Polyester impact resistance modifier

Abstract

Disclosed are polyesters made of (1) about 15 to about 40 weight percent isosorbide monomer repeat units, (2) about 25 to about 60 weight percent dicarboxylic acid or dicarboxylic anhydride monomer repeat units, e.g., succinic acid or succinic anhydride, and (3) about 10 to about 20 weight percent polyhydric alcohol monomer repeat units, e.g., 1,3-propanediol. In some instances, the polymers can also include methyl nadic anhydride or methyl nadic anhydride monomer repeat units. Also disclosed are polymer compositions comprising the polyesters and biodegradable polymers selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoates), and mixtures thereof.

Description

Technical Field

[0001] The present disclosure relates to a polyester suitable for use as an impact modifier and a biodegradable polymer composition incorporating such an impact modifier.

Background Art

[0002] Petroleum-based polymers such as polyethylene (PE), polypropylene (PP), or polyethylene terephthalate (PET) have been used for many years in a wide variety of applications. Such polymers can provide characteristics such as good strength, barrier properties, and / or printability. Unfortunately, after disposal, they do not decompose or decay quickly, either in landfill sites or using domestic composting techniques. That is, films, bags, and other materials made of such polymers may remain in landfill sites for centuries after disposal.

[0003] As a result, the demand for alternative polymers that are derived from biological sources, biodegradable, and / or compostable continues to increase. Examples of such polymers include poly(lactic acid) and poly(hydroxyalkanoate). Such biopolymers offer the clear advantage of biodegradability and / or compostability. Typically, it is desirable to blend various additives with the biopolymers to improve the physical properties of the biopolymers.

[0004] If the additives blended with the biopolymers are not biodegradable and / or not compostable, the environmental benefits of the biopolymers are reduced. As a result, it would seem desirable to provide additives that are themselves biodegradable and / or compostable for incorporation into, for example, poly(lactic acid) and poly(hydroxyalkanoate) for use with biopolymers.

Summary of the Invention

[0005] The above and other needs are met by the compostable polyesters according to the present disclosure.

[0006] In a first embodiment, the present disclosure provides a polyester. According to a particular embodiment, the polyester is composed of: (1) about 15 to about 40 weight percent isosorbide monomer repeating units; (2) about 25 to about 60 weight percent dicarboxylic acid or dicarboxylic acid anhydride monomer repeating units; and (3) about 10 to about 20 weight percent polyhydric alcohol monomer repeating units. All of these weight percentages are based on the total weight of the polyester.

[0007] Polyester also has a weight-average molecular weight of at least 8,000 daltons, as specified by ASTM D5296-05. More preferably, polyester has a weight-average molecular weight of about 10,000 to about 15,000 daltons, as specified by ASTM D5296-05.

[0008] In certain embodiments, dicarboxylic acids or dicarboxylic acid anhydrides are preferably succinic acid, succinic anhydride, glutaric acid, pimelic acid, undecanoic acid, dodecanoic acid, dodecanediic acid, suberic acid, azelaic acid, sebacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, terephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalenedicarboxylic acid, dimethyl 1,8-naphthalate, dimethyl isophthalate, phthalic acid, pyromelitic anhydride, mellitic anhydride, mellitic acid, trimellitic anhydride, 3,3'4,4'-benzophenonetetracarboxylic anhydride, 3,3'4,4'-benzophenonetetracarboxylic acid, trimellitic acid, nadiic anhydride, methylnadiic anhydride, and C36 dimer acid. The following are selected from the group consisting of partially hydrogenated C36 dimer acid, recycled polyethylene terephthalate polymer, recycled polybutylene terephthalate polymer, new polyethylene terephthalate polymer, new polybutylene terephthalate polymer, and mixtures thereof.

[0009] More preferably, the dicarboxylic acid or dicarboxylic acid anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadiic acid anhydride, methylnadiic acid anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof.

[0010] In a particularly preferred embodiment, the dicarboxylic acid or dicarboxylic acid anhydride is a mixture of (1) succinic acid or succinic anhydride, and (2) nadiic acid anhydride, methylnadiic acid anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof. In this embodiment, the polyester is preferably about 25 to about 35 weight percent succinic acid or succinic anhydride and about 10 to about 25 weight percent nadiic acid anhydride, methylnadiic acid anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.

[0011] In some embodiments, the polyhydric alcohol is preferably selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, 1,1,1-trimethylolethane, 1,2,3-trimethylolpropane, methylpropanediol, pentaerythritol, and poly(oxyalkylene) polyols containing repeating monomer units of ethylene oxide, propylene oxide, or butylene oxide, as well as mixtures thereof.

[0012] More preferably, the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methylpropanediol, and mixtures thereof. Even more preferably, the polyhydric alcohol includes 1,3-propanediol.

[0013] In some examples, the dicarboxylic acid or dicarboxylic acid anhydride preferably includes succinic acid or succinic anhydride, and the polyhydric alcohol preferably includes 1,3-propanediol.

[0014] In alternative embodiments, isosorbide can be excluded from the polyester. In such examples, the polyester consists of: (1) about 35 to about 65 weight percent of dicarboxylic acid or dicarboxylic acid anhydride monomer repeating units, selected from the group consisting of succinic acid, succinic anhydride, nadiic acid anhydride, methylnadiic acid anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof; and (2) about 35 to about 65 weight percent of polyhydric alcohol monomer repeating units.

[0015] In a preferred embodiment, the dicarboxylic acid or dicarboxylic acid anhydride is a mixture of (1) succinic acid or succinic anhydride, and (2) nadiic acid anhydride, methylnadiic acid anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof. In this embodiment, the polyester is preferably about 30 to about 40 weight percent succinic acid or succinic anhydride, and about 10 to about 20 weight percent nadiic acid anhydride, methylnadiic acid anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.

[0016] The polyhydric alcohol suitable for this alternative polyester is the same as the polyhydric alcohol described above for polyesters containing isosorbide. Similarly, for this alternative polyester, the weight-average molecular weight of this polyester is at least 8,000 daltons, as specified by ASTM D5296-05. More preferably, this polyester has a weight-average molecular weight of about 10,000 to about 15,000 daltons, as specified by ASTM D5296-05.

[0017] In a second embodiment, the disclosure provides polymer compositions. The polymer compositions typically comprise about 50 to about 95 weight percent of a biodegradable polymer, which is selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoate), and mixtures thereof. The polymer compositions also comprise about 5 to about 50 weight percent of an impact-improved polyester. The impact-improved polyester, in turn, comprises: (1) about 15 to about 40 weight percent of isosorbide monomer repeating units based on the total weight of the polyester; (2) about 25 to about 60 weight percent of dicarboxylic acid or dicarboxylic acid anhydride monomer repeating units based on the total weight of the polyester; and (3) about 10 to about 20 weight percent of polyhydric alcohol monomer repeating units based on the total weight of the polyester. The impact-improved polyester also has a weight-average molecular weight of at least 8000 daltons, as specified by ASTM D5296-05.

