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US20120121839A1 - Process for preparing unsaturated polyester - Google Patents

Process for preparing unsaturated polyester Download PDF

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Publication number
US20120121839A1
US20120121839A1 US13/202,181 US201013202181A US2012121839A1 US 20120121839 A1 US20120121839 A1 US 20120121839A1 US 201013202181 A US201013202181 A US 201013202181A US 2012121839 A1 US2012121839 A1 US 2012121839A1
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US
United States
Prior art keywords
unsaturated polyester
hydroquinone
resin
inhibitor
resin composition
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US13/202,181
Inventor
Marian Henryk Szkudlarek
Johan Franz Gradus Anton Jansen
Stefanus Jacobus Duyvestijn
di Silvana Rensina Antonnietta Silvestre
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DSM IP Assets BV
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DSM IP Assets BV
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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
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
    • Y10T428/1393—Multilayer [continuous layer]

Definitions

  • the present invention relates to a process for preparing unsaturated polyester resin, suitable to be used in the manufacturing of structural parts, comprising itaconate ester units as reactive unsaturations in the resin.
  • Unsaturated polyester resin compositions currently applied for obtaining structural parts often contain considerable quantities of styrene as copolymerizable reactive diluent.
  • styrene may escape during the preparation and curing, but also even during the envisaged long-term use thereof, and causes an undesirable odour, and possibly even also toxic effects.
  • the unsaturated polyester resin is only copolymerizable, the amount of styrene in styrene containing resins can not be reduced further without detrimentally affecting the mechanical properties of the cured composites.
  • an unsaturated polyester resin comprising itaconate ester units as reactive unsaturations is considered homopolymerizable in case at least 25 wt. % of the unsaturated dicarboxylic acid building blocks are capable of homopolymerization, i.e. are itaconic acid building blocks.
  • homopolymerizable unsaturated polyester resins tend to gel (i.e. to polymerize) during its preparation, in particular when applying the standard UP synthesis procedure in which all the raw materials for the resin are mixed and condensed at higher temperatures.
  • the unsaturated polyesters For unsaturated polyesters to be used in the manufacturing of structural parts, the unsaturated polyesters must be able to free radical polymerise (I.e to cure) after having diluted the resin with reactive diluent. This means that gelation during preparation of the unsaturated polyester resin needs to be avoided.
  • WO-A-9727253 describes the synthesis of itaconic based powder coating resins.
  • the homopolymerizable itaconic based unsaturated polyesters have been prepared by either using the prepolymer approach, in which a hydroxyl functional polymer or oligomer is modified in the second step with itaconic acid and condensed to low acid values, or by using the anhydride approach, in which hydroxyl functional polymers are modified with itaconic anhydride resulting in high acid value resins.
  • the unsaturated polyesters as described in this patent application the amount of itaconic acid on the total amount of multifunctional carboxy acids is at most 54%.
  • FR-A-1295841 discloses the preparation of unsaturated polyester comprising itaconate ester units as reactive unsaturations applying the standard unsaturated polyester synthesis procedure in the presence of hydroquinone.
  • a disadvantage of the use of hydroquinone is the viscosity of the obtained resin is relatively high. Lowering the viscosity of the neat resin can be achieved by producing resin with lower molecular weights. However, this may result in a deterioration of the mechanical properties of the cured object.
  • the object of the present invention is to provide a process for preparing unsaturated polyester comprising itaconate ester units as reactive unsaturations, in which the standard unsaturated polyester synthesis procedure can be applied and in which the viscosity of the prepared resin can be decreased compared to when using hydroquinone, while maintaining or even improving the mechanical properties of the cured object.
  • the process comprises reacting at least itaconic acid and/or itaconic anhydride and at least one diol in the presence of an inhibitor having a gelation activity factor less than or equal to 0.5 and having an efficiency factor of from (and including) 0.55 up to 1.
  • an additional advantage of the process of the present invention is that the mechanical properties of a cured object based on a resin prepared with the process according to the invention can be improved, such as tensile strength, tensile modulus, flexural strength, flexural modulus, Barcol hardness and/or HDT.
  • the process of the present invention preferably comprises:
  • gelation activity factor of an inhibitor is defined as the ratio mass gel particles/(mass liquid+mass gel particles), whereby the masses are in g and determined after the resin preparation, whereby the resin preparation is effected using 100 ppm of inhibitor at the start of the resin synthesis.
  • the gelation activity factor is less than or equal to 0.3, more preferably less than or equal to 0.2. Most preferably the gelation activity factor is 0. In case the gelation activity factor is 0, no gel particles are visually observed in the resin. This visual inspection is an easy way to determine if the gelation activity factor is 0.
  • inhibitors with gelation activity factors of 0 are hydroquinone and methyl substituted hydroquinones, such as for example 2-methylhydroquinone.
  • efficiency factor of an inhibitor is defined as the ratio ⁇ 500 / ⁇ 100 in which ⁇ 500 is the viscosity, measured at 125° C. using a cone and plate set-up, of a resin prepared with 500 ppm inhibitor and ⁇ 100 is the viscosity, measured at 125° C. using a cone and plate set-up, of a resin prepared with 100 ppm inhibitor.
  • the inhibitor having a gelation activity factor less than or equal to 0.5 and having an efficiency factor of from 0.55 up to 1 is preferably a methyl substituted hydroquinone, more preferably 2-methyl hydroquinone.
  • the process according to the invention is therefore preferably effected in the presence of 2-methyl hydroquinone.
  • the process according to the invention is preferably effected in the presence of a further inhibitor having an efficiency factor of from 0.3 up to 0.55 (0.55 not included).
  • This further inhibitor preferably has a gelation activity factor less than or equal to 0.5.
  • a preferred further inhibitor is hydroquinone.
  • the process according to the invention is therefore more preferably effected in the presence of 2-methyl hydroquinone and hydroquinone.
  • the invention also relates to a process for preparing an unsaturated polyester resin comprising itaconate ester units as reactive unsaturations by reacting at least itaconic acid and/or itaconic anhydride and at least one diol, wherein the process is effected in the presence of a methyl substituted hydroquinone, preferably in the presence of 2-methyl hydroquinone.
  • the process is effected in the presence of also hydroquinone
  • the process comprises:
  • the inventors found an additional synergistic effect when using a combination of at least one inhibitor with a medium efficiency factor (from (and including) 0.3 up to 0.55) and at least one inhibitor with a high efficiency factor (from (and including) 0.55 up to 1). It has surprisingly been found that using the combination of at least one inhibitor with a medium efficiency factor, such as for example hydroquinone, and at least one inhibitor with a high efficiency factor, such as for example 2-methyl hydroquinone, very good mechanical properties can be obtained of a cured object based on a resin composition comprising reactive diluent and an unsaturated polyester resin comprising itaconate ester as reactive unsaturations.
  • a medium efficiency factor such as for example hydroquinone
  • a high efficiency factor such as for example 2-methyl hydroquinone
  • the molar ratio of the amount of inhibitors with a medium efficiency factor and inhibitors with a high efficiency factor is in the range from 0.2 to 5, more preferably in the range from 0.5 to 2.
  • the process of the present invention is preferably effected in the presence of at least 25 ppm and more preferably at least 50 ppm of inhibitor.
  • the process of the present invention is preferably effected in the presence of at most 2000 ppm, more preferably at most 750 ppm of inhibitor (relative to the amount of raw materials used to prepare the resin).
  • the unsaturated polyester according to the invention comprises itaconate ester units as building blocks having the following structural formula.
  • the itaconic ester units (also referred to as itaconic acid building blocks) contain an ethylenic unsaturation that is able to copolymerize with copolymerizable monomer in which the unsaturated polyester may be diluted.
  • the unsaturated polyester according to the invention can be manufactured by polycondensation of at least a diol and itaconic acid or itaconic acid anhydride as unsaturated dicarboxylic acid.
  • the polycondensation may also be effected in the presence of other dicarboxylic acids containing reactive unsaturations, such as for example maleic acid or anhydride and fumaric acid and/or in the presence of saturated aliphatic dicarboxylic acids or anhydrides, like for example oxalic acid, succinic acid, adipic acid, sebacic acid and/or in the presence of aromatic saturated dicarboxylic acids or anhydrides like for example phthalic acid or anhydride and isophthalic acid.
  • other dicarboxylic acids containing reactive unsaturations such as for example maleic acid or anhydride and fumaric acid and/or in the presence of saturated aliphatic dicarboxylic acids or anhydrides, like for example oxalic acid, succinic acid, adipic acid, sebacic acid and/or in the presence of aromatic saturated dicarboxylic acids or anhydrides like for example phthalic acid or anhydride and isophthalic acid.
  • a diol such as for example 1,2-propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, hydrogenated bisphenol-A. or ethoxylated/propoxylated bisphenol A.
  • the molecular weight of the diol in the unsaturated polyester resin is in the range from 60 to 250 Dalton.
  • at least part of the diols is selected from either isosorbide or 1,3-propanediol or both, preferably derived from a non fossil source like for example corn.
  • the total amount of diacids ranges from 20 to 80 mol % and the total amount of diols ranges from 20 to 80 mol % (in which 100 mol % is sum diols and diacids).
  • the unsaturated polyester according to the invention is preferably homopolymerizable.
  • the unsaturated polyester resin according to the invention preferably at least 25 wt. % of the dicarboxylic acid building blocks are itaconic acid building blocks. More preferably, at least 55 wt. % of the dicarboxylic acid building blocks in the unsaturated polyester according to the invention are itaconic acid building blocks.
  • the unsaturated polyester according to the invention is preferably homopolymerizable.
  • At least part of the itaconic acid or itaconic anhydride is derived from a non-fossil source, for example from corn.
  • the unsaturated polyester comprising itaconate ester units as reactive unsaturations is preferably composed of from 33 to 66 mol % glycol monomers, from 10 to 66 mol % itaconic acid monomers, from 0 to 65 mol % unsaturated diacid monomers (other than itaconic acid monomers, like for example fumaric and maleic acid monomers) and from 0 to 65 mol % diacids other than unsaturated diacid monomers, preferably from 0 to 50 mol % diacids other than unsaturated diacid monomers.
  • the acid value of the itaconate containing unsaturated polyester resin is preferably in the range from 30 to 100 mg KOH/g resin, more preferably from 35 to 75 mg KOH/g resin. As used herein, the acid value of the resin is determined titrimetrically according to ISO 2114-2000.
  • the molar ratio of hydroxyl end groups and carboxylic acid end groups in the unsaturated polyester resin according to the invention is in the range from 0.33 to 0.9. In another embodiment, the molar ratio of hydroxyl end groups and carboxylic acid end groups in the unsaturated polyester resin according to the invention is in the range from 1.1 to 3.
  • the hydroxyl value of the itaconate containing unsaturated polyester resin is preferably higher than 25 and more preferably higher than 40 mg KOH/g resin.
  • the hydroxyl value of the itaconate containing polyester is determined according to ISO 4629-1996.
  • the molecular weight of the unsaturated polyester comprising itaconate ester units as reactive unsaturations is at least 300 Dalton, preferably at least 500 Dalton and more preferably at least 750 Dalton.
  • the molecular weight Mn of the unsaturated polyester comprising itaconate ester units as reactive unsaturations is at most 10.000 Dalton, more preferably at most 5000 Dalton.
  • the molecular weight (Mn) is determined in tetrahydrofurane using GPC according to ISO 13885-1 employing polystyrene standards and appropriate columns designed for the determination of the molecular weights. In a preferred embodiment of the invention, the molecular weight Mn is in the range from 750 to 5000 Dalton.
  • the glass transition temperature T g of the unsaturated polyester is preferably at least ⁇ 70° C. and at most 100° C.
  • the glass transition temperature T g of the unsaturated polyester resin present in the resin composition according to the invention is preferably at least ⁇ 70° C., more preferably at least ⁇ 50° C. and even more preferably at least ⁇ 30° C.
