WO2010059925A1 - Polyesters, leurs procédés de préparation et leur utilisation - Google Patents

Polyesters, leurs procédés de préparation et leur utilisation Download PDF

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Publication number
WO2010059925A1
WO2010059925A1 PCT/US2009/065297 US2009065297W WO2010059925A1 WO 2010059925 A1 WO2010059925 A1 WO 2010059925A1 US 2009065297 W US2009065297 W US 2009065297W WO 2010059925 A1 WO2010059925 A1 WO 2010059925A1
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Prior art keywords
acid
group
mixtures
molecular weight
mixture
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PCT/US2009/065297
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English (en)
Inventor
Michael P. Bigwood
Linda S. Smith
Michael C. Bigwood
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Polymer Phases, Inc.
Cheminnolab Llc
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Application filed by Polymer Phases, Inc., Cheminnolab Llc filed Critical Polymer Phases, Inc.
Priority to US13/130,225 priority Critical patent/US20110224323A1/en
Priority to EP09828282.5A priority patent/EP2367866A4/fr
Publication of WO2010059925A1 publication Critical patent/WO2010059925A1/fr

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    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • 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
    • C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to polyesters that are the crosslinked polycondensation products of a polyoi and a polyacid and methods of their production and use.
  • Preferred polyols and polyacids are sustainable monomers obtained from renewable resources.
  • the crosslinked polycondensation products are formed through a process involving prepolymer formation at a first temperature and then curing the prepolymer by self-crosslinking at a second, higher temperature, or by the addition of a crosslinking agent or a polymerization catalyst at a second temperature.
  • the prepolymer may be stored as a liquid, a solution, a suspension, or as a hardened polymer and then placed in a reactor, such as a heated mold, for curing into the desired shaped article at the second temperature.
  • Sustainable monomers are those monomers that can be manufactured from a readily renewable resource without reliance on fossil fuels as the source of the starting material.
  • the triol glycerol and the triacid citric acid can both be obtained from natural sources without using fossil fuels as a starting material.
  • Polyesters formed from glycerol and certain diacids have been disclosed.
  • US Patent Application Pub. No. 2003/0118692 published June 26, 2003, discloses polycondensation of glycerol and sebacic acid at 120° C under argon for 24 hours before the pressure was reduced from 1 Torr to 40 mTorr over five hours. The reaction mixture was kept at 40 mTorr and 120° C for 48 hours. The resulting polyester was reported to be an elastomer that did not swell or dissolve in water.
  • US2003/0118692 also discloses that this elastomer is a thermoset polymer and that the imcrossiinked prepolymer can be processed into various shapes by curing under vacuum in a mold, such as at 120° C and 100 mTorr.
  • US Patent 7,557,167, issued July 7, 2009 discloses crosslinked polymers produced from a polyol and a saturated aliphatic diacid.
  • the polyol may be glycerol with or without ethylene glycol and the diacid may be sebacic acid.
  • the polyester preferably exhibits shape memory properties.
  • Glycerol and citric acid have been used in low amounts as branching agents for otherwise straight chain polymers.
  • the addition of these branching agents is typically limited to less than five (5) moi % of the total polyester composition.
  • polyesters typically thermoplastic, rather than thermoset.
  • Thermoplastics are polymers held together by intermolecular forces rather than chemical bonds between the polymer molecules.
  • thermosets have one or more chemical bonds (crosslinks) binding the polymer molecules together.
  • obtaining high molecular weight polymers requires expensive processing equipment.
  • processes for producing high molecular weight polylactic acid (PLA) and polyglycolic acid (PGA) are well known. Both PLA and PGA are produced from sustainable starting materials — lactide and giycolide, respectively.
  • forming high molecular weight polyesters from either monomer requires a complex ring-opening polymerization process to prevent the water formed during the reaction from dissolving the polymer as it is formed.
  • Transesterification has been used to increase the molecular weight of polyesters.
  • a carboxy ⁇ c acid or its anhydride is reacted with an alcohol containing two or more hydroxyl groups at high temperature and under vacuum.
  • an alcohol containing two or more hydroxyl groups at high temperature and under vacuum.
  • transesterification reactions often a methyl ester is the starting material. Because the starting material contains a methyl group, rather than a hydroxyl group, the reaction produces methanol, rather than water, as a byproduct. Methanol has a lower boiling point than water and is thus easier to remove.
  • these polyesters are typically straight chain thermoplastics.
  • PET polyethylene terephthalate
  • PET polyethylene terephthalate
  • the first step the ethylene glycol and the methyl terephthalate are reacted at temperatures ranging from 150 0 C to 200 0 C and the methanol byproduct is removed by continuous distillation
  • the second step the mixture is heated to a temperature between 260 0 C to 290 0 C and ethylene glycol is continuously removed to allow the reaction to proceed.
  • polyesters may be increased by increasing the reaction temperature in multiple steps. Typically, these reactions are at low temperatures under vacuum. They often require more than two temperature steps and are completed in a single reactor without time between the temperature steps.
  • the invention provides a crosslinked polycondensation product of (a) one or more polyols selected from the group consisting of: (1) polyols with three or more hydroxyl groups, (2) acetal forms of (1), and (3) mixtures thereof, and (b) one or more polyac ⁇ ds selected from the group consisting of: (1) polyacids with two or more carboxylic groups, (2) anhydrides of (1), (3) esters of (1), and (4) mixtures thereof; in which the molar ratio of polyol to polyacid is from about 1:3 to about 3:1; and the crosslinked polycondensation product is highly-cross linked, as evidenced by either general insolubility in one or more solvents selected from the group consisting of: (1) water, (2) acetone, (3) methyl ethyl ketone, (4) tetrahydrofiiran, (5) dimethylformamide, and (6) dichloromethane, or by a glass transition temperature from about 50 0 C to about 150 0
  • the present invention also provides a method for preparing a crossiinked polyester comprising: (a) mixing one or more polyols selected from the group consisting of: (1) polyols with three or more hydroxyl groups, (2) acetal forms of (1), and (3) mixtures thereof with one or more polyacids selected from the group consisting of: (1) polyacids with two or more carboxylic groups, (2) anhydrides of (1), (3) esters of (1), and (4) mixtures thereof to form a first mixture; wherein the first mixture has a molar ratio of polyol to polyacid from about 1 :3 to about 3 : 1 ; (b) reacting the first mixture at a pressure at or above about one (1) atmosphere and at a temperature from about 80 0 C to about 250 0 C for a period of time from about fifteen (15) minutes to about three hundred (300) minutes to form a low molecular weight prepolymer; (c) optionally mixing the low molecular weight prepolymer with a modification compound selected from the
  • the invention provides a method for preparing a crosslinked polyester by use of a crosslinking agent in addition to the polyol and polyacid.