[0018] In certain embodiments, the dicarboxylic acid or dicarboxylic acid anhydride is preferably succinic acid, succinic anhydride, glutaric acid, pimelic acid, undecanoic acid, dodecanoic acid, dodecanediic acid, suberic acid, azelaic acid, sebacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, terephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalenedicarboxylic acid, dimethyl 1,8-naphthalate, dimethyl isophthalate, phthalic acid, pyromelitic anhydride, or melitic anhydride. The following are selected from the group consisting of: substances, mellitic acid, trimellitic anhydride, 3,3'4,4'-benzophenonetetracarboxylic anhydride, 3,3'4,4'-benzophenonetetracarboxylic acid, trimellitic acid, nadiic anhydride, methylnadiic anhydride, C36 dimer acid, partially hydrogenated C36 dimer acid, recycled polyethylene terephthalate polymer, recycled polybutylene terephthalate polymer, new polyethylene terephthalate polymer, new polybutylene terephthalate polymer, and mixtures thereof.

[0019] More preferably, the dicarboxylic acid or dicarboxylic acid anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadiic acid anhydride, methylnadiic acid anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof.

[0020] In a particularly preferred embodiment, the dicarboxylic acid or dicarboxylic acid anhydride is a mixture of (1) succinic acid or succinic anhydride, and (2) nadiic acid anhydride, methylnadiic acid anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof. In this embodiment, the polyester is preferably about 25 to about 35 weight percent succinic acid or succinic anhydride, and about 10 to about 25 weight percent nadiic acid anhydride, methylnadiic acid anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.

[0021] In some embodiments, the polyhydric alcohol is preferably glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, 1,1,1-trimethylolethane, 1,2,3-trimethylolpropane, methylpropanediol, pentaerythritol, and ethylene oxide, propylene oxide, or butylene oxide monomer repeating units. Selected from the group consisting of poly(oxyalkylene) polyols and mixtures thereof.

[0022] More preferably, the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methylpropanediol, and mixtures thereof. Even more preferably, the polyhydric alcohol includes 1,3-propanediol.

[0023] In some examples, the dicarboxylic acid or dicarboxylic anhydride preferably includes succinic acid or succinic anhydride, and the polyhydric alcohol preferably includes 1,3-propanediol.

[0024] According to certain embodiments, the polymer composition more preferably includes from about 60 to about 85 weight percent of a biodegradable polymer and from about 5 to about 30 weight percent of an impact-modified polyester. Even more preferably, the polymer composition includes from about 7.5 to about 15 weight percent of an impact-modified polyester.

[0025] In some examples, the biodegradable polymer preferably includes poly(lactic acid). In other embodiments, the biodegradable polymer preferably includes at least one poly(hydroxyalkanoate). In some embodiments, the biodegradable polymer preferably includes a mixture of poly(lactic acid) and poly(hydroxyalkanoate). For example, in some embodiments, the polymer composition can include from about 5 to about 25 weight percent of poly(lactic acid) and from about 70 to about 90 weight percent of at least one poly(hydroxyalkanoate), based on the total weight of the polymer composition.

[0026] According to certain embodiments in which the polymer composition includes poly(hydroxyalkanoate), at least one poly(hydroxyalkanoate) is preferably made of poly-3-hydroxybutyrate-co-3-hydroxyhexanoate ( "P(3HB-co-3HHx)").

[0027] In some examples, this (3HB-co-LLx) preferably consists of from about 75 to about 99 mole percent of hydroxybutyrate and from about 1 to about 25 mole percent of hydroxyhexanoate. More preferably, (3HB-co-3HHx) consists of from about 93 to about 98 mole percent of hydroxybutyrate and from about 2 to about 7 mole percent of hydroxyhexanoate.

[0028] In other embodiments, at least one poly(hydroxyalkanoate) may include a terpolymer comprising about 75 to about 99.9 mole percent of 3-hydroxybutyrate monomer repeating units, about 0.1 to about 25 mole percent of 3-hydroxyhexanoate monomer repeating units, and about 0.1 to about 25 mole percent of a third 3-hydroxyalkanoate monomer repeating unit having 5 to 12 carbon atoms.

[0029] According to a particular embodiment, at least one poly(hydroxyalkanoate) preferably has a weight-average molecular weight of about 50,000 daltons to about 2,500,000 daltons, as specified by ASTM D5296-05. More preferably, at least one poly(hydroxyalkanoate) has a weight-average molecular weight of about 500,000 daltons to about 750,000 daltons, as specified by ASTM D5296-05.

[0030] The polymer composition may also include further additives. In some embodiments, the polymer composition contains at least one plasticizer in about 1 to about 10 weight percent and about 0.1 to about It may also include at least one nucleating agent in 5 weight percent and a bulking agent in about 0.1 to about 10 weight percent.

[0031] In some examples, the polymer composition may include additional biodegradable polymers in addition to poly(lactic acid) and / or poly(hydroxyalkanoate). That is, in certain embodiments, the polymer composition may also contain about 5 to about 50 percent by weight of at least one biodegradable polymer selected from the group consisting of poly(caprolactone), poly(ethylene sebacate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate), and mixtures thereof.

[0032] In certain embodiments, the polymer composition is preferably biodegradable, as specified using ASTM standard D5988. Furthermore, in some embodiments, the polymer composition is preferably compostable at home, as specified using ASTM standard D6868.

[0033] The Disclosure also provides various end products that can be formed from the above polymer compositions. Specifically, according to one embodiment, the Disclosure provides a molded sheet made of a polymer composition. In a second embodiment, the Disclosure provides a molded article made of a polymer composition, which is formed by thermoforming, injection molding, or blow molding. In another embodiment, the Disclosure provides a film made of a polymer composition, which is an inflated film or a cast film. In yet another embodiment, the Disclosure provides a fiber made of a polymer composition. [Modes for carrying out the invention]

[0034] This disclosure first provides novel polyesters suitable for use as impact modifiers in biodegradable and / or compostable polymer compositions.

[0035] Generally, polyesters are composed of at least three different monomer repeating units, which are derived from (1) isosorbide, (2) succinic acid or succinic anhydride, and (3) 1,3-propanediol. In terms of quantity, polyesters are typically composed of (1) about 15 to about 40 weight percent isosorbide monomer repeating units, (2) about 25 to about 60 weight percent dicarboxylic acid or dicarboxylic acid anhydride monomer repeating units, and (3) about 10 to about 20 weight percent polyhydric alcohol monomer repeating units.

