US20150291788A1 - Durable polyhydroxyalkanoate compositions - Google Patents

Durable polyhydroxyalkanoate compositions Download PDF

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US20150291788A1
US20150291788A1 US14/379,810 US201314379810A US2015291788A1 US 20150291788 A1 US20150291788 A1 US 20150291788A1 US 201314379810 A US201314379810 A US 201314379810A US 2015291788 A1 US2015291788 A1 US 2015291788A1
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polyhydroxyalkanoate
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hydroxybutyrate
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Alessandro CARFAGNINI
Leonardo BELLOMO
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Sabio Srl
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C08L23/0884—Epoxide-containing esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Definitions

  • the current invention concerns durable polyhydroxyalkanoate compositions. More in particular, the present invention relates to polymeric compositions that are based on polyhydroxyalkanoate polymers, which are biodegradable and renewable bioplastics, and that can be melt processed similar to polypropylene based compositions into various forms such as moulded articles, films, fibers and nonwovens, and the like.
  • Polyhydroxyalkanoates or PHAs are linear polyesters produced in nature by bacterial fermentation of sugar or lipids and hence are considered renewable bioplastics. These bioplastics are produced by bacteria to store carbon and energy. More than 150 different monomers can be combined within this family to give materials with extremely different properties. These polymers are biodegradable. Poly(3-hydroxybutyrate) or P(3HB) is the best well-known and most used member of the class of PHAs.
  • PHAs with short side chains such as polyhydroxybutyrate (PHB), a homopolymer of 3-hydroxybutyric acid units, are crystalline thermoplastics; PHAs with long side chains are more elastomeric. PHAs of microbial origin containing both 3-hydroxybutyric acid units and longer side chain units from C5 to C16 are also known. A number of bacteria which produce copolymers of 3-hydroxybutyric acid and one or more long side chain hydroxyacid units containing from five to sixteen carbon atoms have been identified.
  • a known example of specific two-component copolymers includes PHB-co-3-hydroxyhexanoate.
  • Other biodegradable polymers are polylactic acid (PLA), polycaprolactone (PCL), polybutylene succinate (PBS), polyanhydrides, polyvinyl alcohol (PVA), most starch derivatives, and cellulose esters like cellulose acetate and nitrocellulose and their derivatives (celluloid).
  • PLA and PCL are not considered PHAs since PLA is produced chemically from lactic acid or lactide, and PCL is produced starting from fossil fuel.
  • PHAs are considered fully compostable, meaning they will biodegrade under common composting conditions. These biodegradable polymers are typically used for disposables.
  • US 2009018235 refers to a polymeric composition prepared from a biodegradable polymer defined by poly(hydroxybutyrate) (PHB) or copolymers thereof, and at least one other biodegradable polymer, such as polycaprolactone (PCL) and poly (lactic acid) (PLA), so as to alter its structure.
  • the composition further comprises at least one additive of the type of natural filler and natural fibers, and, optionally, nucleant, thermal stabilizer, processing aid, with the object of preparing an environmentally degradable material.
  • US 2009030112 describes a biodegradable polymeric composition for manufacturing biodegradable articles and films, that comprises PHB, plasticizer obtained from a renewable source, nucleant additive, flow aid additive and a thermal stabilizer additive.
  • EP 781309 A and CA 2231568 both relate to polymeric compositions that are biodegradable and that can be melt processed into various forms, including films, fibers, and nonwovens.
  • the compositions include compatible or semicompatible blends of biodegradable polymers and have physical and thermomechanical integrity. Films formed from preferred polymeric compositions are suitable for use as backsheets in disposable absorbent articles.
  • the polymeric composition includes a polyhydroxyalkanoate and at least one other biodegradable polymer selected from aliphatic polyester-based polyurethanes, a polylactide, polycaprolactone, or a mixture of two or more of these polymers.
  • Biodegradable compositions further comprising PLA and/or starch or similar biodegradable polymers have been used particularly for the manufacturing of disposables.
  • PHAs have also been used in non-disposables or durable goods, as replacement for fossil or petrochemical based polymers. In such applications being made and accordingly being labelled as made a composition from a renewable source is highly appreciated.
  • Biodegradability for non-disposable and/or durable goods is then a disadvantage.
  • the presence of degradability enhancing components like PLA and starch are clearly undesired.
  • PLA being rather crystalline in nature, is undesired also for its lack of thermal stability and rather poor processability.