  • the T g of the unsaturated polyester resin present in the resin composition according to the invention is preferably at most 70° C., more preferably at most 50° C. and even more preferably at most 30° C.
  • the T g is determined by means of DSC (heating rate 5° C./min).
  • the present invention further relates to an unsaturated polyester resin composition
  • unsaturated polyester resin composition comprising unsaturated polyester resin that comprises itaconate ester as reactive unsaturations, and a methyl substituted hydroquinone.
  • a preferred methyl substituted hydroquinone is 2-methyl hydroquinone.
  • the resin composition comprises unsaturated polyester that comprises itaconate ester as reactive unsaturations, and a combination of a methyl substituted hydroquinone, preferably 2-methyl hydroquinone, and hydroquinone.
  • the unsaturated polyester that comprises itaconate ester as reactive unsaturations is preferably homopolymerizable.
  • the resin composition comprises homopolymerisable unsaturated polyester resin comprising itaconate ester units, hydroquinone and 2-methylhydroquinone.
  • the amount of hydroquinone and/or methyl substituted hydroquinone is preferably at least 25 ppm, more preferably at least 50 ppm, preferably at most 2000 ppm, more preferably at most 750 ppm (relative to the total resin composition).
  • the composition further comprises reactive diluent.
  • the unsaturated polyester resin according to the invention can be applied as a powder coating resin.
  • the preparation of powder coating compositions is described by Misev in “Powder Coatings, Chemistry and Technology” (pp. 224-300; 1991, John Wiley) hereby incorporated by reference. Therefore the present invention also relates to a powder coating composition comprising the unsaturated polyester prepared with the process according to the invention.
  • the glass transition temperature T g of the unsaturated polyester resin is preferably at least 20° C., more preferably at least 25° C. and even more preferably at least 30° C. and at most 100° C., more preferably at most 80° C. and even more preferably at most 60° C.
  • a common way to prepare a powder coating composition is to mix the separately weight-out components in a premixer, heat the obtained premix, for example in a kneader, preferably in an extruder to obtain an extrudate, cool down the obtained extrudate until it solidifies and crush it into granules or flakes that are further ground to reduce the particle size followed by appropriate classification to obtain a powder coating composition of the right particle size. Therefore, the invention also relates to a process for the preparation of a powder coating composition according to the invention comprising the steps of:
  • the powder coating composition of the present invention may optionally contain the usual additives, such as for example fillers/pigments, degassing agents, flow agents, or (light) stabilizers.
  • flow agents include Byk 361 N.
  • suitable fillers/pigments include metal oxides, silicates, carbonates or sulphates.
  • suitable stabilizers include UV stabilizers, such as for example phosphonites, thioethers or HALS (hindered amine light stabilizers).
  • degassing agents include benzoin and cyclohexane dimethanol bisbenzoate.
  • Other additives, such as additives for improving tribo-chargeability may also be added.
  • the invention relates to a process for coating a substrate comprising the following steps:
  • the powder coating composition of the present invention may be applied using the techniques known to the person skilled in the art, for example using electrostatic spray or electrostatic fluidized bed.
  • the process according to the invention further comprises the step of diluting the unsaturated polyester resin comprising itaconate ester units with one or more reactive diluents to obtain a resin composition suitable to be applied for construction purposes.
  • the unsaturated polyester comprising itaconate ester units is diluted in styrene, dimethyl itaconate and/or a methacrylate.
  • the amount of reactive diluent in such a resin composition according to the invention is usually in the range from 5 to 75 wt. %, preferably in the range from 20 to 60 wt. %, most preferably in the range from 30 to 50 wt. % (relative to the total amount of unsaturated polyester and reactive diluent).
  • a reactive diluent is a diluent that is able to copolymerize with the unsaturated polyester resin.
  • Ethylenically unsaturated compounds can be advantageously used as reactive diluent.
  • styrene, dimethyl itaconate and/or a methacrylate containing compound is used as reactive diluent.
  • styrene, ⁇ -methylstyrene, 4-methylstyrene, (meth)acrylate containing compounds, N-vinylpyrrolidone and/or N-vinylcaprolactam is used as reactive diluent.
  • styrene and/or (meth)acrylate containing compound is preferably used as reactive diluent and more preferably (meth)acrylate containing compound is used as reactive diluent.
  • itaconic acid or an ester of itaconic acid is used as reactive diluent.
  • the reactive diluent comprises an ester of itaconic acid and at least another ethylenically unsaturated compound, such as for example styrene, ⁇ -methylstyrene, 4-methylstyrene, (meth)acrylates, N-vinylpyrrolidone and/or N-vinylcaprolactam.
  • the resin composition preferably comprises an ester of itaconic acid as reactive diluent and styrene as reactive diluent or a methacrylate containing compound as reactive diluent.
  • a preferred ester of itaconic acid is dimethyl itaconate.
  • the resin composition preferably further comprises a co-initiator for the radical curing of the resin composition, in an amount of from 0.00001 to 10 wt % (relative to the total amount of unsaturated polyester and reactive diluent).
  • a preferred co-initiator is an amine or a transition metal compound.
  • the amine co-initiator that may be present in the composition is preferably an aromatic amine and even more preferably a tertiary aromatic amine.
  • Suitable accelerators include N,N-dimethylaniline, N,N-diethylaniline; toluidines and xylidines such as N,N-diisopropanol-para-toluidine; N,N-dimethyl-p-toluidine; N,N-bis(2-hydroxyethyl)xylidine and -toluidine.
  • the amount of amine in the resin composition (relative to the total amount of unsaturated polyester and reactive diluent). is generally at least 0.00001 wt. % and preferably at least 0.01 wt. % and more preferably at least 0.1 wt. %. Generally, the amount of amine in the resin composition is at most 10 wt. %, preferably at most 5 wt. %.
  • transition metal compounds as co-initiator are compounds of a transition metal with an atomic number of in the range from 22 to 29 or with an atomic number in the range from 38 to 49 or with an atomic number in the range from 57 to 79, such as vanadium, iron, manganese, copper, nickel, molybdenum, tungsten, cobalt, chromium compounds.
  • Preferred transition metals are V, Cu, Co, Mn and Fe.
  • radical inhibitors may be added.
  • These radical inhibitors are preferably chosen from the group of phenolic compounds, benzoquinones, hydroquinones, catechols, stable radicals and/or phenothiazines.
  • the amount of radical inhibitor that can be added may vary within rather wide ranges, and may be chosen as a first indication of the gel time as is desired to be achieved.
  • radical inhibitors that can be used in the resin compositions according to the invention are, for instance, 2-methoxyphenol, 4-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butylphenol, 2,4,6-trimethyl-phenol, 2,4,6-tris-dimethylaminomethyl phenol, 4,4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-isopropylidene diphenol, 2,4-di-t-butylphenol, 6,6′-di-t-butyl-2,2′-methylene di-p-cresol, hydroquinone, 2-methylhydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,6-di-t-butylhydroquinone, 2,6-dimethylhydroquinone, 2,3,5-trimethylhydroquinone, catechol, 4-t-
  • the amount of radical inhibitor in the resin composition according to the invention is in the range from 0.0001 to 10% by weight (relative to the total amount of unsaturated polyester and reactive diluent). More preferably, the amount of inhibitor in the resin composition is in the range from 0.001 to 1% by weight. The skilled man quite easily can assess, in dependence of the type of inhibitor selected, which amount thereof leads to good results according to the invention.
  • the present invention further relates to a process for radically curing the resin composition according to the invention, wherein the curing is effected by adding an initiator to the resin composition as described above.
  • the curing is effected at a temperature in the range from ⁇ 20 to +200° C.
  • the initiator is a photoinitiator, a thermal initiator and/or redox initiator.
  • the initiator is a peroxide compound.
  • a photo initiator is capable of initiating curing upon irradiation
  • Photo initiation is understood to be curing using irradiation with light of a suitable wavelength (photo irradiation). This is also referred to as light cure.
  • a photo-initiating system may consist of a photo initiator as such, or may be a combination of a photo initiator and a sensitizer, or may be a mixture of photo initiators, optionally in combination with one or more sensitizers.
  • the photo initiating system that can be used in the context of the present invention can be chosen from the large group of photo-initiating systems known to the skilled person.
  • a vast number of suitable photo initiating systems can be found in, for instance, Volume 3 of “Chemistry and Technology of UV and EB Formulations”, 2 nd Edition, by K. Dietliker and J. V. Crivello (SITA Technology, London; 1998).
  • the thermal initiator can be selected from azo compounds like for example azo isobutyronitril (AlBN), C—C labile compounds like for example benzopinacole, peroxides, and mixtures thereof.
  • the thermal initiator is preferably an organic peroxide, or a combination of two or more organic peroxides.
  • the redox initiator is preferably an organic peroxide in combination with at least one of the above mentioned co-initiators.
  • suitable peroxides are, for instance, hydroperoxides, peroxy carbonates (of the formula —OC(O)OO—), peroxyesters (of the formula —C(O)OO—), diacylperoxides (of the formula —C(O)OOC(O)—), dialkylperoxides (of the formula —OO—), etc.
  • the present invention further also relates to cured objects or structural parts prepared from unsaturated polyester resin compositions as described above, by curing with an initiator as described above.
  • structural resin compositions are capable of providing structural parts. Generally such resin compositions are non-aqueous systems. They contain at most 5% by weight of water, mainly resulting from the reactions during resin preparation. As meant herein, structural parts are considered to have a thickness of at least 0.5 mm and appropriate mechanical properties. End segments where the resin compositions according to the present invention can be applied are for example automotive parts, boats, chemical anchoring, roofing, construction, containers, relining, pipes, tanks, flooring and windmill blades.
  • the present invention in particular relates to cured objects or structural parts obtained by curing of a resin composition according to the invention with an initiator, preferably comprising a peroxide.
  • the curing is preferably effected by moulding, more preferably the curing is effected by compression moulding to obtain in particular a SMC or BMC part.
  • the moulding is preferably effected at a temperature of at least 130° C., more preferably at least 140° C.; and at a temperature of at most 170° C., more preferably of at most 160° C.
  • the diols, diacids and/or anhydrides, optionally inhibitor and catalyst were charged in a vessel equipped with a packed column, a temperature measurement device and inert gas inlet.
  • the mixture was heated slowly by usual methods to 200° C.
  • the mixture was kept at 200° C. until the distillation of water stopped.
  • the packed column was removed and the mixture was kept under reduced pressure until the acid value reached a value below 50 mg KOH/g resin.
  • the vacuum was relieved with inert gas, and the mixture was cooled down to 130° C. or lower.
  • the solid UP resins were obtained in this way.
  • the solid resin was dissolved in a reactive diluent at temperatures below 80° C.
  • Curing was monitored by means of standard gel time equipment. This is intended to mean that both the gel time (T gel or T 25->35° C. ) and peak time (T peak or T 25->peak ) were determined by exotherm measurements according to the method of DIN 16945 when curing the resin with the peroxide as indicated.
  • the viscosity of the dissolved resin was determined at 23° C. using a physica instrument.
  • the viscosity of the neat resin was determined at 125° C. using a cone and plate setup (Brookfield CAP200+cone 3).
  • Resins were prepared via the standard synthesis procedure with the ingredients and inhibitors as listed in table 1.
  • Resins were prepared via the standard synthesis procedure with the listed ingredients in table 2. The resins were cured using 0.5 wt % of a cobalt solution (NL-49P) followed by 2 wt % Trigonox 44B as peroxide. The curing was monitored with the gel time equipment.
  • NL-49P cobalt solution
  • Trigonox 44B as peroxide
  • an inhibitor with a high efficiency factor results in a resin with a lower viscosity, both as neat resin as diluted resin, as well as an improvement in mechanical properties such as tensile strength, tensile modulus, flexural strength and modulus, barcol hardness and thermal stability (as indicated by HDT).
  • Example 4 compared to Comp Ex I and Example 3 shows that there is a synergistic effect regarding decrease of viscosity and further improvement of mechanical properties as exemplified by the thermal stability (HDT), when using a combination of inhibitors with different efficiency factors, i.e. one inhibitor with a high (0.55-1) and one inhibitor with a medium (0.3-0.55) efficiency factor.
  • HDT thermal stability