[0036] Various dicarboxylic acids and dicarboxylic acid anhydrides are considered suitable for use in the preparation of polyesters. For example, dicarboxylic acids or dicarboxylic acid anhydrides include succinic acid, succinic anhydride, glutaric acid, pimelic acid, undecanoic acid, dodecanoic acid, dodecanediic acid, suberic acid, azelaic acid, sebacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, terephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalenedicarboxylic acid, dimethyl 1,8-naphthalate, dimethyl isophthalate, phthalic acid, pyromelitic anhydride, mellitic anhydride, mellitic acid, trimellitic acid Appropriate selections can be made from the group consisting of acid anhydrides, 3,3'4,4'-benzophenonetetracarboxylic anhydride, 3,3'4,4'-benzophenonetetracarboxylic acid, trimellitic acid, nadiic anhydride, methylnadiic anhydride, C36 dimer acid, partially hydrogenated C36 dimer acid, recycled polyethylene terephthalate polymer, recycled polybutylene terephthalate polymer, new polyethylene terephthalate polymer, new polybutylene terephthalate polymer, and mixtures thereof.

[0037] More preferably, the dicarboxylic acid or dicarboxylic acid anhydride is succinic acid, succinic anhydride The following are selected from the group consisting of nadiic anhydride, methylnadiic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof.

[0038] In a particularly preferred embodiment, the dicarboxylic acid or dicarboxylic acid anhydride is a mixture of (1) succinic acid or succinic anhydride and (2) nadiic acid anhydride, methylnadiic acid anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof. In this embodiment, the polyester is preferably about 25 to about 35 weight percent succinic acid or succinic anhydride and about 10 to about 25 weight percent nadiic acid anhydride, methylnadiic acid anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.

[0039] A certain range of polyhydric alcohols are also considered suitable for polyesters. Suitable polyhydric alcohols can be selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, 1,1,1-trimethylolethane, 1,2,3-trimethylolpropane, methylpropanediol, pentaerythritol, and poly(oxyalkylene) polyols containing repeating monomer units of ethylene oxide, propylene oxide, or butylene oxide, as well as mixtures thereof.

[0040] More preferably, the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methylpropanediol, and mixtures thereof. Even more preferably, the polyhydric alcohol includes 1,3-propanediol.

[0041] In particularly preferred embodiments, the dicarboxylic acid or dicarboxylic acid anhydride preferably includes succinic acid or succinic anhydride, and the polyhydric alcohol preferably includes 1,3-propanediol.

[0042] Polyester also has a weight-average molecular weight of at least 8,000 daltons, as specified by ASTM D5296-05. More preferably, polyester has a weight-average molecular weight of about 10,000 to about 15,000 daltons, as specified by ASTM D5296-05.

[0043] Generally, polyesters can be prepared by adding isosorbide to a reaction flask or other reactor equipped with a nitrogen inlet, vacuum function, heating, and stirring. First, the isosorbide is melted and then vacuum-degassed as a molten mass. Subsequently, the diacitor is added and the contents of the flask are reacted at a maximum temperature of 220°C until the generation of water subsides. Once the generation of water subsides, all of the remaining glycol is added. Esterification is completed at a maximum temperature of 220°C and a low vacuum pressure of 3.3 kPa.

[0044] In alternative embodiments, isosorbide can be excluded from the polyester. In such examples, the polyester consists of: (1) about 35 to about 65 weight percent of dicarboxylic acid or dicarboxylic acid anhydride monomer repeating units, selected from the group consisting of succinic acid, succinic anhydride, nadiic acid anhydride, methylnadiic acid anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof; and (2) about 35 to about 65 weight percent of polyhydric alcohol monomer repeating units.

[0045] In a preferred embodiment, the dicarboxylic acid or dicarboxylic acid anhydride is a mixture of (1) succinic acid or succinic anhydride, and (2) nadiic acid anhydride, methylnadiic acid anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof. In this embodiment, the polyester is preferably about 30 to about 40 weight percent succinic acid or succinic anhydride, and about 10 to about 20 weight percent nadiic acid anhydride, methylnadiic acid anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.

[0046] The polyhydric alcohol suitable for this alternative polyester is the same as the polyhydric alcohol described above for polyesters containing isosorbide. Similarly, for this alternative polyester, the weight-average molecular weight of this polyester is at least 8,000 daltons, as specified by ASTM D5296-05. More preferably, this polyester has a weight-average molecular weight of about 10,000 to about 15,000 daltons, as specified by ASTM D5296-05.

[0047] Polyesters according to this disclosure are suitable for use as impact modifiers in polymer compositions. As used herein, “impact modifier” refers to an additive used to improve the durability and toughness of a polymer resin, where toughness is measured as the area under the stress-strain curve in standard tensile elongation and modulus tests. The toughness of a polymer may also correlate with notched Izod tests. A higher impact number indicates higher toughness.

[0048] The polyesters according to this disclosure are preferably also biodegradable, as specified using ASTM standard D5511. Furthermore, in some embodiments, the polyesters are preferably compostable at home, as specified using ASTM standard D6868.

[0049] This disclosure also provides polymer compositions comprising the polyester as described. Generally, the polymer compositions combine the impact-modifying polyester with at least one biodegradable polymer, the at least one biodegradable polymer being selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoate), and mixtures thereof. Typically, the polymer composition comprises about 5 to about 50 weight percent of the impact-modifying polyester and about 50 to about 95 weight percent of a biodegradable polymer selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoate), and mixtures thereof.

[0050] The polymer composition more preferably comprises about 60 to about 85 weight percent of a biodegradable polymer and about 5 to about 30 weight percent of an impact-resistant polyester. More preferably, the polymer composition comprises about 7.5 to about 15 weight percent of an impact-resistant polyester.

[0051] Again, the impact modifier used in the polymer composition is a polyester according to the above disclosure. That is, the impact modifier polyester is composed of: (1) about 15 to about 40 weight percent isosorbide monomer repeating units, (2) about 25 to about 60 weight percent dicarboxylic acid or dicarboxylic acid anhydride monomer repeating units, and (3) about 10 to about 20 weight percent polyhydric alcohol monomer repeating units. The impact modifier polyester also has a weight-average molecular weight of at least 8000 daltons, as specified by ASTM D5296-05.

[0052] In some examples, the biodegradable polymer preferably comprises poly(lactic acid). In other embodiments, the biodegradable polymer preferably comprises at least one poly(hydroxyalkanoate). Furthermore, in certain embodiments, the biodegradable polymer preferably comprises a mixture of poly(lactic acid) and poly(hydroxyalkanoate). For example In some embodiments, the polymer composition may include, based on the total weight of the polymer composition, about 5 to about 25 weight percent of poly(lactic acid) and about 70 to about 90 weight percent of at least one poly(hydroxyalkanoate).

