Classifications

• • C09D7/1233—
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
  • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
  • C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/02—Preparation of ethers from oxiranes
  • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
  • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/20—Diluents or solvents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic

Definitions

• This invention relates to alkoxylated Bisphenol A compositions containing low residual amounts of Bisphenol A.
• the present invention also relates to methods for making such alkoxylated compositions containing low residual amounts of Bisphenol A, as well as uses for such compositions.
• the alkoxylated compositions containing low residual amounts of Bisphenol A may be utilized in packaging applications (such as indirect and/or direct food contact packaging), printing inks, container linings, and the like.
• Bisphenol compounds including alkoxylated bisphenols, are used as raw materials in many chemical compositions. They are useful as monomers for epoxy, polyester and polyurethane resins and reactive diluents in high solids coatings. These materials are typically made by combining a bisphenol compound with an alkylene oxide compound in the presence of a base catalyst under elevated temperature and pressure. The resulting alkoxylated bisphenol composition contains a certain amount of bisphenol that has not reacted with the alkylene oxide compound. There is a growing demand in the marketplace for materials with low bisphenol content. More specifically, there is an increasing need for materials with low residual Bisphenol A content.
• This invention provides a solution to the problem of creating materials that contain low amounts of residual Bisphenol A, and more specifically, of creating alkoxylated materials that contain low amounts of residual Bisphenol A.
• the inventor has discovered that alkoxylated materials having a Bisphenol A content of less than or equal to 200 ppm can be consistently achieved. This is desirable for end use products, such as direct and/or indirect food contact packaging products, wherein the free Bisphenol A content is significantly reduced.
• This invention relates to alkoxylated bisphenol compositions containing low residual amounts of Bisphenol A.
• the present invention also relates to methods for making such alkoxylated compositions containing low residual amounts of Bisphenol A, as well as uses for such compositions.
• the alkoxylated compositions containing low residual amounts of Bisphenol A may be utilized in packaging applications (such as indirect and/or direct food contact packaging), printing inks, container linings, and the like.
• this invention relates to a composition
• a composition comprising: (a) an alkoxylated Bisphenol A compound represented by structure (I):
• this invention relates to a composition
• a composition comprising: (a) an ethoxylated Bisphenol A compound represented by structure (I):
• this invention relates to a method for preparing an alkoxylated Bisphenol A composition containing low residual Bisphenol A comprising the steps of: (a) providing a molten Bisphenol A compound; (b) adding a sufficient amount of base catalyst to the molten Bisphenol A compound to form a catalyst-containing mixture; (c) heating and pressurizing the catalyst-containing mixture; (d) adding a first amount of at least one alkylene oxide compound to the catalyst-containing mixture; (e) allowing the mixture of step “d” to equilibrate for a period of about 1 hour to about 6 hours; (f) adding a second amount of the at least one alkylene oxide compound to the mixture of step “e;” (g) allowing the mixture of step “f” to further react; and (h) allowing the mixture to cool and provide an alkoxylated Bisphenol A composition comprising residual Bisphenol A in an amount that is greater than zero but less than 200 ppm.
• this invention relates to a method for preparing an alkoxylated Bisphenol A composition containing low residual Bisphenol A comprising the sequential steps of: (a) reacting Bisphenol A with a first amount of alkylene oxide in the presence of at least one alkaline catalyst at elevated temperature and pressure to form a mixture; (b) allowing the reaction to equilibrate for a period of time from about 1 hour to about 6 hours; (c) reacting the mixture of step “a” with a second amount of alkylene oxide in the presence of at least one alkaline catalyst at elevated temperature and pressure; and (d) allowing the mixture to cool and form an alkoxylated Bisphenol A composition comprising residual Bisphenol A in an amount greater than zero and less than 200 ppm.
• Bisphenol A is the product of the reaction of phenol with acetone, wherein the molar ratio of phenol to acetone is about 2:1.
