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WO2018160792A1 - Procédé et formulation pour mousse sans isocyanate - Google Patents

Procédé et formulation pour mousse sans isocyanate Download PDF

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Publication number
WO2018160792A1
WO2018160792A1 PCT/US2018/020379 US2018020379W WO2018160792A1 WO 2018160792 A1 WO2018160792 A1 WO 2018160792A1 US 2018020379 W US2018020379 W US 2018020379W WO 2018160792 A1 WO2018160792 A1 WO 2018160792A1
Authority
WO
WIPO (PCT)
Prior art keywords
acrylate
formulation
acid
foam
bicarbonate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2018/020379
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English (en)
Inventor
Drew Speer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cryovac LLC
Original Assignee
Cryovac LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cryovac LLC filed Critical Cryovac LLC
Publication of WO2018160792A1 publication Critical patent/WO2018160792A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/022—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences

Definitions

  • the presently disclosed subject matter relates generally to methods of making isocyanate-free foam.
  • BPO benzoyl peroxide
  • aromatic amine chemistry is well known for polymerizing unsaturated resins and is used commercially for curing unsaturated polyester composites.
  • one part would have the peroxide and the second part would contain the aromatic amine promoter.
  • the amine induces the formation of free radicals by the reaction with the peroxide. These radicals then initiate the polymerization of unsaturated polyesters and/or reactive diluents.
  • the formulation for making the foam may have a first part, where the first part may have 15% to 45% of at least one bicarbonate dispersed in 40% to 70% of at least one acrylate, and 0.5% to 2% peroxide.
  • the formulation may have a second part, where the second part may have 15% to 40% of at least one acid, and 1 % to 5% of an aromatic amine.
  • the second part may also have water and/or at least one water reducible acrylate.
  • the first part may be separated from the second part.
  • the formulation may also have 0.05% to 3% surfactant, and the surfactant is included in at least one of the first part or the second part.
  • the formulation for making the foam may have a first part, where the first part has 15% to 45% of at least one bicarbonate dispersed in 40% to 70% of at least one acrylate, and 1 % to 5% of an aromatic amine.
  • the formulation may have a second part, where the second part has 15% to 40% of at least one acid, and 0.5% to 2% peroxide.
  • the second part may also have water and/or at least one water reducible acrylate.
  • the first part may be separated from the second part.
  • the formulation may also have 0.05% to 3% surfactant, and the surfactant is included in at least one of the first part or the second part.
  • the method of making a foam may include providing a formulation as described above.
  • the method of making a foam may also include combining the first part and the second part of the formulation to create a froth comprising a generated gaseous blowing agent.
  • the method of making a foam may further include curing the froth by free radical polymerization to produce a foam.
  • the presently disclosed subject matter is directed to a foam.
  • the foam may have 25% to 75% of at least one acrylate, 5% to 40% of at least one water-reducible acrylate, 10% to 40% of at least one acid, 10% to 40% of at least one salt of an acid, 1 % to 5% of an aromatic amine, 0.1 % to 3% of a surfactant, and carbon dioxide.
  • the foam may also have less than or equal to 20% water.
  • FIG. 1 is a representative schematic diagram of an embodiment of the presently disclosed subject matter.
  • the presently disclosed subject matter is directed to a formulation and method for making a foam.
  • the formulation may include a bicarbonate, at least one acrylate, a peroxide, an acid, at least one water-reducible acrylate and an aromatic amine.
  • the term "about”, when referring to a value or to an amount of mass, weight, time, volume, concentration, percentage, and the like can encompass variations of, and in some embodiments, ⁇ 20%, in some embodiments ⁇ 10%, in some embodiments ⁇ 5%, in some embodiments ⁇ 1 %, in some embodiments ⁇ 0.5%, and in some embodiments ⁇ 0.1 %, ⁇ 0.01 %, from the specified amount, as such variations are appropriated in the disclosed package and methods.