  • This aspect provides a method comprising (a) mixing one or more polyols selected from the group consisting of: (1) polyols with three or more hydroxyl groups, (2) aceta ⁇ forms of (1), and (3) mixtures thereof with one or more polyacids selected from the group consisting of: (1) polyacids with two or more carboxylic groups, (2) anhydrides of (1), (3) esters of (1), and (4) mixtures thereof to form a first mixture; wherein the first mixture has a molar ratio of polyol to polyacid from about 1 :3 to about 3:1; (b) reacting the first mixture at a pressure at or above about one (1) atmosphere and at a temperature from about 80 0 C to about 250 0 C for a period of time from about fifteen (15) minutes to about three hundred (300) minutes to form a low molecular weight prepolymer;
  • the invention provides a method for preparing a crosslinked polyester by use of a polymerization catalyst in addition to the polyol and polyacid.
  • This aspect provides a method comprising (a) mixing one or more polyols selected from the group consisting of: (1) polyols with three or more hydroxyl groups, (2) acetal forms of (1), and (3) mixtures thereof with one or more polyacids selected from the group consisting of: (1) polyacids with two or more carboxylic groups, (2) anhydrides of (1), (3) esters of (1), and (4) mixtures thereof to form a first mixture; wherein the first mixture has a molar ratio of polyol to poiyacid from about 1 :3 to about 3:1; (b) reacting the first mixture at a pressure at or above about one (1) atmosphere and at a temperature from about 80 0 C to about 250 0 C for a period of time from about fifteen (15) minutes to about three hundred (300) minutes to form a low molecular weight prepolymer;
  • the invention provides a method of forming a shaped polyester article comprising (a) mixing one or more polyols selected from the group consisting of: (1) polyols with three or more hydroxyl groups, (2) aceta!
  • the invention provides a method of making a shaped polyester article using a crosslinking agent in addition to the polyol and polyacid.
  • This embodiment is a method comprising (a) mixing one or more polyols selected from the group consisting of: (1) polyols with three or more hydroxyl groups, (2) acetal forms of (1), and (3) mixtures thereof with one or more polyacids selected from the group consisting of: (1) polyacids with two or more carboxylic groups, (2) anhydrides of (1), (3) esters of (1), and (4) mixtures thereof to form a first mixture; wherein the first mixture has a molar ratio of polyol to polyacid from about 1 :3 to about 3:1; (b) reacting the first mixture from step (a) at a pressure at or above about one (1) atmosphere and at a temperature from about 80 0 C to about 250 0 C for a period of time from about fifteen (15) minutes to about three hundred (300) minutes to form a low molecular weight prepo
  • the invention provides a method of making a shaped polyester article using a polymerization catalyst in addition to the polyol and polyacid.
  • This embodiment is a method comprising (a) mixing one or more polyols selected from the group consisting of: (1) polyols with three or more hydroxyl groups, (2) acetal forms of (1), and (3) mixtures thereof with one or more polyacids selected from the group consisting of: (1) polyacids with two or more carboxylic groups, (2) anhydrides of (1), (3) esters of (1), and (4) mixtures thereof to form a first mixture; wherein the first mixture has a molar ratio of polyol to polyacid from about 1 :3 to about 3 : 1 ; (b) reacting the first mixture from step (a) at a pressure at or above about one (1) atmosphere and at a temperature from about 80 0 C to about 250 0 C for a period of time from about fifteen (15) minutes to about three hundred (300) minutes to form a low mole
  • polyol refers to any molecule with two or more hydroxyl groups, including acetal forms of these molecules.
  • polyac ⁇ d refers to any carboxylic acid bearing two or more carboxylic groups, including anhydride and ester forms of these molecules.
  • prepolymer refers to the polymer created after the initial heating step of the invention and the terms “final polymer,” “cured polymer,” or “crosslinked polyester” refer to the high molecular weight, crosslinked polymer created after the second step of the invention when the prepolymer is raised to a second temperature.
  • compositions and processes in accordance with the various embodiments of the present invention are suitable for use in making a wide array of finished shaped products and articles of manufacture that require a rigid or semi-rigid form and that also require resistance to water and other solvents.
  • the present invention includes a high molecular weight polymer that is highly crosslinked and that exhibits resistance to water and other solvents. Also included in the present invention is a method of making the high molecular weight polymers that are highly crosslinked and a method of forming shaped products and articles of manufacture using the cured high molecular weight polymer,
  • the cured high molecular weight, highly crosslinked polyesters of the present invention do not require special processing conditions (such as being conducted under vacuum pressure) to remove water and react at lower temperatures than those known in the art.
  • These stable, cured, high molecular weight, highly crosslinked polyesters can be prepared by a step-wise reaction method. The method comprises two steps.
  • low molecular weight polyester prepolymers are synthesized by (i) reacting one or more polyols, or acetals of these polyols, with one or more polyacids, or anhydrides or esters of these polyacids, at a pressure at or above about one (1) atmosphere and at a temperature from about 80 0 C to about 250 0 C for a time from about fifteen (15) minutes to about three hundred (300) minutes.
  • the reaction temperature be above about 100 0 C to allow the water to evaporate.