  • WO 2011/007092 relates to a PHA composition, further including: (A) a core-shell elastomer compound; and (B) an olefin copolymer including an ethylenic monomer having an epoxy function. Said composition exhibits excellent impact properties, in particular under cold conditions.
  • the invention also relates to a method for manufacturing said composition and to parts manufactured from said composition.
  • Component (B) may for instance be Lotader® AX 8900 (see Examples), an acrylic type terpolymer.
  • the compositions are based on PLA and therefore not an ideal replacement of conventional plastics.
  • EP1826241 also discloses a resin composition
  • a resin composition comprising an aliphatic polyester type biodegradable polymer and a copolymer of the core-shell type comprising an acrylic rubber as the core layer and a vinyl-monomer-derived polymer as the shell layer.
  • the biodegradable polymer may be a PHA.
  • the acrylic rubber comprises an alkyl acrylate co-polymer which may also comprise aromatic vinyl monomers.
  • the compositions are exemplified in experiments with several PHAs and a core-shell graft copolymer comprising an acrylic rubber as the core layer and a vinyl monomer-derived polymer as the shell layer (Kane Ace M-400, from Kaneka). Although the copolymer improve some of the mechanical properties, there is still room for further improvement.
  • EP 0701586 A discloses a polyester composition that comprises a biodegradable polyester and a plasticising quantity of a particular plasticizer.
  • P3HB polyhydroxybutyrate
  • PP polypropylene
  • Vincotte is an organisation specialized in certifying biodegradable products. As a result of the increased environmental awareness among customers, there is a growing market for products on a basis of renewable raw materials. That environmentally conscious motivation on the part of customers is exactly the reason why there is a need for an independent, high-quality guarantee of the renewability of raw materials. Vincotte therefore proposes a single to four star “OK biobased” certification system, that provides information on the content of renewable materials in the labelled product.
  • compositions that contain more than 20% (by weight) of non-fossil carbon (single star “OK biobased”), preferably more than 40% wt of non-fossil carbon (double star “OK biobased”) and that can substitute the common PP based compositions for durable mass-produced goods such as mobile phone parts.
  • non-fossil carbon single star “OK biobased”
  • double star “OK biobased” double star “OK biobased”
  • elongation at break (ASTM D638) of greater than 3%, preferably greater than 3.5%, more preferably greater than 4%, an impact resistance (ISO179 1 eU, 23° C., unnotched) of greater than 18 kJ/m 2 , and a flexural modulus (ASTM D790) of greater than 950 MPa, preferably greater than 1000 MPa, more preferably greater than 1500 MPa.
  • ISO179 1 eU, 23° C., unnotched impact resistance
  • ASTM D790 flexural modulus
  • compositions that have improved processing properties.
  • a common PP composition may have a melt flow index (MFI, ASTM D1238 @ 230° C./2.16 kg) of 26 g/10 min. Achieving a similar MFI at a lower temperature will allow milder injection moulding conditions and thus will provide some energy savings while processing the composition.
  • MFI melt flow index
  • a composition that shows better aesthetical properties (gloss), improved ability to be printed, painted or coated (polypropylene requires a special treatment), and improved UV stability. Such compositions have now been found.
  • the current invention provides a composition as claimed in claim 1 .
  • the invention provides a polyhydroxyalkanoate composition having an elongation at break (ASTM D638) greater than 3%, an impact resistance (Charpy test, ISO179 1 eU, 23° C., unnotched) greater than 18 KJ/m 2 and a flexural modulus of at least 950 MPa comprising:
  • a polyhydroxyalkanoate component (I) comprising one or more hydroxyalkanoate copolymers and wherein the content of poly(3-hydroxybutyrate) homopolymer is at most 1 ⁇ 4 th of the total amount of component (I) and less than 5% wt;
  • thermoplastic polymers as a non-polyhydroxyalkanoate component (II), comprising no more than 5% wt biodegradable polymers (ASTM D6400);
  • plasticizers (IV) from 0 to 20% wt of one or more plasticizers (IV).
  • the composition comprises a 3HB copolymer as main PHA component (I).
  • the composition may comprise the 3HB homopolymer, P(3HB), but only up to 5% wt on the PHA composition.
  • it may contain no more than 5% wt of PLA or other biodegradable polymer as component (II) in the PHA composition.
  • the composition further comprises an acrylate polymer and/or thermoplastic polyurethane (TPU).
  • TPU thermoplastic polyurethane
  • it may comprise an epoxidized vegetable oil (preferably epoxidized soybean oil) as plasticizer and/or a filler.