  • additive refers to any substance, chemical, compound or formulation that is added to an initial substance, chemical, compound or formulation in a smaller amount than the initial substance, chemical, compound or formulation to provide additional properties or to change the properties of the initial substance, chemical, compound or formulation.
  • polymerizable resin refers to reactive molecules having three or more sites of ethylenic unsaturation that participate in forming covalent bonds during the free radical polymerization (i.e., have a functionality of three or more) to form larger molecules comprising multiples of the reactive molecules.
  • acrylate includes acrylates, methacrylates, and molecules having combinations of acrylate and methacrylate functionalities.
  • Acrylate functionality includes functionality provided by any of acrylate and methacrylate moieties.
  • Acrylate moieties includes acrylate and methacrylate moieties.
  • acrylate functionality refers to the number of acrylate moieties on the molecule.
  • co-reactant is a molecule having two or fewer sites of ethylenic unsaturation that participate in forming covalent bonds during the free radical polymerization of the polymerizable resin (i.e., have a functionality of two or one).
  • the co-reactant may be a reactive diluent, that is, co-reactant that can also act to lower the viscosity of a solution comprising the polymerizable resin (i.e., act as a solvent or diluent for the polymerizable resin).
  • a co-reactant may be selected to improve one or more characteristics of the cured foam formulation, such as density, tensile strength, compressive strength, toughness, and/or modulus.
  • froth is the expanded mixture at the initial period of the curing process (i.e., polymerization process) comprising the polymerizable resin(s), co- reactants, and other components and a plurality of cells within the mixture created by carbon dioxide and other gases that have come out of solution or have vaporized in response to the decrease in pressure.
  • the froth exists before curing has been completed. All formulation percentages used herein are presented on a “by weight” basis, unless designated otherwise.
  • the presently disclosed subject matter is directed to a formulation for making a foam and methods of making a foam.
  • the formulation may include a bicarbonate, at least one acrylate, a peroxide, an acid, at least one water-reducible acrylate and an aromatic amine.
  • the formulation may be in two parts: a first part and a second part.
  • the first part may be referred to as the A-side.
  • the second part may be referred to as the B-side.
  • the formulation for making a foam may have two parts: the first part may have a bicarbonate, at least one acrylate and a peroxide; and the second part of the formulation for making a foam may have an acid and an aromatic amine.
  • the second part may also have at least one water reducible acrylate.
  • the formulation for making a foam may have two parts: the first part may have a bicarbonate, at least one acrylate and an aromatic amine; and the second part of the formulation for making a foam may have an acid and a peroxide.
  • the second part may also have at least one water reducible acrylate.
  • the first part and the second part may be isolated from one another until mixing the first part and the second part is desired and a gaseous blowing agent may be generated.
  • the formulation for making a foam may include at least one bicarbonate.
  • the bicarbonate may be ammonium bicarbonate, calcium bicarbonate, potassium bicarbonate, sodium bicarbonate, or combinations thereof.
  • the bicarbonate may be aqueous or solid.
  • the at least one bicarbonate may be solid and may be a powder.
  • the at least one bicarbonate may be sodium bicarbonate.
  • the at least one bicarbonate may be solid sodium bicarbonate that is milled.
  • the sodium bicarbonate may be finely milled.
  • the at least one bicarbonate may be sodium bicarbonate and potassium bicarbonate.
  • the formulation may have 15 wt% to 45 wt% of a bicarbonate.
  • the formulation may have 15 wt%, 20 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, 35 wt%, 36 wt%, 40 wt%, 42 wt%, 45 wt% of a bicarbonate or any range between any of these values.
  • the formulation may have 35 wt% sodium bicarbonate.
  • the formulation may have 28 wt% sodium bicarbonate.
  • the formulation may have 30.5 wt% sodium bicarbonate and 5.5 wt% potassium bicarbonate.
  • the bicarbonate may be in the first part. In other embodiments, the bicarbonate may be in the second part.
  • the bicarbonate may be dispersed in at least one acrylate.
  • the bicarbonate may be in the first part at a range of 15-45 wt% and may be dispersed in 40-70 wt% of at least one acrylate.