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Abstract

The present invention relates to a process for preparing an unsaturated polyester resin comprising itaconate ester units as reactive unsaturations by reacting at least itaconic acid and/or itaconic anhydride and at least one diol, wherein the process is effected in the presence of an inhibitor having a gelation activity factor less than or equal to (0.5) and having an efficiency factor of from (0.55) up to 1.

Description

  • The present invention relates to a process for preparing unsaturated polyester resin, suitable to be used in the manufacturing of structural parts, comprising itaconate ester units as reactive unsaturations in the resin.
  • Unsaturated polyester resin compositions currently applied for obtaining structural parts often contain considerable quantities of styrene as copolymerizable reactive diluent. As a result of the presence of styrene, styrene may escape during the preparation and curing, but also even during the envisaged long-term use thereof, and causes an undesirable odour, and possibly even also toxic effects. Thus there is a desire to reduce the styrene emission. Due to the fact that the unsaturated polyester resin is only copolymerizable, the amount of styrene in styrene containing resins can not be reduced further without detrimentally affecting the mechanical properties of the cured composites. Consequently there is a need for homopolymerizable unsaturated polyester resins. As used herein, an unsaturated polyester resin comprising itaconate ester units as reactive unsaturations is considered homopolymerizable in case at least 25 wt. % of the unsaturated dicarboxylic acid building blocks are capable of homopolymerization, i.e. are itaconic acid building blocks.
  • It has however been found that homopolymerizable unsaturated polyester resins tend to gel (i.e. to polymerize) during its preparation, in particular when applying the standard UP synthesis procedure in which all the raw materials for the resin are mixed and condensed at higher temperatures.
  • For unsaturated polyesters to be used in the manufacturing of structural parts, the unsaturated polyesters must be able to free radical polymerise (I.e to cure) after having diluted the resin with reactive diluent. This means that gelation during preparation of the unsaturated polyester resin needs to be avoided.
  • WO-A-9727253 describes the synthesis of itaconic based powder coating resins. In this publication, the standard UP synthesis procedure, in which all the raw materials for the resin are mixed and condensed at higher temperatures, is not applied. The homopolymerizable itaconic based unsaturated polyesters have been prepared by either using the prepolymer approach, in which a hydroxyl functional polymer or oligomer is modified in the second step with itaconic acid and condensed to low acid values, or by using the anhydride approach, in which hydroxyl functional polymers are modified with itaconic anhydride resulting in high acid value resins. The unsaturated polyesters as described in this patent application, the amount of itaconic acid on the total amount of multifunctional carboxy acids is at most 54%.
  • FR-A-1295841 discloses the preparation of unsaturated polyester comprising itaconate ester units as reactive unsaturations applying the standard unsaturated polyester synthesis procedure in the presence of hydroquinone. A disadvantage of the use of hydroquinone is the viscosity of the obtained resin is relatively high. Lowering the viscosity of the neat resin can be achieved by producing resin with lower molecular weights. However, this may result in a deterioration of the mechanical properties of the cured object.
  • The object of the present invention is to provide a process for preparing unsaturated polyester comprising itaconate ester units as reactive unsaturations, in which the standard unsaturated polyester synthesis procedure can be applied and in which the viscosity of the prepared resin can be decreased compared to when using hydroquinone, while maintaining or even improving the mechanical properties of the cured object.
  • This object has been surprisingly been achieved in that the process comprises reacting at least itaconic acid and/or itaconic anhydride and at least one diol in the presence of an inhibitor having a gelation activity factor less than or equal to 0.5 and having an efficiency factor of from (and including) 0.55 up to 1. An additional advantage of the process of the present invention is that the mechanical properties of a cured object based on a resin prepared with the process according to the invention can be improved, such as tensile strength, tensile modulus, flexural strength, flexural modulus, Barcol hardness and/or HDT.
  • The process of the present invention preferably comprises:
      • (i) charging the reactor with itaconic acid and/or itaconic anhydride and optionally other dicarboxylic acids, at least one diol and an inhibitor,
      • (ii) heating the reactor till a temperature of from 180 to 200° C. until the acid value of the formed unsaturated polyester is below 60,
      • (iii) cooling the formed resin, preferably to from 20 to 120° C., and
      • (iv) optionally diluting the resin with reactive diluent,
        wherein the inhibitor has a gelation activity factor less or equal to 0.5 and an efficiency factor of from (and including) 0.55 up to 1.
  • As used herein, gelation activity factor of an inhibitor is defined as the ratio mass gel particles/(mass liquid+mass gel particles), whereby the masses are in g and determined after the resin preparation, whereby the resin preparation is effected using 100 ppm of inhibitor at the start of the resin synthesis.
  • Preferably, the gelation activity factor is less than or equal to 0.3, more preferably less than or equal to 0.2. Most preferably the gelation activity factor is 0. In case the gelation activity factor is 0, no gel particles are visually observed in the resin. This visual inspection is an easy way to determine if the gelation activity factor is 0.
  • Examples of inhibitors with gelation activity factors of 0 are hydroquinone and methyl substituted hydroquinones, such as for example 2-methylhydroquinone.
  • As used herein, efficiency factor of an inhibitor is defined as the ratio η500/η100 in which η500 is the viscosity, measured at 125° C. using a cone and plate set-up, of a resin prepared with 500 ppm inhibitor and η100 is the viscosity, measured at 125° C. using a cone and plate set-up, of a resin prepared with 100 ppm inhibitor.
  • The inhibitor having a gelation activity factor less than or equal to 0.5 and having an efficiency factor of from 0.55 up to 1 is preferably a methyl substituted hydroquinone, more preferably 2-methyl hydroquinone. The process according to the invention is therefore preferably effected in the presence of 2-methyl hydroquinone.
  • The process according to the invention is preferably effected in the presence of a further inhibitor having an efficiency factor of from 0.3 up to 0.55 (0.55 not included). This further inhibitor preferably has a gelation activity factor less than or equal to 0.5. A preferred further inhibitor is hydroquinone. The process according to the invention is therefore more preferably effected in the presence of 2-methyl hydroquinone and hydroquinone.
  • The invention also relates to a process for preparing an unsaturated polyester resin comprising itaconate ester units as reactive unsaturations by reacting at least itaconic acid and/or itaconic anhydride and at least one diol, wherein the process is effected in the presence of a methyl substituted hydroquinone, preferably in the presence of 2-methyl hydroquinone. Preferably, the process is effected in the presence of also hydroquinone Preferably, the process comprises:
      • (i) charging the reactor with itaconic acid and/or itaconic anhydride and optionally other dicarboxylic acids, at least one diol and an inhibitor,
      • (ii) heating the reactor till a temperature of from 180 to 200° C. until the acid value of the formed unsaturated polyester is below 60,
      • (iii) cooling the formed resin, preferably to from 20 to 120° C., and
      • (iv) optionally diluting the resin with reactive diluent,
        wherein the inhibitor is a methyl substituted hydroquinone, preferably 2-methyl hydroquinone. Preferably, the inhibitor is hydroquinone and a methyl substituted hydroquinone. More preferably, the inhibitor is hydroquinone and 2-methyl hydroquinone.
  • Surprisingly the inventors found an additional synergistic effect when using a combination of at least one inhibitor with a medium efficiency factor (from (and including) 0.3 up to 0.55) and at least one inhibitor with a high efficiency factor (from (and including) 0.55 up to 1). It has surprisingly been found that using the combination of at least one inhibitor with a medium efficiency factor, such as for example hydroquinone, and at least one inhibitor with a high efficiency factor, such as for example 2-methyl hydroquinone, very good mechanical properties can be obtained of a cured object based on a resin composition comprising reactive diluent and an unsaturated polyester resin comprising itaconate ester as reactive unsaturations.
  • Preferably, the molar ratio of the amount of inhibitors with a medium efficiency factor and inhibitors with a high efficiency factor is in the range from 0.2 to 5, more preferably in the range from 0.5 to 2.
  • The process of the present invention is preferably effected in the presence of at least 25 ppm and more preferably at least 50 ppm of inhibitor. The process of the present invention is preferably effected in the presence of at most 2000 ppm, more preferably at most 750 ppm of inhibitor (relative to the amount of raw materials used to prepare the resin).
  • The unsaturated polyester according to the invention comprises itaconate ester units as building blocks having the following structural formula.
  • Figure US20120121839A1-20120517-C00001
  • The itaconic ester units (also referred to as itaconic acid building blocks) contain an ethylenic unsaturation that is able to copolymerize with copolymerizable monomer in which the unsaturated polyester may be diluted. The unsaturated polyester according to the invention can be manufactured by polycondensation of at least a diol and itaconic acid or itaconic acid anhydride as unsaturated dicarboxylic acid. The polycondensation may also be effected in the presence of other dicarboxylic acids containing reactive unsaturations, such as for example maleic acid or anhydride and fumaric acid and/or in the presence of saturated aliphatic dicarboxylic acids or anhydrides, like for example oxalic acid, succinic acid, adipic acid, sebacic acid and/or in the presence of aromatic saturated dicarboxylic acids or anhydrides like for example phthalic acid or anhydride and isophthalic acid. In the polymerisation is further used a diol, such as for example 1,2-propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, hydrogenated bisphenol-A. or ethoxylated/propoxylated bisphenol A.
  • According to a preferred embodiment the molecular weight of the diol in the unsaturated polyester resin is in the range from 60 to 250 Dalton. In a preferred embodiment at least part of the diols is selected from either isosorbide or 1,3-propanediol or both, preferably derived from a non fossil source like for example corn.