• the Bisphenol A alkoxylated materials having low Bisphenol A content disclosed herein may contain a distribution of Bisphenol A oligomers. More specifically, the Bisphenol A alkoxylated materials having low Bisphenol A content disclosed herein may contain a Poisson Distribution of Bisphenol A oligomers.
• component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
• This invention encompasses an alkoxylated Bisphenol A composition represented by general structure (I):
• the term “residual Bisphenol A” is intended to include amounts of Bisphenol A greater than zero but less than 200 ppm, or greater than zero but less than 100 ppm, or greater than zero but less than 60 ppm. In one aspect, the term “residual” is intended to mean “unreacted.” In yet another aspect, the term “residual Bisphenol A” is intended to include amounts of Bisphenol A in the range from 1 to 200 ppm, or in the range from 1 to 100 ppm, or in the range from 1 to 60 ppm.
• the term “residual Bisphenol A” is intended to include amounts of Bisphenol A greater than zero but less than 5% by weight of the total composition, or greater than zero but less than 3% by weight of the total composition, greater than zero but less than 1% by weight of the total composition, or greater than zero but less than 0.5% by weight of the total composition.
• the term “residual Bisphenol A” is intended to include amounts of Bisphenol A in the range from 0.0001% to 5% by weight of the total composition, or in the range from 0.0001% to 3% by weight of the total composition, or in the range from 0.0001% to 1% by weight of the total composition, or in the range from 0.0001% to 0.5% by weight of the total composition.
• Bisphenol A compounds are generally known to those skilled in the art. They include, for example, those Bisphenol A compounds disclosed in U.S. Pat. No. 6,858,759 to Oyevaar et al.; U.S. Pat. No. 7,696,388 to Belfadhel et al.; and U.S. Pat. No. 8,044,248 to Palmer; as well as those commercially available from Milliken & Company under the trade name Syn Fac.
• the Bisphenol A compound is represented by general structure (II):
• Typical alkylene oxides which may be employed to alkoxylate the Bisphenol A compound include alkylene oxide monomers containing from two to twenty carbon atoms, or more preferably, from two to six carbon atoms.
• suitable alkylene oxide include Ethylene Oxide; Propylene Oxide; Butylene Oxide; oxetane; tetrahydrafuran; and mixtures thereof.
• the ratio of at least one alkylene oxide compound and a Bisphenol A compound may be in the range from about 50 to 1 and about 2 to 1.
• Bisphenol A alkoxylates are prepared by means of the base-catalyzed addition of at least one alkylene oxide compound to a Bisphenol A compound at elevated temperature and pressure.
• the Bisphenol A compound may be in a molten state.
• a reactor is charged with solvent, Bisphenol A and a catalyst. Water is stripped from the reactor, and then the alkylene oxide compound is added to achieve the desired level of ethoxylation.
• Bisphenol A ethoxylates are prepared by means of the base-catalyzed addition of an Ethylene Oxide to Bisphenol A at elevated temperature and pressure.
• a typical reaction scheme may generally be carried out as shown below:
• alkylene oxide e.g. Ethylene Oxide
• the addition of alkylene oxide is carried out as rapidly as possible until all the alkylene oxide has been added.
• the speed with which alkoxylated Bisphenol A can be made is greater and production amounts and/or rates are higher.
• the degree of polymerization of the resulting alkoxylated Bisphenol A is determined by the total amount of alkylene oxide added and by the combination of x+y in the reaction scheme.
• the degree of polymerization may be any integer, and/or fraction of an integer, greater than 2.
• x+y is between 2.2 and 50.
• any alkaline catalyst and/or alkaline metal catalyst may be utilized in the present alkoxylation reaction process.
• base catalysts that may be suitable for use in the alkoxylation reaction process include potassium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, lithium hydroxide, and the like, and mixtures thereof.
• small amounts of the alkaline catalyst are needed.
• the amount of alkaline catalyst included in the alkoxylation reaction process is in the range from about 0.001% to 5% by weight, or in the range from about 0.01% to about 3% by weight, or in the range from about 0.1% to about 1% by weight.
• processing temperatures may be in the range from about 90° C. to about 200° C., or in the range from about 115° C. to about 175° C., or in the range from about 125° C. to about 165° C.
• Pressures may be in the range from about 5 psi to about 160 psi, or in the range from about 5 psi to about 100 psi, or in the range from about 5 psi to about 70 psi.
