polymeric mixture composition of polylactic acid with polyhydroxyalkanoate, method of preparing said

专利摘要:
toughening of polylactic acid with polyhydroxyalkanoates. the present invention relates to polymeric mixtures of polylactic acid (pla) and polyhydroxyalkanoate. in certain embodiments, pha is a multiphase copolymeric mixture that has a totally amorphous phase with a glass transition temperature below 20ºc and has between about 45% of the total pha. methods of making the compositions of the invention are also described. the invention also includes articles, film and laminates that comprise the compositions.
公开号:BR112012029305B1
申请号:R112012029305
申请日:2011-05-17
公开日:2020-04-07
发明作者:K Krishnaswamy Rajendra
申请人:Cj Cheiljedang Corp；Cj Res Center Llc；Metabolix Inc；
IPC主号:

专利说明:

Descriptive Report of the Invention Patent for COMPOSITION OF POLYMERIC MIXTURE OF POLYLACTIC ACID WITH POLYHYDROXYALANCANATE, METHOD OF PREPARATION OF THE REFERRED COMPOSITION, MULTILAYER LAMINATE, ARTICLES AND FILM UNDERSTANDING.
CORRELATED DEPOSIT REQUESTS [001] This claim claims the benefit of US provisional application No. 61 / 345,458, filed on May 17, 2010 and US provisional application No. 61 / 356,986, filed on June 21, 2010. All lessons from the above requests are hereby incorporated by reference.
BACKGROUND OF THE INVENTION [002] Polylactic acid (PLA) is a commercial bio-based polymer that is known to be biodegradable in an industrial composting environment. The glass transition temperature of the PLA is around 55 to 60 ° C and can be highly crystalline depending on its stereochemistry and processing conditions. As a result of its high crystallinity, the PLA has a tensile modulus of about 2 to 3 GPa, which is considerably higher than that of polyethylene and polypropylene. However, the toughness of PLA is, in general, considered to be quite low and unsuitable for many applications.
[003] There have been several attempts to increase the tenacity of
PLA by mixing it with other additives and polymers. One of the PLA (INGEO®) suppliers, NatureWorks, found on the Internet at natureworksllc that describes part of the polymer blend approaches used to increase PLA toughness. Although part of the polymeric mixture approaches is promising, the options become very limited when the biodegradability of the components of the mixture is taken into account.
[004] A recent review article (K. S. Anderson, et al.,
Petition 870190136302, of 12/19/2019, p. 6/88
2/68
Polymer Reviews, 48, 85 (2008)) described the various approaches used to toughen PLA using different components of the mixture. Some plasticizers like citrate esters help to increase the toughness of PLA; However, this increase in toughness comes at the expense of tensile strength which is decreased by a factor of about seven (L. V. Labrecque, et al., Journal of Applied Polymer Science, 66, 1,507 (1997)). The use of low molecular weight polyethylene glycol (PEG) as a polymeric plasticizer also seemed to improve the toughness of PLA; However, the tensile strength was still considerably compromised, although not to the extent of the citrate ester plasticizer (M. Baiardo, et al., Journal of Applied Polymer Science, 90, 1.731 (2003)). Polycaprolactone (PCL) is a biodegradable aliphatic polyester that has been mixed with PLA with some modest improvements in toughness depending on the nature of the mixture preparation and the use of compatibilizing agents (L. Wang, et al., Degradation and Stability Polymer, 59 , 161 (1998); ME Broz, et al., Biomaterials, 24, 4,181 (2003); H. Tsuji and Y. Ikada, Journal of Applied polymer Science, 60, 2,367 (1996); M. Hiljanen-Vainio, et al., Macromolecular Chemistry and Physics, 197, 1,503 (1996)). More recently, reactive mixing of PLA with polyacrylic acid followed by physical mixing of polyethylene glycol in solution has shown promise to increase PLA toughness while maintaining modulus and tensile strength (RM Rasal, DE Hirt, Macromolecular Materials and Engineering, 295, Iss .3, 204 (2010)). However, this process has only improved the toughness of the PLA by approximately 10 times.
[005] The most significant improvement in PLA toughness has been reported in U.S. Patent No. 5,883,199 by McCarthy and co-workers. In this invention, mixtures of PLA with polybutylene succinate adipate (PBSA) (BIONOLLE 3001 with Showa Highpolymer
Petition 870190136302, of 12/19/2019, p. 7/88
3/68
Co. Ltd, Japan) showed a remarkable improvement in elongation and tensile strength over the PLA homopolymer. Specifically, a 70/30 PLA / PBSA (weight percent) mixture showed a 50-fold improvement in tensile strength at break and a 25-fold increase in tensile strength. However, although PBSA is a known biodegradable polymer, it is currently synthesized from petrochemical starting material and therefore has no biological basis.
[006] Polyhydroxyalkanoates (PHAs) are a unique material to address the issue of PLA toughness due to the fact that PHAs are easily mixed with PLA, they have a biological basis and are biodegradable in several different environments. The PLA / PHA mixtures were prepared and characterized by several research groups. They include mixtures of PLA with poly-3-hydroxybutyrate (P3HB) homopolymers and poly-3-hydroxybutyrate-co-hydroxyvalerate (PHBV) copolymers that showed small improvements in PLA toughness at load levels of about 10 to 30 percent (JS Yoon, WS Lee, KS Kim, IJ Chin,
M. N. Kim and C. Kim, European Polymer Journal, 36, 435 (2000); B. M. P. Ferreira, C. A. C. Zavaglia and E. A. R. Duek, Journal of Applied polymer Science, 86, 2898 (2002); I. Noda, M. M. Satkowski, A. E. Dowrey and C. Marcott, Macromolecular Bioscience, 4, 269 (2004); K. M. Schreck and M. A. Hillmeyer, Journal of Biotechnology, 132, 287 (2007)). Noda and co-workers (I. Noda, MM Satkowski, AE Dowrey and C. Marcott, Macromolecular Bioscience, 4, 269 (2004)) observed a 7-fold increase in tensile strength in PLA at a 20 percent load in weight of a poly-3-hydroxybutyrate-co-3-hydroxy-hexanoate copolymer (P3HB-3HH) only for time scales for which the PHA remained non-crystalline. It should be noted that the time scale can be theoretically manipulated to be as ex
Petition 870190136302, of 12/19/2019, p. 8/88
4/68 tense for 2 to 4 years depending on the size scale of the dispersed PHA domains. While an 80/20 mix of PLA / P3HB-3HH looks promising, others have had difficulty reproducing this result (K. M. Schreck and M. A. Hillmeyer, Journal of Biotechnology, 132, 287 (2007)).
[007] Therefore, there is a need to produce mixtures of polylactic acid and polyhydroxyalkanoates with improved reproducible mechanical properties for the general composition.
SUMMARY OF THE INVENTION [008] Polymeric mixtures of polylactic acids (PLAs) and polyhydroxyalkanoates (PHAs) are described herein. In a first aspect of the invention, the polymeric blend composition comprises polylactic acid and a PHA polymer, copolymer or mixture thereof which has a glass transition temperature of about -5 ° C to about -50 ° C. In a second aspect of the invention, the polymeric mixture composition is polylactic acid (PLA) and a multiphase copolymeric mixture of PHA, with a phase of the copolymeric mixture of PHA being an amorphous rubber phase, with a glass transition temperature (Tg ) between about -15 ° C and about -40 ° C, and has between 5 to 45% of the total PHA in the composition.
[009] In particular embodiments of the first or second aspects of the invention, the PHA comprises an amorphous rubber phase comprising a copolymer of 3-hydroxybutyrate (3HB) and 4-hydroxybutyrate (4HB) with a weight% of 4HB of about 25% at about 50%, a PHA copolymer that has 3HB and 4HB with a 4HB weight% of about 25% to about 40%, a PHA copolymer that has 3HB and 4HB with a 4HB weight% about 25% to about 35%, a PHA copolymer that has 3HB and 3HH with a 3% by weight of about 25% to about 50%, one cup
Petition 870190136302, of 12/19/2019, p. 9/88
5/68 polymer that has 3HB and 5-hydroxyvalerate (5HV) with a weight% of 5HV from about 25% to about 60% or copolymer that has 3HB and
3-hydroxyoctanoate (3HO) with a weight% HO of about 15% to about 60%.
[0010] In a third aspect of the invention, the composition is a mixture of PLA and PHA, where PHA is a mixture of about 34% to about 38% P3HB, about 22% to about 26% copolymer of P3HB-4HB with about 8% to about 14% by weight of 4HB and about 38% to about 42% copolymer of P3HB-4HB with about 25% to about 33% by weight of 4HB, a plasticizer (for example, CITROFLEX), a peroxide branching agent, a coagent (for example, pentaerythritol triacrylate), and may optionally include additional additives (for example, anti-slip agent (s), compatibilizer (s) ( as maleic anhydride)). In addition, other polyesters can be added, for example, hyper-branched or dendritic polyesters.
[0011] In a fourth aspect of the invention, the composition is a mixture of PLA and PHA, where PHA is a mixture of about 10% to about 14% P3HB, about 46% to about 50% copolymer of P3HB-4HB with about 8% to about 14% by weight of 4HB and 38 to 42% copolymer of P3HB-4HB with 25 to 33% by weight of 4HB, a plasticizer (for example, CITROFLEX), a peroxide branching agent, a coagent (e.g., pentaerythritol triacrylate), and may optionally include additional additives (e.g., compatibilizer) and / or dendritic polyesters.
[0012] The amorphous rubber phase in these PHA mixtures refers to the P3HB-4HB copolymer which has, for example, about 25% to about 33% by weight of 4HB. The high 4HB content of this copolymer suppresses the crystallinity of the 3HB component that produces a completely amorphous copolymer that has a Tg in the range of -15 to
Petition 870190136302, of 12/19/2019, p. 10/88
6/68
40 ° C. Figure 1 shows a DSC thermogram of the PHA rubber phase with Tg measured at -15 ° C. Note that there was no Tm detected by DSC in this copolymer of P3HB-4HB which indicates that this is a completely amorphous material.
[0013] In other embodiments of the invention, compositions of a polymeric mixture of polylactic acid (PLA) and a multiphase copolymeric mixture of PHA are described, wherein a phase of the copolymeric mixture of PHA is a rubber phase with a degree of crystallinity between about 0 and 5%, a Tg between about -15 ° C and about 40 ° C and has between about 5% to about 45% of the total PHA. In particular embodiments, the rubber phase is a PHA copolymer that has 3HB and 4HB with a 4% weight by weight of about 25% to about 50%, a PHA copolymer that has 3HB and 4HB with a weight% from 4HB of about 25% to about 40%, a PHA copolymer that has 3HB and 4HB with a 4% weight by weight of about 25% to about 35%, a PHA copolymer that has 3HB and 3HH with a weight% of 3HH of about 25% to about 50%, a copolymer that has 3HB and 5HV with a weight% of 5HV of about 25 to about 60% or a copolymer that has 3HB and 3HO with a HO% wt from about 15% to about 60%.
[0014] In other embodiments, the mixing compositions are biodegradable, compostable and bio-based.
