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KR-20260065929-A - Phosphate-containing emulsion-based binder

KR20260065929AKR 20260065929 AKR20260065929 AKR 20260065929AKR-20260065929-A

Abstract

The present invention relates to a monomer composition comprising 5 wt.% to 15 wt.% of a phosphorus-containing monomer and a method for preparing a polymer dispersion from the monomer composition.

Inventors

  • 가오, 보
  • 에베르트, 마르티나
  • 브라움, 만프레트
  • 클라머, 엘리자베트
  • 쾨멜트, 자비네

Assignees

  • 에보니크 오퍼레이션즈 게엠베하

Dates

Publication Date
20260511
Application Date
20240910
Priority Date
20230911

Claims (15)

  1. A monomer composition comprising the following: Based on the total weight of the monomer composition, (a) 5 wt.% to 15 wt.% of phosphorus-containing monomer; (b) 70 wt.% to 95 wt.% of straight-chain or branched C1-18 alkyl (meth)acrylate; and (c) 0 wt.% to 15 wt.% of one or more additional ethylene-based unsaturated comonomers different from monomers (a) and (b); and (d) a base selected from the group consisting of ammonia and 2-amino-2-methyl-1-propanol, present in the composition in a molar ratio of (a) to (d) of 1:1.1 to 1:1.2, preferably 1:1.1.
  2. A monomer composition according to claim 1, wherein the phosphorus-containing monomer (a) is selected from the chemical formula (I): Here R1 represents H or methyl, and R m represents O - or OH, and R n represents O - , OH, Z , X 2 -P(=O) R n + 1 R m + 1 , and n and m independently represent integers from 2 to 15, and X1 and X2 independently represent O, CH2 , S, and NH, and L represents a hydrocarbon linker containing one or more optional heteroatoms.
  3. A monomer composition according to claim 1, wherein the phosphorus-containing monomer (a) is selected from the chemical formula (Ia): Here R1 represents H or methyl, and R n , R m independently represents O - , OH, Z , OP(=O) R n + 1 R m + 1 , and n and m independently represent integers from 2 to 15, and x represents an integer between 1 and 20, and x' represents an integer from 1 to 20.
  4. A monomer composition according to claim 1, wherein the phosphorus-containing monomer (a) is 2-hydroxyethyl-methacrylate-phosphate (HEMA-P).
  5. A monomer composition according to claim 1, wherein the base (d) is 2-amino-2-methyl-1-propanol.
  6. A monomer composition according to claim 1, wherein monomer (b) is selected from the group consisting of straight-chain or branched C1-4 alkyl (meth)acrylates.
  7. In claim 1, a monomer composition comprising the following: Based on the total weight of the monomer composition, (a) 5 wt.% to 15 wt.%, preferably 10 wt.% to 15 wt.% of a phosphorus-containing monomer according to formula (I); (b) 75 wt.% to 95 wt.%, preferably 80 wt.% to 95 wt.% of straight-chain or branched C1-18 alkyl (meth)acrylate; and (c) 0 wt.% to 10 wt.% of one or more additional comonomers; and (d) a base selected from the group consisting of ammonia and 2-amino-2-methyl-1-propanol, present in the composition in a molar ratio of (a) to (d) of 1:1.1 to 1:1.2, preferably 1:1.1.
  8. In claim 1, a monomer composition comprising the following: (a) 5 wt.% to 15 wt.% phosphorus-containing monomer; (b1) 40 wt.% to 50 wt.% of methyl methacrylate; (b2) 40 wt.% to 50 wt.% of n-butyl acrylate; and (d) 2-amino-2-methyl-1-propanol present in the composition in a molar ratio of (a) to (d) of 1:1.1.
