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Polyesters Containing Metathesized Natural Oil Derivatives and Methods of Making

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Polyesters Containing Metathesized Natural Oil Derivatives and Methods of Making (19) TZZ¥ZZ Z_T (11) EP 3 004 204 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C08G 63/685 (2006.01) 26.04.2017 Bulletin 2017/17 (86) International application number: (21) Application number: 14733013.8 PCT/US2014/038957 (22) Date of filing: 21.05.2014 (87) International publication number: WO 2014/193713 (04.12.2014 Gazette 2014/49) (54) POLYESTERS CONTAINING METATHESIZED NATURAL OIL DERIVATIVES AND METHODS OF MAKING POLYESTER MIT METATHESIERTEN ERDÖLDERIVATEN UND VERFAHREN ZU HERSTELLUNG DÉRIVÉS D’HUILENATURELLE AYANT SUBIUNE MÉTATHÈSECONTENANT DES POLYESTERS ET PROCÉDÉS DE PRODUCTION (84) Designated Contracting States: (72) Inventors: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB • HUNT, Zachary GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Simpsonville, SC 29680 (US) PL PT RO RS SE SI SK SM TR • CHRISTENSEN, S., Alexander Northwoods, IL 60185 (US) (30) Priority: 31.05.2013 US 201361829667 P (74) Representative: Ede, Eric et al (43) Date of publication of application: Murgitroyd & Company 13.04.2016 Bulletin 2016/15 Scotland House 165-169 Scotland Street (73) Proprietor: Elevance Renewable Sciences, Inc. Glasgow G5 8PL (GB) Woodridge, IL 60517 (US) (56) References cited: US-A1- 2003 013 627 US-A1- 2012 010 303 Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 3 004 204 B1 Printed by Jouve, 75001 PARIS (FR) EP 3 004 204 B1 Description BACKGROUND 5 [0001] Polyesters, which are polymers containing an ester group (-C(-O)-O-C-) as part of their repeating chemical structure, are used in a wide variety of applications. Polyester fibers may be used in textiles and as reinforcing fibers in rubbers or in rigid composite materials. Polyester films or coatings may be flexible or rigid, with representative applications including but not limited to food or beverage containers, metallized films and photographic films and tapes. Representative applications of rigid polyester plastics including but are not limited to housings for electronic devices and automotive parts. 10 [0002] As with polymers in general, the physical properties of a polyester are determined by the chemical structure of the polyester, the nature of any other ingredients added to the polyester, and the processing techniques used to form a material from the polyester. For example, the chemical structure of a polyester may include aromatic and/or aliphatic organic groups. Alteration of the chemical structure, size and/or frequency of these groups in a polyester can allow for modification of the properties of the polymer. 15 [0003] It is desirable to expand the chemical structures present in polyesters, so as to expand the useful properties that can be provided by the polymers. For example, properties such as flexibility, toughness, etc. can be improved by incorporating chemical groups that lower the modulus or that can absorb energy, respectively. This expansion of chemical structures may be accomplished through post-polymerization processing, such as reaction with other reagents or blending with other polymers. It is especially desirable, however, to expand the chemical structures by introducing new chemical 20 structures in the monomeric building blocks from which the polymer is formed. [0004] It would be desirable to provide polyesters that include chemical groups not previously observed in a polyester. Preferably such modified polyesters can be formed using conventional synthetic techniques and equipment, without requiring post-polymerization treatment. Preferably the modified polyesters can be formed using monomeric building blocks that are readily available and inexpensive. 25 SUMMARY [0005] The scope of the present invention is defined solely by the appended claims, and is not affected to any degree by the statements within this summary. 30 [0006] In one aspect, a polymeric composition is provided that includes the reaction product of monomers, where the monomers include a first monomer having at least two carboxylate functional groups, and a second monomer having at least two hydroxyl functional groups. The second monomer is a reaction product of a metathesized natural oil and a bis(hydroxyalkyl)amine. 35 BRIEF DESCRIPTION OF THE DRAWINGS [0007] The invention can be better understood with reference to the following drawings and description. The compo- nentsin thefigures arenot necessarilyto scale and arenot intended toaccurately representmolecules or theirinteractions, emphasis instead being placed upon illustrating the principles of the invention. Moreover, in the figures, like referenced 40 numerals designate corresponding parts throughout the different views. FIG. 1 depicts a reaction scheme for a metathesis reaction of a natural oil. FIG. 2 depicts a method of making a polymeric composition. 