[0015] In another embodiment of the first, second, third or fourth aspect of the invention, the compositions further include a branching agent. In particular embodiments, the branching agent is selected from: dicumyl peroxide, tamil-2-ethylhexyl peroxide carbonate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2, 5dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-amyl peroxy) hexane, 2,5-bis (t-butylperoxy) -2,5-dimethyl- hexane, 2,5-dimethyl-di (tbutylperoxy) hexine-3, di-t-butyl peroxide, benzoyl peroxide, pePetition 870190136302, from 12/19/2019, p. 11/88
7/68 di-t-amyloxide, t-butyl cumyl peroxide, n-butyl-4,4-bis (tbutylperoxy) valerate, 1,1-di (t-butylperoxy) -3,3,5-trimethyl -cyclohexane, 1,1di (t-butylperoxy) cyclohexane, 1,1-di (t-amylperoxy) -cyclohexane, 2,2-di (tbutylperoxy) butane, ethyl-3,3-di ( t-butylperoxy) butyrate, 2,2-di (tamylperoxy) propane, ethyl-3,3-di (t-amylperoxy) butyrate, t-butylperoxyacetate, t-amylperoxyacetate, t-butylperoxybenzoate, tamylperoxybenzoate, and di-t-butyldiperoxyphthalate or combinations thereof. In certain embodiments of the first, second, third and fourth aspects of the invention, the branching agent is 2,5-Dimethyl-
2,5-di (tert-butylperoxy) hexane 2,5-Dimethyl-2,5-di (tert-butylperoxy) hexane.
[0016] In certain embodiments of the invention, the compositions of the first, second, third and fourth aspects of the invention are produced by reacting, in the molten state, the polymers with a branching agent in the presence of a coagent (also referred to herein) a crosslinking agent), thus forming a branched polymeric mixture. The reaction conditions are suitable for reacting the branching agent alone or with a crosslinking agent and a polymeric mixture. A branched polymer is a polymer with a branch of the polymer chain or crosslinking of two or more polymer chains.
[0017] The crosslinking agent when reacted, for example, in an epoxide group (s), functional epoxy compound, or double bond (s), binds to another molecule, for example, a polymer or branched polymer. As a consequence, the multiple molecules become cross-linked through the reactive group in the cross-linking agent. A functional epoxy compound is a crosslinking agent that comprises two or more functional epoxy groups.
[0018] In certain embodiments, the crosslinking agent functional group is a functional epoxy compound, for example, a polymer of
Petition 870190136302, of 12/19/2019, p. 12/88
8/68 functional epoxy styrene acrylic, functional epoxy acrylic copolymer, functional epoxy polyolefin copolymer, oligomers comprising glycidyl groups with functional epoxy side chains, a functional epoxy poly (ethylene-glycidyl methacrylate-methacrylate), or an epoxidized oil , poly (ethylene-cometacrylate-coglycidyl methacrylate, ethylene-n-butyl acrylate-glycidyl methacrylate or combinations thereof.
[0019] In another embodiment, the crosslinking agent contains at least two reactive double bonds. Such cross-linking agents include, but are not limited to, the following: diallyl phthalate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol penta-acrylate, diethylene glycol dimethacrylate, bis (2-methacrylate) of the same.
[0020] One or more additives can also be included in the compositions of any aspect of the invention and methods of the invention. Types of additives include, but are not limited to, pastifiers, clarifiers, nucleating agents, thermal stabilizers, inorganic fillers, anti-slip agents, and anti-blocking agents. Although sometimes they are not needed in the mix, compatibilizers can also be added. In particular embodiments of the first and second aspects of the invention, a nucleating agent is added. In other embodiments of the first and second aspects of the invention, a nucleating agent and a compatibilizer are added, in certain of these embodiments, the nucleating agent is cyanuric acid or boron nitride and the compatibilizer is maleic anhydride.
[0021] In yet another embodiment, a method of producing a tenacified biodegradable article comprising a branched PLA and a multiphase copolymeric mixture of PHA, comprising the steps of: mixing, in a molten state, PLA and PHA and an
Petition 870190136302, of 12/19/2019, p. 13/88
9/68 branching under conditions that cause the PLA / PHA mixture to fuse and branch, thus forming a fused branched polymer composition; and forming an article from the fused branched polymeric composition; thus forming an article which comprises a tenacified biodegradable branched polymeric composition of PLA / PHA. Articles, films and laminates comprising the compositions of the invention are also described.
BRIEF DESCRIPTION OF THE DRAWINGS [0022] The above will become apparent from the more particular description of exemplary modalities of the invention, as illustrated in the accompanying drawings in which similar reference characters refer to the same parts over the different views. The drawings are not necessarily to scale, instead, the emphasis is on illustrating modalities of the present invention.
[0023] Figure 1 is a DSC (second heat cycle) graph of rubber phase 3-hydroxybutyrate-co-4-hydroxybutyrate copolymer (P3HB-4HB copolymer) showing a Tg at -15 ° C with no Tm detected indicating a fully amorphous PHA phase. [0024] Figure 2 is a graph showing the tensile modules versus the percentage by weight of PHA C mixture in the composition.
[0025] Figure 3 is a graph showing breakdown stress versus the percentage by weight of PHA C mixture in the composition. [0026] Figure 4 is a graph showing elongation versus the percentage by weight of PHA C mixture in the composition.
[0027] Figure 5 is a graph showing toughness versus the percentage by weight of PHA C mixture in the composition. DETAILED DESCRIPTION [0028] Polylactic acid (PLAs) and polyhydroxyalkanoate (PHAs) compositions are described in this document, where the PHA component is a multiphase copolymer mixture of PHA, in which
Petition 870190136302, of 12/19/2019, p. 14/88
10/68 a phase of the PHA copolymeric mixture is an amorphous rubber phase, with a Tg between -40 ° C and -15 ° C and, and has between 5 to 45% of the total PHA in the composition. In other embodiments, the PHA blend includes a phase that is, for the most part, amorphous with 0 to 5% crystallinity, this PHA blend is termed as containing a rubber phase. In still other embodiments, the PLA / PHA blend compositions additionally include a branching agent and, optionally, a coagent.
[0029] The PLA / PHA compositions of the invention show increased toughness over PLA compositions. As described in this document, the toughness of the PLA is increased with the addition of the multiphase copolymer mixture of PHA, for example, when 30 weight percent of a PHA, a copolymer PHA of
3-hydroxybutyrate-4-hydroxybutyrate (P3HB-P4HB) is mixed with PLA. In certain embodiments, PLA is reactively mixed with PHA components. In particular, when these polymers are mixed in the molten state in the presence of a branching agent, for example, organic peroxide, the resulting compositions exhibit many unexpected synergies in melt rheology, thermal stability, processing and mechanical properties, such as film processing and film properties.
[0030] The improvement of the toughness found was even greater in the PHA mixtures that were prepared with the use of a mixture, in a molten state, reactive than without a mixture, in a molten state, reactive.
[0031] This approach produced toughness values that were statistically higher than the best values as reported with mixtures of PLA / polybutylene succinic acid (PBS) or polyethylene succinic adipate (PBSA) in U.S. Patent No. 5,883,199. Specifically, with about 30 weight percent of a copolymer of
Petition 870190136302, of 12/19/2019, p. 15/88
11/68
10 to 12% P4HB in a PLA composition, an approximately 60-fold increase in tensile strength at break and an approximately 35-fold increase in tensile strength can be achieved. This approach to improving PLA toughness significantly improves the overall biodegradability of the PLA mixture.
[0032] PHAs themselves include homopolymers, copolymers or
Mixed PHAs. Fully amorphous PHAs (which have 0% crystallinity and no melting point temperatures observed) and generally amorphous or rubber phase PHAs include
4-hydroxybutyrate, 3-hydroxyhexanoate, 5-hydroxyvalerate or 3hydroxyoctanoate, and combinations thereof. The resulting PHA can be a mixture, copolymer, mixture or combination of one, two or three or more PHA components.
[0033] The pure P4HB homopolymer is a fully amorphous rubber polymer at room temperature with a glass transition temperature significantly lower (Tg = -40 ° C) than that of pure PLA (Tg = 55 to 60 ° C). When combined with 3-hydroxybutyrate in a copolymer, where 25% by weight of> 4HB percentage, the copolymer retains its rubber properties (Tg = -15 ° C to -40 ° C). If the rubbery PHA copolymer is mixed with other polymers, it readily forms a separate rubber phase which imparts a toughening effect to the general polymer mixture. Due to this property and its proven biodegradability in various environments, it is a beneficial material for improving the toughness properties of PLA while maintaining the biodegradability or general decomposition of the mixture.
[0034] The toughness of PLAs is further modified through reactive mixing with PHAs. In particular, when the PLA and PHA polymers are reactively mixed, in a molten state, in the
Petition 870190136302, of 12/19/2019, p. 16/88
12/68 presence of a branching agent, for example, an organic peroxide, the resulting PLA / PHA mixture exhibits significant improvements in elongation and tensile strength that extends the product application range of normally brittle PLA polymers. In certain respects, the process of reactively mixing PLA and PHA together further includes the use of a coagent, such as a multifunctional carboxylic acid acrylate, or a crosslinking agent, such as an epoxide-containing acrylate copolymer, resulting in further improvements in mechanical properties of PLA.
[0035] Combining (for example, mixing or blending) PLA and PHA in the presence of peroxide provides the following benefits compared to combining polymeric mixtures or mixtures without any reactive chemistry: (1) elongation by superior tensile (2) superior tensile strength and (3) improved thermal stability and / or more satisfactory melt stability, resulting in a wider processing window for the overall composition and subsequent applications of these compositions in the production of articles, films and the like.
[0036] The invention provides polymeric blend compositions of
Branched PLA / PHA and polymer preparation methods of branched PLA / PHA blend with improved elongation and tensile strength. The polymeric compositions comprise the preparation of branched PLA and PHA compositions containing P4HB. The use of branching, straightening or coagents further improves the desired properties of the polymeric blend composition on the starting compositions without crosslinking or branching agents and coagents. In one aspect, crosslinking agents comprise two or more reactive groups such as double bonds or epoxides. These crosslinking agents react with and become covalently bound
Petition 870190136302, of 12/19/2019, p. 17/88
13/68 (connected) to the polymer. The connection of multiple chains through these crosslinking agents forms a branched polymeric mixture. The branched polymeric mixture has increased elongation and tensile strength over the starting polymeric mixture.
[0037] The temperatures experienced by a polymer during processing can cause a drop in resistance to melting due to thermal degradation, which can, in turn, cause difficulties in processing the polymer (s). The increased melt strength is therefore useful as it allows polymers to be processed over a wider temperature range. A broader processing window is specifically important in certain polymer applications, such as in the production of blown film (that is, in the prevention or reduction of bubble breakage), or extrusion of film by molding, thermoformed articles (that is, prevention or reduction of sheet bending during thermoforming), extruded profile articles (ie, prevention or reduction of bending), non-woven fibers, monofilament, etc. In addition, articles produced from the compositions described in this document exhibit greater elongation and tensile strength while maintaining biodegradability. The increases in tensile strength can be 10 to 40 times greater. The increases in elongation can be 10 to 60 times greater. The increase in tensile strength can be 10 to 20, 20 to 30 or 25 to 35 times. The stretch increase can be 20 to 30, 30 to 40 or 45 to 60 times.
