WO2017023173A1 - Composition mélange maître de polyester - Google Patents

Composition mélange maître de polyester Download PDF

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Publication number
WO2017023173A1
WO2017023173A1 PCT/NL2016/050568 NL2016050568W WO2017023173A1 WO 2017023173 A1 WO2017023173 A1 WO 2017023173A1 NL 2016050568 W NL2016050568 W NL 2016050568W WO 2017023173 A1 WO2017023173 A1 WO 2017023173A1
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WO
WIPO (PCT)
Prior art keywords
poly
furandicarboxylate
composition according
nucleating agent
ethylene
Prior art date
Application number
PCT/NL2016/050568
Other languages
English (en)
Inventor
Hajime Nakajima
Jesper Gabriël VAN BERKEL
Jeffrey John Kolstad
Original Assignee
Furanix Technologies B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Furanix Technologies B.V. filed Critical Furanix Technologies B.V.
Publication of WO2017023173A1 publication Critical patent/WO2017023173A1/fr

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Classifications

    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • WO 2013/062408 discloses a process, wherein the dimethyl ester of 2,5-FDCA is transesterified with ethylene glycol, or bis(2-hydroxyethyl)-2,5-furandicarboxylate is used as starting material.
  • the transesterification product or this starting material is then subjected to polycondensation and after a drying/crystallization step the polycondensate is subjected to solid state polymerization to enhance the molecular weight of the polycondensate.
  • the product may be used as water bottles, fibers or films.
  • KR 20140003167 describes a polyester polymer with excellent transparency which is manufactured by using a biomass originated furandicarboxylate ester compound with ethylene glycol.
  • the polyesters thus produced yield b* values in the range of 6 to 10.
  • furandicarboxylic acid has been used. These polyesters have more color and have b* values in the range 25 to 34.
  • the beneficial effect can be achieved when the nucleating agent is added to the poly(alkylene furandicarboxylate) via a concentrated mixture of the nucleating agents with the poly(alkylene furandicarboxylate), i.e. a so-called masterbatch. Due to the use of a masterbatch the distribution of the small amounts of nucleating agents that are sufficient to obtain the desired crystallizing effect can be achieved with ease and accuracy. Accordingly, the present invention provides for a masterbatch polyester composition comprising poly(alkylene furandicarboxylate) and a nucleating agent, wherein the amount of nucleating agent is in the range of 3 to 30 %wt, based on the composition.
  • the inorganic compound is preferably selected from the group consisting of talc, titanium dioxide, silica, boron nitride, metal carbonate, clays, metal silicates and combinations thereof.
  • the metal carbonate may comprise an alkali metal or an alkaline earth metal.
  • the carbonate can be sodium or potassium carbonate, or calcium carbonate. It is also possible to use salts with other metals, such as zinc carbonate.
  • the metal silicates may be selected from alkali metal silicates, such as sodium silicate, and alkaline earth metal silicate, such as calcium or magnesium silicate.
  • the silicates used are clays or zeolites, such as sepiolite (magnesium silicate clay), mordenite (aluminumsilicate containing alkali metal, alkaline earth metal and/or hydrogen ions). Other natural silicates may also be employed, such as mica. Silica may also be used.
  • silica When silica is used in the nucleating agent, the silica may be natural crystalline silica such as sand or quartz or amorphous fused silica.
  • the silica or silicates may be selected from naturally occurring minerals (e.g. sepiolite, mica, quartz), but also from synthetic silica or silicates (e.g. fused silica, synthetic zeolites).
  • aromatic acid examples include benzoic acid, furoic acid, 2,5-furandicarboxylic acid, pyrimidine carboxylic acid (also known as orotic acid), pyridine carboxylic acid, tetrahydroxy hexanedioic acid (also known as mucic acid).
  • the nucleating agent comprises an organic salt.
  • Such an organic salt suitably comprises a metal anion and an organic cation.
  • the metal anion is suitably an alkali metal ion or an alkaline earth metal ion. Examples are the sodium, potassium, calcium and magnesium ions.
  • the cation may be derived from a wide range of organic compounds, which typically include an acid functionality.