  9. A method for preparing a polymer dispersion comprising the following steps: (i) a step of filling a reactor with water, a buffer material, and at least one surfactant; (ii) A step of preparing a monomer composition comprising the following: Based on the total weight of the monomer composition, (a) 5 wt.% to 15 wt.% of phosphorus-containing monomer; (b) 70 wt.% to 95 wt.% of straight-chain or branched C1-18 alkyl (meth)acrylate; and (c) 0 wt.% to 15 wt.% of one or more additional ethylene-based unsaturated comonomers different from monomers (b) and (c); and (d) a base selected from the group consisting of ammonia and 2-amino-2-methyl-1-propanol, present in the composition in a molar ratio of (a) to (d) of 1:1.1 to 1:1.2, preferably 1:1.1; (iii) A step of preparing a pre-emulsion comprising the following: (a) the monomer composition prepared in step (ii); and (b) water; and (c) at least one surfactant; (iv) a step of preparing an aqueous initiator solution 1 comprising 0.1 wt.% to 0.5 wt.% of initiator 1 based on the total amount of the monomer composition; (v) a step of adding 5% to 15% of the initiator solution 1 prepared in step (iv) to a reactor; (vi) a step of adding 5% to 15% of the pre-emulsion prepared in step (iii) to a reactor to provide a seed-emulsion; (vii) a step of supplying the remaining 85% to 95% of the pre-emulsion prepared in step (iii) to a reactor; (viii) a step of supplying 85% to 95% of the initiator solution 1 prepared in step (iv) to a reactor; (ix) a step of preparing an aqueous initiator solution 2 comprising 0.1 wt.% to 0.5 wt.% of initiator 2 and 0.05 wt.% to 0.3 wt.% of reducing agent; and (x) A step of supplying the initiator solution 2 prepared in step (ix) to a reactor to provide a desired polymer dispersion.
  10. A method according to claim 9, wherein the buffering substance is selected from the group consisting of sodium tetraborate, sodium carbonate, and acetate buffering agents.
  11. A method according to claim 9, wherein the surfactant used in step (i) is selected from the group consisting of anionic emulsifiers, nonionic emulsifiers, and mixtures thereof.
  12. A method according to claim 9, wherein initiator 1 and initiator 2 may be the same or different and are selected from the group consisting of tert-butyl hydroperoxide (TBHP), cumene hydroperoxide, hydrogen peroxide, ammonium persulfate, sodium persulfate, and potassium persulfate.
  13. Polymer dispersion comprising the following: (A) A polymer comprising 20 wt.% to 80 wt.%, preferably 30 wt.% to 60 wt.%, more preferably 30 wt.% to 40 wt.%, of the following: Based on the total weight of the monomer composition, (a) 5 wt.% to 15 wt.%, preferably 10 wt.% to 15 wt.% of a phosphorus-containing monomer according to formula (I); (b) 75 wt.% to 95 wt.%, preferably 80 wt.% to 95 wt.% of straight-chain or branched C1-18 alkyl (meth)acrylate; and (c) 0 wt.% to 10 wt.% of one or more additional comonomers; and (d) 2-amino-2-methyl-1-propanol present in the composition in a molar ratio of (a) to (d) of 1:1.1 to 1:1.2, preferably 1:1.1; and (B) 20 wt.% to 80 wt.%, preferably 40 wt.% to 70 wt.%, more preferably 60 wt.% to 70 wt.% of water.
  14. In paragraph 13, a polymer dispersion comprising the following: (A) A polymer comprising 20 wt.% to 80 wt.%, preferably 30 wt.% to 60 wt.%, more preferably 30 wt.% to 40 wt.%, of the following: (a) 5 wt.% to 15 wt.% phosphorus-containing monomer; (b1) 40 wt.% to 50 wt.% of methyl methacrylate; and (b2) 40 wt.% to 50 wt.% of n-butyl acrylate; and (d) 2-amino-2-methyl-1-propanol present in the composition in a molar ratio of (a) to (d) of 1:1.1 to 1:1.2, preferably 1:1.1; and (B) 20 wt.% to 80 wt.%, preferably 40 wt.% to 70 wt.%, more preferably 60 wt.% to 70 wt.% of water.
  15. A polymer dispersion according to claim 13 or 14, wherein the phosphorus-containing monomer (a) is 2-hydroxyethyl-methacrylate-phosphate (HEMA-P).