  • the reaction occurs at a temperature range from about 110 0 C to about 250 0 C.
  • This first step of the reaction may occur at a temperature range from about 110 0 C to about 150 0 C, about 120 0 C to about 140 0 C, about 130 0 C to about 180 0 C , about 140 0 C to about 170 0 C, about 130 0 C to about 160 0 C, about 140 0 C to about 160 °C, about 140 0 C to about 190 0 C, about 130 0 C to about 180 0 C, about 150 0 C to about 200 0 C, about 160 0 C to about 200 0 C, about 170 0 C to about 200 0 C, about 180 0 C to about 200 0 C, about 190 0 C to about 220 0 C, about 200 0 C to about 230 0 C, about 210 0 C to about 240 0 C, or about 160 0 C to about 240 0 C.
  • the first step prepolymer reaction not be catalyzed with any esterification catalyst, including, but not limited to, sulfuric, methyl sulfonic, benzyl sulfonic, para-toluene sulfonic, boric, and phosphoric acids.
  • any esterification catalyst including, but not limited to, sulfuric, methyl sulfonic, benzyl sulfonic, para-toluene sulfonic, boric, and phosphoric acids.
  • the low molecular weight prepolymers are further reacted to form a final cured polymer that has a high molecular weight and is highly crosslinked.
  • the prepolymer may be mixed with one or more polymer modification compounds, including, but not limited to, polymer additives, plasticizers, and foam blowing agents.
  • the prepolymer or the prepolymer mixture is then cured in a further reaction step at a pressure at or above about one (1) atmosphere and a temperature from about 175 0 C to about 400 0 C for a period of time from about three (3) seconds to about sixty (60) minutes.
  • this curing step occurs at a pressure at or above about one (I) atmosphere and a temperature from about 175 0 C to about 300 0 C, about 190 0 C to about 300 0 C, about 190 0 C to about 200 0 C, about 200 0 C to about 300 0 C , about 250 0 C to about 300 0 C, about 175 0 C to about 250 0 C, about 175 0 C to about 220 0 C, about 200 0 C to about 400 0 C, about 250 0 C to about 400 0 C, or about 300 0 C to about 400 0 C for a period of time from about five (5) seconds to about sixty (60) minutes, about thirty (30) seconds to about sixty (60) minutes, about five (5) minutes to about sixty (60) minutes, about twenty (20) minutes to about sixty (60) minutes, about forty (40) minutes to about sixty (60) minutes, about five (5) seconds to about thirty (30) minutes, about two (2) minutes to about thirty (30) minutes, about five (5)
  • a crosslinking agent or a polymerization catalyst may be used.
  • Any crosslinking agent that contains two or more functional groups that can react with either the hydroxyl or carboxylic groups of the prepolymers may be used, including, but not limited to, (1) aromatic diisocyanates, (2) aliphatic diisocyanates, (3) polymeric diisocyanates, (4) cycloaliphatic diepoxides, (5) aromatic diepoxides, (6) diepoxides with oxyalkyl backbones, (7) 2,2,4-trimethy!-l,3-pentane diol mono isobuty late, (8) glycerin, (9) trimethylol propane, and (10) mixtures thereof,
  • the second step of the polymerization with a cross linking agent occurs at or above one (1) atmosphere and occurs at a temperature of about 20 °C to about 50 0 C, about 30 0 C to about 60 0 C, about 40 0 C to about 70 0 C, about 50 0 C to about 80 0 C, about 60 0 C to about 90 0 C, about 70 0 C to about 100 0 C, about 80 0 C to about 110 0 C, about 90 0 C to about 120 0 C, about 100 0 C to about 130 °C, or about 60 0 C to about 130 0 C for a period of about thirty (30) seconds to about thirty (30) minutes, about one (1) minute to about thirty (30) minutes, about five (5) minutes to about thirty (30) minutes, about fifteen (15) minutes to about thirty (30) minutes,
  • Polymerization catalysts that may be used in the second heating step include, but are not limited to, (1) sulfuric acid, (2) phenylsulfonic acid, (3) benzene sulfonic acid, and (4) para-toluene sulfonic acid ("pTSA").
  • the addition of the polymerization catalyst allows for curing at temperatures from about 130 0 C to about 250 0 C at or above one (1) atmosphere pressure for about thirty (30) seconds to about sixty (60) minutes.
  • the reaction time required for the second step may be decreased to a period of about five (5) minutes by the addition of pTSA without negatively affecting the degree of crosslinking or other final polymer properties.
  • One or more polymerization catalysts may be used.
  • the second step of the polymerization with a polymerization catalyst occurs at or above one (1) atmosphere and occurs at a temperature of about 130 0 C to about 160 0 C, about 140 0 C to about 170 0 C, about 150 0 C to about 180 0 C, about 160 0 C to about 190 0 C, about 170 0 C to about 200 0 C, about 150 0 C to about 200 0 C, about 130 0 C to about 180 0 C, about 180 0 C to about 230 0 C, about 190 0 C to about 240 0 C, about 200 0 C to about 240 0 C, or about 140 0 C to about 200 0 C, for a period of about thirty (30) seconds to about thirty (30) minutes, about one (1) minute to about thirty (30) minutes, about five (5) minutes to about thirty (30) minutes, about fifteen (15) minutes to about thirty (30) minutes, about five (5) minutes to about sixty (60) minutes, about ten (10) minutes to about sixty (60)
  • the resulting polymer condensation product exhibits a high molecular weight and is highly crosslinked, as may be evidenced by general insolubility in one or more solvents, including, but not limited to, water, acetone, methyl ethyl ketone (MEK), tetrahydrofuran, dimethylformamide, and dichloromethane.
  • general insolubility in a solvent may be demonstrated by generally accepted methods. One method is to immerse a sample of a substance into the solvent and observe the material over time to determine if it dissolves.