  • the acid functionality may be provided by any of the acids that are mentioned above as suitable organic acid included as such in the nucleating agent.
  • the nucleating agent preferably comprises an organic salt of the group selected from a metal salt of an aliphatic C8-C3o-carboxylic acid, an optionally substituted aromatic acid, an optionally substituted aromatic diacid, an optionally substituted cycloaliphatic dicarboxylic acid and combinations thereof.
  • the substituent may suitably be a C C 6 alkyl group, a C C 6 alkoxy group, a hydroxyl group, a halogen atom, a nitro group, sulfonyl-containing moieties or any combination thereof.
  • Suitable aliphatic acids include stearic acid, oleic acid, lauric acid and montanic acid.
  • Suitable aromatic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene carboxylic acid, naphthalene acetic acid and any combination thereof.
  • suitable heterocyclic acids include furoic acid, furandicarboxylic acid.
  • the most preferred organic compounds are saccharin (i.e. 2H-1A 6 ,2-benzothiazol-1 ,1 ,3- trione), and the metal salts of saccharin.
  • the nucleating agent therefore preferably includes saccharin or a salt of saccharin, wherein the salt may be selected from alkali and alkaline earth metal salt. Suitable examples are the sodium salt of saccharin and the calcium salt of saccharin. It has been found that the use of the metal salts of saccharin provides excellent crystallization results.
  • the masterbatch polyester composition according to the present invention comprises a poly(alkylene furandicarboxylate).
  • the poly(alkylene furandicarboxylate) typically comprises
  • the poly(alkylene furandicarboxylate) comprises a poly(alkylene 2,5-furandicarboxylate).
  • the poly(alkylene 2,5-furandicarboxylate) suitably comprises only 100% 2,5-FDCA as diacid building blocks. Since the diol preferably comprises ethylene glycol, the poly(alkylene furandicarboxylate) is preferably poly(ethylene 2,5- furandicarboxylate).
  • the carboxylic acid end groups are determined by using the titration method according to ASTM D7409, adapted for poly(ethylene 2,5-furandicarboxylate).
  • a thus modified method thereof involves the titration of a 4% w/v solution of poly(ethylene 2,5-furandicarboxylate) in ortho-cresol with 0.01 M KOH in ethanol as titrant to its equivalence point, using 0.5 mg of bromocresol green (2,6-dibromo-4-[7-(3,5-dibromo-4-hydroxy-2-methyl-phenyl)-9,9-dioxo-8- oxa-9A6-thiabicyclo[4.3.0]nona-1 ,3,5-trien-7-yl]-3-methyl-phenol) in 0.1 ml ethanol as indicator.
  • poly(ethylene 2,5-furandicarboxylate) suitably has a hydroxyl end group content in the range of 30 to 200 meq/kg and/or a furoic acid end group content in the range of 0 to 15 meq/kg.
  • the poly(ethylene 2,5-furandicarboxylate) preferably has a relative content of carboxylic acid end groups, expressed as the fraction of the molar amount of carboxylic acid end groups divided by the sum of the molar amounts of hydroxyl end groups and carboxylic acid end groups, in the range of 0.10 to 0.70.
  • the content of DEG is determined from the integral of the shifts at 3.82 to 3.92 ppm, representing four protons.
  • the decarboxylated end groups are found at a shift of 7.64-7.67 ppm, representing one proton.
  • the polyester also comprises methyl ester end groups, the methyl signal will occur at about 3.97 ppm, representing 3 protons.
  • the molecular weight of the poly(ethylene 2,5-furandicarboxylate) is expressed in terms of intrinsic viscosity.
  • the relative viscosity ( ⁇ ⁇ 6 ⁇ ) is determined in a 60/40 w/w mixture of phenol and tetrachloroethane at 30 °C and a concentration (c) of 0.4 g/dL. This procedure is similar to the ASTM D4603 standard for the determination of the inherent viscosity for poly( ethylene terephthalate).
  • the intrinsic viscosity is then calculated using the Billmyer equation:
  • Intrinsic viscosity (IV) ⁇ ⁇ ⁇ -1 +3 ⁇ ( ⁇ ⁇ ⁇ ) ⁇ /(4*c)
  • the poly(ethylene 2,5-furandicarboxylate) suitably consists of ethylene 2,5- furandicarboxylate units for at least 90 mole%, preferably for at least 95 mole%.
  • the balance may comprise other monomer units, such as other diols and diacids.
  • other suitable monomer diols include diethylene glycol
  • other suitable monomer diacids include terephthalic acid, adipic acid, phthalic acid and isophthalic acid.