[0038] The increased melt strength is useful as it allows polymers to be formed under a wider temperature range when the polymer is processed. The stability of the polymer decreases at processing temperatures and may accordingly undergo a drop in melt strength. This can cause difficulties in processing these polymers. Additionally, the improvement
Petition 870190136302, of 12/19/2019, p. 18/88
14/68 shown in films manufactured from the methods and compositions described in this document are greater tensile strength, tear strength, and greater puncture resistance.
[0039] The films produced by the compositions described in this document can also be used to manufacture laminates. Biodegradable laminates comprising the compositions of the invention are suitable for coating other layers such as paper to produce articles or containers. The laminate is produced, for example, by coextruding a composition of the invention on a layer of paper or with another mixture or thermoplastic composition. Other layers of thermoplastic polymers or additional layers of a composition of the invention can also be included or stacked to form laminates. For example, adhesive layers can also be added or other polymer layers that impart particular desired properties. For example, mixed materials or laminates can be different and enhanced by varying compositions to change the degree of hardness, softness, flexibility, stickiness, toughness, ductility, processability, opacity and the like. Additives, such as anti-blocking agents, plasticizers and the like are also contemplated.
[0040] In certain aspects, the laminate can have 1 to 15 layers, for example, 2 layers, 3 layers, 4 layers or 5 layers, 6 layers, 7 layers, 8 layers, 10 layers, 11 layers, 12 layers, 13 layers, 14 layers or 15 layers. The overall size of the laminate is about 10 microns to about 100 microns, for example, 10 to 50 microns, 20 to 60 microns, 25 to 75 microns. Each individual layer can be about 1 to about 2 microns, for example, about 1 to about 5 microns, about 2 to about 4 microns, about 2 to about 5 microns. For each laminate, at least one layer is a composition of the invention, for
Petition 870190136302, of 12/19/2019, p. 19/88
For example, the composition of the first, second, third or fourth aspect of the invention. In certain embodiments, the compositions of the invention comprise more than one layer, for example, two, three, four or more.
[0041] The branched compositions and methods of the invention improve the melt resistance of polymeric compositions, a desirable property for many polymer product applications. Fusion resistance is a rheological property that can be measured in a number of ways. One measure is G 'where G' is the polymer storage module measured at melt processing temperatures.
[0042] For use in the present invention, amorphous refers to the state of the PHA that is not crystalline, for example, no lattice structure characteristic of a crystalline state. The degree of crystallinity for the invention described in this document is the fractions of the polymer that exist in an ordered state, which has a lattice structure. In certain embodiments, a phase of multiphasic PHA has between about 0 to about 5% crystallinity, for example, the degree of crystallinity in percent is about 0, or is minimally observed less than about 1%. In a preferred embodiment, the degree of crystallinity of a phase of the multiphase PHA is below 3%, for example, below 2% or below 1% or ranges or numbers calculated between these percentages, such as 2.5%. The degree of crystallinity calculated for the compositions of the invention is minimal and can be determined by various methods, for example, density calculations, X-rays and electron diffraction, differential scanning calorimetry, infrared absorption (FTIR), Raman spectroscopy and the like.
[0043] Tg is the glass transition temperature or the glass transition temperature of the rubber. It is defined as the temperature where the
Petition 870190136302, of 12/19/2019, p. 20/88
16/68 polymer chains begin to coordinate molecular movements. Physically, the polymer module starts to fall several orders of magnitude until the polymer finally reaches a rubbery state.
[0044] The physical and rheological properties of polymeric materials depend on the molecular weight and distribution of the polymer. The molecular weight is calculated in several ways. Unless otherwise stated, molecular weight refers to the weight average molecular weight.
[0045] Average numerical molecular weight (Mn) represents the arithmetic mean of the distribution, and is the sum of the products of the molecular weights of each fraction, multiplied by its molar fraction (£ NiMi / £ Ni).
[0046] Average molecular weight (Mw) is the sum of the products of the molecular weight of each fraction, multiplied by its weight fraction (£ NiMi2 / £ NiMi). Mw is, in general, greater than or equal to Mn.
[0047] The average weight molecular weight of the PHA amorphous rubber phase or the multiphase PHA rubber phase used in the compositions of the invention is in the range between about 100,000 to about 600,000 as measured by light scattering and GPC with standards of polystyrene. In particular modalities, the molecular weight is about 125,000; 150,000; or about 175,000.
[0048] One way to increase melt resistance is by branching the polymers (PLA, PHA and combinations thereof), and several methods for accomplishing this are described in this document. The branching of PLA and PHAs is a result of the reaction of polymers with branching agents, for example, peroxides. In addition, crosslinking agents, for example, reactive compounds (compounds with epoxy groups and compounds with reactive double bonds) that enhance or increase the branching of the polymer, can also be used.
Petition 870190136302, of 12/19/2019, p. 21/88
17/68 [0049] The addition of other reactive polymeric compounds, such as reactive acrylics or reactive hydroxyls can also be used to generate and modify the branching architecture of PLA / PHA mixtures. The use and selection of additives for these compositions results in optimized properties. All of these methods are described in this document.
[0050] The invention provides polymeric blend compositions of
Biodegradable branched and unbranched PLA / PHA that do not require the use of a compatibilizer to mix and mix that other thermoplastic / PLA polymeric compositions do. In these other compositions, the compatibilizer is necessary to improve the properties of the mixtures and to increase the compatibility of the polymer composition, specifically immiscible polymers.
Polylactic acid (PLA) [0051] Polylactic acid (PLA) is a bio-based, biodegradable thermoplastic polyester that is currently produced on a large scale for commercial applications in the range of non-woven fibers to packaging films. The production of PLA is usually carried out by bacterial fermentation of corn sugar (dextrose) whereby the sugar is, in the first place, converted into lactic acid. The lactic acid through a series of synthetic reactions is then polymerized, using tin-based catalysts in polylactic acid. Depending on the type of catalyst used in the synthesis, L or D-polylactic acids (PLLA or PLDA) can be obtained. PLLA is 37% crystalline with a Tg of approximately 50 to 60 ° C and a Tm of approximately 173 to 178 ° C. The mechanical properties of PLLA are reported to be similar to PETE. The abbreviation PLA usually refers to the structural form of PLLA. When PLLA and PLDA are mixed together, they can form eutectoid stereo complexes with improved properties (higher Tm 50 ° C) than PLLA or
Petition 870190136302, of 12/19/2019, p. 22/88
18/68
PDLA. This has been investigated as biodegradable materials for high temperature applications.
[0052] It was found that the biodegradability of PLA occurred mainly through the hydrolysis of the functional polyester groups present in PLA. Degradation is essentially a two-step process by which PLA is first decomposed under high humidity and temperature (industrial / municipal type composting) to produce lower molecular weight chains or lactic monomer. The second stage is the consumption of low molecular weight PLA and lactic acid through microbes present in nature.
[0053] Several companies are currently manufacturing PLA from sugar feed sources. These include NatureWorks (USA), Galactic (Belgium), Hycail (Netherlands), Toyota (Japan). NatureWorks, a joint venture between Cargill and Teijin that has been operating since 2003, is currently the largest commercial producer of PLA resin.
[0054] One disadvantage of processing PLA in several products is that it is an extremely brittle material. Therefore, it must be mixed with other polymers in order to expand its processing window during formation. A potential problem with this approach is that additives to PLA also have an effect on its biodegradability. The additive that has been most successful in helping to process PLA without adversely affecting its biodegradability is polybutylene-succinate (PBS) or polybutylene-succinatoadipate (PBSA). PBS and PBSA are biodegradable aliphatic polyesters. Adding high molecular weight extrusion grade PBSA (BIONOLLE 3001 from Showa Highpolymer Co. Ltd, Japan) to the PLA resulted in the best improvements recorded in overall toughness (see, for example, US Patent No. 5,883,199, incorporated here in as a reference). A mixture of PLA / PBSA at
Petition 870190136302, of 12/19/2019, p. 23/88
19/68
70/30 showed an approximately 50-fold increase in tensile strength at break and an approximately 25-fold increase in tensile strength compared to PLA. Although the addition of PBSA to the PLA does not compromise the composting capacity of the PLA, it dilutes the bio-based content since PBS and PBSA are based on non-renewable petroleum raw materials.
[0055] Polyhydroxyalkanoates (PHAs) are an exclusive solution to those problems since they are bio-based, biodegradable and readily capable of mixing with PLA. As described in this document, the addition of a rubbery PHA (Tg from about -15 ° C to about -40 ° C), for example, polyester PHA
4-hydroxybutyrate to PLA, followed by reactive mixing, improves elongation and tensile strength beyond those of PLA / PBS or mixtures of PLA / PBSA.
Polyhydroxyalkanoates (PHAs) [0056] Polyhydroxyalkanoates are biological polyesters synthesized by a wide range of natural and genetically engineered bacteria as well as genetically engineered crops (Braunegg et al., (1998), J. Biotechnology 65: 127 to 161 ; Madison and Huisman, 1999, Microbiology and Molecular Biology Reviews, 63:21 to 53; Poirier, 2002, Progress in Lipid Research 41: 131 to 155). These polymers are biodegradable thermoplastic materials produced from renewable resources, with the potential for use in a wide range of industrial applications (Williams & Peoples, CHEMTECH 26:38 to 44 (1996)).
[0057] Microbial strains useful for producing PHAs include Alcaligenes eutrophus (renamed Ralstonia eutropha), Alcaligenes latus, Azotobacter, Aeromonas, Comamonas, Pseudomonads, and genetically engineered organisms including genetically manipulated microbes such as Pseudomonas, Ralstonia and Escherichia.
Petition 870190136302, of 12/19/2019, p. 24/88
20/68 [0058] In general, a PHA is formed by enzymatic polymerization of one or more monomeric units within a living cell. More than 100 different types of monomers have been incorporated into PHA polymers (Steinbüchel and Valentin, 1995, FEMS Microbiol. Lett. 128: 219 to 228). Examples of monomer units incorporated in PHAs for this invention include 2-hydroxybutyrate, glycolic acid 3 hydroxybutyrate (hereinafter referred to as 3HB), 3-hydroxypropionate (hereinafter referred to as 3HP), 3-hydroxyvalerate (hereinafter referred to as 3HV) , 3-hydroxyhexanoate (hereinafter referred to as 3HH), 3-hydroxyheptanoate (hereinafter referred to as 3HH), 3-hydroxyoctanoate (hereinafter referred to as 3HO), 3-hydroxynonanoate (hereinafter referred to as 3HN) , 3-hydroxydecanoate (hereinafter referred to as 3HD), 3-hydroxydodecanoate (hereinafter referred to as 3HDd), 4-hydroxybutyrate (hereinafter referred to as 4HB), 4hydroxyvalerate (hereinafter referred to as 4HV),
5-hydroxyvalerate (hereinafter referred to as 5HV), and 6-hydroxyhexanoate (hereinafter referred to as 6HH). 3-hydroxy acid monomers incorporated into PHAs are the (D) or (R) 3-hydroxy acid isomer with the exception of 3HP which does not have a chiral center. For compositions included in this document, the PHA composition does not include poly (lactic acid).