  • the formulation for making a foam may include at least one acrylate.
  • the acrylate may be 2-hydroxyethyl methacrylate, acrylated polyester oligomers, bisphenol A diacrylates, dipropylene glycol diacrylate, epoxy acrylates, ethoxylated bisphenol A diacrylate, isobornyl acrylate, PEG 600 diacrylate, polyethylene glycol diacrylates, propylene glycol diacrylates, polypropylene glycol diacrylate, bisphenol A dimethacrylate, acrylated polyester oligomer, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, zinc diacrylate or combinations thereof.
  • the acrylate may be a solid, a liquid or a paste.
  • the at least one acrylate may be trimethylolpropane triacrylate (TMPTA), dipropylene glycol diacrylate and 2-hydroxyethyl methacrylate.
  • TMPTA trimethylolpropane triacrylate
  • the at least one acrylate may be TMPTA, dipropylene glycol diacrylate, PEG 600 diacrylate and 2-hydroxyethyl methacrylate.
  • the at least one acrylate may be TMPTA and dipropylene glycol diacrylate.
  • the at least one acrylate may be TMPTA.
  • the at least one acrylate may be dipropylene glycol diacrylate.
  • the at least one acrylate may be PEG 600 diacrylate.
  • the at least one acrylate may be 2-hydroxyethyl methacrylate.
  • the at least one acrylate may be TMPTA, dipropylene glycol diacrylate, ethoxylated (10 moles) bisphenol A diacrylate and 2-hydroxyethyl meth
  • the formulation may have 50 wt% to 90 wt% of at least one acrylate.
  • the formulation may have 40 wt% to 70 wt% of at least one acrylate.
  • the formulation may have 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt% of at least one acrylate or any range between these values.
  • the at least one acrylate is in the first part. In other embodiments, the at least one acrylate is in the second part. In further embodiments, the at least one acrylate is in the first part and the second part.
  • the formulation may have 50 wt% to 80 wt% of at least one acrylate in the first part.
  • the formulation may have 40 wt% to 70 wt% of at least one acrylate in the first part.
  • the first part may have 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt% of at least one acrylate or any range between these values.
  • the formulation may have 5 wt% to 30 wt% of at least one acrylate in the second part.
  • the second part may have 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt% of at least one acrylate or any range between these values.
  • the formulation for making a foam may include a peroxide.
  • the formulation for making a foam may include a plurality of peroxides.
  • the peroxide may be barium peroxide, dibenzoyi peroxide, methyl ethyl ketone peroxide, hydrogen peroxide sodium peroxide, t-butyl peroxybenzoate or combinations thereof.
  • the peroxide may be a solid, a liquid or a paste.
  • the peroxide may be a finely milled solid.
  • the peroxide may be a dibenzoyi peroxide.
  • the peroxide may be a dibenzoyi peroxide dispersion or solution.
  • the dibenzoyi peroxide dispersion may be 40% dibenzoyi peroxide in a plasticizer.
  • the formulation may have 1 wt% to 5 wt% of a peroxide.
  • the formulation may have 1 .0 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt%, 5.0 wt% of a peroxide or any range between these values.
  • the peroxide may be 2.5 wt% of 40% dibenzoyi peroxide in a plasticizer.
  • the peroxide may be in the first part.
  • the peroxide may be in the second part.
  • the formulation for making a foam may include at least one acid.
  • the acid may be acetic acid, citric acid, malic acid, tartaric acid, lactic acid, methacrylic acid, 2- hydroxyethylmethacrylate acid phosphate, poly(acrylic acid), phosphoric acid, phosphate esters of 2-hydroxyethyl methacrylate or combinations thereof.
  • the acid may be a solid, a liquid, a solution, or a paste.
  • the acid may be on a dry basis.
  • the acid may be aqueous citric acid.
  • the at least one acid may be citric acid and methacrylic acid.
  • the citric acid may be a 59% citric acid solution.