[0053] According to a particular embodiment in which the polymer composition comprises a poly(hydroxyalkanoate), at least one of the poly(hydroxyalkanoate) is preferably poly-3-hydroxybutyrate-co-3-hydroxyhexanoate ("P(3HB-co-3HHx)").

[0054] In some examples, (3HB-co-3HHx) is preferably composed of about 75 to about 99 mole percent of hydroxybutyrate and about 1 to about 25 mole percent of hydroxyhexanoate. More preferably, (3HB-co-3HHx) is composed of about 93 to about 98 mole percent of hydroxybutyrate and about 2 to about 7 mole percent of hydroxyhexanoate.

[0055] In other embodiments, at least one poly(hydroxyalkanoate) may include a terpolymer comprising about 75 to about 99.9 mole percent of 3-hydroxybutyrate monomer repeating units, about 0.1 to about 25 mole percent of 3-hydroxyhexanoate monomer repeating units, and about 0.1 to about 25 mole percent of a third 3-hydroxyalkanoate monomer repeating unit having 5 to 12 carbon atoms.

[0056] According to a particular embodiment, at least one poly(hydroxyalkanoate) preferably has a weight-average molecular weight of about 50,000 daltons to about 2,500,000 daltons, as specified by ASTM D5296-05. More preferably, at least one poly(hydroxyalkanoate) has a weight-average molecular weight of about 500,000 daltons to about 750,000 daltons, as specified by ASTM D5296-05.

[0057] The polymer composition may also include further additives. For example, the polymer composition may include plasticizers, nucleating agents, and / or fillers. In some embodiments, the polymer composition may also include at least one plasticizer in about 1 to about 10 weight percent, at least one nucleating agent in about 0.1 to about 5 weight percent, and a filler in about 0.1 to about 10 weight percent.

[0058] Suitable nucleating agents for use in polymer compositions can be selected from the group consisting of, for example, pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clay, dipentaerythritol, sorbitol, and mixtures thereof.

[0059] Suitable fillers for use in polymer compositions can be selected from the group consisting of, for example, aragonite, clay, calcium carbonate, cellulose, nanocellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starch, diatomaceous earth, titanium dioxide, nanoclay, mica, and mixtures thereof.

[0060] Suitable plasticizers for use in polymer compositions include, for example, sebacate esters, citrate esters, adipate fatty acid esters, succinate fatty acid esters, and glucaric acid fatty acid esters, lactate esters, alkyl diesters, citrate esters, alkyl methyl esters, dibenzoate esters, propylene carbonate, caprolactone diol with a number average molecular weight of 200 to 10,000 g / mol, poly(ethylene) glycol with a number average molecular weight of 400 to 10,000 g / mol, vegetable oil esters, long-chain alkyl acids, adipate esters, glycerol, isosorbide derivatives, or mixtures thereof, HALLGREEN IM-8830 ester, HALLGREEN R-8010 ester, and hydroxybutyrate. The following can be selected: polyhydroxyalkanoate copolymers containing at least 18 mole percent of hydroxyalkanoate monomer repeating units other than t, and mixtures thereof.

[0061] Furthermore, in certain embodiments, the polymer composition may include additional biodegradable polymers in addition to poly(lactic acid) and / or poly(hydroxyalkanoate). That is, in certain embodiments, the polymer composition may also contain about 5 to about 50 percent by weight of at least one biodegradable polymer selected from the group consisting of poly(caprolactone), poly(ethylene sebacate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate), and mixtures thereof.

[0062] In certain embodiments, the entire polymer composition is preferably biodegradable, as specified using ASTM standard D5988. Furthermore, in some embodiments, the polymer composition is preferably compostable at home, as specified using ASTM standard D6868.

[0063] Various end products can be formed from polymer compositions according to this disclosure. That is, according to one embodiment, this disclosure provides a molded sheet made of a polymer composition. In a second embodiment, this disclosure provides a molded article made of a polymer composition, which is formed by thermoforming, injection molding, or blow molding. In another embodiment, this disclosure provides a film made of a polymer composition, which is an inflated film or a cast film. In yet another embodiment, this disclosure provides a fiber made of a polymer composition.

[0064] Embodiment This disclosure will be further illustrated by the following embodiments:

[0065] Embodiment 1. A polyester comprising: about 15 to about 40 weight percent of isosorbide monomer repeating units based on the total weight of the polyester; about 25 to about 60 weight percent of dicarboxylic acid or dicarboxylic acid anhydride monomer repeating units based on the total weight of the polyester; and about 10 to about 20 weight percent of polyhydric alcohol monomer repeating units based on the total weight of the polyester, wherein the weight-average molecular weight is at least 8000 daltons, as specified by ASTM D5296-05.

[0066] Embodiment 2. The dicarboxylic acid or dicarboxylic acid anhydride is succinic acid, succinic anhydride, glutaric acid, pimelic acid, undecanoic acid, dodecanoic acid, dodecanediic acid, suberic acid, azelaic acid, sebacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, terephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalenedicarboxylic acid, dimethyl 1,8-naphthalate, dimethyl isophthalate, phthalic acid, pyromelitic anhydride, mellitic anhydride, mellitic acid, trimellitic acid anhydride The polyester according to Embodiment 1, selected from the group consisting of water, 3,3'4,4'-benzophenonetetracarboxylic anhydride, 3,3'4,4'-benzophenonetetracarboxylic acid, trimellitic acid, nadiic anhydride, methylnadiic anhydride, C36 dimer acid, partially hydrogenated C36 dimer acid, recycled polyethylene terephthalate polymer, recycled polybutylene terephthalate polymer, new polyethylene terephthalate polymer, new polybutylene terephthalate polymer, and mixtures thereof.

[0067] Embodiment 3. The dicarboxylic acid or dicarboxylic acid anhydride is succinic acid, succinic anhydride, nadiic anhydride, methylnadiic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C3 A polyester according to Embodiment 1 or 2, selected from the group consisting of 6-dimer acids and mixtures thereof.

[0068] Embodiment 4. The polyester according to any one of the prior embodiments, wherein the dicarboxylic acid or dicarboxylic acid anhydride comprises (1) succinic acid or succinic anhydride, and (2) nadiic acid anhydride, methylnadiic acid anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof.

[0069] Embodiment 5. The polyester according to any one of the prior embodiments, wherein the polyester comprises about 25 to about 35 weight percent succinic acid or succinic anhydride, and about 10 to about 25 weight percent nadiic anhydride, methylnadiic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.