  • Polyhydroxyalkanoates are known. P(3HB) is the most common representative of this class of biobased polyesters. However, it has been found that the mechanical and thermal properties of this homopolymer are insufficient. On the other hand, it has been found that the use of a copolymer of a hydroxyalkanoate (with one or more dissimilar hydroxyalkanoates) does allow for compositions that have the desirable mechanical and thermal properties (close to or better than those of polypropylene-based compositions).
  • the definition of a copolymer indicates that there is at least one repeating unit that is dissimilar to the hydroxyalkanoate used as the main repeating unit; it excludes homopolymers.
  • Component (I) therefore preferably comprises one or more copolymers of a 3-hydroxyalkanoate. More preferably, the PHA composition comprises one or more copolymers of 3-hydroxybutyrate and a 3-hydroxyalkanoate with more than 4 carbon atoms; and/or one or more copolymers of 3-hydroxybutyrate and a 4-hydroxyalkanoate with 4 or more carbon atoms; and/or a terpolymer of 3-hydroxybutyrate and two or more hydroxyalkanoates as component (I).
  • Typical and preferred examples of such copolymers include the copolymer of 3-hydroxybutyrate and 4-hydroxybutyrate p(3HB-co-4HB), the copolymer of 3-hydroxybutyrate and 3-hydroxyvalerate p(3HB-co-3HV), the copolymer of 3-hydroxybutyrate and 3-hydroxyhexanoate p(3HB-co-3HH) or a copolymer of 3-hydroxybutyrate and 3-hydroxyoctanoate p(3HB-co-3HO).
  • P(3HB-co-3HV) is most preferred.
  • blends of polyhydroxyalkanoates may be used. Such blends may even comprise a minor amount of homopolymers (i.e., up to 1 ⁇ 4 th on the blend of such polyhydroxyalkanoates). On the other hand, the presence of homopolymers is preferably avoided.
  • the PHA composition preferably contains less than 5, preferably less than 3% wt poly(3-hydroxybutyrate) homopolymer.
  • the polyhydroxyalkanoate is preferably present in an amount of 35 to 85% wt.
  • a durable composition may be made, with at least 35% wt of a polyhydroxyalkanoate component (I). This is surprising since this component in principle is highly biodegradable.
  • the expression “durable”, used in respect of the composition, is the opposite of biodegradable.
  • durable and biodegradable are terms that have not been clearly defined. According to Wikipedia, a durable good or a hard good in economics is a good that does not quickly wear out, or more specifically, one that yields utility over time rather than being completely consumed in one use. Highly durable goods such as refrigerators, cars, or mobile phones usually continue to be useful for three or more years of use, so durable goods are typically characterized by long periods between successive purchases. Examples of consumer durable goods include cars, household goods (home appliances, consumer electronics, furniture, etc.), sports equipment, and toys.
  • Nondurable goods or soft goods are the opposite of durable goods. They may be defined either as goods that are immediately consumed in one use or ones that have a lifespan of less than 3 years.
  • Biodegradable compositions are compositions that in accordance with the ASTM D6400 standard undergo at least 60% biodegradation within 180 days. A durable composition on the other hand should stay well below 10% biodegradation under this condition.
  • Component (II) may be selected from one or more of the thermoplastic polymers (IIa), or (IIb) defined hereinafter.
  • thermoplastic polyurethane (IIa) is used as component (II), more preferably a TPU have a Melting Point (measured according to ASTM3418) lower than 200, preferably lower than 190, more preferably lower than 180° C.
  • the thermoplastic polyurethane (IIa) may suitably have a glass transition temperature Tg lower than 40° C. (measured according to ISO 11357) and/or a hardness lower than 56 Shore D (measured according to ASTM D2240).
  • Thermoplastic polyurethanes (TPUs) are particularly advantageous as component (IIa), such as the TPUs described in U.S. Pat. No. 5,344,882 and U.S. Pat. No.
  • thermoplastic polyurethanes suited for use in the compositions of the present invention can be selected from those commercially available or can be made by processes known in the art. See, for example, Rubber Technology, 2nd edition, edited by Maurice Morton (1973), Chapter 17, Urethane Elastomers, D. A. Meyer, especially pp. 453-6.
  • Thermoplastic polyurethanes used herein are derived from the reaction of polyester or polyether polyols with diisocyanates and optionally also from the further reaction of such components with chain-extending agents such as low molecular weight polyols, preferably diols, or with diamines to form urea linkages.