  • the formulation may have 15 wt% to 50 wt% of at least one acid.
  • the formulation may have 15 wt% to 40 wt% of at least one acid.
  • the formulation may have 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt% of at least one acid or any range between these values.
  • the formulation may have 30 wt% of at least one acid.
  • the formulation may have 38% of at least one acid.
  • the formulation may have 43% of at least one acid.
  • the formulation may have at least one acid in the second part.
  • the formulation may have 26 wt% aqueous citric acid.
  • the formulation may have 33 wt% aqueous citric acid. In further embodiments, the formulation may have 38 wt% aqueous citric acid.
  • the formulation may have 4% methacrylic acid. In some embodiments, the formulation may have 5 wt% methacrylic acid. In further embodiments, the formulation may have 10 wt% methacrylic acid.
  • the formulation for making a foam may include at least one water-reducible acrylate.
  • the at least one water-reducible acrylate may be metallic diacrylates, metallic methacrylates, ethoxylated or propoxylated triacrylates, ethoxylated diacrylates, propoxylated diacrylates, or any combination thereof.
  • the at least one water reducible acrylate may be zinc diacrylate, ethoxylated (3 moles) trimethylol propane triacrylate, ethoxylated (9 moles) trimethylol propane triacrylate, ethoxylated (10 moles) trimethylol propane triacrylate, ethoxylated (15 moles) trimethylol propane triacrylate, polyethylene glycol diacrylate, 2-hydroxyethyl methacrylate or any combination thereof.
  • the at least one water-reducible acrylate may be 2-hydroxyethyl methacrylate phosphate, ethoxylated bisphenol A diacrylate, PEG 600 diacrylate, PEG 400 diacrylate, polyethylene glycol diacrylates, triacrylates, diacrylates, zinc diacrylate or combinations thereof.
  • the at least one water-reducible acrylate may be zinc diacrylate.
  • the at least one water-reducible acrylate may be zinc diacrylate and other reducible acrylates.
  • the at least one water-reducible acrylate may be ethoxylated (20 moles) trimethylolpropane triacrylate and zinc diacrylate.
  • the at least one water-reducible acrylate may be ethoxylated (9 moles) trimethylolpropane triacrylate and zinc diacrylate.
  • the at least one water-reducible acrylate may be ethoxylated (20 moles) trimethylolpropane triacrylate, ethoxylated (9 moles) trimethylolpropane triacrylate and zinc diacrylate.
  • the at least one water-reducible acrylate may be 30% aqueous zinc diacrylate.
  • the formulation may have 15 wt% to 45 wt% of at least one water-reducible acrylate.
  • the formulation may have 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% of at least one water reducible acrylate or any range between these values.
  • the formulation may have at least one water reducible acrylate in the second part.
  • the formulation for making a foam may include an aromatic amine.
  • the aromatic amine may be ⁇ , ⁇ -dimethyl aniline, N-methyl aniline, N,N- dimethyltoluidine, N-methyltoluidine, N-(2-hydroxyethyl)-N-methyl-p-toluidine, N-alkyl aniline, N-alkyl toluidine, or any combination thereof.
  • the aromatic amine may be N-(2- hydroxyethyl)-N-methyl-p-toluidine (MHPT).
  • the formulation may have an aromatic amine in the first part.
  • the formulation may have an aromatic amine in the second part. In general, the aromatic amine will be in the part that does not contain peroxide.
  • the formulation may have 1 wt% to 5 wt% of an aromatic amine.
  • the formulation may have 1 wt%, 1 .25 wt%, 1.5 wt%, 1 .75 wt%, 1 .9 wt%, 2.0 wt%, 2.25 wt%, 2.5 wt%, 2.75 wt%, 3 wt%, 3.25 wt%, 3.5 wt%, 3.75 wt%, 4 wt%. 4.25 wt%, 4.5 wt%, 4.85 wt%, 5 wt% of an aromatic amine or any range between these values.
  • the formulation may have 1 .9 wt% of MHPT in the second part of the formulation.