[0059] In some embodiments, the PHA in the methods described in this document is a homopolymer (where all monomer units are the same). Examples of PHA homopolymers include poly 3-hydroxyalkanoates (for example, poly 3-hydroxypropionate (hereinafter referred to as P3HP), poly 3hydroxybutyrate (hereinafter referred to as P3HB)
Petition 870190136302, of 12/19/2019, p. 25/88
21/68 and poly 3-hydroxyvalerate), poly 4-hydroxyalkanoates (for example, poly 4hydroxybutyrate (hereinafter referred to as P4HB), or poly 4-hydroxyvalerate (hereinafter referred to as P4HV)) and poly 5-hydroxyalkanoates (for example, poly 5 hydroxyvalerate (hereinafter referred to as P5HV)).
[0060] In certain embodiments, the starting PHA can be a copolymer (containing two or more different monomer units) in which the different monomers are randomly distributed in the polymer chain. Examples of PHA copolymers include poly 3-hydroxybutyrate-co-3-hydroxypropionate (hereinafter referred to as PHB3HP), poly 3-hydroxybutyrate-co-4hydroxybutyrate (hereinafter referred to as P3HB4HB), poly 3-hydroxybutyrate-co-4 -hydroxyvalerate (hereinafter referred to as PHB4HV), poly 3-hydroxybutyrate-co3-hydroxyvalerate (hereinafter referred to as PHB3HV), poly 3-hydroxybutyrate-co-3-hydroxyhexanoate (hereinafter referred to as PHB3HH) and poly 3-hydroxybutyrate-co-
5-hydroxyvalerate (hereinafter referred to as PHB5HV).
[0061] By selecting the types of monomer and controlling the ratios of the monomeric units in a given PHA copolymer, a wide range of material properties can be achieved. Although examples of PHA copolymers that have two different monomer units have been provided, PHA can have more than two different monomer units (for example, three different monomer units, four different monomer units, five different monomer units, six different monomer units) . An example of a PHA that has 4 different monomer units would be PHB-co-3HH-co-3HO-co-3HD or PHB-co-3-HO
Petition 870190136302, of 12/19/2019, p. 26/88
22/68 co-3HD-co-3HDd (these types of PHA copolymers are hereinafter referred to as PHB3HX). Typically, where PHB3HX has 3 or more monomer units, the 3HB monomer has at least 70% by weight of the total monomers, preferably 85% by weight of the total monomers, most preferably more than 90% by weight of the total monomers , for example, 92%, 93%, 94%, 95%, 96% by weight of the copolymer and the HX comprises one or more monomers selected from 3HH, 3HO, 3HD, 3HDd.
[0062] The homopolymer (where all the monomeric units are identical) P3HB and 3-hydroxybutyrate copolymers (P3HB3HP, P3HB4HB, P3HB3HV, P3HB4HV, P3HB5HV, P3HB3HHP, hereinafter referred to as the last document in this document) another monomer is of particular interest for production and commercial applications. It is useful to describe these copolymers by reference to their material properties as follows. Type 1 PHB copolymers typically have a glass transition temperature (Tg) in the range of 6 ° C to -10 ° C, and a TM melting temperature between 80 ° C to 180 ° C. Type 2 PHB copolymers typically have a Tg of -20 ° C to -50 ° C and Tm of 55 ° C to 90 ° C. In particular embodiments, the PHB type 2 copolymer has a phase component with a Tg of -15 ° C to -45 ° C and no Tm.
[0063] PHB type 1 copolymers have two monomer units and a majority of their monomer units have the 3-hydroxybutyrate monomer, by weight, in the copolymer, for example, more than 78% 3-hydroxybutyrate monomer. The preferred PHB copolymers for this invention are biologically produced from renewable resources and are selected from the following group of PHB copolymers:
[0064] PHB3HV is a type 1 PHB copolymer where the content of
3HV is in the range of 3% to 22% by weight of the polymer and,
Petition 870190136302, of 12/19/2019, p. 27/88
Preferably in the range of 4% to 15% by weight of the copolymer, for example: 4% 3HV; 5% of 3HV; 6% of 3HV; 7% of 3HV; 8% of 3HV; 9% of 3HV; 10% 3HV; 11% 3HV; 12% of 3HV; 13% 3HV; 14% of 3HV; 15% 3HV;
[0065] PHB3HP is a type 1 PHB copolymer where the content of
3HP is in the range of 3% to 15% by weight of the copolymer and, preferably, in the range of 4% to 15% by weight of the copolymer, for example: 4% of 3HP; 5% 3HP; 6% 3HP; 7% 3HP; 8% 3HP; 9% of 3HP; 10% 3HP; 11% 3HP; 12% of 3HP. 13% 3HP; 14% 3HP; 15% of 3HP.
[0066] PHB4HB is a PHB type 1 copolymer where the content of
4HP is in the range of 3% to 15% by weight of the copolymer and, preferably, in the range of 4% to 15% by weight of the copolymer, for example: 4% of 4HB; 5% of 4HB; 6% of 4HB; 7% of 4HB; 8% of 4HB; 9% of 4HB; 10% 4HB; 11% 4HB; 12% 4HB; 13% 4HB; 14% of 4HB; 15% of 4HB.
[0067] PHB4HV is a type 1 PHB copolymer where the content of
4HV is in the range of 3% to 15% by weight of the copolymer and, preferably, in the range of 4% to 15% by weight of the copolymer, for example: 4% of 4HV; 5% of 4HV; 6% of 4HV; 7% of 4HV; 8% of 4HV; 9% of 4HV; 10% 4HV; 11% of 4HV; 12% 4HV; 13% 4HV; 14% of 4HV; 15% of 4HV.
[0068] PHB5HV is a type 1 PHB copolymer where the content of
5HV is in the range of 3% to 15% by weight of the copolymer and, preferably, in the range of 4% to 15% by weight of the copolymer, for example: 4% of 5HV; 5% of 5HV; 6% of 5HV; 7% of 5HV; 8% of 5HV; 9% of 5HV; 10% 5HV; 11% 5HV; 12% 5HV; 13% 5HV; 14% of 5HV; 15% of 5HV.
[0069] PHB3HH is a type 1 PHB copolymer where the content of
3HH is in the range of 3% to 15% by weight of the copolymer and,
Petition 870190136302, of 12/19/2019, p. 28/88
Preferably in the range of 4% to 15% by weight of the copolymer, for example: 4% 3HH; 5% 3HH; 6% 3HH; 7% 3HH; 8% 3HH; 9% 3HH; 10% 3HH; 11% 3HH; 12% 3HH; 13% 3HH; 14% 3HH; 15% 3HH;
[0070] PHB3HX is a type 1 PHB copolymer where the content of
3HX is composed of 2 or more monomers selected from 3HH, 3HO, 3HD and 3HDd and the 3HX content is in the range of 3% to 12% by weight of the copolymer and, preferably, in the range of 4% to 10% in copolymer weight, for example: 4% 3HX; 5% 3HX; 6% 3HX; 7% 3HX; 8% 3HX; 9% 3HX; 10% 3HX by weight of the copolymer.
[0071] PHB type 2 copolymers have a content of 3HB between 80% and 5% by weight of the copolymer, for example, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45% , 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5% by weight of the copolymer.
[0072] PHB4HB is a PHB type 2 copolymer where the content of
4HP is in the range of 20% to 60% by weight of the copolymer and, preferably, in the range of 25% to 50% by weight of the copolymer, for example: 25% of 4HB; 30% of 4HB; 35% of 4HB; 40% of 4HB; 45% of 4HB; 50% by weight of 4HB of the copolymer.
[0073] PHB5HV is a type 2 PHB copolymer where the content of
5HV is in the range of 20% to 60% by weight of the copolymer and, preferably, in the range of 25% to 50% by weight of the copolymer, for example: 25% of 5HV; 30% of 5HV; 35% of 5HV; 40% of 5HV; 45% of 5HV; 50% 5HV by weight of the copolymer.
[0074] PHB3HH is a type 2 PHB copolymer where the content of
3HH is in the range of 35% to 95% by weight of the copolymer and, preferably, in the range of 40% to 80% by weight of the copolymer, for example: 40% of 3HH; 45% of 3HH; 50% 3HH; 55% 3HH, 60% 3HH; 65% 3HH; 70% 3HH; 75% 3HH; 80% of 3HH in
Petition 870190136302, of 12/19/2019, p. 29/88
25/68 weight of the copolymer.
[0075] PHB3HX is a type 2 PHB copolymer where the content of
3HX is composed of 2 or more monomers selected from 3HH, 3HO, 3HD and 3HDd and the content of 3HX is in the range of 30% to 95% by weight of the copolymer and, preferably, in the range of 35% to 90% in copolymer weight, for example: 35% 3HX; 40% 3HX; 45% 3HX; 50% 3HX; 55% 3HX 60% 3HX; 65% 3HX; 70% 3HX; 75% 3HX; 80% 3HX; 85% 3HX; 90% 3HX by weight of the copolymer.
[0076] PHAs for use in the methods, compositions and pellets described in this invention are selected from: PHB or a type 1 PHB copolymer; a mixture of PHB PHA with a type 1 PHB copolymer where the PHB content by weight of PHA in the PHA mixture is in the range of 5% to 95% by weight of PHA in the PHA mixture; a mixture of PHB PHA with a type 2 PHB copolymer where the PHB content by weight of the PHA in the PHA mixture is in the range of 5% to 95% by weight of the PHA in the PHA mixture; a PHA mixture of a type 1 PHB copolymer with a different type 1 PHB copolymer and where the content of the first type 1 PHB copolymer is in the range of 5% to 95% by weight of the PHA in the PHA mixture; a mixture of PHA of a type 1 PHB copolymer with a type 2 PHB copolymer of PHA where the content of the type 1 PHB copolymer is in the range of 30% to 95% by weight of the PHA in the PHA mixture; a mixture of PHB PHA with a PHB type 1 copolymer and a PHB type 2 copolymer where the PHB content is in the range of 10% to 90% by weight of the PHA in the PHA mixture, where the copolymer content of Type 1 PHB is in the range of 5% to 90% by weight of PHA in the PHA mixture and where the copolymer content of PHB type 2 is in the range of 5% to 90% by weight of PHA in the PHA mixture.
Petition 870190136302, of 12/19/2019, p. 30/88
26/68 [0077] The mixture of PHB PHA with a PHB type copolymer is a mixture of PHB with PHB3HP where the PHB content in the PHA mixture is in the range of 5% to 90% by weight of the PHA in the mixture of PHA and the 3HP content in PHB3HP is in the range of 7% to 15% by weight of PHB3HP.
[0078] The mixture of PHB PHA with a PHB type copolymer is a mixture of PHB with PHB3HV where the PHB content of the PHA mixture is in the range of 5% to 90% by weight of the PHA in the PHA mixture and the content of 3HV in PHB3HV is in the range of 4% to 22% by weight of PHB3HV.
[0079] The mixture of PHB PHA with a PHB type copolymer is a mixture of PHB with PHB4HB where the PHB content of the PHA mixture is in the range of 5% to 90% by weight of the PHA in the PHA mixture and the content of 4HP in PHB4HB is in the range of 4% to 15% by weight of PHB4HB.