  • Nucleating agents may also be used in the crystallization of polyesters in different situations. Polymer crystallization can be conducted for a number of reasons, each of which would then be performed under different conditions. For example, to create a semi-crystalline part in an injection molding machine it would be desired to have a rapid crystallization of the polyester during cooling from the melt. On the other hand, for crystallization of material prior to drying of reclaimed scrap, it would be desired to have the polymer crystallize rapidly from the glassy state, or on the up-heat. In either case the obtained polyester composition comprises semi-crystalline poly(alkylene furandicarboxylate).
  • the polyester has suitably been prepared from using a diester of 2,5- FDCA, in particular the dimethyl ester of 2,5-FDCA, and ethylene glycol as starting materials. That involves a low content of carboxylic end groups. Moreover, it also means that the polyester chains have a number of methyl end groups.
  • the polyester composition suitably contains poly(ethylene 2,5-furandicarboxylate) having a methyl end group content in the range of 15 to 100 meq/kg.
  • the composition comprising the nucleating agent and poly(ethylene 2,5-furandicarboxylate) with a carboxylic acid end group content of at most 14 meq/kg is novel.
  • the amount of the nucleating agent can therefore vary within wide ranges.
  • the nucleating agent may be present in high amounts so that the resulting composition can be used as masterbatch.
  • the polyester composition may also be the eventual polyester composition with a lower concentration of nucleating agent. It is then irrelevant how such a polyester composition has been produced. It may have been prepared by blending a masterbatch with a high concentration to a batch of poly(ethylene 2,5-furandicarboxylate).
  • nucleating agents are suitably those described above for the masterbatch composition.
  • the nucleating agent is selected from the group consisting of inorganic compounds, organic salts, organic acids, waxes, polymers and combinations thereof.
  • the nucleating agent comprises saccharin or a metal salt thereof.
  • the molecular weight of the poly(ethylene 2,5-furandicarboxylate) in the novel polyester composition suitably is greater than 0.45 dL/g and more preferably in the range of 0.45 to 1.0 dL/g. If the polyester is to undergo an additional step of solid stating then the molecular weight is preferably in the range of 0.45 to 0.75 dL/g.
  • the poly(ethylene 2,5-furandicarboxylate) in the novel polyester composition according to the present invention has a molecular weight expressed as intrinsic viscosity of at least 0.45 dL/g.
  • the intrinsic viscosity is a measure closely linked to the weight average molecular weight Mw.
  • the weight average molecular weight and the number average molecular weight can also be determined through the use of gel permeation chromatography (GPC). GPC measurement is suitably performed at 25 °C. For the calculation polystyrene standards are used.
  • As eluent suitably a solvent mixture of chloroform:2-chlorophenol 6:4 (vol/vol) can be used.
  • the poly(ethylene 2,5-furandicarboxylate) having a certain degree of crystallinity then also has a melting point.
  • the melting point of a polymer is easily determined by DSC and measured at the top of the endothermic peak.
  • the IS01 1357-3 standard describes such a melting determination.
  • the poly(ethylene 2,5-furan dicarboxylate) in the novel polyester composition suitably has a melting point of at least 215 °C. In highly crystalline polyester the melting point may exceed 230 °C, and even be as high as 245 °C.
  • a masterbatch of a poly(ethylene 2,5-furandicarboxylate) (“PEF-1 ”) and nucleating agent was prepared by combining dried samples of the poly(ethylene 2,5-furandicarboxylate) and nucleating agent into an extruder and by extruding the combined materials at 255 °C.
  • PEF-1 had a number average molecular weight (Mn) of 22700, and a weight average molecular weight (Mw) of 49,000.
  • the polyester has a carboxylic acid end group content of 33 meq/kg, a hydroxyl end group content of 55 meq/kg and a furoic acid end group content of 10 meq/kg.
  • PEF- 2 poly(ethylene 2,5-furandicarboxylate)
  • PEF-2 had a Mn of 28,570, a Mw of 68400, a carboxylic end group of 3.4 meq/kg, a hydroxyl end group content of 92 meq/kg; a furoic acid end group content of 3.0 meq/kg and a diethylene glycol content of 2.4 %mole.
  • the preparation procedure was the same as in Example 1.
  • a masterbatch was prepared by extrusion of PEF-2 and the nucleating agent at 255 °C.