  • the formulation for making a foam may have at least one additive.
  • the formulation may include 0.005 wt%, 0.007 wt%, 0.008 wt%, 0.01 wt%, 0.05 wt%, 0.075 wt%, 0.1 wt%, 0.2 wt%, 0.5 wt%, 0.75 wt%, 1.0 wt%, 1 .2 wt%, 1 .4 wt%, 1 .44 wt%, 1 .75%, 1 .8 wt%, 1 .82%, 1.83 wt%, 2.0 wt%, 3.0 wt%, 4.0%, 4.5 wt%, 4.6 wt%, 4.62 wt%, 5.0 wt%, 5.25 wt%, 5.3 wt%, 5.32 wt%, 5.5 wt%, 6 wt%, 7 wt%, 10 wt% of at least one additive or any additive or
  • the at least one additive may be a dye, flame retardant, pigment dispersing agent, reinforcing agent, nucleating agent, surfactant, unsaturated polyester type resin or combinations thereof.
  • the at least one additive may be a dye and a pigment dispersing agent.
  • the at least one additive may be a dye, a pigment dispersing agent and a silicon surfactant.
  • the at least one additive may be a dye, a pigment dispersing agent, and a silicon surfactant.
  • the at least one additive may be aluminum hydroxide, cellulose fibers, a dye, a pigment dispersing agent, silicas, a silicon surfactant, and chitin nanowhiskers.
  • the formulation may have at least one additive in the first part, the second part or both the first and the second part.
  • the at least one additive may be a pigment dispersing agent and a silicone surfactant in the first part.
  • the at least one additive may be a dye and a silicone surfactant in the second part.
  • the at least one additive may be a dye, silicone surfactant, and 2-hydroxyethyl methacrylate phosphate in the second part.
  • the at least one additive may be a pigment dispersing agent and a silicone surfactant in the first part and a dye and a silicone surfactant in the second part.
  • the at least one additive may be a pigment dispersing agent and a silicone surfactant in the first part and a dye and a silicone surfactant in the second part.
  • the formulation may have 0.05 wt% to 3 wt% of a surfactant.
  • the formulation may have 0.05 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.75 wt%, 1 .0 wt%, 1 .25 wt%, 1.5 wt%, 1 .75 wt%, 2.0 wt%, 2.25 wt%, 2.5 wt%, 2.75 wt%, 3.0 wt% of a surfactant or any range between any of these values.
  • the method of making a foam may include providing the formulation mentioned previously.
  • FIG. 1 represents an embodiment of a method of making the foam.
  • the first part may be in vessel A 5, and the second part may be in vessel B 20.
  • the first part may be transported to a mixing chamber 15 by stream 10 that connects vessel A 5 to the mixing chamber 15.
  • the second part may be transported to a mixing chamber 15 by stream 25 that connects vessel B 20 to the mixing chamber 15.
  • the method of making a foam may include combining the first part and the second part of the formulation to create a froth with a generated gaseous blowing agent by any suitable means.
  • the first part and the second part may be mixed together in the mixing chamber 15.
  • a stream of the first part, for example, in stream 10 may be impinged or entrained with a stream of the second part, for example, in stream 25.
  • a stream of the second part, for example, in stream 25 may be impinged or entrained with a stream of the first part, for example, in stream 10.
  • the first part and the second part may be hand mixed or mixed by a machine.
  • the mixing device may be a static mixing device.
  • the mixing device may be a disposable mixing device.
  • the step of combining is performed with a static mixer.
  • the step of combining may be done at various temperatures. In some embodiments,
  • the step of combining may be done at ambient temperature. In other embodiments, the step of combining may be done at a temperature of 5°C to 60°C. The temperature may be 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, or any range between these values.
  • the resulting mixture in stream 30 may be expanded to create a froth.
  • the froth may be transported to a dispensing chamber 35 by stream 30 that connects the mixing chamber 15 to the dispensing chamber 35.
  • the dispensing chamber 35 may dispense the froth using stream 40.