45 FIG. 3 depicts a representative reaction scheme for a polymerization of a monomer having at least two carboxylic acid functional groups, and a monomer having at least two hydroxyl functional groups, where the monomer having at least two hydroxyl functional groups includes a group derived from a metathesized natural oil. 50 FIG. 4 depicts a representative reaction scheme for a polymerization of adipic acid with a monomer having at least two hydroxyl functional groups, where the monomer having at least two hydroxyl functional groups includes a group derived from a metathesized natural oil. FIG. 5 depicts a representative reaction scheme for a polymerization of phthalic anhydride with a monomer having 55 at least two hydroxyl functional groups, where the monomer having at least two hydroxyl functional groups includes a group derived from a metathesized natural oil. 2 EP 3 004 204 B1 DETAILED DESCRIPTION [0008] A polymeric composition includes a reaction product of a monomer having at least two carboxylate functional groups, and a monomer having at least two hydroxyl functional groups, where the monomer having at least two hydroxyl 5 functional groups includes a group derived from a metathesized natural oil. The use of a monomer containing a metath- esized natural oil derivative can provide additional options for providing polymeric materials having useful combinations of properties, including but not limited to mechanical properties, crosslink density, and post-polymerization reactivity. The use of a monomer containing a metathesized natural oil derivative also may provide certain advantages over commercial polymeric materials, including but not limited to simpler and/or more cost-effective production, reduced 10 variability, improved sourcing, and increased biorenewability. [0009] A polymeric composition includes the reaction product of monomers, including a first monomer having at least two carboxylate functional groups, and a second monomer having at least two hydroxyl functional groups. The second monomer is a reaction product of a metathesized natural oil and a bis(hydroxyalkyl)amine. [0010] A polymeric composition may be any composition that includes a polymeric substance. The polymeric compo- 15 sition may have any of a variety of forms, including but not limited to monolithic solid, porous solid, coating, membrane, foam, fiber, particle, gel, liquid, or mixtures of these. The polymeric composition may be one of many components in a homogeneous or heterogeneous mixture. [0011] The polymeric composition includes a polymeric substance that is the reaction product of monomers that include a first monomer having at least two carboxylate functional groups (-C(-O)-), and a second monomer having at least two 20 hydroxyl functional groups (-OH). The first monomer having at least two carboxylate functional groups may include a carboxylic acid group (-C(=O)OH), an acyl halide group (-C(=O)X, where X is F, Cl, Br or I), an ester group (-C(=O)O- C-), an anhydride group (-C(=O)O-C(=O)-), or mixtures of these. A first monomer may have a single anhydride group, as this functional group includes two carboxylate groups. [0012] The first monomer having at least two carboxylate functional groups may include two carboxylic acid groups, 25 two acyl halide groups, two ester groups or an anhydride group. The first monomer having at least two carboxylate functional groups may include one or more carboxylic acid groups, in combination with one or more acyl halide groups, one or more ester groups and/or one or more anhydride groups. [0013] A hydroxyl functional group can undergo a condensation reaction with a carboxylic acid group, an acyl halide group, an ester group or an anhydride group to form an ester group (-C(=O)O-C-), which covalently links the substance 30 that was bonded to the carboxylic acid, acyl halide, ester or anhydride group and the substance that was bonded to the hydroxyl group. See, for example, Scheme 1, in which R A, RB, RB’ and Rz are organic groups, and X is a halide selected from F, Cl, Br and I. 35 40 45 50 [0014] Multiple condensation reactions between monomers having at least two carboxylate functional groups, and monomers having at least two hydroxyl functional groups can form an extended chain or network that contains multiple ester groups, each of which covalently links the substances that were bonded to the carboxylate groups and the sub- 55 stances that were bonded to the hydroxyl groups. See, for example, the polymerization reaction of a diol monomer and a diacid monomer depicted in Scheme 2, in which Rc and R D are organic groups, and n is at least 1. 3 EP 3 004 204 B1 5 10 The extended chain or network is a polymeric substance, typically referred to as a "polyester" due to the prevalence of 15 ester groups in the substance. [0015] The polymeric substance may include groups other than ester groups as the covalent linkage between the substances that were bonded to the hydroxyl groups and the substances that were bonded to the carboxylate groups.
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