  • Thermoplastic polyurethanes are generally composed of soft segments, for example polyether or polyester polyols, and hard segments, usually derived from the reaction of the low molecular weight diols and diisocyanates. While a thermoplastic polyurethane with no hard segments can be used, those most useful will contain both soft and hard segments. Processes for making TPUs are well known and include both single or multiple step polymerizations.
  • this TPU is a block copolymer. Excellent results have been achieved with a polyurethane that is based on a saturated polyester, preferably based on adipic acid, reacted with an aromatic isocyanate, preferably 4,4′-methylenediphenyl diisocyanate (MDI).
  • MDI 4,4′-methylenediphenyl diisocyanate
  • the PU is a block copolymer commercially available as Laripur® 8025. This component may be used as sole component (II), but is preferably used in combination with another thermoplastic polymer, as discussed hereinafter.
  • thermoplastic polymer as component (II) is an acrylic polymer with a value of Melt flow Index (ASTM D1238, 175° C./2.16 kg) higher than 0.25 g/10 min and/or a glass transition temperature, Tg, less than 150° C., preferably less than 120° C., more preferably less than 100° C.
  • Tg glass transition temperature
  • suitable are methacrylate/butadiene/styrene multiphase composite interpolymers such as those available from Rohm & Haas Co under the tradename PARALOID.
  • This component is preferably a crosslinked butadiene acrylonitrile elastomer, and/or a crosslinked acrylate terpolymer, more preferably a crosslinked styrene-acrylate elastomer. Most preferably this component is a block copolymer of acrylate, styrene and acrylonitrile, commercially available as Sunigum® P2100.
  • the acrylic polymer may be a terpolymer (IIb2) containing maleic and/or glycidyl groups.
  • a terpolymer IIb2 containing maleic and/or glycidyl groups.
  • U.S. Pat. No. 5,380,785 incorporated herein by reference, specifically discloses acrylate terpolymer rubbers being comprised of repeat units which are comprised of (a) butyl acrylate, or optionally a mixture of butyl acrylate and 2-ethylhexyl acrylate containing up to about 40 percent 2-ethylhexyl acrylate, (b) at least one member selected from the group consisting of methyl methacrylate, ethyl methacrylate, methyl acrylate and ethyl acrylate, (c) acrylonitrile, (d) styrene, (e) a half ester maleate soap and (f) a cros slinking agent.
  • SunigumTM P95 is a suitable component, that is a copolymer rubber obtained by copolymerization of styrene, acrylonitrile, butyl acrylate, methyl methacylate, acrylic acid, methacrylic acid, and divinyl benzene.
  • a copolymer rubber obtained by copolymerization of styrene, acrylonitrile, butyl acrylate, methyl methacylate, acrylic acid, methacrylic acid, and divinyl benzene.
  • U.S. Pat. No. 5,616,651 and U.S. Pat. No. 6,337,374 describe the composition and preparation of the copolymer rubber and are incorporated herein by reference.
  • this is a terpolymer of ethylene, an acrylate or methacrylate e.g.
  • Thermoplastic polyurethane polymers (IIa) and acrylic polymers (IIb, IIb1 or IIb2) can contain monomers derived from renewable natural sources.
  • biodegradable compositions it is common to use a biodegradable polymer as component (II) in addition to the PHA.
  • a biodegradable polymer undergo at least 60% biodegradation within 180 days in accordance with the ASTM D6400 standard.
  • Examples are PLA; PCL; PBS; aliphatic polyanhydrides; polyvinyl alcohol (PVA); starch and starch derivatives, and cellulose esters and their derivatives.
  • PLA and PVA are frequently used as carrier in pigment masterbatch compositions. Accordingly, such polymer, if present at all, should not comprise more than 5% wt of the composition.
  • PLA adversely affects the mechanical properties of the PHA composition.
  • the presence of PLA results in a lesser impact resistance measured according to the Charpy test, (ISO 179 1 eU, unnotched), and a reduced elongation at break (ASTM D638).
  • the presence of PBS as single component (II) results only in a marginal improvement for the elongation at break, whereas both the elongation at break and the impact resistance greatly improve upon use of a TPU.
  • component (II) is not only essential for the durability of the PHA composition; it also significantly improves the mechanical properties (impact resistance and elongation at break).
  • a synergistic effect was found for the elongation at break when a combination of an acrylic polymer and a TPU was used.
  • the acrylic polymer can be any acrylic polymer, but is preferably selected from acrylic block copolymer (IIb1) and an acrylic terpolymer (IIb2), as described above. If a combination of components is used, then the combination of components TPU and acrylic polymer is used in relative weight amounts of 3:1 to 1:3, preferably 2:1 to 1:2.