[0080] The mixture of PHB PHA with a PHB type copolymer is a mixture of PHB with PHB4HV where the PHB content of the PHA mixture is in the range of 5% to 90% by weight of the PHA in the PHA mixture and the content of 4HV in PHB4HV is in the range of 4% to 15% by weight of PHB4HV.
[0081] The mixture of PHB PHA with a PHB type copolymer is a mixture of PHB with PHB5HV where the PHB content of the PHA mixture is in the range of 5% to 90% by weight of the PHA in the PHA mixture and the content of 5HV in PHB5HV is in the range of 4% to 15% by weight of PHB5HV.
[0082] The mixture of PHB PHA with a PHB type copolymer is a mixture of PHB with PHB3HH where the PHB content of the PHA mixture is in the range of 5% to 90% by weight of the PHA in the PHA mixture and the content of 3HH in PHB3HH is in the range of 4% to 15% by weight of PHB3HH.
Petition 870190136302, of 12/19/2019, p. 31/88
27/68 [0083] The mixture of PHB PHA with a PHB type copolymer is a mixture of PHB with PHB3HX where the PHB content of the PHA mixture is in the range of 5% to 90% by weight of the PHA in the mixture of PHA and the content of 3HX in PHB3HX is in the range of 4% to 15% by weight of PHB3HX.
[0084] The PHA blend is a blend of a type 1 PHB copolymer selected from the group PHB3HV, PHB3HP, PHB4HB, PHBV, PHV4HV, PHB5HV, PHB3HH and PHB3HX with a second type 1 PHB copolymer that is different from the first type PHB copolymer PHB type 1 and is selected from the group PHB3HV, PHB3HP, PHB4HB, PHBV, PHV4HV, PHB5HV, PHB3HH and PHB3HX where the content of the first type 1 PHB copolymer in the PHA mixture is in the range of 10% to 90% by weight of the Total PHA in the mixture.
[0085] The mixture of PHB PHA with a PHB type copolymer is a mixture of PHB with PHB4HB where the PHB content in the PHA mixture is in the range of 30% to 95% by weight of the PHA in the PHA mixture and the content of 4HP in PHB4HB is in the range of 20% to 60% by weight of PHB4HB.
[0086] The mixture of PHB PHA with a PHB type copolymer is a mixture of PHB with PHB5HV where the PHB content in the PHA mixture is in the range of 30% to 95% by weight of the PHA in the PHA mixture and the content of 5HV in PHB5HV is in the range of 20% to 60% by weight of PHB5HV.
[0087] The mixture of PHB PHA with a PHB type copolymer is a mixture of PHB with PHB3HH where the PHB content in the PHA mixture is in the range of 35% to 95% by weight of the PHA in the PHA mixture and the content of 3HH in PHB3HH is in the range of 35% to 90% by weight of PHB3HX.
[0088] The mixture of PHB PHA with a PHB type copolymer is a mixture of PHB with PHB3HX where the PHB content in the mixture
Petition 870190136302, of 12/19/2019, p. 32/88
28/68 PHA is in the range of 30% to 95% by weight of PHA in the PHA mixture and the content of 3HX in PHB3HX is in the range of 35% to 90% by weight of PHB3HX.
[0089] The PHA mixture is a mixture of PHB with a PHB type 1 copolymer and a PHB type 2 copolymer where the PHB content in the PHA mixture is in the range of 10% to 90% by weight of the PHA in the the PHA mixture, the type 1 PHB copolymer content of the PHA mixture is in the range of 5% to 90% by weight of the PHA in the PHA mixture and the type 2 PHB copolymer content in the PHA mixture is in the range range of 5% to 90% by weight of the PHA in the PHA mixture.
[0090] For example, a PHA mixture can have a content of
PHB in the PHA mixture in the range of 10% to 90% by weight of the PHA in the PHA mixture, a PHB3HV content in the PHA mixture in the range of 5% to 90% by weight of the PHA in the PHA mixture, where the content of 3HV in PHB3HV is in the range of 3% to 22% by weight of PHB3HV, and a PHBHX content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture where the 3HX content in PHBHX is in the range of 35% to 90% by weight of PHBHX.
[0091] For example, a PHA mixture can have a content of
PHB in the PHA mixture in the range of 10% to 90% by weight of the PHA in the PHA mixture, a PHB3HV content in the PHA mixture in the range of 5% to 90% by weight of the PHA in the PHA mixture, where the content of 3HV in PHB3HV is in the range of 3% to 22% by weight of PHB3HV, and a PHB4HP content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture where the content of 4HP in PHB4HB is in the range of 20% to 60% by weight of PHB4HB.
[0092] For example, a PHA mixture can have a content of
PHB in the PHA mixture in the range of 10% to 90% by weight of the PHA in the PHA mixture, a PHB3HV content in the PHA mixture in the range
Petition 870190136302, of 12/19/2019, p. 33/88
29/68
5% to 90% by weight of PHA in the PHA mixture, where the 3HV content in the PHB3HV is in the range of 3% to 22% by weight of the PHB3HV, and a PHB5HV content in the PHA mixture in the range of 5% at 90% by weight of the PHA in the PHA mixture where the 5HV content in the PHB5HV is in the range of 20% to 60% by weight of the PHB5HV.
[0093] For example, a PHA mixture can have a content of
PHB in the PHA mixture in the range of 10% to 90% by weight of the PHA in the PHA mixture, a PHB4HP content in the PHA mixture in the range of 5% to 90% by weight of the PHA in the PHA mixture, where the content of 4HP in PHB4HB is in the range of 4% to 15% by weight of PHB4HB, and a PHB4HP content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture where the content of 4HP in PHB4HB is in the range of 20% to 60% by weight of PHB4HB.
[0094] For example, a PHA mixture can have a content of
PHB in the PHA mixture in the range of 10% to 90% by weight of the PHA in the PHA mixture, a PHB4HP content in the PHA mixture in the range of 5% to 90% by weight of the PHA in the PHA mixture, where the content of 4HP in PHB4HB is in the range of 4% to 15% by weight of PHB4HB, and a PHB5HV content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture and where the content of 5HV in PHB5HV it is in the range of 30% to 90% by weight of PHB5HV.
[0095] For example, a PHA mixture can have a content of
PHB in the PHA mixture in the range of 10% to 90% by weight of the PHA in the PHA mixture, a PHB4HP content in the PHA mixture in the range of 5% to 90% by weight of the PHA in the PHA mixture, where the content of 4HP in PHB4HB is in the range of 4% to 15% by weight of PHB4HB, and a PHB3HX content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture and where the content of 3HX in PHB3HX it is in the range of 35% to 90% by weight of PHB3HX.
[0096] For example, a PHA mixture can have a content of
Petition 870190136302, of 12/19/2019, p. 34/88
30/68
PHB in the PHA mixture in the range of 10% to 90% by weight of the PHA in the PHA mixture, a PHB4HV content in the PHA mixture in the range of 5% to 90% by weight of the PHA in the PHA mixture, where the content of 4HV in PHB4HV is in the range of 3% to 15% by weight of PHB4HV, and a PHB5HV content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture where the content of 5HV in PHB5HV is in the range of 30% to 90% by weight of PHB5HV.
[0097] For example, a PHA mixture can have a content of
PHB in the PHA mixture in the range of 10% to 90% by weight of PHA in the PHA mixture, a PHB3HH content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, where the content of 3HH in PHB3HH is in the range of 3% to 15% by weight of PHB3HH, and a PHB4HP content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture where the content of 4HP in PHB4HB is in the range of 20% to 60% by weight of PHB4HB.
[0098] For example, a PHA mixture can have a content of
PHB in the PHA mixture in the range of 10% to 90% by weight of PHA in the PHA mixture, a PHB3HH content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, where the content of 3HH in PHB3HH is in the range of 3% to 15% by weight of PHB3HH, and a PHB5HV content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture where the 5HV content in PHB5HV is in the range of 20% to 60% by weight of PHB5HV.
[0099] For example, a PHA mixture can have a content of
PHB in the PHA mixture in the range of 10% to 90% by weight of PHA in the PHA mixture, a PHB3HH content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, where the content of 3HH in PHB3HH is in the range of 3% to 15% by weight of PHB3HH, and a PHB3HX content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture where the content of 3HX in PHB3HX if
Petition 870190136302, of 12/19/2019, p. 35/88
31/68 is in the range of 35% to 90% by weight of the PHB3HX.
[00100] For example, a PHA mixture can have a PHB content in the PHA mixture in the range of 10% to 90% by weight of the PHA in the PHA mixture, a PHB3HX content in the PHA mixture in the range of 5% to 90% by weight of PHA in the PHA mixture, where the 3HX content in the PHB3HX is in the range of 3% to 12% by weight of the PHB3HX, and a PHB3HX content in the PHA mixture in the range of 5% to 90 % by weight of PHA in the PHA mixture where the content of 3HX in PHB3HX is in the range of 35% to 90% by weight of PHB3HX.
[00101] For example, a PHA mixture can have a PHB content in the PHA mixture in the range of 10% to 90% by weight of the PHA in the PHA mixture, a PHB3HX content in the PHA mixture in the range of 5% at 90% by weight of PHA in the PHA mixture, where the 3HX content in the PHB3HX is in the range of 3% to 12% by weight of the PHB3HX, and a PHB4HP content in the PHA mixture in the range of 5% to 90 % by weight of PHA in the PHA mixture where the content of 4HP in PHB4HB is in the range of 20% to 60% by weight of PHB4HB.
[00102] For example, a PHA mixture can have a PHB content in the PHA mixture in the range of 10% to 90% by weight of the PHA in the PHA mixture, a PHB3HX content in the PHA mixture in the range of 5% at 90% by weight of PHA in the PHA mixture, where the 3HX content in the PHB3HX is in the range of 3% to 12% by weight of the PHB3HX, and a PHB5HV content in the PHA mixture in the range of 5% to 90 % by weight of PHA in the PHA mixture where the 5HV content in PHB5HV is in the range of 20% to 60% by weight of PHB5HV.
[00103] The PHA blend is a blend as disclosed in U.S. published application No. 2004/0220355, by Whitehouse, published on November 4, 2004, which is incorporated herein in its entirety by reference.
[00104] Microbial systems for producing copolyte PHBV
Petition 870190136302, of 12/19/2019, p. 36/88
32/68 PHB numbers are disclosed, for example, in U.S. Patent No. 4,477,654 to Holmes, which is incorporated herein in its entirety by reference. U.S. published application No. 2002/0164729 (also incorporated herein in its entirety for reference) by Skraly and Sholl describes systems useful for producing PHB copolymer PHB4HB. Processes useful for producing PHB copolymer PHB3HH have been described (Lee et al., 2000, Biotechnology and Bioengineering 67: 240 to 244; Park et al., 2001, Biomacromolecules 2: 248 to 254). The processes for producing PHB3HX from PHB copolymers have been described by Matsusaki et al. (Biomacromolecules 2000, 1:17 to 22).
[00105] In determining molecular weight, techniques such as gel permeation chromatography (GPC) can be used. In the methodology, a polystyrene standard is used. PHA may have a polystyrene equivalent molecular weight (in daltons) of at least 500, at least 10,000, or at least 50,000 and / or less than 2,000,000, less than 1,000,000, less than 1,500,000, and less than 800,000. In certain embodiments, preferably, PHAs generally have an average molecular weight in the range of 100,000 to 700,000. For example, the molecular weight range for PHB and type 1 PHB copolymers for use in this application is in the range of 400,000 daltons to 1.5 million daltons as determined by the GPC method and the molecular weight range for type 2 PHB copolymers for use in this order, 100,000 to 1.5 million daltons.