Description

Phosphate-containing emulsion-based binder The present invention relates to a monomer composition comprising 5 wt.% to 15 wt.% of a phosphorus-containing monomer and a method for preparing a polymer dispersion from the monomer composition. Unsaturated (meth)acrylate-based phosphate esters, such as 2-hydroxyethyl methacrylate-phosphate (HEMA-P), are adhesion promoters widely known to provide improved adhesion to polar substrates in applications such as adhesives or coating resins. Additionally, the incorporation of (meth)acrylate-based phosphate esters can improve corrosion resistance in emulsion-based coating formulations due to the improved adhesion. Furthermore, phosphorus-based compounds are widely known to improve flame retardant properties. The incorporation of unsaturated (meth)acrylate-based phosphate esters into polymeric resins results in the formation of flame-retardant materials. Flame retardant properties are very important in the coating industry, especially for flammable materials such as wood coatings. In these applications, halogen-free coatings are particularly desirable. WO 2022/089879 relates to a reactive diluent system for composite resins comprising (a) a reactive diluent composition comprising an organic (meth)acrylate-based phosphorus compound and (b) an accelerator system. Composite resins are reactive resins. They cure upon final application. They consist of a resin (e.g., vinyl ester or unsaturated polyester resin) dissolved in a reactive diluent. The standard reactive diluent for vinyl ester and unsaturated polyester resins is styrene, but derivatives of styrene (e.g., tert-butyl styrene) or vinyl toluene may also be used. (Meth)acrylates are a new reactive diluent. HEMA-P can be used as a co-reactive diluent in composite resins to improve flame retardant properties. In contrast, in this patent application, HEMA-P is incorporated into an aqueous dispersion by emulsion polymerization and used as a binder. During emulsion polymerization, HEMA-P copolymerizes with various other unsaturated monomers by radical polymerization. After emulsion polymerization, no polymerizable HEMA-P remains. The binder consists of a dispersion of acrylic copolymer (small particles) in water. The dispersion is stabilized by a surfactant already used during emulsion polymerization. Subsequently, the acrylic binder can be formulated into a water-based paint by adding pigments, fillers, preservatives, flame retardant additives (e.g., ammonium polyphosphate), or any other conventional additives. US 6,710,161 B2 relates to a polymer composition containing copolymer particles having phosphite groups and a method for preparing said polymer composition. The specification discloses that the copolymer particles may contain phosphite monomers in an amount ranging from 0.1 to 20 wt.%, preferably from 0.5 to 10 wt.%, and more preferably from 1 to 6 wt.%, based on the weight of the copolymer particles. Examples 2 and 3 disclose the preparation of a polymer composition containing 3.9 wt.% phosphoethyl methacrylate, wherein the polymerization of the phosphite monomers is carried out in an aqueous reaction medium having a pH of less than 2. That is, this implies that the incorporation of phosphoethyl methacrylate is successful only under strongly acidic conditions. However, aqueous ammonia is added after polymerization to raise the pH. The result suggests that the preparation of the polymer composition using a low pH method results in increased solvent resistance. Stability data for the produced polymer composition having a phosphoethyl methacrylate content of more than 3.9 wt.% was not reported. EP 2 945 991 B1 relates to a coating composition comprising an aqueous dispersion of polymer particles, wherein the polymer particles generally comprise 0.1 to 6 weight percent of structural units of a phosphoric acid monomer or its salt (see [0007]). The preferred concentration of the structural unit of the phosphite monomer is 0.2 to 4 wt.%, more preferably 0.5 to 2 wt.% (see [0013]). Both Working Examples 1 and 2 contain 2 wt.% of phosphoethyl methacrylate (PEM), resulting in an active substance content of only 1.2 wt.%. An aqueous dispersion of polymer particles can be prepared by forming at least a partially neutralized solution of a phosphoric acid monomer and then contacting the solution with vinyl acetate and optionally a sulfuric acid monomer or its salt, and/or an acrylate monomer under emulsion polymerization conditions (see [0017]). Suitable neutralizing agents disclosed include ammonia, KOH, NaOH, ethanolamine, and aminomethylpropanol (see [0017]). The polymer particles contain a large amount of vinyl acetate and substantially no methyl methacrylate (see [0019]). Stability data for the produced polymer composition having a phosphoethyl methacrylate content of more than 1.2 wt.% was not reported. According to the latest technology, polymer compositions containing more than 5 wt.% of P-containing monomers, particularl