[0070] Embodiment 6. The polyester according to any one of the prior embodiments, wherein the polyhydric alcohol is selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, 1,1,1-trimethylolethane, 1,2,3-trimethylolpropane, methylpropanediol, pentaerythritol, and poly(oxyalkylene) polyols containing repeating monomer units of ethylene oxide, propylene oxide, or butylene oxide, and mixtures thereof.

[0071] Embodiment 7. The polyester according to any one of the prior embodiments, wherein the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methylpropanediol, and mixtures thereof.

[0072] Embodiment 8. The polyester according to any one of the prior embodiments, wherein the polyhydric alcohol comprises 1,3-propanediol.

[0073] Embodiment 9. The polyester according to any one of the prior embodiments, wherein the dicarboxylic acid or dicarboxylic acid anhydride comprises succinic acid or succinic anhydride, and the polyhydric alcohol comprises 1,3-propanediol.

[0074] Embodiment 10. The polyester is the polyester according to any one of the prior embodiments, wherein the weight-average molecular weight is approximately 10,000 to approximately 15,000 daltons, as specified by ASTM D5296-05.

[0075] Embodiment 11. A polymer composition comprising: about 50 to about 95 weight percent of a biodegradable polymer selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoate), and mixtures thereof; and about 5 to about 50 weight percent of an impact-resistant polyester, wherein the impact-resistant polyester comprises, based on the total weight of the polyester, about 15 to about 40 weight percent of isosorbide monomer repeating units; based on the total weight of the polyester, about 25 to about 60 weight percent of dicarboxylic acid or dicarboxylic acid anhydride monomer repeating units; and based on the total weight of the polyester, about 10 to about 20 weight percent of polyhydric alcohol monomer repeating units, wherein the polyester has a weight-average molecular weight of at least 8000 daltons, as specified by ASTM D5296-05.

[0076] Embodiment 12. The dicarboxylic acid or dicarboxylic acid anhydride is succinic acid, succinic anhydride, glutaric acid, pimelic acid, undecanoic acid, dodecanoic acid, dodecanediic acid, suberic acid, azelaic acid, sebacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, terephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalenedicarboxylic acid, dimethyl 1,8-naphthalate, dimethyl isophthalate, phthalic acid, pyromelitic anhydride, mellitic anhydride, mellitic acid, trimellitic acid anhydride A polymer composition according to Embodiment 11, selected from the group consisting of water, 3,3'4,4'-benzophenonetetracarboxylic anhydride, 3,3'4,4'-benzophenonetetracarboxylic acid, trimellitic acid, nadiic anhydride, methylnadiic anhydride, C36 dimer acid, partially hydrogenated C36 dimer acid, recycled polyethylene terephthalate polymer, recycled polybutylene terephthalate polymer, new polyethylene terephthalate polymer, new polybutylene terephthalate polymer, and mixtures thereof.

[0077] Embodiment 13. The polymer composition according to Embodiment 11 or 12, wherein the dicarboxylic acid or dicarboxylic acid anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadiic anhydride, methylnadiic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof.

[0078] Embodiment 14. The polymer composition according to any one of Embodiments 11 to 13, wherein the dicarboxylic acid or dicarboxylic acid anhydride comprises (1) succinic acid or succinic anhydride, and (2) nadiic acid anhydride, methylnadiic acid anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof.

[0079] Embodiment 15. The polymer composition according to any one of Embodiments 11 to 14, wherein the polyester comprises about 25 to about 35 weight percent succinic acid or succinic anhydride, and about 10 to about 25 weight percent nadiic anhydride, methylnadiic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.

[0080] Embodiment 16. The polymer composition according to any one of Embodiments 11 to 15, wherein the polyhydric alcohol is selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, 1,1,1-trimethylolethane, 1,2,3-trimethylolpropane, methylpropanediol, pentaerythritol, and poly(oxyalkylene) polyols containing repeating monomer units of ethylene oxide, propylene oxide, or butylene oxide, and mixtures thereof.

[0081] Embodiment 17. The polymer composition according to any one of Embodiments 11 to 16, wherein the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methylpropanediol, and mixtures thereof.

[0082] Embodiment 18. The polymer composition according to any one of Embodiments 11 to 17, wherein the polyhydric alcohol comprises 1,3-propanediol.

[0083] Embodiment 19. The polymer composition according to any one of Embodiments 11 to 18, wherein the dicarboxylic acid or dicarboxylic acid anhydride comprises succinic acid or succinic anhydride, and the polyhydric alcohol comprises 1,3-propanediol.

[0084] Embodiment 20. The polymer composition according to any one of Embodiments 11 to 19, wherein the impact-resistant polyester has a weight-average molecular weight of about 10,000 to about 15,000 daltons, as specified by ASTM D5296-05.

[0085] Embodiment 21. The polymer composition according to any one of Embodiments 11 to 20, wherein the polymer composition comprises about 60 to about 85 weight percent of the biodegradable polymer and about 5 to about 30 weight percent of the impact-resistant polyester.

[0086] Embodiment 22. The polymer composition according to any one of Embodiments 11 to 21, wherein the biodegradable polymer comprises poly(lactic acid).

[0087] Embodiment 23. The polymer composition according to any one of Embodiments 11 to 22, wherein the biodegradable polymer comprises at least one poly(hydroxyalkanoate).

[0088] Embodiment 24. The polymer composition according to Embodiment 23, wherein the at least one poly(hydroxyalkanoate) comprises poly-3-hydroxybutyrate-co-3-hydroxyhexanoate ("P(3HB-co-3HHx)").

[0089] Embodiment 25. The polymer composition according to Embodiment 24, wherein P(3HB-co-3HHx) comprises about 75 to about 99 mole percent of hydroxybutyrate and about 1 to about 25 mole percent of hydroxyhexanoate.

[0090] Embodiment 26. The polymer composition according to Embodiment 24, wherein P(3HB-co-3HHx) comprises about 93 to about 98 mole percent of hydroxybutyrate and about 2 to about 7 mole percent of hydroxyhexanoate.

[0091] Embodiment 27. The polymer composition according to Embodiment 23, wherein the at least one poly(hydroxyalkanoate) comprises a terpolymer made of about 75 to about 99.9 mole percent of 3-hydroxybutyrate monomer repeating units, about 0.1 to about 25 mole percent of 3-hydroxyhexanoate monomer repeating units, and about 0.1 to about 25 mole percent of a third 3-hydroxyalkanoate monomer repeating unit having 5 to 12 carbon atoms.

[0092] Embodiment 28. The at least one poly(hydroxyalkanoate) is ASTM The polymer composition according to Embodiment 23, wherein, as specified by D5296-05, the weight-average molecular weight is approximately 50,000 daltons to approximately 2,500,000 daltons.