  • Preferably the total amount of diacids ranges from 20 to 80 mol % and the total amount of diols ranges from 20 to 80 mol % (in which 100 mol % is sum diols and diacids).
  • The unsaturated polyester according to the invention is preferably homopolymerizable. In the unsaturated polyester resin according to the invention, preferably at least 25 wt. % of the dicarboxylic acid building blocks are itaconic acid building blocks. More preferably, at least 55 wt. % of the dicarboxylic acid building blocks in the unsaturated polyester according to the invention are itaconic acid building blocks.
  • The unsaturated polyester according to the invention is preferably homopolymerizable. Preferably at least 25 wt. %, more preferably at least 55 wt. %, of the unsaturated dicarboxylic acid building blocks are itaconic acid building blocks.
  • In a preferred embodiment, at least part of the itaconic acid or itaconic anhydride is derived from a non-fossil source, for example from corn.
  • The unsaturated polyester comprising itaconate ester units as reactive unsaturations is preferably composed of from 33 to 66 mol % glycol monomers, from 10 to 66 mol % itaconic acid monomers, from 0 to 65 mol % unsaturated diacid monomers (other than itaconic acid monomers, like for example fumaric and maleic acid monomers) and from 0 to 65 mol % diacids other than unsaturated diacid monomers, preferably from 0 to 50 mol % diacids other than unsaturated diacid monomers.
  • The acid value of the itaconate containing unsaturated polyester resin is preferably in the range from 30 to 100 mg KOH/g resin, more preferably from 35 to 75 mg KOH/g resin. As used herein, the acid value of the resin is determined titrimetrically according to ISO 2114-2000.
  • In one embodiment, the molar ratio of hydroxyl end groups and carboxylic acid end groups in the unsaturated polyester resin according to the invention is in the range from 0.33 to 0.9. In another embodiment, the molar ratio of hydroxyl end groups and carboxylic acid end groups in the unsaturated polyester resin according to the invention is in the range from 1.1 to 3.
  • The hydroxyl value of the itaconate containing unsaturated polyester resin is preferably higher than 25 and more preferably higher than 40 mg KOH/g resin. As used herein, the hydroxyl value of the itaconate containing polyester is determined according to ISO 4629-1996.
  • Preferably, the molecular weight of the unsaturated polyester comprising itaconate ester units as reactive unsaturations is at least 300 Dalton, preferably at least 500 Dalton and more preferably at least 750 Dalton. Preferably, the molecular weight Mn of the unsaturated polyester comprising itaconate ester units as reactive unsaturations is at most 10.000 Dalton, more preferably at most 5000 Dalton. The molecular weight (Mn) is determined in tetrahydrofurane using GPC according to ISO 13885-1 employing polystyrene standards and appropriate columns designed for the determination of the molecular weights. In a preferred embodiment of the invention, the molecular weight Mn is in the range from 750 to 5000 Dalton.
  • The glass transition temperature Tg of the unsaturated polyester is preferably at least −70° C. and at most 100° C. In case the unsaturated polyester is applied for construction purposes, the glass transition temperature Tg of the unsaturated polyester resin present in the resin composition according to the invention is preferably at least −70° C., more preferably at least −50° C. and even more preferably at least −30° C. The Tg of the unsaturated polyester resin present in the resin composition according to the invention is preferably at most 70° C., more preferably at most 50° C. and even more preferably at most 30° C. As used herein, the Tg is determined by means of DSC (heating rate 5° C./min).
  • The present invention further relates to an unsaturated polyester resin composition comprising unsaturated polyester resin that comprises itaconate ester as reactive unsaturations, and a methyl substituted hydroquinone. A preferred methyl substituted hydroquinone is 2-methyl hydroquinone. In a preferred embodiment, the resin composition comprises unsaturated polyester that comprises itaconate ester as reactive unsaturations, and a combination of a methyl substituted hydroquinone, preferably 2-methyl hydroquinone, and hydroquinone. The unsaturated polyester that comprises itaconate ester as reactive unsaturations is preferably homopolymerizable. In a preferred embodiment, the resin composition comprises homopolymerisable unsaturated polyester resin comprising itaconate ester units, hydroquinone and 2-methylhydroquinone. The amount of hydroquinone and/or methyl substituted hydroquinone is preferably at least 25 ppm, more preferably at least 50 ppm, preferably at most 2000 ppm, more preferably at most 750 ppm (relative to the total resin composition).
  • In one embodiment, the composition further comprises reactive diluent.
  • In one embodiment, the unsaturated polyester resin according to the invention can be applied as a powder coating resin. The preparation of powder coating compositions is described by Misev in “Powder Coatings, Chemistry and Technology” (pp. 224-300; 1991, John Wiley) hereby incorporated by reference. Therefore the present invention also relates to a powder coating composition comprising the unsaturated polyester prepared with the process according to the invention. In case the unsaturated polyester according to the invention is applied in a powder coating composition, the glass transition temperature Tg of the unsaturated polyester resin is preferably at least 20° C., more preferably at least 25° C. and even more preferably at least 30° C. and at most 100° C., more preferably at most 80° C. and even more preferably at most 60° C.
  • A common way to prepare a powder coating composition is to mix the separately weight-out components in a premixer, heat the obtained premix, for example in a kneader, preferably in an extruder to obtain an extrudate, cool down the obtained extrudate until it solidifies and crush it into granules or flakes that are further ground to reduce the particle size followed by appropriate classification to obtain a powder coating composition of the right particle size. Therefore, the invention also relates to a process for the preparation of a powder coating composition according to the invention comprising the steps of:
      • a. mixing the components of the powder coating composition comprising the unsaturated polyester according to the invention to obtain a premix
      • b. heating the obtained premix, preferably in an extruder, to obtain an extrudate
      • c. cooling down the obtained extrudate to obtain a solidified extrudate and
      • d. breaking the obtained solidified extrudate into smaller particles to obtain the powder coating composition
        and preferably comprising the further step of classifying the thus prepared powder particles via a sieve and collect sieve fraction with particle size below 90 μm.
  • The powder coating composition of the present invention may optionally contain the usual additives, such as for example fillers/pigments, degassing agents, flow agents, or (light) stabilizers. Examples of flow agents include Byk 361 N. Examples of suitable fillers/pigments include metal oxides, silicates, carbonates or sulphates. Examples of suitable stabilizers include UV stabilizers, such as for example phosphonites, thioethers or HALS (hindered amine light stabilizers). Examples of degassing agents include benzoin and cyclohexane dimethanol bisbenzoate. Other additives, such as additives for improving tribo-chargeability may also be added.
  • In another aspect, the invention relates to a process for coating a substrate comprising the following steps:
      • 1) applying a powder coating composition comprising the unsaturated polyester according to the invention to a substrate such that the substrate is partially or fully coated with a coating.
      • 2) heating the obtained partially or fully coated substrate for such time and to such temperature such that the coating is at least partially cured.
  • The powder coating composition of the present invention may be applied using the techniques known to the person skilled in the art, for example using electrostatic spray or electrostatic fluidized bed.
  • In a preferred embodiment of the invention, the process according to the invention further comprises the step of diluting the unsaturated polyester resin comprising itaconate ester units with one or more reactive diluents to obtain a resin composition suitable to be applied for construction purposes. In a preferred embodiment, the unsaturated polyester comprising itaconate ester units is diluted in styrene, dimethyl itaconate and/or a methacrylate.
  • The amount of reactive diluent in such a resin composition according to the invention is usually in the range from 5 to 75 wt. %, preferably in the range from 20 to 60 wt. %, most preferably in the range from 30 to 50 wt. % (relative to the total amount of unsaturated polyester and reactive diluent).
  • The diluent will be applied, for instance, for lowering of the viscosity of the resin composition in order to make handling thereof more easy. For clarity purpose, a reactive diluent is a diluent that is able to copolymerize with the unsaturated polyester resin. Ethylenically unsaturated compounds can be advantageously used as reactive diluent. Preferably, styrene, dimethyl itaconate and/or a methacrylate containing compound is used as reactive diluent. In one embodiment of the invention, styrene, α-methylstyrene, 4-methylstyrene, (meth)acrylate containing compounds, N-vinylpyrrolidone and/or N-vinylcaprolactam is used as reactive diluent. In this embodiment, styrene and/or (meth)acrylate containing compound is preferably used as reactive diluent and more preferably (meth)acrylate containing compound is used as reactive diluent. In another embodiment, itaconic acid or an ester of itaconic acid is used as reactive diluent. In a more preferred embodiment, the reactive diluent comprises an ester of itaconic acid and at least another ethylenically unsaturated compound, such as for example styrene, α-methylstyrene, 4-methylstyrene, (meth)acrylates, N-vinylpyrrolidone and/or N-vinylcaprolactam. In this embodiment, the resin composition preferably comprises an ester of itaconic acid as reactive diluent and styrene as reactive diluent or a methacrylate containing compound as reactive diluent. A preferred ester of itaconic acid is dimethyl itaconate.
  • The resin composition preferably further comprises a co-initiator for the radical curing of the resin composition, in an amount of from 0.00001 to 10 wt % (relative to the total amount of unsaturated polyester and reactive diluent). A preferred co-initiator is an amine or a transition metal compound.
  • The amine co-initiator that may be present in the composition is preferably an aromatic amine and even more preferably a tertiary aromatic amine. Suitable accelerators include N,N-dimethylaniline, N,N-diethylaniline; toluidines and xylidines such as N,N-diisopropanol-para-toluidine; N,N-dimethyl-p-toluidine; N,N-bis(2-hydroxyethyl)xylidine and -toluidine. The amount of amine in the resin composition (relative to the total amount of unsaturated polyester and reactive diluent). is generally at least 0.00001 wt. % and preferably at least 0.01 wt. % and more preferably at least 0.1 wt. %. Generally, the amount of amine in the resin composition is at most 10 wt. %, preferably at most 5 wt. %.