• the amount of time between the first addition of alkylene oxide and the second addition of alkylene oxide is in the range of from about 1 hour and about 6 hours, or in the range from about 2 hours and about 5 hours, or in the range from about 2.5 hours and about 3.5 hours. In one aspect, the amount of time the reaction is stopped after addition of the first amount of alkylene oxide is about 3 hours.
• the method for preparing the composition of the present invention may be characterized as a non-continuous process.
• Solvents may be used in the alkylation reaction process of the present invention.
• non-protic solvents may be useful.
• the solvent utilized in the alkoxylation reaction process may be one that is non-reactive with the alkylene oxide material.
• suitable solvents that may be utilized include, without limitation, organic solvents such as toluene, ketones, and the like, and mixtures thereof.
• the present invention is directed to a low residual Bisphenol A alkoxylated material and the process for making such material.
• the alkylene oxide addition process step after approximately 2 moles of alkylene oxide has been added and allowing the reaction mixture to equilibrate for a short period of time before alkylene oxide addition is resumed, then the resulting alkoxylated Bisphenol A product contains significantly lower residual Bisphenol A.
• Additional processing steps may be optionally employed to further neutralize and/or filter the resulting alkoxylated Bisphenol A product.
• Additional processing steps may be optionally employed to further neutralize and/or filter the resulting alkoxylated Bisphenol A product.
• Several of these optional steps are disclosed, for example, in U.S. Pat. No. 6,342,641 to VanDahm et al., which is entirely incorporated by reference herein.
• the alkoxylated Bisphenol A of the present invention may be useful for end-use applications such as, and without limitation, direct and/or indirect food packaging materials, container linings, printing inks and any other application wherein it is desirable to incorporate a processing additive as described herein.
• Each of the Examples was prepared using standard reactor equipment and was carried out under elevated temperature and pressure.
• the amount of residual Bisphenol A was determined by means of gas chromatography using an Agilent Model 6890 Gas Chromatograph equipped with a 15 meter DB-5 capillary column and a Flame Ionization Detector. Amounts were quantified by comparison to external Bisphenol A standards.
• 2593 grams of a four mole ethoxylate of Bisphenol A was prepared through reaction of 1374 grams of molten Bisphenol A with a first amount of 575 grams (2.2 moles) of Ethylene Oxide in the presence of 4 grams of Potassium Hydroxide at 130° C. and a post reaction time of 3 hours.
• the resultant amount of unreacted Bisphenol A was 440 ppm.
• 640 grams (1.8 moles) of a second additional amount of Ethylene Oxide was reacted at 130° C. and a post reaction of 1 hour.
• the resultant amount of unreacted Bisphenol A was 33 ppm.
• 2593 grams of a four mole ethoxylate of Bisphenol A was prepared through reaction of 1374 grams of molten Bisphenol A with a first amount of 575 grams (2.2 moles) of Ethylene Oxide in the presence of 4 grams of Potassium Hydroxide at 130° C. and a post reaction time of 3 hours.
• the resultant amount of unreacted Bisphenol A was 480 ppm.
• 640 grams (1.8 moles) of a second additional amount of Ethylene Oxide was reacted at 130° C. and a post reaction of 1 hour.
• the resultant amount of unreacted Bisphenol A was 44 ppm.
• 2505 grams of a three mole ethoxylate of Bisphenol A was prepared through reaction of 1541 grams of molten Bisphenol A with a first amount of 645 grams (2.2 moles) of Ethylene Oxide in the presence of 4 grams of Potassium Hydroxide at 130° C. and a post reaction time of 3 hours.
• the resultant amount of unreacted Bisphenol A was 841 ppm.
• 315 grams (0.8 mole) of a second additional amount of Ethylene Oxide was reacted at 130° C. and a post reaction of 1 hour.
• the resultant amount of unreacted Bisphenol A was 36 ppm.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

Priority Applications (8)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=48523076

Family Applications (2)

Family Applications After (1)

Country Status (7)

Cited By (2)

Families Citing this family (6)

Citations (11)

Family Cites Families (5)

• 2012
  • 2012-11-26 US US13/684,663 patent/US20130139721A1/en not_active Abandoned
  • 2012-11-29 CN CN201280060224.0A patent/CN104203568B/zh active Active
  • 2012-11-29 MX MX2014006329A patent/MX349025B/es active IP Right Grant
  • 2012-11-29 WO PCT/US2012/066932 patent/WO2013085783A1/en active Application Filing
  • 2012-11-29 BR BR112014013573-8A patent/BR112014013573B1/pt active IP Right Grant
  • 2012-11-29 CA CA2866811A patent/CA2866811C/en active Active
  • 2012-11-29 EP EP12795316.4A patent/EP2788184B1/en active Active
• 2015
  • 2015-01-12 US US14/594,271 patent/US9056963B2/en active Active

Patent Citations (11)

Also Published As

Similar Documents

Legal Events