  • Another method is to measure one or more dimensions of a poiymer sample before immersion, then to measure the polymer sample after set time periods to determine if there has been a change in the specific dimension, which may then be expressed as a percentage.
  • the time period used to determine general insolubility is twenty-four (24) hours.
  • the resulting cured polymer has a Tg measurement that will fall within the range of from about 50 0 C to about 150 0 C.
  • the Tg is from about 50 0 C to about 80 0 C, from about 60 0 C to about 90 0 C, from about 70 0 C to about 100 0 C, from about 80 0 C to about 110 0 C, from about 9O 0 C to about 120 0 C, from about 100 0 C to about 130 0 C, from about 80 0 C to about 120 0 C, from about 110 0 C to about 140 0 C, from about 120 0 C to about 140 0 C, or from about 130 0 C to about 150 0 C .
  • Tg is significantly higher than those disclosed in the prior art. See, for example, D. Pramanick and T. T. Ray, "Synthesis and Biodegradation of Copolyesters from Citric Acid and Glycerol," Polymer Bulletin 19, 365-370, 368 (1988), which discloses Tg measurements for citric acid/glycero! polymers that range between 6 0 C and 22 0 C. As illustrated in Example 3, the Tg measurements for citric acid/glycerol polymers of the present invention range from 106 0 C to 140 0 C. As illustrated in the Examples set out below, the Tg for the cured polymer is higher than the Tg of the prepolymer. For reference, both polystyrene and methyl methacrylate have glass transition temperatures of about 100 0 C. Additionally, the resulting cured polymer of the invention is not an elastomer.
  • the copolymer can be therm oset into a variety of final products or articles of manufacture by curing the polymer using molds (such as molds fired in ovens, mold casting equipment, or injection molds), extruders, film casting equipment, spray guns, or other shape-forming or thermoforming equipment.
  • molds such as molds fired in ovens, mold casting equipment, or injection molds
  • extruders such as film casting equipment, spray guns, or other shape-forming or thermoforming equipment.
  • the properties of the prepolymer, and thus the cured polymer may be manipulated by varying the molar ratio of polyol to polyacid.
  • the polyohpolyacid molar ratio may range from about 1 :3 to about 3:1.
  • the initial polyokpolyacid molar ratio is about 1 :1. If a more flowable prepolymer is desired, the polyol:polyacid molar ratio is increased to a range from about 1 :1 to about 3:1.
  • the polyol :polyacid molar ratio may be decreased to a range from about 1:1 to about 1 :3.
  • the molar ratio of polyohpolyacid is about 1 :2 to about 2: 1 ; or about 1 : 1.5 to about 1.5: 1.
  • the polyol may be any molecule with three or more hydroxyl groups, including, but not limited to linear or cyclic (Ci-Ce) trihydroxy alkanes, linear or cyclic (CrCe) trihydroxy alkenes, including the acetal forms of these molecules.
  • the polyol is one or more of the following: glycerol, isopropylidene glycerol (solketal), pentaerythritol, 1,2,4-bunatetrioI, and their acetal forms.
  • naturally occurring, sustainable polyols are preferred, including, but not limited to, glycerol.
  • the polyacid may be any molecule with two or more carboxylic groups, including, but not limited to, linear dicarboxylic acids where the acid groups are separated by an aliphatic chain of variable length (for example, succinic, adipic, and sebacic acids), unsaturated hydrocarbon chains of various lengths (for example, maleic and fumaric acids), dicarboxylic acids containing a saturated or aromatic ring (for example, phthalic and terephthalic acids), and linear or cyclic, aliphatic or unsaturated tricarboxylic acids (for example, citric and trimellitic acids), and anhydrides and esters of these carboxylic acids.
  • linear dicarboxylic acids where the acid groups are separated by an aliphatic chain of variable length (for example, succinic, adipic, and sebacic acids), unsaturated hydrocarbon chains of various lengths (for example, maleic and fumaric acids), dicarboxylic acids containing a saturated or aromatic ring (for example, phthal
  • naturally occurring, sustainable polyacids are preferred, including, but not limited to adipic, succinic, citric, cis-aconitic, isocitr ⁇ c, alpha-ketoglutaric, fumaric, maleic, sebacic, and oxalacetic acids.
  • the polyacid is an aliphatic diacid, anhydride, or ester thereof.
  • the polyol is glycerol or its acetal and the polyacid is citric acid, its anhydride, or its esters.
  • Both glycerol and citric acid are non-toxic, sustainable starting materials; thus, prepolymers and cured polymers resulting from glycerol and citric acid have the advantage of being produced from sustainable materials.
  • the cured polymer does not include a diol, such as ethylene glycol, and the inventive methods do not include polymerization of polyol and polyacid with a diol, especially with ethylene glycol.
  • the cured polymer is not made from a mixture of sebacic acid and glycerol, and the inventive methods do not include polymerization of sebacic acid and glycerol.
  • the prepolymers may be self-crossl inked to form the cured polymer by additional heating of the prepolymers.
  • Typical applications for the self-crosslinked cured polymer include foams, including, but not limited to, packaging materials; flexible and semi-flexible films; and thermoset formed products.
  • blowing agents may be used. These blowing agents, include, but are not limited to, carbon dioxide, water vapor, carbonate salts, isocyanate, gaseous hydrocarbons, halogenated hydrocarbons, and alcohols. When water is used as a blowing agent, the resulting cured polymer foam exhibits a low density. In certain embodiments, the foam blowing agents do not include porogens, such as sodium chloride.
  • plasticizers including, but not limited to linear (Ci-Ce) or cyclic (C3-C6) aliphatic mono- or di-ethers of ethylene glycol or glycerol, and cosolvents, including, but not limited to, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, and 2,2,4-trimethyl-l,3,-pentane diol monoisobutylate, may be added to the prepolymers before curing into the final polymer, Plasticizers result in a more flexible cured polymer or cured polymer foam, while cosolvents are useful in producing clear cured polymer coatings.