Abstract

La présente invention concerne une composition mélange maître de polyester comprenant du poly(furandicarboxylate d'alkylène) et un agent de nucléation, la quantité d'agent de nucléation étant dans la plage de 3 à 30 % en poids, par rapport à la composition. L'agent de nucléation peut être choisi dans le groupe constitué par des composés inorganiques, des sels organiques, des acides organiques, des cires, des polymères et des combinaisons de ces derniers. Après le mélange de la composition mélange maître avec un lot de poly(furandicarboxylate d'alkylène), une composition de polyester semi-cristallin peut être obtenue.
PCT/NL2016/050568 2015-08-04 2016-08-04 Composition mélange maître de polyester WO2017023173A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201562200690P 2015-08-04 2015-08-04
US62/200,690 2015-08-04
NL2015264 2015-08-04
NL2015264A NL2015264B1 (en) 2015-08-04 2015-08-04 Masterbatch polyester composition.

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107118521A (zh) * 2017-05-04 2017-09-01 中国科学院宁波材料技术与工程研究所 一种聚呋喃二甲酸乙二醇酯树脂组合物及其制备方法和应用
CN107216619A (zh) * 2017-05-24 2017-09-29 中国科学院宁波材料技术与工程研究所 一种改善聚呋喃二甲酸乙二醇酯结晶性能的方法、产品和应用
WO2019059544A1 (fr) * 2017-09-22 2019-03-28 에스케이케미칼 주식회사 Composition de résine de polyester

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11618204B2 (en) 2016-11-28 2023-04-04 Furanix Technologies B.V. Thermoformed article of poly(ethylene 2,5 furandicarboxylate) polyester

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US20090018264A1 (en) * 2007-07-12 2009-01-15 Canon Kabushiki Kaisha Resin composition
WO2010077133A1 (fr) 2008-12-30 2010-07-08 Furanix Technologies B.V. Procédé pour préparer un polymère ayant un fragment 2,5-furanedicarboxylate dans le squelette du polymère et (co)polymères ainsi préparés
WO2010132740A2 (fr) 2009-05-14 2010-11-18 Archer Daniels Midland Company Oxydation de composés de furfural
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WO2013120989A2 (fr) 2012-02-17 2013-08-22 Uhde Inventa-Fischer Gmbh Procédé de préparation d'un polyester ou copolyester hétéroaromatique de poids moléculaire élevé
KR20140003167A (ko) 2012-06-29 2014-01-09 롯데케미칼 주식회사 투명성이 우수한 폴리에스터 중합체 및 이의 제조방법
WO2014204296A1 (fr) * 2013-06-21 2014-12-24 Stichting Dutch Polymer Institute Polyester semi-cristallin
WO2015095466A2 (fr) * 2013-12-20 2015-06-25 E. I. Du Pont De Nemours And Company Cristallisation nucléée du poly(triméthylène-2,5-furanne-dicarboxylate) (ptf) et articles obtenus à partir de celui-ci
WO2015137806A1 (fr) * 2014-03-11 2015-09-17 Furanix Technologies B.V. Procédé permettant d'améliorer le poids moléculaire d'un polyester

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107118521A (zh) * 2017-05-04 2017-09-01 中国科学院宁波材料技术与工程研究所 一种聚呋喃二甲酸乙二醇酯树脂组合物及其制备方法和应用
CN107216619A (zh) * 2017-05-24 2017-09-29 中国科学院宁波材料技术与工程研究所 一种改善聚呋喃二甲酸乙二醇酯结晶性能的方法、产品和应用
WO2019059544A1 (fr) * 2017-09-22 2019-03-28 에스케이케미칼 주식회사 Composition de résine de polyester

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