[0093] Embodiment 29. The at least one poly(hydroxyalkanoate) is ASTM The polymer composition according to Embodiment 23, wherein, as specified by D5296-05, the weight-average molecular weight is approximately 500,000 daltons to approximately 750,000 daltons.

[0094] Embodiment 30. The polymer composition according to any one of Embodiments 11 to 29, wherein the polymer composition comprises about 5 to about 25 weight percent of poly(lactic acid) and about 70 to about 90 weight percent of at least one poly(hydroxyalkanoate).

[0095] Embodiment 31. A polymer composition according to any one of Embodiments 11 to 30, further comprising: Approximately 1 to approximately 10 weight percent of at least one plasticizer, Approximately 0.1 to approximately 5 weight percent of at least one nucleating agent, and A bulking agent of approximately 0.1 to 10 weight percent.

[0096] Embodiment 32. The polymer composition according to any one of Embodiments 11 to 31, wherein the polymer composition is biodegradable as specified using ASTM Standard D5988.

[0097] Embodiment 33. The polymer composition according to any one of Embodiments 11 to 32, wherein the polymer composition is compostable at home, as specified using ASTM Standard D6868.

[0098] Embodiment 34. A polymer composition according to any one of Embodiments 11 to 33, further comprising about 5 to about 50 weight percent of at least one biodegradable polymer selected from the group consisting of poly(caprolactone), poly(ethylene sebacate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate), and mixtures thereof.

[0099] Embodiment 35. A molded sheet comprising the polymer composition described in any one of Embodiments 11 to 34.

[0100] Embodiment 36. A molded article comprising a polymer composition according to any one of Embodiments 11 to 34, the article being formed by thermoforming, injection molding, or blow molding.

[0101] Embodiment 37. A film comprising the polymer composition described in any one of Embodiments 11 to 34, wherein the film is an inflated film or a cast film.

[0102] Embodiment 38. A fiber comprising the polymer composition described in any one of Embodiments 11 to 34. [Examples]

[0103] The following non-limiting embodiments illustrate various additional aspects of the present invention. Unless otherwise specified, temperatures are in degrees Celsius, and percentages are weight percentages based on the dry weight of the formulation.

[0104] Example 1 800 grams of isosorbide and 5 grams of phosphorous acid were added to a reaction flask equipped with a nitrogen inlet and vacuum capability. The reaction temperature was raised to 100°C, the contents of the flask were aspirated to maximum vacuum, and then the vacuum was released with an inert gas such as nitrogen. This vacuum cycle was performed three times. Next, 1279 grams of succinic acid was added, and one more vacuum cycle was performed. Then, the reactor temperature was raised to a maximum of 220°C, during which time water was continuously removed in the receiver. Once the generation of water had settled, 416 grams of propanediol were added to the reactor. The temperature was slowly raised again to a maximum of 210°C. To complete the reaction, 1 gram of tin(II) ethylhexanoate was added, and vacuum was applied. The material was maintained until the appropriate molecular weight details were obtained.

[0105] Example 2 416 kg of isosorbide and 2.27 kg of phosphorous acid were added to a 1514 L stainless steel reactor equipped with a nitrogen inlet and vacuum function. The reaction temperature was raised to 100°C, the contents of the reactor were aspirated to maximum vacuum, and then the vacuum was released with an inert gas such as nitrogen. This vacuum cycle was performed three times. Next, 590 kg of succinic acid was added, and the vacuum cycle was performed one more time. Then, the reactor temperature was raised to a maximum of 220°C, during which time water was continuously removed in the receiver. Once the generation of water had settled down, 216 kg of propanediol was added to the reactor. The temperature was then slowly raised again to a maximum of 210°C. Ethyl hexane was added to complete the reaction. 453 grams of tin(II) phosphate were added. The material was maintained until the appropriate molecular weight details were obtained.

[0106] Example 3 575 grams of isosorbide, 888 grams of partially hydrogenated dimer acid, and 5 grams of phosphorous acid were added to a reaction flask equipped with a nitrogen inlet and vacuum function. The reaction temperature was raised to 100°C, the contents of the reactor were aspirated to maximum vacuum, and then the vacuum was released with an inert gas such as nitrogen. This vacuum cycle was performed three times. Next, 733 grams of succinic acid was added, and the vacuum cycle was performed one more time. Then, the reactor temperature was raised to a maximum of 220°C, during which time water was continuously removed in the receiver. Once the generation of water had settled, 299 grams of propanediol was added to the reactor. The temperature was slowly raised again to a maximum of 220°C. To complete the reaction, 1 gram of tin(II) ethylhexanoate was added, and a vacuum was applied. The materials were maintained until the appropriate molecular weight details were obtained.

[0107] Example 4 2314 grams of polyester and 186 grams of methylnadiic anhydride from Example 2 were placed in a reaction flask equipped with a nitrogen inlet and a vacuum function. The reactor temperature was raised to a maximum of 220°C, during which time the water was continuously removed from the receiver. Towards the end of the reaction, 0.63 grams of tin(II) ethylhexanoate was added. The materials were maintained until the appropriate molecular weight details were obtained.

[0108] Example 5 1124 grams of 1,6-hexanediol, 548 grams of succinic acid, and 827 grams of methylnadiic anhydride were placed in a reaction flask equipped with a nitrogen inlet and vacuum function. The reactor temperature was then raised to a maximum of 210°C, during which time the water was continuously removed from the receiver. Towards the end of the reaction, 0.63 grams of tin(II) ethylhexanoate was added. The materials were maintained until the appropriate molecular weight details were obtained.

[0109] Example 6 1155 grams of 1,6-hexanediol, 563 grams of succinic acid, and 783 grams of nadiic anhydride were added to a reaction flask equipped with a nitrogen inlet and vacuum function. The reactor temperature was then raised to a maximum of 210°C, during which time the water was continuously removed from the receiver. Towards the end of the reaction, 0.63 grams of tin(II) ethylhexanoate was added. The materials were maintained until the appropriate molecular weight details were obtained.

[0110] Example 7 1191 grams of 1,6-hexanediol, 871 grams of succinic acid, and 438 grams of methylnadiic anhydride were placed in a reaction flask equipped with a nitrogen inlet and vacuum function. The reactor temperature was then raised to a maximum of 210°C, during which time the water was continuously removed from the receiver. Towards the end of the reaction, 0.63 grams of tin(II) ethylhexanoate was added. The materials were maintained until the appropriate molecular weight details were obtained.

[0111] Examples 8-20 In each of these examples, a polymer composition was prepared by incorporating one of the impact-resistant polyesters from Examples 1 to 7. The polymer composition was extruded using a 27 mm twin-screw Entek kneading extruder. In Examples 8 to 15, 19, and 20, the extruded material samples were tested for tensile strength and elongation using an Instron 34™-10 according to ATM D638 (Type I sample). Impact strength tests were performed using an Instron 9050 tester according to ATM D256 (Test Method A). In Examples 16 to 18, the extruded material samples were tested using an Instron CEAST 9050 Pendulum. The restoring force was tested using an Impact System test apparatus in accordance with ASTM D4812-19.