  • sebacic acid is used in addition to a first polyacid. The addition of the sebacic acid will also result in a more flexible final cured polymer, with flexibility generally increasing with the concentration of sebacic acid.
  • a polyurethane foam is formed under ambient conditions.
  • the isocyanate-catalyzed polyurethane cured polymer foam increases in rigidity as the concentration of isocyanate is increased.
  • the isocyanate-catalyzed polyurethane cured polymer may be used as an adhesive or coating by curing at temperatures from about 130 0 C to about 250 0 C; and preferably from about 140 0 C to about 160 0 C when used on metals.
  • percentages are weight percents (wt %); ratios are molar ratios.
  • the following units are used, unless otherwise noted: grams (g); milliliters (niL); centipoises (cps); minutes (min); hours (hr); and degrees Celsius ( 0 C).
  • the viscosity was measured by first calibrating a Pasteur pipette by measuring the time necessary for a fixed quantity of a standardized glycerol in water solution of known viscosity to drain from the pipette. The pipette was cleaned and a solution of 33 wt % prepolymer in deionized water was prepared. A fixed quantity of the solution was then placed in the Pasteur pipette and the time necessary for the solution to fully drain from the pipette was measured. The viscosity was calculated by comparing the time required for the solution to pass through the pipette with the time required for the standardized glycerol in water to pass through the same pipette. [0046] For each example disclosing gSass transition temperatures, unless otherwise noted, the glass transition temperatures were calculated using a differential scanning calorimeter.
  • BAYHYDUR 302 (Bayer Material Science, Pittsburgh, PA), used in Examples 21 and 22, is a water-dispersible solvent-free poly-isocyanate crosslinking agent for use in two-component waterborne polyurethane coatings.
  • Example 1 Preparation of a Glycerol/Citric Acid Prepolymer
  • Samples of a glycerol/citric acid prepolymer were prepared by the following method. 4.04 g glycerol and 8.09 g anhydrous citric acid (approximately 1 : 1 moiar ratio) were added to a 20 mL PYREX vial and mixed together. The vial was flushed with nitrogen for one (1) minute and then heated in a 145 0 C oil bath at atmospheric pressure for three (3) hours. After three hours, the vial was removed from the oil bath and cooled to room temperature. The resulting prepolymer was clear and glassy with a viscosity of 6 cps.
  • Example 2 Preparation of a Glycerol/Citric Acid Prepolymer With Varied Reaction Times
  • Samples of a glycerol/citric acid prepolymer were prepared by the following method. 60.69 g glycerol and 140.55 g anhydrous citric acid (approximately 1 :1 molar ratio) were added to a 150 mL Erienmeyer flask and mixed together. The vial was flushed with nitrogen for one (1) minute and then heated in a 160 0 C oil bath at atmospheric pressure with magnetic stirring. Samples were taken in ten (10) minute increments from twenty (20) minutes after heating was begun to eighty (80) minutes after heating was begun. Glass transition temperatures were calculated for each sample. As reaction time increased, the glass transition temperature increased. The results appear in Table 1.
  • Example 2 The glycerol/citric acid prepolymers of Example 2 were heated in a differential scanning calorimeter to obtain their glass transition temperatures. Each sample was heated from -30 0 C to 250 0 C at a constant temperature increase of 10 °C/min. (See Example 2, Table 1.) The resulting cured polymer samples were then retested using a differential scanning calorimeter to determine the glass transition temperatures of the cured polymer. The results appear in Table 2.
  • Samples of a solketal/citric acid prepolymer were prepared by the following method. 5.61 g solketal and 8.09 g anhydrous citric acid (approximately 1:1 molar ratio) were added to a 20 mL PYREX vial and mixed together. The vial was flushed with nitrogen for one (1) minute and then heated in a 140 0 C oil bath at atmospheric pressure for three (3) hours. After three hours, the vial was removed from the oil bath and cooled to room temperature. The prepolymer was light brown and glassy with a viscosity of 14 cps.
  • Example 5 Preparation of a Solketal/Citric Acid/Sulfuric Acid Prepolymer
  • Example 6 Preparation of a Glycerol/Maleic Acid Prepolymer
  • Samples of a glycerol/maleic acid prepolymer were prepared by the following method. 3.97 g glycerol and 7.46 g maleic acid (approximately 1 : 1 molar ratio) were added to a 20 mL PYREX vial and mixed together. The vial was flushed with nitrogen for one (1) minute and then heated in a 145 0 C oil bath at atmospheric pressure for three (3) hours. After three hours, the vial was removed from the oil bath and cooled to room temperature. The resulting prepolymer was clear and glassy with a viscosity of 6 cps.
  • Example 7 Preparation of a Glycerol/Fumaric Acid Prepoiymer and Cured Polymer
  • Samples of a glycerol/ftimaric acid prepolymer were prepared by the following method. 32.00 g glycerol and 58.00 g fumaric acid (approximately 1:1 molar ratio) were added to a 250 mL Erlenmeyer flask and mixed together. The flask was flushed with nitrogen for one (1) minute. The flask was immersed in a 200 0 C oil bath at atmospheric pressure, with stirring, for three (3) hours. After three (3) hours, the flask was removed from the oil bath and the residual white liquid was poured on to a TEFLON sheet and allowed to cool to room temperature. The cooled prepolymer was weighed and the mixture recorded a total weight loss of 12.55 g, indicating a 67% conversion rate. After cooling, the prepolymer was rigid and slightly tacky.
  • the cooled polymer was then heated in a differential scanning calorimeter to obtain its glass transition temperature.
  • a sample was heated from -30 0 C to 250 0 C at a constant temperature increase of 10 °C/min,
  • the resulting cured polymer sample was then retested using the differential scanning calorimeter to determine the glass transition temperature of the cured polymer.
  • the prepolymer had a glass transition temperature of 55.03 0 C and the cured polymer had a glass transition temperature of 71.55 0 C.