  • the method of making a foam may further include curing the froth by free radical polymerization to produce a foam.
  • the first part and the second part may be combined at a mixing pressure of, for example, at least any one of 10 psig, 100 psig, 200 psig, 300 psig, 350 psig, 500 psig, and 800 psig, for example in mixing chamber 15 to form a resulting mixture.
  • the resulting mixture may have an initial temperature, for example, of at least 5°C, 10°C, 20°C, 30°C, 40°C, 50°C, and 60°C or any range between these values.
  • the curing reaction begins upon mixing, for example, within the mixing chamber 15.
  • the step of expanding the resulting mixture in stream 30 to create the froth may occur by discharging the mixture directly from the mixing chamber 15 to ambient conditions (not illustrated), or alternatively by discharging the mixture into a dispensing chamber 35. In the latter case, the froth may then be discharged from the dispensing chamber 35 to allow the curing process to proceed to completion and create the foam outside of the dispensing chamber.
  • a blowing agent may be generated during the step of mixing.
  • a blowing agent may be added during the step of mixing.
  • the blowing agent may be a generated gaseous blowing agent.
  • the generated gaseous blowing agent is carbon dioxide.
  • the polymerizable resin along with any of the additional ingredients within the froth are cured to create a solidified matrix surrounding or encasing the cellular structure of the plurality of cells to create the foam.
  • the temperature of the mixture or froth may be elevated in a controlled fashion to help control the rate of the curing reaction, as well as potentially extending the curing reaction. Typically the curing is exothermic, so that the temperature of the system will typically rise after initiation of the curing reaction.
  • the curing may be 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 3 minutes, 4 minutes or any range between these values.
  • the foam may be tack free in 2 minutes or less.
  • the foam may be tack free in 2 minutes, 1 10 seconds, 100 seconds, 90 seconds, 80 seconds, 70 seconds, 60 seconds, 50 seconds, 40 seconds, 30 seconds, 20 seconds, 10 seconds or any range between these values.
  • tack free is the period from the start of the cure to a point when the foam is sufficiently robust to resist damage by touch or in ad hoc testing. Tack free time can be determined as the point when the surface of the foam is no longer sticky when touched.
  • the method of making a foam may include providing a formulation.
  • the formulation may have a first part comprising 15% to 45% of at least one bicarbonate dispersed in 40% to 70% of at least one acrylate, and 1 % to 5% peroxide.
  • the formulation may have a first part comprising 15% to 45% of at least one bicarbonate dispersed in 40% to 70% of at least one acrylate, and 1 % to 5% of an aromatic amine.
  • the formulation may have a second part comprising 15% to 40% of at least one acid, 1 % to 5% of an aromatic amine.
  • the formulation may have a second part comprising 15% to 40% of at least one acid, and 1 % to 5% peroxide.
  • the second part may include water.
  • the second part may have at least one water reducible acrylate.
  • the first part may be separated from the second part.
  • the formulation may have 0.05% to 3% surfactant, and the surfactant may be included in at least one of the first part or the second part.
  • the method may include combining the first part and the second part of the formulation to create a froth with a generated gaseous blowing agent.
  • the method may include curing the froth by free radical polymerization to produce a foam.
  • the bicarbonate reacts with the at least one acid in the formulation to generate a gaseous blowing agent and water.
  • the gaseous blowing agent may be carbon dioxide.
  • the bicarbonate is sodium bicarbonate.
  • the bicarbonate is sodium bicarbonate and potassium bicarbonate.
  • milled bicarbonate the foam may have a lower density.
  • the average particle size of standard sodium bicarbonate is about 40 microns and produces a foam with good properties.
  • a lower density foam may be produced by using milled bicarbonate with an average particle size of about 9 microns.
  • the particle size of the bicarbonate can be used to control the initial dissolution/reaction rate with the acid.
  • the formulation for making a foam has a peroxide that is dibenzoyl peroxide. Dibenzoyl peroxide splits homolytically into two free radicals that initiate polymerization of the at least one acrylate.