  • Examples of suitable transition metal compounds as co-initiator are compounds of a transition metal with an atomic number of in the range from 22 to 29 or with an atomic number in the range from 38 to 49 or with an atomic number in the range from 57 to 79, such as vanadium, iron, manganese, copper, nickel, molybdenum, tungsten, cobalt, chromium compounds. Preferred transition metals are V, Cu, Co, Mn and Fe.
  • After having diluted the unsaturated polyester according to the invention with reactive diluent, additional radical inhibitors may be added. These radical inhibitors are preferably chosen from the group of phenolic compounds, benzoquinones, hydroquinones, catechols, stable radicals and/or phenothiazines. The amount of radical inhibitor that can be added may vary within rather wide ranges, and may be chosen as a first indication of the gel time as is desired to be achieved.
  • Suitable examples of radical inhibitors that can be used in the resin compositions according to the invention are, for instance, 2-methoxyphenol, 4-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butylphenol, 2,4,6-trimethyl-phenol, 2,4,6-tris-dimethylaminomethyl phenol, 4,4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-isopropylidene diphenol, 2,4-di-t-butylphenol, 6,6′-di-t-butyl-2,2′-methylene di-p-cresol, hydroquinone, 2-methylhydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,6-di-t-butylhydroquinone, 2,6-dimethylhydroquinone, 2,3,5-trimethylhydroquinone, catechol, 4-t-butylcatechol, 4,6-di-t-butylcatechol, benzoquinone, 2,3,5,6-tetrachloro-1,4-benzoquinone, methylbenzoquinone, 2,6-dimethylbenzoquinone, napthoquinone, 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-ol (a compound also referred to as TEMPOL), 1-oxyl-2,2,6,6-tetramethylpiperidine-4-one (a compound also referred to as TEMPON), 1-oxyl-2,2,6,6-tetramethyl-4-carboxyl-piperidine (a compound also referred to as 4-carboxy-TEMPO), 1-oxyl-2,2,5,5-tetramethylpyrrolidine, 1-oxyl-2,2,5,5-tetramethyl-3-carboxylpyrrolidine (also called 3-carboxy-PROXYL), galvinoxyl, aluminium-N-nitrosophenyl hydroxylamine, diethylhydroxylamine, phenothiazine and/or derivatives or combinations of any of these compounds.
  • Advantageously, the amount of radical inhibitor in the resin composition according to the invention is in the range from 0.0001 to 10% by weight (relative to the total amount of unsaturated polyester and reactive diluent). More preferably, the amount of inhibitor in the resin composition is in the range from 0.001 to 1% by weight. The skilled man quite easily can assess, in dependence of the type of inhibitor selected, which amount thereof leads to good results according to the invention.
  • The present invention further relates to a process for radically curing the resin composition according to the invention, wherein the curing is effected by adding an initiator to the resin composition as described above. Preferably, the curing is effected at a temperature in the range from −20 to +200° C., The initiator is a photoinitiator, a thermal initiator and/or redox initiator. Preferably, the initiator is a peroxide compound.
  • As meant herein, a photo initiator is capable of initiating curing upon irradiation Photo initiation is understood to be curing using irradiation with light of a suitable wavelength (photo irradiation). This is also referred to as light cure.
  • A photo-initiating system may consist of a photo initiator as such, or may be a combination of a photo initiator and a sensitizer, or may be a mixture of photo initiators, optionally in combination with one or more sensitizers.
  • The photo initiating system that can be used in the context of the present invention can be chosen from the large group of photo-initiating systems known to the skilled person. A vast number of suitable photo initiating systems, can be found in, for instance, Volume 3 of “Chemistry and Technology of UV and EB Formulations”, 2nd Edition, by K. Dietliker and J. V. Crivello (SITA Technology, London; 1998).
  • The thermal initiator can be selected from azo compounds like for example azo isobutyronitril (AlBN), C—C labile compounds like for example benzopinacole, peroxides, and mixtures thereof. The thermal initiator is preferably an organic peroxide, or a combination of two or more organic peroxides.
  • The redox initiator is preferably an organic peroxide in combination with at least one of the above mentioned co-initiators. Examples of suitable peroxides are, for instance, hydroperoxides, peroxy carbonates (of the formula —OC(O)OO—), peroxyesters (of the formula —C(O)OO—), diacylperoxides (of the formula —C(O)OOC(O)—), dialkylperoxides (of the formula —OO—), etc.
  • The present invention further also relates to cured objects or structural parts prepared from unsaturated polyester resin compositions as described above, by curing with an initiator as described above. As used herein, structural resin compositions are capable of providing structural parts. Generally such resin compositions are non-aqueous systems. They contain at most 5% by weight of water, mainly resulting from the reactions during resin preparation. As meant herein, structural parts are considered to have a thickness of at least 0.5 mm and appropriate mechanical properties. End segments where the resin compositions according to the present invention can be applied are for example automotive parts, boats, chemical anchoring, roofing, construction, containers, relining, pipes, tanks, flooring and windmill blades.
  • The present invention in particular relates to cured objects or structural parts obtained by curing of a resin composition according to the invention with an initiator, preferably comprising a peroxide. According to one embodiment, the curing is preferably effected by moulding, more preferably the curing is effected by compression moulding to obtain in particular a SMC or BMC part. The moulding is preferably effected at a temperature of at least 130° C., more preferably at least 140° C.; and at a temperature of at most 170° C., more preferably of at most 160° C.
  • The invention is now demonstrated by means of a series of examples and comparative examples. All examples are supportive of the scope of claims. The invention, however, is not restricted to the specific embodiments as shown in the examples.
    • Standard Resin Synthesis
  • The diols, diacids and/or anhydrides, optionally inhibitor and catalyst were charged in a vessel equipped with a packed column, a temperature measurement device and inert gas inlet. The mixture was heated slowly by usual methods to 200° C. The mixture was kept at 200° C. until the distillation of water stopped. The packed column was removed and the mixture was kept under reduced pressure until the acid value reached a value below 50 mg KOH/g resin. Then the vacuum was relieved with inert gas, and the mixture was cooled down to 130° C. or lower. The solid UP resins were obtained in this way. Next the solid resin was dissolved in a reactive diluent at temperatures below 80° C.
    • Monitoring of Curing
  • Curing was monitored by means of standard gel time equipment. This is intended to mean that both the gel time (Tgel or T25->35° C.) and peak time (Tpeak or T25->peak) were determined by exotherm measurements according to the method of DIN 16945 when curing the resin with the peroxide as indicated.
    • Mechanical Property Determination
  • For the determination of mechanical properties 4 mm castings were prepared. After 16 hrs the castings were released from the mould and postcured using 24 hr at 60 C followed by 24 hr at 80 C.
  • Mechanical properties of the cured objects were determined according to ISO 527-2. The Heat Distortion Temperature (HDT) was measured according to ISO 75-A.
  • The viscosity of the dissolved resin was determined at 23° C. using a physica instrument. The viscosity of the neat resin was determined at 125° C. using a cone and plate setup (Brookfield CAP200+cone 3).
    • Comparative experiments A-G and Example 1
  • Resins were prepared via the standard synthesis procedure with the ingredients and inhibitors as listed in table 1.
  • TABLE 1
    Comp E
    Ex 1 Comp A Comp B Comp C Comp D (no inhibitor added) Comp F Comp G (
    Itaconic acid (g) 732 732 732 732 732 732 732 732
    Propylene glycol (g) 471 471 471 471 471 471 471 471
    2-methyl hydroquinone 0.12
    (100 ppm)
    Hydroquinone 0.12
    (100 ppm)
    t-butyl hydroquinone 0.12
    (100 ppm)
    Tempol 0.12
    (100 ppm)
    p-methoxy phenol 0.12
    (100 ppm)
    Benzoquinone 0.12
    (100 ppm)
    2-methyl 0.12
    benzoquinone (100 ppm)
    Acid value of the resin 44 45 45 45 45 45 45 45
    (mgKOH/g resin)
    Viscosity @ 125° C. 3.62 9.21 Gel Gel Gel Gel Gel Gel
    (cone and plate) dPa · s
    Gelation Acitity factor 0 0 1 1 1 Not relevant 1 1
  • These experiments clearly show the fact that employing itaconates in the preparation of unsaturated polyesters the inhibitors should be inhibitors with a low gelation activity factor as employing inhibitors with a high gelation activity factor resulted in a gel which can no longer be used. Furthermore, comparing Example 1 with Comparative Experiments A shows that methyl substituted hydroquinone is a more efficient inhibitor compared to hydroquinone because the viscosity of the neat resin at 125° C. is much lower.
    • Comparative Experiments H-I and Example 2-4
  • Resins were prepared via the standard synthesis procedure with the listed ingredients in table 2. The resins were cured using 0.5 wt % of a cobalt solution (NL-49P) followed by 2 wt % Trigonox 44B as peroxide. The curing was monitored with the gel time equipment.
  • TABLE 2
    Comp H Comp I Example 2 Example 3 Example 4
    Itaconic acid (g) 732 732 732 732 732
    Propylene glycol (g) 471 471 471 471 471
    Hydroquinone 0.12 (100 ppm) 0.6 (500 ppm) 0.3 (250 ppm)
    2-methyl hydroquinone 0.12 (100 ppm) 0.6 (500 ppm) 0.3 (250 ppm)
    Viscosity @ 125° C. (cone and plate) 9.21 4.25 3.62 2.43 2.05
    dPa · s
    Acid value of the resin (mgKOH/g 45 44 44 44 46
    resin)
    Efficiency factor = η500 ppm/η100 ppm 0.46 0.67
    Reactive diluent styrene styrene Styrene styrene styrene
    Solid content % 65 65 65 65 65
    Viscosity @23° C. mPa · s 1518 816 839 747 623
    Tensile strength (MPa) 46 58 72 79 74
    Tensile modulus (GPa) 2.1 2.6 3.4 3.4 3.8
    Elongation at break (%) 4.7 4.3 2.9 4 2.7
    Flexural strength (MPa) 73 87 105 106 117
    Flexural modulus (GPa) 2.3 2.8 3.2 3.3 3.8
    Barcol Hardness 27 35 34 40 48
    HDT (° C.) 77 85 96 95 103
  • These examples show that hydroquinone has a medium efficiency factor (=η500ppm/η100ppm). and 2-methyl hydroquinone has a high efficiency factor. Furthermore Ex 2 vs Comp Ex H or Ex 3 vs Comp Ex I shows that an inhibitor with a high efficiency factor results in a resin with a lower viscosity, both as neat resin as diluted resin, as well as an improvement in mechanical properties such as tensile strength, tensile modulus, flexural strength and modulus, barcol hardness and thermal stability (as indicated by HDT). Furthermore Example 4 compared to Comp Ex I and Example 3 shows that there is a synergistic effect regarding decrease of viscosity and further improvement of mechanical properties as exemplified by the thermal stability (HDT), when using a combination of inhibitors with different efficiency factors, i.e. one inhibitor with a high (0.55-1) and one inhibitor with a medium (0.3-0.55) efficiency factor.