  • Samples of a glycerol/anhydrous citric acid prepolymer were prepared by the following method. 21.56 g glycerol and 39.01 g anhydrous citric acid (approximately 1.15:1 molar ratio) were added to a 200 mL Erienmeyer flask and mixed together. The flask was flushed with nitrogen for one (1) minute. The flask was immersed in a 140 0 C oil bath at atmospheric pressure, with stirring, for one (1) hour. After one (1) hour, the flask was removed from the oil bath and the prepolymer was allowed to cool to room temperature.
  • Samples of a glycerol/anhydrous citric acid prepolymer were prepared by the following method. 39.88 g glycerol and 39.87 g anhydrous citric acid (approximately 2.09:1 molar ratio) were added to a 200 niL Erlenmeyer flask and mixed together. The flask was flushed with nitrogen for one (1) minute. The flask was immersed in a 140 0 C oil bath at atmospheric pressure, with stirring, for one (1) hour. After one (1) hour, the flask was removed from the oi! bath and the prepolymer was allowed to cool to room temperature.
  • Samples of a glycerol/anhydrous citric acid prepolymer were prepared by the following method, 360.8 g of glycerol were heated to 135 0 C in a PYREX dish on hot plate. The glycerol was magnetically stirred and under a nitrogen pad at atmospheric pressure. When the glycerol reached 135 0 C, 683 g of anhydrous citric acid (approximately 1.1 :1 molar ratio) were added. The mixture was reheated to 135 0 C over a period of thirty (30) minutes. After reaching 135 0 C, the temperature was maintained for twenty (20) minutes. The mixture was then cooled to room temperature.
  • Example 11 Preparation of a Glycerol/Citric Acid Prepolymer
  • Samples of a glycerol/anhydrous citric acid prepolymer were prepared by the following method. 357.0 g of glycerol were heated to 135 0 C in a PYREX dish on hot plate. The glycerol was magnetically stirred and under a nitrogen pad at atmospheric pressure. When the glycerol reached 135 0 C, 494.8 g of anhydrous citric acid (approximately 1.5:1 molar ratio) were added. The mixture was reheated to 135 0 C over a period of twenty-five (25) minutes. After reaching 135 0 C, the temperature was maintained for twenty (20) minutes. The mixture was then cooled to room temperature. [0071] Example 12: Preparation of a Giycerol/Citric Acid Cured Polymer Foam
  • a sample of 1.69 g of the glycerol/citric acid prepolymer as prepared in Example 1 was heated at approximately 204 0 C at atmospheric pressure in an oven for ten (10) minutes.
  • the cured polymer was cooled.
  • the cured polymer weighed 1.53 g and was a clear, semi-rigid foam with a density of 0.35 g/cc.
  • Example 13 Preparation of a Glycerol/Citric Acid Cured Polymer Foam
  • a sample of 1.78 g of the glycerol/citric acid prepolymer as prepared in Example 9 was heated at approximately 182 0 C at atmospheric pressure in an oven for 30 minutes. The cured polymer was cooled. The cured polymer formed a hard foam.
  • Example 15 Preparation of a Giycerol/Citric Acid Cured Polymer Foam
  • a mixture of 3.03 g of the glycerol/citric acid prepolymer as prepared in Example 8 and 0.6 g glycerol was heated at approximately 182 0 C at atmospheric pressure in an oven for thirty (30) minutes.
  • the cured polymer was cooled.
  • the cured polymer weighed 3.05 g and had formed a clear, small-cell hard foam.
  • the foam softened to a soft foam after continuous exposure to atmospheric moisture for a period of two (2) weeks.
  • Example 16 Preparation of a Giycerol/Citric Acid Cured Polymer Foam
  • a mixture of 1.41 g of the glycerol/citric acid prepolymer as prepared in Example 1 and 0.26 g water was heated at approximately 204 0 C at atmospheric pressure in an oven for ten (10) minutes.
  • the cured polymer was cooied.
  • the cured polymer weighed 1.13 g and had formed a clear, rigid foam with a density of 0.19 g/cc.
  • Example 17 Preparation of a Glycerol/Citric Acid Cured Polymer Glass Coating
  • a homogeneous mixture of 6.75 of the glycerol/citric acid prepolymer as prepared in Example 8 and 2.89 g of diethylene glycol monobutyl ether was prepared by stirring at room temperature. Using a drawdown blade, a 1.5 mm wet film of the homogeneous mixture was applied to a glass slide. The coated glass slide was heated at 160 0 C in an oven for twenty (20) minutes. The resulting cured polymer coating was clear and non-tacky.
  • Example 18 Preparation of a Glycerol/Citric Acid Cured Polymer
  • a small amount of the glycerol/citric acid prepoiymer as prepared in Example 1 was placed between two flat metal strips and two flat wooden strips. Separately, a small amount of the glycerol/citric acid prepolymer as prepared in Example 8 was placed between two flat metal strips and two flat wooden strips. The strips were placed into a 191 0 C oven and allowed to cure for twenty (20) minutes. The strips were then removed from the oven and allowed to cool to room temperature. After cooling, all strips adhered to each other. Attempts were made to separate each set of strips. The metal strips adhered with the cured polymer made from the glycerol/citric acid prepolymer as prepared in Example 1 were difficult to separate by twisting.
  • Example 19 Resistance of a Glycerol/Citric Acid Cured Polymer Adhesive to Common Solvents
  • Example 18 Using the method of Example 18, three sets of adhered metal strips and three sets of adhered wooden strips were made by adhering two strips with a small amount of the glycerol/citric acid prepolymer as prepared in Example 1.
  • One sample from each set (one adhered metal strip set and one adhered wooden strip set) was placed in a 1 normal solution of sodium hydroxide, deionized water, and a 1 normal solution of hydrochloric acid, respectively.
  • the cured polymer adhesive adhering the metal strips dissolved in five (5) minutes in the 1 normal sodium hydroxide solution.
  • the cured polymer adhesive adhering the wooden strips dissolved in ten (10) minutes in the 1 normal sodium hydroxide solution.