  • the non-polyhydroxyalkanoate component (II) is used in an amount of 10 to 35% wt.
  • fillers are commonly used in moulded articles.
  • common fillers may be used.
  • component (III) may be selected from mineral fillers, synthetic fillers or mixtures thereof, preferably mineral fillers selected from talc, carbonates, silicates (more preferably clays and zeolites), and/or metal oxides (more preferably titanium oxide, zinc oxide, magnesium oxide).
  • the amount of fillers in the composition may vary widely. Preferably, the amount of filler is between 10 and 30% wt.
  • epoxidized oil provides the best balance of elongation at break and resistance to heat softening.
  • the oil may have a fossil origin or a vegetable origin.
  • the epoxidized oil can be aliphatic, including cycloaliphatic, or aromatic but preferably does not have olefinic unsaturation which is subject to oxidative degradation.
  • Preferred examples of such compounds are epoxy substituted ethers, esters, phosphonates and the like as well as high molecular weight polymers which are epoxy substituted.
  • Most preferred compounds are those comprised of at least 6 carbon atoms including 1,2-epoxyoctadecane, styrene epoxide, butyl-epoxy stearate, epoxidized polybutadiene, poly(alkylglycidyl)ethers, p-chlorophenoxypropylene oxide, dicyclopentadiene diepoxide, diglycidyl ether of bisphenol A, epoxidized fatty acid triglycerides such as epoxidized soybean oil, linseed oil, sunflower seed oil, safflower oil, hempseed oil, oiticica oil, sesame oil, cottonseed oil, castor oil, olive oil, peanut oil, rapeseed oil, coconut oil, babassu oil, palm oil and the like.
  • component (IV) is an epoxidized oil with a vegetable source, more preferably epoxidized soybean oil. Using an epoxidized oil with a vegetable source allows the percentage of non-fossil carbon to go even further up. Component (IV) is preferably used in an amount of 1 to 15% wt.
  • the polyhydroxyalkanoate composition may contain one or more common additives.
  • Suitable additives include antioxidants, anti-hydrolysis agents, UV stabilizing agents, pigments and surface modification agents.
  • Other additives that may be used include blowing agents, mould release agents, anti-scratch agents and antibiotics.
  • the fillers, plasticizers and additives that can be used in the composition according to the invention may be obtained from natural sources or synthetic sources. Some of them may suitably be derived from renewable natural sources.
  • composition of the present invention is preferably used in conventional moulding processes under typical process conditions.
  • the temperature settings may be slightly lower than those used when a polypropylene based composition is used. Aside from this, no further adaptation of equipment and the like is needed. Indeed, being able to substitute PP based compositions is one of the merits of the current invention.
  • the composition of the present invention is preferably used for the preparation of durable goods, allowing these durable goods to be labelled as containing more than 20 preferably more than 40, more preferably more than 60% wt non-fossil carbon.
  • the durable goods made from the present composition are believed to be novel. They too may be labelled or marketed as containing more than 50% wt non-fossil carbon. Accordingly this patent also claims the articles made from the composition of the present invention. In particular articles made for automotive applications, household goods (home appliances, consumer electronics, furniture, etc.), sports equipment, and toys.
  • Table 1 shows a comparison between a PP based composition based on 69.2% wt polypropylene, 0.5% wt antioxidant; 0.8% wt titanium dioxide and 29.5% wt talc and a PHA composition according to the invention, containing 56.5% wt P(3HB-co-3HV), 16.0% wt TPU, 0.5% wt antioxidant, 3.5% wt epoxidized soybean oil and 23.5% wt talc.
  • the table shows that the PHA composition is very similar to the PP based composition, even outperforming the PP based composition in terms of flexural modulus, thermal properties and gloss.
  • the table here below represents the amounts of the ingredients of the PP-based composition and the PHA-based composition.
  • Table 2 shows the components used in this model experiment. In this case, no plasticizer was present.
  • One composition was made with TPU as component (II), the comparative composition was made used PLA.
  • Table 3 the effect on the mechanical properties is illustrated. This table clearly shows the adverse effect on both resilience and elongation at break.
  • Table 4 shows a composition containing the pure PHA (comparative) and compositions containing TPU polymer, acrylic polymer or a mixture of polyurethane and acrylic polymers.
  • Table 5 reports measures of physical properties.