[0112] For each example, a control sample was also prepared, extruded, and tested in the same manner as the test sample. In each example, the composition of the control sample was the same as that of the test sample, except that the impact-modifying polyester was excluded from the polymer composition.

[0113] Example 8 In a 27mm kneading extruder, 42.5 kg of PHA, 453 g of pentaerythritol, and 172 g of Joncryl 4468 were mixed with 2.27 kg of the reaction product from Example 1, and the kneading extruder was operated. When the plastic was tested, it exhibited a tensile strength of 26379 kPa (compared to 24097 kPa for the control); an elongation of 8.9% (compared to 10.6% for the control); and an impact strength of 0.344 J / cm (compared to 0.288 J / cm for the control).

[0114] Example 9 In a 27mm kneading extruder, 40 kg of PHA, 453 g of pentaerythritol, and 340 g of Joncryl 4468 were mixed with 4.53 kg of the reaction product from Example 1, and the kneading extruder was operated. When the plastic was tested, it exhibited a tensile strength of 24242 kPa (compared to 24097 kPa for the control); an elongation of 11.3% (compared to 10.6% for the control); and an impact strength of 0.408 J / cm (compared to 0.288 J / cm for the control).

[0115] Example 10 In a 27mm kneading extruder, 40 kg of PHA, 317 g of Joncryl 4468, and 453 g of pentaerythritol were mixed with 4.5 kg of the reaction product from Example 1, and the kneading extruder was operated. When the plastic was tested, it exhibited a tensile strength of 19981 kPa (compared to 27303 kPa for the control); an elongation of 2.2% (compared to 9.3% for the control); and an impact strength of 0.259 J / cm (compared to 0.301 J / cm for the control).

[0116] Example 11 In a 27mm kneading extruder, 37.6 kg of PHA, 498 g of Joncryl 4468, and 453 g of pentaerythritol were mixed with 6.8 kg of the reaction product from Example 1, and the kneading extruder was operated. When the plastic was tested, it exhibited a tensile strength of 26745 kPa (compared to 27303 kPa for the control); an elongation of 11.5% (compared to 9.3% for the control); and an impact strength of 0.256 J / cm (compared to 0.301 J / cm for the control).

[0117] Example 12 In a 27mm kneading extruder, 40.6 kg of PHA and 227 kg of boron nitride were mixed with 4.53 kg of the reaction product from Example 1, and the kneading extruder was operated. When the plastic was tested, it exhibited a tensile strength of 19960 kPa (compared to 24097 kPa for the control); an elongation of 11.8% (compared to 10.6% for the control); and an impact strength of 0.232 J / cm (compared to 0.288 J / cm for the control).

[0118] Example 13 In a 27mm kneading extruder, 42.9 kg of PHA and 227 grams of boron nitride were added, along with 2.27 kg of the reaction product from Example 6, and the kneading extruder was operated. When the plastic was tested, it showed a tensile strength of 16899 kPa (compared to a control of 24097 kPa); elongation of 15.5% (compared to a control of 10.6%); and impact strength of 0.275 J / cm (compared to a control of 10.6%). The control group showed a reading of 0.288 J / cm³.

[0119] Example 14 In a 27mm kneading extruder, 40.6 kg of PHA and 227 grams of boron nitride were added, along with 4.53 kg of the reaction product from Example 6, and the kneading extruder was operated. When the plastic was tested, it exhibited a tensile strength of 12941 kPa (compared to 24097 kPa for the control); an elongation of 16.6% (compared to 10.6% for the control); and an impact strength of 0.324 J / cm (compared to 0.288 J / cm for the control).

[0120] Example 15 In a 27mm kneading extruder, 40.6 kg of PHA and 227 grams of boron nitride were added, along with 4.53 kg of the reaction product from Example 5, and the kneading extruder was operated. When the plastic was tested, it exhibited a tensile strength of 19167 kPa (compared to 24097 kPa for the control); an elongation of 18.4% (compared to 10.6% for the control); and an impact strength of 0.277 J / cm (compared to 0.288 J / cm for the control).

[0121] Example 16 In a 27mm kneading extruder, 42.87 kg of PHA and 227 grams of boron nitride were added, along with 2.27 kg of the reaction product from Example 6, and the kneading extruder was operated. When the plastic was tested, it showed a restoring force of 66.9 kJ / m². 2 This was observed, and for comparison, the control was 14.5 kJ / m³. 2 That was the case.

[0122] Example 17 In a 27mm kneading extruder, 40.6 kg of PHA and 227 grams of boron nitride were added, along with 4.53 kg of the reaction product from Example 6, and the kneading extruder was operated. When the plastic was tested, it showed a restoring force of 67.1 kJ / m². 2 This was observed, and for comparison, the control was 14.5 kJ / m³. 2 That was the case.

[0123] Example 18 In a 27mm kneading extruder, 40.6 kg of PHA and 227 grams of boron nitride were added, along with 4.53 kg of the reaction product from Example 7, and the kneading extruder was operated. When the plastic was tested, it showed a restoring force of 39.5 kJ / m². 2 This was observed, and for comparison, the control was 14.5 kJ / m³. 2 That was the case.

[0124] Example 19 In a 27mm kneading extruder, 40.6 kg of PHA and 227 grams of boron nitride were added, along with 4.53 kg of the reaction product from Example 4, and the kneading extruder was operated. When the plastic was tested, it showed a restoring force of 11.1 kJ / m². 2 The result was as follows, and for comparison, the control was 2.34 kJ / m³. 2 That was the case.

[0125] Example 20 In a 27mm kneading extruder, 44kg of PHA was added to 1.36kg of the reaction product from Example 3, and the kneading extruder was operated. When the plastic was tested, it exhibited a tensile strength of 1386kPa (compared to 1572kPa for the control), an elongation of 5.3% (compared to 5.6% for the control), and an impact strength of 0.167J / cm (compared to 0.301J / cm for the control).

[0126] From the above, it can be seen that the impact-resistant polyesters according to this disclosure can bring about improvements in a wide range of mechanical properties compared to bioplastics. For example, a fourfold increase in impact strength or an 11% increase in elongation can be achieved without a corresponding loss of tensile strength. In other words, the impact-resistant polyesters of this disclosure enable the tuning of the mechanical properties of bioplastics to suit specific end applications.