Claims (16)

1. Process for preparing an unsaturated polyester resin comprising itaconate ester units as reactive unsaturations by reacting at least itaconic acid and/or itaconic anhydride and at least one diol, wherein the process is effected in the presence of an inhibitor having a gelation activity factor less than or equal to 0.5 and having an efficiency factor of from 0.55 up to 1.
2. Process according to claim 1, wherein the inhibitor having a gelation activity factor less than or equal to 0.5 and having an efficiency factor of from 0.55 up to 1 is a methyl substituted hydroquinone.
3. Process according to claim 1, wherein the inhibitor having a gelation activity factor less than or equal to 0.5 and having an efficiency factor of from 0.55 up to 1 is 2-methyl hydroquinone.
4. Process according to claim 1, wherein the process is effected in the presence of a further inhibitor having an efficiency factor of from 0.3 up to 0.55.
5. Process according to claim 4, wherein the further inhibitor is hydroquinone.
6. Process according to claim 1, wherein the gelation activity factor is 0.
7. Process according to claim 1, wherein the unsaturated polyester resin is a homopolymerizable unsaturated polyester.
8. Process according to claim 1, wherein the process is effected in the presence of hydroquinone and 2-methyl hydroquinone.
9. Resin composition comprising unsaturated polyester resin comprising itaconate ester units and a methyl substituted hydroquinone.
10. Resin composition according to claim 9, wherein the methyl substituted hydroquinone is 2-methyl hydroquinone and the resin composition further comprises hydroquinone.
11. Resin composition according to claim 9, wherein the unsaturated polyester resin comprising itaconate ester units is homopolymerizable.
12. Resin composition according to claim 9, wherein the composition further comprises reactive diluent.
13. Cured object or structural part obtained from a resin composition according to claim 9 by curing with an initiator.
14. Cured object or structural part according to claim 13, wherein the initiator comprises a peroxide
15. Use of the cured object or structural part of claim 13 in automotive parts, boats, chemical anchoring, roofing, construction, containers, relining, pipes, tanks, flooring or windmill blades.
16. Powder coating composition comprising an unsaturated polyester resin composition according to claim 9.
US13/202,181 2009-03-25 2010-03-24 Process for preparing unsaturated polyester Abandoned US20120121839A1 (en)