  • Entry 4 Entry 5 in comparison to Entry 3 show that the presence of the claimed non-HPA component (II), either an acrylic polymer or TPU polymer improve the values of both Resilience and Elongation at break.
  • the claimed non-HPA component (II) either an acrylic polymer or TPU polymer improve the values of both Resilience and Elongation at break.
  • Entry 5 in comparison to Entry 4 shows that the presence of acrylic polymers leads to a higher value of elongation at break than the one exhibited by a composition containing the same amount of TPU.
  • an object made of a material whose composition is Entry 5 will withstand a higher deformation before breaking down than one whose composition is Entry 4.
  • Entry 4 shows that the presence of TPU leads to a higher value of Vicat than the one exhibited by a composition containing the same amount of acrylic polymer.
  • Entry 6 shows a synergistic effect of the use of both acrylic polymers and TPU when elongation at break value is kept in consideration.
  • Table 6 shows compositions containing different plasticizers wherein epoxidized soybean oil is the preferred plasticizer according to the invention. Although glycerine, triethyl citrate and polyadipate are conventional plasticizers, in the current composition they are not preferred. In Table 7 the results are reported.
  • Entry 10 Entry 11, Entry12, Entry13 show different values of Elongation at break.
  • the highest value is given by Entry 10 where epoxidized soybean oil is used.
  • epoxidized Soybean oil is preferred because represents the best trade-off between the properties of Elongation at Break and resistance to heat softening.
  • Table 8 shows compositions according to the invention containing different amounts of epoxidized soybean oil. In Table 9 the results are reported.
  • Entry 14 increases with the increased amount of the plasticizer. Flexural modulus decreases with the increase of the amount of plasticizer. Entry 16 is a flexible material that has a high resistance to shocks.
  • Entry 14 Entry 15 Entry 16 Izod test, ASTM D256 J/m 30.6 30.7 38.3 notched (0°) Charpy test, ISO179 1eU kJ/m 2 41.8 66.8 81.9 unnotched (23°) Charpy test, ISO179 1eU kJ/m 2 34.6 44.8 52.0 unnotched (0° C.) Elongation ASTM D638 % 10.9 29.7 14.1 at break Flexural ASTM D790 MPa 2928 2157 1611 Modulus Vicat ASTMD1525 ° C. 96.4 74.5 58.4 (50° C./ hr; 50N)
  • Table 10 shows compositions containing no non-HPA component (II) or different components (II). In Table 11 the results are reported.
  • Entry 7 shows the lowest values of resilience and elongation at break in comparison to both Entry 8 and Entry 9.
  • a comparison between Entry 8 and Entry 9 shows that TPU is more effective (about the twice) in comparison to an aliphatic polyester such as PBS.
  • Entry 7 Entry 8 Entry 9 P(3HB-CO-3HV) 80% 60% 60% TPU 20% PBS 20% Talc 20% 20% 20% 100% 100% 100% 100%
  • compositions were made according to the preferred embodiment of the invention. All showed excellent properties.
  • compositions according to the present invention in comparison to a composition comprising a core-shell type acrylic rubber thermoplastic polymer three compositions were prepared. In Entry 17 no thermoplastic polymer was added. In Entry 18 the same acrylic polymer as added in experiment 2 of Example 7 was added, and in Entry 19 a core-shell graft copolymer comprising an acrylic rubber as the core layer and a vinyl monomer-derived polymer as the shell layer (Kane Ace M-410, from Kaneka) was added. The compositions are recorded in Table 14.
  • composition according to the invention performs better than the other two compositions.
  • compositions according to the present invention containing a mixture of PHAs a composition was prepared as indicated in Table 16. The performance thereof was tested. The results of the tests are shown in Table 17.

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CN115087698A (zh) * 2019-12-10 2022-09-20 提克纳有限责任公司 包含其他生物基聚合物的纤维素酯组合物
WO2022218978A1 (en) * 2021-04-14 2022-10-20 Food Sourcing Specialists, S.L. An injection molding material for producing molded articles
WO2023034242A1 (en) * 2021-09-01 2023-03-09 Ohio State Innovation Foundation Plasticized biopolymer compositions and methods of making thereof
CN114134096A (zh) * 2022-02-07 2022-03-04 清华大学 3-羟基丁酸、4-羟基丁酸和3-羟基戊酸三元共聚物p(3hb-4hb-3hv)及其微生物生产
WO2024087609A1 (zh) * 2022-10-28 2024-05-02 北京蓝晶微生物科技有限公司 含多元酸的聚羟基烷酸酯组合物及聚羟基烷酸酯成型体

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