[00106] In certain embodiments, the PHA can have a linear average molecular weight equivalent of about 150,000 Daltons to about 500,000 Daltons and a polydispersity index of about 2.5 to about 8.0. For use in the present invention, the weight average molecular weight and linear weight average molecular weight are determined by gel permeation chromatography, using, for example, chloroform as both an eluent and a diluent for the
Petition 870190136302, of 12/19/2019, p. 37/88
33/68 PHA samples. Calibration curves to determine molecular weights are generated using linear polystyrenes as molecular weight standards and a 'elution volume vs log MW' calibration method.
Mixtures of pla and pha and combinations thereof [00107] In certain embodiments, polymers for use in methods and compositions are mixed in the presence of additives (for example, nucleating agent (s), compatibilizer (s), additive (s) anti-slip (s) and the like, coagents and branching agents to form compositions with enhanced toughness properties The percentages of PLA in the PLA / PHA mixture are 50% to 95% by weight, for example 70 to 95%. compositions of the invention, the percentages of PLA and PHA of the total polymeric composition are in the range of about 95% PLA to about 5% PHA or about 50% PLA to about 50% PHA. the PLA / PHA ratio can be 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 55/45 or 50/50.
Polyhydroxyalkanoates and branched polylactic acid [00108] The term branched polymer refers to a PLA or PHA with chain branching and / or crosslinking of two or more chains. Branching into side chains is also contemplated. Branching can be accomplished using several methods. The polymeric PLA / PHA mixtures described above can be branched by branching agents through free radical-induced crosslinking of the polymer. Polyhydroxyalkanoate polymers can be branched in any of the ways described in US Patent Nos. 6,620,869, 7,208,535, 6,201,083, 6,156,852, 6,248,862, 6,201,083 and 6,096,810 all of which are hereby incorporated by reference in their entirety.
[00109] The polymers of the invention can also be made
Petition 870190136302, of 12/19/2019, p. 38/88
34/68 mified according to any of the methods disclosed in international publication No. WO 2010/008447, entitled Methods For Branching PHA Using Thermolysis or international publication No. WO 2010/008445, entitled Branched Composition of PHAs, Methods For Their Production, And Use In Applications, both were published in English on January 21, 2010, and designated in the United States. These applications are hereby incorporated by reference in their entirety.
Branching agents [00110] Branching agents, also called free radical initiators, for use in the compositions and method described in this document include organic peroxides. Peroxides are reactive molecules, and react with previously branched polymer molecules or polymers by removing a hydrogen atom from the polymer main chain, leaving a radical behind. The polymer molecules that have such radicals in their main chain are free to combine with each other, creating branched polymer molecules. Branching agents are selected from any suitable initiator known in the art, such as peroxides, azoderivatives (e.g., azo-nitriles), peresters, and peroxy carbonates. Peroxides suitable for use in the present invention include, but are not limited to, organic peroxides, for example, organic dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5dimethyl-2 , 5-di (t-amylperoxy) hexane, 2,5-bis (t-butylperoxy) -2,5-dimethylhexane (available from Akzo Nobel as TRIGANOX® 101), 2,5dimethyl-di (t-butylperoxy) hexine -3, di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, di-t-amyl peroxide, t-amylperoxy-2ethylhexylcarbonate (TAEC), cumyl t-butyl peroxide, n-butyl-4,4 -bis (tbutylperoxy) valerate, 1,1-di (t-butylperoxy) -3,3,5-trimethyl-cyclohexane, 1,1bis (t-butylperoxy) -3,3,5-trimethylcyclohexane (CPK ), 1,1-di (tPetition 870190136302, of 12/19/2019, page 39/88
35/68 butylperoxy) cyclohexane, 1,1-di (t-amylperoxy) -cyclohexane, 2,2-di (tbutylperoxy) butane, ethyl-3,3-di (t-butylperoxy) butyrate, 2, 2-di (tamylperoxy) propane, ethyl-3,3-di (t-amylperoxy) butyrate, t-butylperoxyacetate, t-amylperoxyacetate, t-butylperoxybenzoate, tamilperoxybenzoate, di-t-butyldiperoxyphthalate, and the like. Combinations and mixtures of peroxides can also be used. Examples of free radical initiators include those mentioned in this document, as well as those described in, for example, Polymer Handbook, 3rd Ed., J. Brandrup & EH Immergut, John Wiley and Sons, 1989, Chap. 2. Irradiation ( for example, electronic beam or gamma irradiation) can also be used to generate polymer branching. [00111] As discussed above, when peroxides decompose, they form very high energy radicals that can extract a hydrogen atom from the polymer main chain. These radicals have short half-lives, thus limiting the population of branched molecules that is produced during the active period of time. Additives [00112] In certain embodiments, several additives are added to the compositions. Examples of such additives include, but are not limited to, antioxidants, pigments, compatibilizers, thermal and UV stabilizers, inorganic and organic fillers, pastifiers, nucleating agents, anti-slip agents, anti-blocking agents and radical scavengers. In addition, polyfunctional coagents such as divinyl benzene, trialyl cyanurate and the like can be added. Such coagents can be added to one or more of these additives for easier incorporation into the polymer. For example, the coagent can be mixed with a plasticizer, for example, a non-reactive plasticizer, for example, a citric acid ester, and then formulated with the polymer under conditions to induce branching. Other coagents useful in the compositions of the invention, for example,
Petition 870190136302, of 12/19/2019, p. 40/88
36/68 compositions of the first, second, third or fourth aspect are hyper-branched or dendritic polyesters, such as dendritic and hyper-branched acrylates available from Sartomer, for example, BOLTRON ™ H20.
[00113] In poly-3-hydroxybutyrate compositions for use in the methods and compositions described in this document, for example, plasticizers are often used to change the glass transition temperature and composition module, but surfactants can also be used . Lubricants can also be used, for example, in injection molding applications. Therefore, plasticizers, surfactants and lubricants can all be included in the general composition.
[00114] In other embodiments, the compositions and methods of the invention include one or more pastifiers. Examples of plasticizers include phthalic compounds (including, but not limited to, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, phthalate diisoctyl, tippril phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate, butyl benzyl butyl phthalate butyl octyl, benzyl octyl phthalate, n-decyl nhexyl phthalate, n-octyl phthalate, and n-decyl phthalate), phosphoric compounds (including, but not limited to, tricresyl phosphate, trioctyl phosphate, phosphate of triphenyl, diphenyl octyl phosphate, diphenyl cresyl phosphate, and trichlorethyl phosphate), adipic compounds (including, but not limited to, dibutoxyethoxyethyl adipate (DBEEA), dioctyl adipate, diisoctyl adipate, di-n-octyl adipate, didecyl adipate act, diisodecyl adipate, noctil n-decyl adipate, n-hepty adipate, and n-nonyl adipate), sebaceous compounds (including, but not limited to, dibutyl sebacate, dioctyl sebacate, diisoctyl sebacate and butyl benzyl sebacate ),
Petition 870190136302, of 12/19/2019, p. 41/88
37/68 azelaic compounds, citrus compounds (including, but not limited to, triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate and acetyl trioctyl citrate), glycolic compounds (including, but not limited to a, methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate and butyl phthalyl ethyl glycolate), trimellitic compounds (including, but not limited to, trioctyl trimellitate and n-decyl tri-n-octyl trimelite), isomeric compounds phthalic (including, but not limited to, dioctyl isophthalate and dioctyl terephthalate), ricinoleic compounds (including, but not limited to, methyl acetyl recinoleate and butyl acetyl recinoleate), polyester compounds (including, but not limited to limiting to reaction products of selected diols of butane diol, ethylene glycol, propane 1,2 diol, propane 1,3 diol, polyethylene glycol, glycerol, diacids selected from adipic acid, succinic acid nico, succinic anhydride and hydroxy acids such as hydroxysearic acid, epoxidized soybean oil, chlorinated paraffins, chlorinated fatty acid esters, fatty acid compounds, vegetable oils, pigments, and acrylic compounds. Plasticizers can be used alone respectively or in combinations with each other.
[00115] In certain embodiments, the compositions and methods of the invention include one or more surfactants. Surfactants are generally used to remove dust, lubricate, reduce surface tension and / or densify. Examples of surfactants include, but are not limited to, mineral oil, castor oil and soybean oil. A mineral oil surfactant is Drakeol 34, available from Penreco (Dickinson, Texas, USA). Maxsperse W-6000 and W-3000 solid surfactants are available from Chemax Polymer Additives (Piedmont, South Carolina, USA). Nonionic surfactants with HLB values in the range of about 2 to about 16 can be used, examples are TWEEN-20, TWEEN-65, Span-40 and Span 85.
[00116] Anionic surfactants include: aliphatic carboxylic acidsPetition 870190136302, from 12/19/2019, p. 42/88
38/68 cos such as lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid; fatty acid soaps such as sodium salts or potassium salts of the above aliphatic carboxylic acids; salts of N-acyl-N-methylglycine, N-acyl-N-methyl-beta-alanine, salts of N-acylglutamic acid, salts of polyoxyethylene alkyl ether carboxylic acid, acylated peptides, salts of alkyl benzene sulfonic acid, salts of alkylnaphthalenesulfonic acid, salt of naphthalenesulfonic acid-formalin polycondensation products, melamine sulphonic acid salt-formalin polycondensation products, dialkylsulfosuccinic acid ester salts, alkyl sulfosuccinate disals, polyoxyethylene alkylsulfosuccinic acid salts, alpha sulfosalonic acid salts, N-acylmethyltaurine, sodium dimethyl 5-sulfoisophthalate, sulfated oil, ester salts of higher sulfuric acid ether, polyoxyethylene sulfuric acid ether salts, upper secondary alcohol ethoxysulfates, polyoxyethylene alkyl phenyl sulfuric acid ether salts, monoglissulfate, acid ester salts sulfuric fatty acid alkylolamides o, polyoxyethylene alkyl phosphoric acid ether salts, polyoxyethylene alkyl phosphoric acid ether salts, alkyl phosphoric acid salts, alkylamine bistridecylsulfosuccinates, sodium oxide, sodium dioctyl sulfosuccinate, sodium dihexylsulfosuccinate, duccinosulfosyl duccinyl oxides sodium, alkylamine guanidine polyoxyethanol, esters of ethoxylated alcohol medium of sodium sulfosuccinate, esters of nonylphenol ethoxylated sodium disodium sulfosuccinate, disodium isodecylsulfosuccinate, disodium Noctadecylsulfosuccinamide, N- (1,2-dicarboxymethylsulfonylsulfonylside) disodium didodecyldiphenyl oxide, sodium diisopropylnaphthalenesulfonate, and neutralized condensed sodium naphthalenesulfonate products. [00117] One or more lubricants can also be added to the compositions and methods of the invention. Lubricants are usually
Petition 870190136302, of 12/19/2019, p. 43/88
39/68 tees used to reduce adhesion to hot-processed metal surfaces and may include polyethylene, paraffin oils, and paraffin waxes in combination with metallic stearates. Other lubricants include stearic acid, amide waxes, ester waxes, metal carboxylates and carboxylic acids. Lubricants are usually added to polymers in the range of about 0.1 percent to about 1 weight percent, in general, from about 0.7 percent to about 0.8 weight percent of the compound. Solid lubricants are heated and melted before or during mixing.
