 0 to 40°C, measured using differential scanning calorimetry; and / or The minimum film-forming temperature is 0 to 30°C, as measured by the instrument according to the minimum film-forming temperature; and / or The total residual monomers in the emulsion obtained after synthesis via emulsion polymerization are less than 1000 ppm, or less than 500 ppm, as measured by gas chromatography.
10. A paint, preferably an emulsified paint, comprising or consisting of an intumescent paint composition as defined in any one of claims 1-9.
11. Use of one or more copolymers as defined in claim 1 or an intumescent paint composition as defined in any one of claims 1-9 for use in intumescent coatings.
12. Preparation of an intumescent paint composition by applying (a) as defined in any one of claims 1-9 to obtain the intumescent coating.
13. Preparation of an intumescent coating by applying the intumescent paint composition as defined in any one of claims 1-9 to a surface and drying the intumescent paint composition.
14. A coated article comprising an intumescent coating obtained by applying and drying the intumescent paint composition as defined in any one of claims 1-9.
15. The coated article according to claim 14, wherein the polymer binder is present in the intumescent coating in an amount of 5% to 30% by weight, based on the total weight of the coating.