[0127] The above description of preferred embodiments of the present invention is provided for explanatory and illustrative purposes only. It is not intended to be exhaustive, nor is it intended to limit the invention to the disclosed form. Obvious modifications or alterations are possible in light of the above teachings. The embodiments have been selected and described in an effort to provide the best explanation of the principles of the present invention and its practical applications, thereby enabling those skilled in the art to utilize the invention in various embodiments with various modifications to suit a particular purpose of use. All such modifications and alterations, when interpreted in accordance with the breadth given thereto fairly, lawfully, and equitably, fall within the scope of the present invention as defined by the appended claims.

Claims

1. It is made of polyester, and the following: An amount of isosorbide monomer repeating units of approximately 40 weight percent or less, Approximately 25 to approximately 60 weight percent of dicarboxylic acid or dicarboxylic acid anhydride monomer repeating units, and It consists only of repeating units of polyhydric alcohol monomers, comprising approximately 10 to 20 weight percent. The total amount of isosorbide monomer repeating units, dicarboxylic acid or dicarboxylic acid anhydride monomer repeating units, and polyhydric alcohol monomer repeating units is 100% by weight. According to ASTM D5296-05, the weight-average molecular weight is at least 8000 daltons. The dicarboxylic acid or dicarboxylic acid anhydride comprises a mixture of (1) succinic acid or succinic anhydride, and (2) nadiic acid anhydride or methylnadiic acid anhydride. The polyhydric alcohol is selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, 1,1,1-trimethylolethane, 1,2,3-trimethylolpropane, methylpropanediol, pentaerythritol, and poly(oxyalkylene) polyols containing repeating monomer units of ethylene oxide, propylene oxide, or butylene oxide, as well as mixtures thereof. The aforementioned polyester.

2. The polyester according to claim 1, wherein the polyester comprises about 25 to about 35 weight percent succinic acid or succinic anhydride, and about 10 to about 25 weight percent nadiic anhydride or methylnadiic anhydride.

3. The polyester according to claim 1, wherein the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methylpropanediol, and mixtures thereof.

4. The polyester according to claim 1, wherein the polyhydric alcohol comprises 1,3-propanediol.

5. The polyester according to claim 1, wherein the polyester has a weight-average molecular weight of about 10,000 to about 15,000 daltons, as specified by ASTM D5296-05.

6. A polymer composition, the following: A biodegradable polymer selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoate), and mixtures thereof, in an amount of approximately 50 to approximately 95 percent by weight, and It contains approximately 5 to 50 percent by weight of impact-resistant improved polyester, The aforementioned impact-resistant improved polyester is An amount of isosorbide monomer repeating units of approximately 40 weight percent or less, Approximately 25 to approximately 60 weight percent of dicarboxylic acid or dicarboxylic acid anhydride monomer repeating units, and It consists only of repeating units of polyhydric alcohol monomers, comprising approximately 10 to 20 weight percent. The total amount of isosorbide monomer repeating units, dicarboxylic acid or dicarboxylic acid anhydride monomer repeating units, and polyhydric alcohol monomer repeating units is 100% by weight. The polyester, as specified by ASTM D5296-05, has a weight-average molecular weight of at least 8000 daltons. The dicarboxylic acid or dicarboxylic acid anhydride comprises a mixture of (1) succinic acid or succinic anhydride, and (2) nadiic acid anhydride or methylnadiic acid anhydride. The polyhydric alcohol is selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, 1,1,1-trimethylolethane, 1,2,3-trimethylolpropane, methylpropanediol, pentaerythritol, and poly(oxyalkylene) polyols containing repeating monomer units of ethylene oxide, propylene oxide, or butylene oxide, as well as mixtures thereof. The aforementioned polymer composition.

7. The polymer composition according to claim 6, wherein the polyester comprises about 25 to about 35 weight percent succinic acid or succinic anhydride and about 10 to about 25 weight percent nadiic anhydride or methylnadiic anhydride.

8. The polymer composition according to claim 6, wherein the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methylpropanediol, and mixtures thereof.

9. The polymer composition according to claim 6, wherein the polyhydric alcohol comprises 1,3-propanediol.

10. The polymer composition according to claim 6, wherein the impact-resistant polyester has a weight-average molecular weight of 10,000 to 15,000 daltons, as specified by ASTM D5296-05.

11. The polymer composition according to claim 6, comprising about 60 to about 85 weight percent of the biodegradable polymer and about 5 to about 30 weight percent of the impact-resistant polyester.

12. The polymer composition according to claim 6, wherein the biodegradable polymer comprises poly(lactic acid).

13. The polymer composition according to claim 6, wherein the biodegradable polymer comprises at least one poly(hydroxyalkanoate).

14. The polymer composition according to claim 13, wherein the at least one poly(hydroxyalkanoate) comprises poly-3-hydroxybutyrate-co-3-hydroxyhexanoate ("P(3HB-co-3HHx)").

15. The polymer composition according to claim 14, wherein P(3HB-co-3HHx) comprises about 75 to about 99 mole percent of hydroxybutyrate and about 1 to about 25 mole percent of hydroxyhexanoate.

16. The polymer composition according to claim 14, wherein P(3HB-co-3HHx) comprises about 93 to about 98 mole percent of hydroxybutyrate and about 2 to about 7 mole percent of hydroxyhexanoate.

17. The polymer composition according to claim 13, wherein the at least one poly(hydroxyalkanoate) has a weight-average molecular weight of 50,000 daltons to 2,500,000 daltons, as specified by ASTM D5296-05.

18. The polymer composition according to claim 13, wherein the at least one poly(hydroxyalkanoate) has a weight-average molecular weight of 500,000 daltons to 750,000 daltons, as specified by ASTM D5296-05.

19. The polymer composition according to claim 6, wherein the polymer composition comprises, based on the total weight of the polymer composition, about 5 to about 25 weight percent of poly(lactic acid) and about 70 to about 90 weight percent of at least one poly(hydroxyalkanoate).

20. Furthermore, the following: Approximately 1 to approximately 10 weight percent of at least one plasticizer, A nucleating agent in an amount of at least one type, in a quantity of approximately 0.1 to approximately 5 weight percent, and Approximately 0.1 to 10 weight percent of a bulking agent, The polymer composition according to claim 6, comprising:

21. The polymer composition according to claim 6, wherein the polymer composition is biodegradable as specified using ASTM standard D5988.

22. The polymer composition according to claim 6, wherein the polymer composition is compostable at home, as specified using ASTM standard D6868.

23. A molded sheet comprising the polymer composition described in claim 6.

24. A molded article comprising the polymer composition described in claim 6, wherein the article is formed by thermoforming, injection molding, or blow molding.

25. A film comprising the polymer composition described in claim 6, wherein the film is an inflated film or a cast film.

26. A fiber comprising the polymer composition described in claim 6.