[00118] In film applications of the compositions and methods described in this document, anti-block master batch is also added. A suitable example is a mixture of anti-blocking master batch of erucamide (20% by weight) diatomaceous earth (15% by weight) master batch of nucleating agent (3% by weight), pelleted in PHA (62% by weight). Others are known to those skilled in the polymer processing field.
Cross-linking agents [00119] Cross-linking agents, also referred to as coagents, used in the methods and compositions of the invention are cross-linking agents that comprise two or more reactive functional groups such as epoxides or double bonds. These cross-linking agents modify the properties of the polymer. These properties include, but are not limited to, melt strength or toughness. One type of cross-linking agent is a functional epoxy compound. For use in the present invention, functional epoxy compound is intended to include compounds with two or more epoxide groups that have the ability to increase the melt resistance of polyhydroxyalkanoate polymers via branching, for example, end branching as described above .
[00120] When a functional epoxy compound is used as the
Petition 870190136302, of 12/19/2019, p. 44/88
40/68 crosslinking agent in the disclosed methods, a branching agent is optional. As such, one embodiment of the invention is a method of branching a starting polyhydroxyalkanoate (PHA) polymer, which comprises reacting a starting PHA with a functional epoxy compound. Alternatively, the invention is a branching method of a starting polyhydroxyalkanoate polymer, which comprises reacting a starting PHA, a branching agent and a functional epoxy compound. Alternatively, the invention is a branching method of a starting polyhydroxyalkanoate polymer, which comprises reacting a starting PHA, and a functional epoxy compound in the absence of a branching agent. Such functional epoxy compounds may include functional epoxy styrene acrylic polymers (such as, but not limited to, for example, JONCRYL® ADR-4368 (BASF), or MP-40 (Kaneka)), copolymers and acrylic oligomers and / or polyolefin containing glycidyl groups incorporated as side chains (such as, but not limited to, for example, LOTADER® (Arkema), poly (ethylene-glycidyl methacrylate-cometacrylate)), and epoxy oils (such as, but not limited to, for example, epoxidized soy beans, olive oils, flaxseed, palm, coconut peanuts, seaweed, cod liver, or mixtures thereof, for example, Merginat ESBO (Hobum, Hamburg, Germany) and EDENOL® B 316 (Cognis, Dusseldorf, Germany)).
[00121] For example, reactive acrylic or functional acrylic crosslinking agents are used to increase the molecular weight of the polymer in the branched polymeric compositions described herein. Such cross-linking agents are sold commercially. BASF, for example, sells multiple compounds under the trade name JONCRYL®, which are described in U.S. Patent No. 6,984,694 to Blasius et al., Oligomeric chain extenders for processing, post-processing and recycling of condensation polymers, synthe
Petition 870190136302, of 12/19/2019, p. 45/88
41/68 sis, compositions and applications, hereby incorporated in full, as a reference. One such compound is JONCRYL® ADR-4368CS, which is styrene glycidyl methacrylate and is discussed below. Another is MP-40 (Kaneka). And yet another is the Petra line from Honeywell, see, for example, U.S. Patent No. 5,723,730. Such polymers are often used in plastic recycling (for example, in recycling polyethylene terephthalate) to increase the molecular weight (or even simulate the increase in molecular weight) of the polymer being recycled. Such polymers often have the general structure:
Ri Ri Ri
R ₁ and R ₂ are H or alkyl
R ₃ is alkyl x and y are 1-20 z is 2-20 [00122] EI du Pont de Nemours & Company sells multiple reactive compounds under the trade name ELVALOY®, which are ethylene copolymers, such as acrylate copolymers, elastomeric terpolymers , and other copolymers. One such compound is ELVALOY® PTW, which is a copolymer of ethylene-n-butyl acrylate and glycidyl methacrylate. Omnova sells similar compounds under the trade names SX64053, SX64055 and SX64056. Other entities also supply such compounds commercially.
[00123] Specific polyfunctional polymeric compounds with reactive functional epoxy groups are styrene copolymers
Petition 870190136302, of 12/19/2019, p. 46/88
42/68 acrylate. These materials are based on oligomers with styrene and acrylate building blocks that have glycidyl groups incorporated as side chains. A high number of epoxy groups per oligomer chain is used, for example, 5, greater than 10, or greater than 20. These polymeric materials generally have a molecular weight greater than 3,000, specifically greater than 4,000, and more specifically, greater than 6,000. These are commercially available from S.C. Johnson Polymer, LLC (now owned by BASF) under the material name ADR 4368 JONCRYL®. Other types of functional polymeric materials with multiple epoxy groups are copolymers and oligomers of acrylic and / or polyolefin containing glycidyl groups incorporated as side chains. A further example of such a polyfunctional carboxy-reactive material is a co- or terpolymer including ethylene and glycidyl methacrylate (GMA) units, available under the trade name LOTADER® resin, sold by Arkema. Such materials may additionally comprise non-glycidyl methacrylate units. An example of this type is poly (ethylene-glycidyl methacrylate-cometacrylate).
[00124] Fatty acid esters or naturally occurring oils containing epoxy (epoxy) groups can also be used. Examples of naturally occurring oils are olive oil, linseed oil, soybean oil, babassu oil, peanut oil, coconut oil, kelp oil, cod liver oil, or a mixture of these compounds. Particular preference is given to an epoxidized soybean oil (for example, Merginat ESBO from Hobum, Hamburg, or EDENOL® B 316 from Cognis, Dusseldorf), but others can also be used. [00125] Another type of cross-linking agent is agents with two or more double bonds. Crosslinking agents with two or more double bonds crosslink PHAs when reacting later on the double bonds. Examples of these include: diaryl phthalate, tetra acrylate
Petition 870190136302, of 12/19/2019, p. 47/88
43/68 pentaerythritol, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, diethylene glycol dimethacrylate, bis (2 methacryloxyethyl) phosphate.
[00126] In general, it appears that compounds with terminal epoxides perform more satisfactorily than those with epoxide groups located elsewhere on the molecule.
[00127] Compounds that have a relatively high number of end groups are the most desirable. Molecular weight can also play a role in this regard, and compounds with higher numbers of end groups in relation to their molecular weight (for example, JONCRYL®s are in the 3,000 to 4,000 g / mol range) are likely to perform more satisfactorily than compounds with a lower number of final groups in relation to their molecular weight (for example, Omnova products have molecular weights in the range of 100,000 to 800,000 g / mol).
Nucleating agents [00128] If desired, an optional nucleating agent is added to the compositions of the invention to assist in their crystallization. In certain embodiments, the nucleating agent assists in the crystallization of the compositions. Nucleating agents for various polymers are simple substances, metallic compounds including composite oxides, for example, carbon black, calcium carbonate, salts and synthesized silicic acid, silica, zinc white, clay, kaolin, basic magnesium carbonate, mica, talc, quartz powder, diatomite, dolomite powder, titanium oxide, zinc oxide, antimony oxide, barium sulfate, calcium sulfate, alumina, calcium silicate, metal salts of organophosphates, and boron nitride; Low molecular weight organic compounds that have a metal carboxylate group, for example, metallic salts such as octylic acid, toluic acid, heptanoic acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, stearic acidPetition 870190136302, of 19 / 12/2019, p. 48/88
44/68 rich, behenic acid, cerotic acid, montanic acid, melissic acid, benzoic acid, p-tert-butylbenzoic acid, terephthalic acid, terephthalic acid monomethyl ester, isophthalic acid, and isophthalic acid monomethyl ester; High molecular weight organic compounds that have a metal carboxylate group, for example, metal salts such as: polyethylene containing carboxyl group obtained by oxidation of polyethylene; polypropylene containing carboxyl group obtained by oxidation of polypropylene; olefin copolymers, such as ethylene, propylene and butene-1, with acrylic or methacrylic acid; styrene copolymers with acrylic or methacrylic acid; olefin copolymers with maleic anhydride; and styrene copolymers with maleic anhydride; high molecular weight organic compounds, for example: alpha-olefins branched at their position 3 carbon atom and which have no less than 5 carbon atoms, such as 3,3 dimethylbutene-1,3methylbutene-1,3-methylpentene -1,3-methylhexene-1, and 3,5,5-trimethylhexene-1; vinylcycloalkane polymers such as vinylcyclopentane, vinylcyclohexane, and vinylnorbornane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; poly (glycolic acid); cellulose; cellulose esters; and cellulose ethers; phosphoric or phosphorous acid and its metallic salts, such as diphenyl phosphate, diphenyl phosphite, metal salts of bis (4-tert-butylphenyl) phosphate, and methylene bis- (2,4-tert-butylphenyl) phosphate; sorbitol derivatives such as bis (p-methylbenzylidene) sorbitol and bis (petylbenzylidene) sorbitol; and thioglycolic anhydride, ptoluenesulfonic acid and its metallic salts. The above nucleating agents can be used alone or in combinations with each other. In particular embodiments, the nucleating agent is cyanuric acid. In certain embodiments, the nucleating agent may also be another polymer (for example, polymeric nucleating agents such as PHB).
[00129] In certain embodiments, the nucleating agent is selected
Petition 870190136302, of 12/19/2019, p. 49/88
45/68 swimming: cyanuric acid, carbon black, mica talc, silica, boron nitride, clay, calcium carbonate, salts and synthesized silicic acid, metal salts of organophosphates, and kaolin. In particular embodiments, the nucleating agent is cyanuric acid.
[00130] In various embodiments, where the nucleating agent is dispersed in a liquid vehicle, the liquid vehicle is a plasticizer, for example, a citric compound or an adipic compound, for example, acetylcitrate tributyrate (CITROFLEX® A4, Vertellus, Inc ., High Point,
NC), or DBEEA (dibutoxyethoxyethyl adipate), a surfactant, for example, Triton X-100, TWEEN-20, TWEEN-65, Span-40 or Span 85, a lubricant, a volatile liquid, for example, chloroform, heptane, or pentane, an organic liquid or water.
[00131] In other embodiments, the nucleating agent is aluminum hydroxy diphosphate or a compound comprising a nitrogen-containing heteroaromatic core. The nitrogen-containing heteroaromatic nucleus is pyridine, pyrimidine, pyrazine, pyridazine, triazine or imidazole.
[00132] In particular embodiments, the nucleating agent may include hydroxy aluminum diphosphate or a compound comprising a heteroaromatic nitrogen-containing core. The nitrogen-containing heteroaromatic nucleus is pyridine, pyrimidine, pyrazine, pyridazine, triazine or imidazole. The nucleating agent may have a chemical formula selected from the group consisting of
R
Formula 1
Formula 2
Formula 3
Formula 4 ^R 1
Formula 5
Petition 870190136302, of 12/19/2019, p. 50/88
46/68
R ¹
Formula 6, [00133] and combinations thereof, each R1 being, independently, H, NR2R2, OR2, SR2, SOR2, SO2R2, CN, COR2, CO2R2, CONR2R2, NO2, F, Cl, Br, or I; and each R2 is, independently, H or C1-C6 alkyl.