  • the cured polymer adhesive adhering both the metal and wooden strips dissolved after forty-five (45) minutes in the deionized water.
  • the cured polymer adhesive adhering both the metal and wooden strips did not dissolve in the 1 normal hydrochloric acid solution.
  • Example 20 Resistance of a Glycerol/Citric Acid Cured Polymer Adhesive to Common Solvents
  • Example 21 Preparation of a Glycerol/Citric Acid Cured Polymer Metal Coating
  • a homogeneous mixture of 70.1 g of the glycerol/citric acid prepolymer as prepared in Example l l, 30 g of diethylene glycol monobutyl ether, and 1.43 g BAYHYDUR 302 (Bayer Material Science, Pittsburgh, PA) was prepared by stirring at room temperature. The mixture foamed slightly. Using a drawdown blade, a 3 mm wet film of the homogeneous mixture was applied to a metal panel. The coated metal panel was air-dried for fifteen (15) minutes and then was heated at 138 0 C in an oven for fifteen (15) minutes. The resulting cured polymer coating was clear and non-tacky.
  • Example 22 Preparation of a Glycerol/Citric Acid Polyurethane Foam Using a Polyisocyanate Crosslinking Agent
  • the foam was initially very brittle, but, upon standing, hardened into a very hard foam.
  • the second sample produced approximately one (1) liter of foam.
  • the foam was firm.
  • the third sample produced about one (1) liter of foam.
  • the foam was flexible and had a Sow density.
  • Example 23 Preparation of a Givcerol/Citric Acid Cured Polymer Coating Using a para-Toluene Sulfonic Acid Catalyst
  • a glycerol/citric acid prepolymer as prepared in Example 1 was made. Based on weight loss, the polymer conversion rate for the prepolymer was approximately 43%. After the prepolymer was cooled to room temperature, it was mixed with deionized water to form a 64 wt % solids solution. Samples of the solution were taken to test the effect of varying additions of para-toluene sulfonic acid (pTSA) catalyst on the required reaction time for the cured polymer. One sample was used as a control without pTSA added. pTSA levels of 1, 5, and 10 wt % (solids pTSA:solids solution) were evaluated.
  • pTSA para-toluene sulfonic acid
  • Example 24 Preparation of a Glycerol/Citric Acid Cured Polymer Coating Using a para-Toluene Sulfonic Acid Catalyst
  • Example 23 was repeated two additional times using different curing temperatures.
  • the glycerol/citric acid prepolymer did not cure into the final cured polymer.
  • the samples were cured for five (5) minutes at 204 0 C, the glycerol/citric acid prepoiymer cured into a final cured polymer.
  • the dissolution test was repeated. After curing at 204 0 C, the 1,00% pTSA addition showed increased resistance to dissolution, and the 5.00% and 10,00% pTSA additions showed no signs of dissolution. None of the cured samples dissolved in MEK.
  • Example 25 Preparation of a Glycerol/Citric Acid/Fumaric Acid Prepolymer and Cured Polymer
  • Samples of a glycerol/citric acid/fumaric acid prepolymer were prepared by the following method. 30.73 g glycerol, 29.04 g anhydrous citric acid, and 32.04 g fumaric acid (approximately 1 :0.5:0.5 molar ratio) were added to a 250 mL Erlenmeyer flask and mixed together, The flask was flushed with nitrogen for one (1) minute. The flask was immersed in a 190 0 C oil bath at atmospheric pressure, with stirring, for twenty (20) minutes, then transferred to a 160 0 C oil bath at atmospheric pressure, with stirring, for thirty-five (35) minutes. Then the flask was removed from the oil bath and allowed to cool to room temperature.
  • the cooled polymer was then heated in a differentia! scanning calorimeter to obtain its glass transition temperature, A sample was heated from -30 0 C to 250 0 C at a constant temperature increase of 10 °C/min.
  • the resulting cured polymer sample was then retested using the differential scanning calorimeter to determine the glass transition temperature of the cured polymer.
  • the prepolymer had a glass transition temperature of 55.94 0 C and the cured polymer had a glass transition temperature of 104.65 "C.
  • Samples of a glycerol/citric acid/sebacic acid prepolymer were prepared by the following method. First, 220 g glycerol was added to a 1.5 L beaker and heated in a 200 "C oil bath while being magnetically stirred. After the glycerol reached 200 0 C, 224 g sebacic acid were added and magnetically stirred at 200 0 C for thirty (30) minutes. After thirty (30) minutes, 200.42 g citric acid were added to the mixture. After the citric acid addition, the temperature was reduced to 160 0 C and the mixture was magnetically stirred at 160 0 C for thirty (30) minutes. After thirty (30) minutes, the polymer was cooled and weighed. Based on weight loss of the cooled polymer, the conversion rate was 50.6%.
  • Example 27 Preparation of a Glyeerol/Fumaric Acid/Sebacic Acid Prepolvmer

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention porte sur des produits de polycondensation réticulés de : (a) polyols choisis dans le groupe constitué par : (1) les polyols avec au moins trois groupes hydroxyle, (2) les formes acétals de (1), et (3) leurs mélanges, et (b) les polyacides choisis dans le groupe constitué par : (1) les polyacides avec au moins deux groupes carboxyliques, (2) les anhydrides de (1), (3) les esters de (1), et (4) leurs mélanges. Les polyesters résultants ont un rapport molaire de polyol à polyacide d'environ 1:3 à environ 3:1 et sont hautement réticulés. Les monomères préférés sont des monomères renouvelables tels que le glycérol, l'acide citrique, l'acide fumarique et l'acide sébacique. L'invention porte sur des procédés de chauffage à deux étapes pour préparer les polyesters de masse moléculaire élevée.