  • the primary decomposition product of dibenzoyl peroxide is benzoic acid.
  • the foam produced may have benzoic acid in addition to the at least one acid that was in the formulation.
  • the foam may have benzoic acid, citric acid, methacrylic acid, and/or their salts.
  • the foam may have at least one acrylate, at least one water-reducible acrylate, at least one acid, at least one salt of an acid, an aromatic amine, carbon dioxide, and a surfactant.
  • the foam may also have water.
  • the foam may have 25% to 75% of at least one acrylate, 5% to 40% of at least one water-reducible acrylate, 10% to 40% of at least one acid, 10% to 40% of at least one salt of an acid, 1 % to 5% of an aromatic amine, 0.1 % to 3% of a surfactant, and carbon dioxide.
  • the foam may have less than or equal to 20% water.
  • the foam i.e., cellular plastic
  • the foam may have a density of 0.25 pounds per cubic foot (pcf), 0.5 pcf, 1 .0 pcf, 1 .1 pcf, 1 .2 pcf, 1 .3 pcf, 1 .4 pcf, 1 .5 pcf, 1 .6 pcf, 1 .7 pcf, 1 .8 pcf, 1 .9 pcf, 2.0 pcf, 2.1 pcf, 2.5 pcf, 3.0 pcf, 4.0 pcf, and 5.0 pcf, or any range between these values.
  • pcf pounds per cubic foot
  • the foam may have a density of less than or equal to 3.0 pcf.
  • the density of the foam as used herein is the apparent density measured according to ASTM D1622-08, which is incorporated herein in its entirety by reference.
  • the foam may have a compressive strength at 10% strain of at least any of the following: 0.1 psi, 0.5 psi, 0.8 psi, 1 .0 psi, 1 .1 psi, 1.2 psi, 1.3 psi, 1 .4 psi, 1.5 psi, 2.0 psi, 2.5 psi, 3.0 psi, and 3.5 psi, or any range between these values, for example at from 10 to 50% compression.
  • the foam may have a compressive strength of greater than or equal to 1 psi at 10% strain.
  • the compressive strength is measured according to ASTM 1621 -00, as modified by reference to 10% strain.
  • the foam may have a compressive strength at 25% strain of at least any of the following: 0.8 psi, 0.9 psi, 1 .0 psi, 1 .2 psi, 1 .3 psi, 1.4 psi, 1.5 psi, 1 .6 psi, 1.7 psi, 1 .8 psi, 1.9 psi, 2.0 psi, and 2.5 psi, or any range between these values, for example at from 10 to 50% compression.
  • the compressive strength is measured according to ASTM 1621 -00, as modified by reference to 25% strain.
  • the foam may have a compressive strength at 50% strain of at least any of the following: 0.8 psi, 1 .0 psi, 1 .1 psi, 1 .2 psi, 1 .3 psi, 1.4 psi, 1.5 psi, 1 .6 psi, 1.7 psi, 1 .8 psi, 1 .9 psi, 2.0 psi, 2.1 psi, 2.2 psi, 2.3 psi, 2.4 psi, and 2.5 psi, or any range between these values, for example at from 10 to 50% compression.
  • the compressive strength is measured according to ASTM 1621 -00, as modified by reference to 50% strain.
  • the foam may have a configuration, for example, of any of a sheet, plank, slab, block, board, and molded shape.
  • the foam may be a solid foam.
  • the foam may be used for any one or more of void fill, blocking or bracing, thermal insulation, cushioning, package cushioning, sound insulation or vibration dampening.
  • the formulations used to make the foam are free of isocyanate reactants, such as those used in formulating polyurethane foams, so that the final foam of the present disclosure is free from isocyanates or isocyanate residues.
  • any numerical value ranges recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value.
  • the amount of a component or a value of a process variable e.g., temperature, pressure, time
  • the amount of a component or a value of a process variable may range from any of 1 to 90, 20 to 80, or 30 to 70, or be any of at least 1 , 20, or 30 and/or at most 90, 80, or 70, then it is intended that values such as 15 to 85, 22 to 68, 43 to 51 , and 30 to 32, as well as at least 15, at least 22, and at most 32, are expressly enumerated in this specification.