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Families Citing this family (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102361906B (en) * 2009-03-25 2014-07-09 帝斯曼知识产权资产管理有限公司 Unsaturated polyester
JP5610194B2 (en) * 2010-04-19 2014-10-22 三菱レイヨン株式会社 Polyester resin for toner and method for producing the same
JP5541522B2 (en) * 2010-11-04 2014-07-09 Ｄｉｃ化工株式会社 Molding material, molded product, flooring and method for producing molded product
WO2012130963A1 (en) * 2011-03-30 2012-10-04 Dsm Ip Assets B.V. Unsaturated polyester resin composition
WO2012130975A1 (en) * 2011-03-30 2012-10-04 Dsm Ip Assets B.V. Unsaturated polyester resin composition
US8933170B2 (en) 2011-05-18 2015-01-13 Sabic Global Technologies B.V. Bio-sourced transparent and ductile polycarbonate blends
US8841404B2 (en) 2011-05-18 2014-09-23 Sabic Global Technologies B.V. Flame retardant bio-based polymer blends
US20120296019A1 (en) * 2011-05-18 2012-11-22 Haseena Aripuram Parakkal High heat and flame retardant bio-sourced polycarbonate
CN103059310B (en) * 2011-10-21 2015-04-29 中国科学院化学研究所 Double-bond-containing biodegradable polyester multi-block copolymer and preparation method thereof
JP2013159715A (en) * 2012-02-06 2013-08-19 Panasonic Corp Unsaturated polyester resin material and fiber-reinforced plastic-molded material obtained by molding the same
WO2013148933A1 (en) * 2012-03-30 2013-10-03 Segetis, Inc. Reactive diluents, methods of reacting, and thermoset polymers derived therefrom
JPWO2013183196A1 (en) * 2012-06-05 2016-01-28 パナソニックＩｐマネジメント株式会社 Unsaturated polyester resin, unsaturated polyester resin material, and fiber-reinforced plastic molding material formed by molding unsaturated polyester resin material
WO2013187401A1 (en) 2012-06-13 2013-12-19 三菱レイヨン株式会社 Toner polyester resin, method for producing same, and toner
JP6446781B2 (en) * 2012-12-07 2019-01-09 三菱ケミカル株式会社 Polyester resin for toner, method for producing the same, and toner
CN103351915A (en) * 2013-06-19 2013-10-16 安徽富华电子集团有限公司 Metal wiredrawing lubricant and preparation method thereof
CN103351923A (en) * 2013-06-19 2013-10-16 安徽富华电子集团有限公司 Copper and aluminum wiredrawing liquid and preparation method thereof
CN103351920A (en) * 2013-06-19 2013-10-16 安徽富华电子集团有限公司 Lubricant for high-speed fine wiredrawing of copper wire and preparation method thereof
CN103351919A (en) * 2013-06-19 2013-10-16 安徽富华电子集团有限公司 Microemulsion semisynthetic copper wiredrawing liquid composition and preparation method thereof
CN103351918A (en) * 2013-06-19 2013-10-16 安徽富华电子集团有限公司 Aqueous wiredrawing lubricant and preparation method thereof
EP2821454B1 (en) 2013-07-02 2017-03-29 Nitto Europe N.V Unsaturated photo-curable bio-based adhesive composition
CN103819621B (en) * 2014-01-24 2016-03-23 青岛科技大学 A kind of preparation method of methylene-succinic acid class copolyesters of macromolecular network structure
SG11201608263PA (en) * 2014-04-04 2016-10-28 Ppg Ind Ohio Inc Branched polyester polymers and soft touch coatings comprising the same
EP2957611A1 (en) 2014-06-20 2015-12-23 Nitto Denko Corporation Debondable adhesive composition
EP2957303A1 (en) 2014-06-20 2015-12-23 Nitto Denko Corporation Curable composition and skin adhesive
CN106459656A (en) 2014-06-24 2017-02-22 比克化学股份有限公司 Unsaturated polyester resin systems with latent thickening tendencies
CN104387930A (en) * 2014-12-09 2015-03-04 韦良富 Anticorrosive powder paint for automobile accessories
PL235856B1 (en) * 2015-03-03 2020-11-02 Pulverit S P A Coating composition in the form of the thermally hardened powder
DE102015105993A1 (en) * 2015-04-20 2016-10-20 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Means for generating a printed image and use thereof as printing ink, in particular for 3D printing
JP2016103029A (en) * 2015-12-24 2016-06-02 三菱レイヨン株式会社 Toner including polyester resin for toner
CN110114386A (en) * 2016-11-01 2019-08-09 亚什兰许可和知识产权有限公司 Good weatherability, the anti-ultraviolet unsaturated polyester resin containing fumaric acid
US10655025B2 (en) * 2018-05-17 2020-05-19 Xerox Corporation Curable unsaturated crystalline polyester powder and methods of making the same
JP7338281B2 (en) * 2019-07-12 2023-09-05 コニカミノルタ株式会社 Products containing plastic parts and their recycling methods
TW202138424A (en) 2020-02-17 2021-10-16 日商東洋紡股份有限公司 Aromatic polyester and method for producing same
JP2023514383A (en) * 2020-02-24 2023-04-05 エーシーアール ザ サード ビー．ブイ． UNSATURATED POLYESTER RESIN COMPOSITION AND METHOD FOR MANUFACTURING SAME
EP4165139A4 (en) * 2020-06-12 2024-06-19 Swimc Llc Unsaturated resins and coating compositions therefrom
KR102484293B1 (en) * 2020-09-16 2023-01-05 에코리엔트샤인 (주) Environment-friendly composition for phosphorescent stone materials having improved durability and constructing method for road flooring using the same
CN114644730B (en) * 2020-12-17 2023-04-25 北京化工大学 Itaconic acid ester resin with high light transmittance and preparation method thereof
PT117321B (en) 2021-07-01 2024-07-02 Inst Superior Tecnico HIGH PERFORMANCE UNSATURATED POLYESTER RESINS BASED ON RENEWABLE RESOURCES
DE102022212050A1 (en) 2022-11-14 2024-05-16 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Composition for producing a polymer, use of the composition for producing a polymer, and polymer
CN116199871B (en) * 2023-02-24 2024-08-09 四川轻化工大学 All-bio-based polyester and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1295841A (en) * 1961-07-24 1962-06-08 Basf Ag Process for the production of polymers based on unsaturated polyester resins, stable to saponifying agents
US4409077A (en) * 1977-10-25 1983-10-11 Sumitomo Chemical Co., Ltd. Ultraviolet radiation curable coating composition
US5942556A (en) * 1996-11-27 1999-08-24 Ppg Industries Ohio, Inc. Stabilized radiation curable compositions based on unsaturated ester and vinyl ether compounds
US6541657B2 (en) * 2000-03-24 2003-04-01 Nippon Shokubai Co., Ltd Unsaturated carboxylate and its production process and use