PCT/US2009/065297 2008-11-20 2009-11-20 Polyesters, leurs procédés de préparation et leur utilisation WO2010059925A1 (fr)

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WO2011097428A1 (fr) * 2010-02-05 2011-08-11 The Procter & Gamble Company Modification du point de gélification dans la fabrication de résines alkydes
EP2444441A1 (fr) * 2010-10-19 2012-04-25 Universiteit van Amsterdam Procédé pour la préparation de polymère moussant
EP2628757A1 (fr) 2012-02-17 2013-08-21 Universiteit van Amsterdam Procédé pour la préparation de polymère moussant
US20140080973A1 (en) * 2011-04-14 2014-03-20 Universiteit Van Amsterdam Composite material comprising synthetic filler and specific polymer
US8980774B2 (en) 2012-06-15 2015-03-17 Hexion Inc. Compositions and methods for making polyesters and articles therefrom
EP2718369A4 (fr) * 2011-06-07 2015-04-08 Polymer Phases Inc Polyesters durcis par ultraviolet provenant de matières renouvelables
WO2016061666A1 (fr) * 2014-10-24 2016-04-28 University Of Guelph Formulations de polyesters à base de glycérol et leurs mélanges avec des matières plastiques et leurs procédés de fabrication
WO2016207517A1 (fr) 2015-06-24 2016-12-29 Saint-Gobain Isover Mousses polyester thermodurcies et procede de fabrication
US10323355B2 (en) * 2011-04-14 2019-06-18 Plantics B.V. Composite material comprising bio-filler and specific polymer
FR3075208A1 (fr) * 2017-12-18 2019-06-21 Saint-Gobain Isover Procede de fabrication de mousses polyester thermodurcies avec etape de preoligomerisation
WO2019122669A1 (fr) 2017-12-18 2019-06-27 Saint-Gobain Isover Procede de fabrication de mousses polyester thermodurcies a base de sucres hydrogenes
FR3089984A1 (fr) * 2018-12-18 2020-06-19 Saint-Gobain Isover Utilisation de diols linéaires pour la fabrication de mousses polyester biosourcées

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WO2011097428A1 (fr) * 2010-02-05 2011-08-11 The Procter & Gamble Company Modification du point de gélification dans la fabrication de résines alkydes
US20130266788A1 (en) * 2010-10-19 2013-10-10 Universiteit Van Amsterdam Process for preparing foamed polymer
EP2444441A1 (fr) * 2010-10-19 2012-04-25 Universiteit van Amsterdam Procédé pour la préparation de polymère moussant
WO2012052385A1 (fr) 2010-10-19 2012-04-26 Universiteit Van Amsterdam Procédé pour la préparation de mousse de polymère
CN103249756A (zh) * 2010-10-19 2013-08-14 阿姆斯特丹大学 制备发泡聚合物的方法
US9127120B2 (en) 2010-10-19 2015-09-08 Universiteit Van Amsterdam Process for preparing foamed polymer
US10323355B2 (en) * 2011-04-14 2019-06-18 Plantics B.V. Composite material comprising bio-filler and specific polymer
US10315058B2 (en) * 2011-04-14 2019-06-11 Plantics B.V. Composite material comprising synthetic filler and specific polymer
US20140080973A1 (en) * 2011-04-14 2014-03-20 Universiteit Van Amsterdam Composite material comprising synthetic filler and specific polymer
EP2718369A4 (fr) * 2011-06-07 2015-04-08 Polymer Phases Inc Polyesters durcis par ultraviolet provenant de matières renouvelables
WO2013121033A1 (fr) 2012-02-17 2013-08-22 Universiteit Van Amsterdam Procédé pour la préparation de polymère en mousse
US10745534B2 (en) 2012-02-17 2020-08-18 Plantics B.V. Process for preparing foamed polymer
EP2628757A1 (fr) 2012-02-17 2013-08-21 Universiteit van Amsterdam Procédé pour la préparation de polymère moussant
US10280276B2 (en) 2012-02-17 2019-05-07 Plantics B.V. Process for preparing foamed polymer
US8980774B2 (en) 2012-06-15 2015-03-17 Hexion Inc. Compositions and methods for making polyesters and articles therefrom
US9550894B2 (en) 2012-06-15 2017-01-24 Hexion Inc. Compositions and methods for making polyesters and articles therefrom
WO2016061666A1 (fr) * 2014-10-24 2016-04-28 University Of Guelph Formulations de polyesters à base de glycérol et leurs mélanges avec des matières plastiques et leurs procédés de fabrication
WO2016207517A1 (fr) 2015-06-24 2016-12-29 Saint-Gobain Isover Mousses polyester thermodurcies et procede de fabrication
JP2018524444A (ja) * 2015-06-24 2018-08-30 サン−ゴバン イゾベール 熱硬化ポリエステル発泡体及びその製造方法
US10584224B2 (en) 2015-06-24 2020-03-10 Saint-Gobain Isover Thermoset polyester foams and manufacturing method
RU2716417C2 (ru) * 2015-06-24 2020-03-11 Сэн-Гобэн Изовер Термореактивные сложнополиэфирные пеноматериалы и способ изготовления
FR3037964A1 (fr) * 2015-06-24 2016-12-30 Saint Gobain Isover Mousses polyester thermodurcies et procede de fabrication
FR3075208A1 (fr) * 2017-12-18 2019-06-21 Saint-Gobain Isover Procede de fabrication de mousses polyester thermodurcies avec etape de preoligomerisation
WO2019122669A1 (fr) 2017-12-18 2019-06-27 Saint-Gobain Isover Procede de fabrication de mousses polyester thermodurcies a base de sucres hydrogenes
WO2019122667A1 (fr) * 2017-12-18 2019-06-27 Saint-Gobain Isover Procede de fabrication de mousses polyester thermodurcies avec etape de preoligomerisation
FR3089984A1 (fr) * 2018-12-18 2020-06-19 Saint-Gobain Isover Utilisation de diols linéaires pour la fabrication de mousses polyester biosourcées
WO2020128283A1 (fr) 2018-12-18 2020-06-25 Saint-Gobain Isover Utilisation de diols linéaires pour la fabrication de mousses polyester biosourcées

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