  • Tables 1 , 3, 5, 7, and 9 lists the A-side formulation for examples 1 -25 and Tables 2, 4, 6, 8, and 10 lists the B-side formulation for examples 1 -25.
  • Table 1
  • Examples 1 -25 were tested for density, compressive strength (at 10%, 25% and 50%). The slope and ratio (10%/d) were also calculated. The "slope" is the slope of the compressive strength data, thus a greater slope means a greater increase in
  • Examples 1 -1 1 show that example 1 had the lowest density of 1 .57 pcf and example 10 had the highest density of 2.09 pcf.
  • the compressive strength was determined at 10%, 25% and 50% compressive strain.
  • Example 1 showed the least resistance to compressive stresses due perhaps to having the lowest density out of examples 1 -1 1 .
  • Example 1 had a compressive strength of 1 psi at 10% strain and 1 .28 psi at 50% strain.
  • examples 3 and 9 had the highest compressive strength at 10% strain.
  • Example 10 had the highest resistance to compressive stresses when compared to examples 1 -9 and 1 1 due perhaps to having the highest density.
  • Example 10 had a compressive strength of 1 .33 psi at 10% and 1 .8 psi at 50%.
  • Examples 3, 5, 8, and 9 had the highest strength to density ratio when compared to all of the examples in Tables 1 1 and 12.
  • Table 13
  • Examples 13 and 14 had the lowest density, although example 17 had the greatest compressive strength to density ratio compared to all of the examples in Table 13.
  • Examples 19 and 22 had the lowest density and example 19 had a high pressive strength to weight ratio compared to all of the examples in Table 14.
  • Examples 23 and 24 had lower density values than example 25.
  • Example 24 had the best compressive strength to density ratio when compared to examples 23 and 24.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé de fabrication de mousse. La formulation décrite comprend une première partie comportant au moins un bicarbonate dispersé dans au moins un acrylate et un peroxyde. La formulation comprend une seconde partie comportant au moins un acide, une amine aromatique, éventuellement de l'eau et éventuellement au moins un acrylate réductible dans l'eau. La formulation contient également un tensioactif dans au moins ladite première ou seconde partie. Le procédé comprend la combinaison de la première et de la seconde partie de la formulation pour créer une écume à l'aide de l'agent d'expansion gazeux généré. La mousse est durcie par polymérisation radicalaire pour produire une mousse.
PCT/US2018/020379 2017-03-02 2018-03-01 Procédé et formulation pour mousse sans isocyanate Ceased WO2018160792A1 (fr)

Applications Claiming Priority (2)

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US201762465923P 2017-03-02 2017-03-02
US62/465,923 2017-03-02

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023168269A1 (fr) * 2022-03-01 2023-09-07 University Of Maryland, College Park Systèmes et procédés de fabrication et d'utilisation de gels poreux superabsorbants

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013077865A1 (fr) * 2011-11-22 2013-05-30 Cryovac, Inc. Procédé de fabrication d'une mousse
US20130203878A1 (en) * 2010-08-03 2013-08-08 Ferro Corporation Polymer Composite Foams
EP2735585A1 (fr) * 2012-11-21 2014-05-28 Sealed Air Corporation (US) Procédé de production de mousse

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130203878A1 (en) * 2010-08-03 2013-08-08 Ferro Corporation Polymer Composite Foams
WO2013077865A1 (fr) * 2011-11-22 2013-05-30 Cryovac, Inc. Procédé de fabrication d'une mousse
EP2735585A1 (fr) * 2012-11-21 2014-05-28 Sealed Air Corporation (US) Procédé de production de mousse

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023168269A1 (fr) * 2022-03-01 2023-09-07 University Of Maryland, College Park Systèmes et procédés de fabrication et d'utilisation de gels poreux superabsorbants

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