Family Cites Families (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2610961A (en) † 1949-12-31 1952-09-16 Gen Electric Stabilization of thixotropic compositions comprising polyesters with quinone
US2632753A (en) † 1950-02-23 1953-03-24 Libbey Owens Ford Glass Co Polyester compositions stabilized with p-benzoquinone
US2610168A (en) † 1951-08-17 1952-09-09 Libbey Owens Ford Glass Co Polyesters stabilized with substituted p-benzoquinones
GB806730A (en) * 1955-12-21 1958-12-31 Basf Ag Improvements in the production of unsaturated polyester resins and of copolymers therefrom
GB901603A (en) † 1960-01-16 1962-07-18 Bayer Ag Solutions of unsaturated copolymerisable polyester resins in monomeric unsaturated copolymerisable compounds
DE1269989B (en) * 1961-05-26 1968-06-12 Atlas Chem Ind Solidified fiber fleece as reinforcement for composite materials
US3210441A (en) † 1961-09-11 1965-10-05 Glidden Co Air-drying unsaturated polyester resins and coating compositions employing same
GB1049890A (en) 1962-11-30 1966-11-30 Albert Ag Chem Werke Improvements in or relating to resins
US3326860A (en) * 1962-12-04 1967-06-20 Union Oil Co Polyester resin composition
FR1539073A (en) * 1966-07-29 1968-09-13 Cincinnati Milling Machine Co Copper coated plastic panels, and their manufacture
NL135706C (en) * 1966-07-29 1900-01-01
US3539441A (en) † 1967-12-15 1970-11-10 Ppg Industries Inc Emulsifiable compositions
GB1282854A (en) † 1969-02-14 1972-07-26 Toa Gosei Chem Ind Polyester polyacrylate monomers and oligomers, their preparation and compositions comprising them
NL166489C (en) † 1972-06-20 1981-08-17 Akzo Nv METHOD FOR STABILIZING BY U.V. Slightly curable unsaturated polyester resins.
US3953403A (en) 1972-06-28 1976-04-27 Toyo Boseki Kabushiki Kaisha Powder coating composition
DE2251469C3 (en) * 1972-10-20 1978-06-08 Bayer Ag, 5090 Leverkusen Highly reactive resin compositions that can be hardened by UV light and contain acrylamide methylol ether
DE2427275C2 (en) 1974-06-06 1982-02-25 Bayer Ag, 5090 Leverkusen Unsaturated polyester resins that are difficult to saponify
US4112018A (en) * 1974-06-06 1978-09-05 Bayer Aktiengesellschaft Unsaturated polyester resins suitable for the production of cross-linked polyesters which are difficult to saponify
FR2288118A1 (en) * 1974-10-16 1976-05-14 Hitachi Ltd Unsatd polyester with improved hardening reactivity - prepd by ring opening polymerisation of acid anhydride and alkylene oxide
US4303696A (en) * 1975-05-07 1981-12-01 Design Cote Corp. Radiation curing of prepolymer coating compositions
US4539390A (en) * 1984-03-29 1985-09-03 Eastman Kodak Company High molecular weight unsaturated polyesters of cyclohexanedimethanols
DE3643007A1 (en) * 1986-12-17 1988-06-30 Basf Ag CURABLE POLYESTER MOLDING MATERIALS
US4788108A (en) * 1987-06-15 1988-11-29 Ppg Industries, Inc. Ultraviolet light curable compositions based on iminated unsaturated polyesters for application to porous substrates
MX169697B (en) * 1987-12-28 1993-07-19 Ppg Industries Inc IMPROVEMENTS TO RADIATION-FRAGABLE COMPOSITIONS BASED ON UNSATURATED POLYESTERS AND COMPOUNDS HAVING AT LEAST TWO GROUPS OF VINYL ETER
CA2017071A1 (en) * 1989-06-02 1990-12-02 Stephen H. Harris Unsaturated polyester gel coats containing 2-methyl-1,3-propanediol
US5408013A (en) 1991-08-12 1995-04-18 Hitachi Chemical Co., Ltd. Unsaturated polyester resin composition and sheet-form molding material using the same
JPH05320579A (en) * 1992-05-19 1993-12-03 Kanegafuchi Chem Ind Co Ltd Topcoating composition
DE4314866A1 (en) 1993-05-05 1994-11-10 Bayer Ag Radically curable lacquer composition and its use as furniture lacquer
DE4321533A1 (en) * 1993-06-29 1995-01-12 Herberts Gmbh Binder and coating composition, their production and use
JPH08134339A (en) * 1994-11-09 1996-05-28 Hitachi Chem Co Ltd Unsaturated polyester resin composition, production of cured product and molding material
JP3241967B2 (en) * 1995-05-01 2001-12-25 三菱自動車工業株式会社 Vibration-damping resin composition and structural vibration-damping resin molding using the same
US5650531A (en) † 1995-06-28 1997-07-22 Industrial Technology Research Institute Highly pendant phosphorus-containing reactive oligomer flame retardant
CN1067407C (en) * 1995-09-26 2001-06-20 财团法人工业技术研究院 Making method for phosphorus series non-inflammable unsaturated polyester
NL1002153C2 (en) 1996-01-23 1997-08-04 Dsm Nv Radiation curable powder paint binder composition.
US6025409A (en) * 1996-02-29 2000-02-15 Dsm N.V. Radiation curable coating composition
JPH1017662A (en) * 1996-07-03 1998-01-20 Showa Highpolymer Co Ltd Production of high-melting unsaturated polyester
JPH1036766A (en) * 1996-07-26 1998-02-10 Nippon Synthetic Chem Ind Co Ltd:The Resin composition for patty
BE1010774A3 (en) † 1996-11-28 1999-01-05 Dsm Nv Binding compound for coatings
JP3770350B2 (en) * 1997-03-07 2006-04-26 東洋紡績株式会社 High molecular weight unsaturated polyester resin and method for producing the same
JP3642669B2 (en) * 1997-12-18 2005-04-27 三井化学株式会社 Biodegradable soft lure
JP3439352B2 (en) * 1998-09-24 2003-08-25 住友電気工業株式会社 Thermoplastic polyester resin, insulated wires, electrically insulated cables and heat shrink tubing from it
JP2000169569A (en) * 1998-12-07 2000-06-20 Toyobo Co Ltd Polyester polymerization catalyst and polyester produced using same
JP2001152000A (en) * 1999-11-25 2001-06-05 Takeda Chem Ind Ltd Flame-retardant unsaturated polyester resin composition
JP2001002769A (en) * 1999-06-25 2001-01-09 Takeda Chem Ind Ltd Phosphorus-containing unsaturated polyester resin and resin composition containing the same
JP2002212274A (en) * 2001-01-17 2002-07-31 Hitachi Chem Co Ltd Unsaturated polyester resin composition and its manufacturing method, and thermosetting molding material using the same and plastic molded article
JP2003183370A (en) * 2001-12-25 2003-07-03 Nippon Chem Ind Co Ltd Phosphorus-containing unsaturated polyester, its manufacturing method, phosphorus-containing unsaturated polyester resin, phosphorus-containing unsaturated polyester resin composition, molding material obtained by using the same, and laminated board
US6608167B1 (en) * 2002-03-26 2003-08-19 E. I. Du Pont De Nemours And Company Bis(2-hydroxyethyl isosorbide); preparation, polymers derived therefrom, and enduses thereby
US6818730B2 (en) * 2002-04-26 2004-11-16 E. I. Du Pont De Nemours And Company Process to produce polyesters which incorporate isosorbide
DE10225943A1 (en) * 2002-06-11 2004-01-08 Basf Ag Process for the preparation of esters of polyalcohols
KR100991962B1 (en) * 2002-10-08 2010-11-04 앳슈랜드 라이센싱 앤드 인텔렉츄얼 프라퍼티 엘엘씨 Dicapped Unsaturated Polyester Laminating Polyester Resins with Reduced Emission Levels of VOC's
JP2004217799A (en) * 2003-01-15 2004-08-05 Japan Composite Co Ltd Method for manufacturing unsaturated polyester and unsaturated polyester resin
JP2004250548A (en) * 2003-02-19 2004-09-09 Osaka Gas Co Ltd Resin composition for lining containing unsaturated polyester resin
ATE412718T1 (en) 2004-05-07 2008-11-15 Cytec Surface Specialties Sa RADIATION CURED LOW-GLOSS POWDER COATS
DE102004049544A1 (en) * 2004-10-12 2006-04-13 Degussa Ag Radiation-curable modified, unsaturated, amorphous polyesters
CN1292014C (en) * 2004-11-18 2006-12-27 华东理工大学华昌聚合物有限公司 Synthesis of p-phenyl unsaturated polyester resin by using waste polyester material
US20060160986A1 (en) * 2005-01-18 2006-07-20 Hazen Benjamin R Low viscosity unsaturated polyester resin with reduced VOC emission levels
DE102005002388A1 (en) * 2005-01-19 2006-07-27 Degussa Ag Aqueous, radiation-curable modified, unsaturated, amorphous polyester
EP1715388B1 (en) * 2005-04-22 2008-11-19 Canon Kabushiki Kaisha Toner
CN100498556C (en) * 2005-04-22 2009-06-10 佳能株式会社 Toner
US8188166B2 (en) † 2005-07-29 2012-05-29 Aoc, Llc Unsaturated polyester resin compositions with improved weatherability
DE102006012274A1 (en) * 2006-03-15 2007-09-20 Votteler Lackfabrik Gmbh & Co. Kg Lacquer for surface coating of molded parts
JP4883346B2 (en) * 2006-03-23 2012-02-22 Ｄｉｃ株式会社 Active energy ray-curable resin composition for powder coating
US7629124B2 (en) * 2006-06-30 2009-12-08 Canon U.S. Life Sciences, Inc. Real-time PCR in micro-channels
JP2010503736A (en) 2006-09-15 2010-02-04 スティッチング ダッチ ポリマー インスティテュート Process for the production of polyesters based on dianhydrohexitol
JP4668887B2 (en) * 2006-11-22 2011-04-13 株式会社リコー Toner, image forming apparatus using the same, image forming method, and process cartridge
JP4662958B2 (en) * 2007-03-05 2011-03-30 株式会社リコー Toner and two-component developer
US8114560B2 (en) * 2007-05-11 2012-02-14 Ricoh Company, Ltd. Toner, image forming apparatus, image forming method, and process cartridge using the toner
CN101250256B (en) * 2008-03-28 2012-07-04 武汉理工大学 Method for synthesizing unsaturated polyester resin
CN102365338A (en) * 2009-02-27 2012-02-29 Ppg工业俄亥俄公司 Biomass derived radiation curable liquid coatings
CN102356357B (en) * 2009-03-19 2015-04-22 三菱化学成像公司 Bio-toner containing bio-resin, method for making the same, and method for printing with bio-toner containing bio-resin
CN102361906B (en) * 2009-03-25 2014-07-09 帝斯曼知识产权资产管理有限公司 Unsaturated polyester
US9034982B2 (en) * 2009-08-12 2015-05-19 Ashland Licensing And Intellectual Property, Llc Formulations comprising isosorbide-modified unsaturated polyester resins and low profile additives which produce low shrinkage matrices

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1295841A (en) * 1961-07-24 1962-06-08 Basf Ag Process for the production of polymers based on unsaturated polyester resins, stable to saponifying agents
US4409077A (en) * 1977-10-25 1983-10-11 Sumitomo Chemical Co., Ltd. Ultraviolet radiation curable coating composition
US5942556A (en) * 1996-11-27 1999-08-24 Ppg Industries Ohio, Inc. Stabilized radiation curable compositions based on unsaturated ester and vinyl ether compounds
US6541657B2 (en) * 2000-03-24 2003-04-01 Nippon Shokubai Co., Ltd Unsaturated carboxylate and its production process and use

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US20120095160A1 (en) 2012-04-19
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BRPI1009833A2 (en) 2016-03-15
ES2525146T3 (en) 2014-12-18
CN102361905B (en) 2013-11-06
CN102361905A (en) 2012-02-22
CN102361907A (en) 2012-02-22
BRPI1011702A2 (en) 2016-03-22
CN102361908B (en) 2014-07-09
ES2477891T3 (en) 2014-07-18
ES2525146T5 (en) 2018-04-12
JP2012521466A (en) 2012-09-13
CN102361907B (en) 2014-06-04
CN102361906A (en) 2012-02-22
EP2411441A1 (en) 2012-02-01
ES2524373T3 (en) 2014-12-05
BRPI1011702B1 (en) 2020-10-20
BRPI1011703B1 (en) 2020-09-15
JP2012521467A (en) 2012-09-13
US20120101226A1 (en) 2012-04-26
JP2012521468A (en) 2012-09-13
BRPI1011703A2 (en) 2016-03-22
BRPI1011723B1 (en) 2020-09-15
EP2411442B1 (en) 2015-09-30
CN102361908A (en) 2012-02-22
WO2010108962A1 (en) 2010-09-30
EP2411445B2 (en) 2017-12-20
WO2010108964A1 (en) 2010-09-30
EP2411444B1 (en) 2014-09-24

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