The nucleating agent may be a nucleating agent as described in U.S. published application No. 2005/0209377, by Allen Padwa, which is incorporated herein by reference in its entirety.
[00135] Another nucleating agent for use in the compositions and methods described in this document is ground as described in international publication No. WO 2009/129499, published in English on October 22, 2009, and which designates the United States, which it is hereby incorporated by reference, in its entirety. In short, the nucleating agent is ground in a liquid vehicle until at least 5% of the cumulative solid volume of the nucleating agent exists as particles with a particle size of 5 microns or less. The liquid carrier allows the nucleating agent to be wet milled. In other embodiments, the nucleating agent is ground in a liquid vehicle until at least 10% of the cumulative solid volume, at least 20% of the cumulative solid volume, at least 30% or at least 40% to 50% of the nucleating agent can exist as particles with a particle size of 5 microns or less, 2 microns or less or 1 micron or less. In alternative embodiments, the nucleating agent is ground by other methods, such as jet milling and the like. In addition, other methods are used that reduce the particle size.
Petition 870190136302, of 12/19/2019, p. 51/88
47/68 [00136] The cumulative solid volume of particles is the combined volume of particles in dry form in the absence of any other substance. The cumulative solid volume of the particles is determined by determining the volume of the particles before dispersing them in a liquid or polymer vehicle, for example, by pouring them dry into a graduated cylinder or other suitable device for volume measurement. alternatively, the cumulative solid volume is determined by light scattering.
Application of the compositions [00137] For the manufacture of useful articles, the compositions described in this document are preferably processed at a temperature above the crystalline melting point of the polymers, but below the decomposition point of any of the ingredients (eg example, the additives described above, with the exception of some branching agents) of the polymeric composition. While in a thermoplasticized condition, the polymeric composition is processed in a desired shape, and subsequently cooled to adjust the shape and induce crystallization. Such shapes may include, but are not limited to, a fiber, filament, film, blade, rod, tube, bottle, or other shape. Such processing is carried out using any technique known in the art, such as, but not limited to, extrusion, injection molding, compression molding, blowing or blow molding (for example, blown film, foam blowing), calendering , rotational molding, casting (for example, molded blade, molded film), or thermoforming. Thermoforming is a process that uses films or thermoplastic sheets. The polymeric composition is processed into a film or slide. The polymer sheet is then placed in a furnace and heated. When soft enough to be formed, it is transferred to a mold and formed into a shape.
Petition 870190136302, of 12/19/2019, p. 52/88
48/68 [00138] During thermoforming, when the softening point of a semicrystalline polymer is reached, the polymer sheet begins to arch. The window between softening and tilting is usually narrow. Therefore, it may be difficult to move the softened polymer sheet into the mold quickly enough. The polymer branch can be used to increase the melt resistance of the polymer so that the blade is more readily processed and maintains its structural integrity. Measure the bending of a sample piece of polymer when it is heated when it is, therefore, a way of measuring the relative size of this processing window for thermoforming.
[00139] The compositions described in this document can be processed into films of varying thickness, for example, films of uniform thickness in the range of 1 to 200 microns, for example, 10 to 75 microns, 75 to 150 microns, or 50 to 50 microns 100 microns. The film layers can additionally be stacked to form multilayer films of the same or different thicknesses or compositions of the same or different compositions.
[00140] Blow molding, which is similar to thermoforming and is used to produce deep inlay products such as bottles and similar products with deep interiors, also benefits from the increased elasticity and melt resistance and reduced arching of the polymeric compositions described herein. document.
[00141] Articles produced from the compositions can be annealed according to any of the methods disclosed in international publication No. WO 2010/008445, which was published, in English, on January 21, 2010, and designated the United States, and entitled Branched PHA Compositions, Methods For Their Production, and Use In Applications, which was deposited in English and designated the United States. That application is hereby incorporated as a reference in
Petition 870190136302, of 12/19/2019, p. 53/88
49/68 in its entirety.
[00142] As described in the present document, annealing and thermo-treatment means a treatment in which the polymeric composition processed into a product in non-liquid form is subsequently (i.e., after the film is formed) heated for a period of time. This has been found to provide surprising and unexpected properties of puncture resistance and tear resistance in the films comprising the compositions of the invention. Preferably, the flat film is heated to about 80 ° C to about 140 ° C for about 5 seconds to about 90 minutes, more preferably, to about 90 ° C to about 130 ° C for about 10 minutes to about 70 minutes, and most preferably at about 110 ° C to about 125 ° C for about 15 minutes to about 60 minutes.
[00143] The compositions described in this document are provided in any suitable form suitable for an intended application. For example, the composition is supplied on a pellet for subsequent production of films, coatings, moldings or other articles, or films, coatings, moldings and other articles.
[00144] The polymeric compositions of the present invention can be used to create, but not limited to, a wide variety of useful products, for example, automotive, durable for the consumer, disposable for the consumer, construction, electrical, medical products , and packaging. For example, polymeric compositions can be used to produce, but not limited to, films (for example, packaging films, agricultural film, straw film, erosion control, hay wrapper, groove film, wrapper film food, pallet wrapping, protective wrapping for automobiles and home appliances and home appliance wrappers, etc.), bags (for example, garbage bags, shopping bags, overhead bags
Petition 870190136302, of 12/19/2019, p. 54/88
50/68, compostable bags, etc.), hygiene articles (for example, diapers, feminine hygiene products, incontinence products, disposable wipes, etc.), coatings for pelleted products (for example, fertilizers, herbicides, pesticides , pelleted seeds, etc.), packaging (including, but not limited to, packaging and containers for food or beverage products, cosmetic products, detergents and cleaning products, personal care products, pharmaceuticals and health products), golf tees, caps and closure systems, agricultural supports and stakes, paper and cardboard coverings (for example, for cups, plates, boxes, etc.), thermoformed products (for example, trays, containers, yogurt pots, bridges plants, spaghetti bowls, moldings, etc.), accommodation (for example, for electronic items, for example, cell phone, PDA covers, music player covers, computer covers or, printers, calculators, LCD projectors, connectors, chip trays, circuit breakers, plugs, and the like), wire and cable products (including, but not limited to, wire, cable and wire and cable coatings for vehicles, cars, trucks, airplanes, aerospace, construction, military, telecommunications, installation energy, alternative energy, and electronics components, industrial products (such as, but not limited to, containers, bottles, drums, material handles, gears, bearings, gaskets and seals, valves, wind turbines, and safety equipment), transportation products (such as, but not limited to, automotive aftermarket parts, bumpers, window seals, instrument panels, consoles , electrical parts under the hood, and engine covers), appliances and appliance parts (such as, but not limited to, refrigerators, freezers, washers, dryers, toasters, blenders vacuum cleaners, coffee makers and mixers), articles for use in building and construction (such as, but
Petition 870190136302, of 12/19/2019, p. 55/88
51/68 not limited to, fences, decks and rails, floors, floor coverings, pipes and fittings, wainscoting, ornaments, windows, doors, molding, and wall coverings), consumer goods and parts for consumer goods ( such as, but not limited to, portable power tools, rakes, shovels, lawn mowers, shoes, boots, golf clubs, fishing poles, and boats), health care equipment (including, but not limited to , wheel chains, beds, test equipment, analyzers, laboratory software, ostomy, IV sets, injury care, drug delivery, inhalers, and packaging). Briefly, the polymeric products described in this document can be used to produce items currently produced from conventional petroleum-based polymers.
[00145] The specific examples below should be interpreted as merely illustrative, and not limiting the rest of the description in any way. Without further elaboration, it is believed that one skilled in the art can, based on the description of the present invention, use the present invention to its fullest extent. All publications cited in the present invention are incorporated herein by reference in their entirety.
Examples
Experimental Methods
Measurement of Tensile Properties [00146] The control PLA homopolymer and PLA mixtures were molded by compacting pellets to form plates that were about 0.2 mm thick using a molding temperature of 200 ° C. The pellets were kept at 200 ° C for about one minute in the compaction molding machine before being abruptly cooled to room temperature. The tensile properties of these plates were then measured on an Instron 3345
Petition 870190136302, of 12/19/2019, p. 56/88
52/68 according to ASTM D882 at a speed of about 51 mm / min at room temperature. The modulus (MPa) was measured from the angular coefficient of the stress-elongation curve, the tensile elongation was measured as a% change in the sample length before rupture, the tensile strength (MPa) was measured as the maximum force reached before rupture divided by the sample area (MPa) and the tensile strength (J) was calculated as the area under the stress-elongation curve. Tensile tensile strength and tensile strength are the indicators that will be used to assess the toughness of the control PLA and the various mixtures.
Measurement of Fusion Resistance and Viscosity [00147] The resistance to melting, G ', and viscosity, η *, were measured using oscillatory torsional rheology. The measurements were performed using an AR2000 TA Instruments rheometer that employs a strain amplitude of 1%. First, the pellets (or powder) were molded into 25 mm diameter discs that were about 1,200 microns thick. The disk specimens were molded in a compaction molding machine set at about 165 to 177 ° C, with the molding time of about 30 seconds. These molded discs were then placed between the 25 mm parallel plates of the AR2000 rheometer, balanced at 185 ° C, and subsequently cooled to 160 ° C for the frequency sweep test. A span of 800 to 900 microns was used, depending on the normal forces exerted by the polymer. The density of melted PHB material was determined to be about 1.10 g / cm3 at 160 ° C; this value was used in all calculations.
[00148] Specifically, the disk specimen was placed between the plates of the parallel rheometer plate set at 185 ° C. After the final gap was reached, the excess material on the sides of the plates was scraped. The specimen was then cooled to 160 ° C where the
Petition 870190136302, of 12/19/2019, p. 57/88
53/68 frequency (from 625 rad / s to 0.10 rad / s) was then performed; Frequencies below 0.1 rad / s have been avoided due to considerable degradation over time during these lower frequency measurements. Specimen loading, span adjustment and excess trimming, all performed with the plates set at 185 ° C, take about 2 minutes. This was controlled in ± 10 seconds to minimize sample variability and degradation. Cooling from 180 ° C to 160 ° C (test temperature) was carried out in about four minutes. Exposure at 180 ° C ensures a fully melted polymer, while testing at 160 ° C ensures minimal degradation during measurement.
[00149] During the frequency scan performed at 160 ° C, the following data was collected as a function of measurement frequency: η * or complex viscosity, G 'or elastic modulus (elastic or solid contribution to viscosity) and G ”or loss module (viscous or liquid contribution to viscosity). For simplicity purposes, G 'measured at an imposed frequency of 0.25 rad / s will be used as a measure of melt strength. Larger G 'reflect resistance to greater melting.
Measurement of Thermal Properties [00150] The glass transition of a P3HB-4HB rubber phase was measured using a Q100 TA Instruments differential scanning colorimeter (DSC) with autosampler. 8 to 12 mg of a PHA sample was carefully weighed in an aluminum container sealed with an aluminum lid. The sample was then placed in the DSC under a nitrogen purge and analyzed using a heating-cooling-heating cycle. The heating / cooling range was -70 ° C to 200 ° C with a heating rate of 10 ° C / min and cooling rate of 5 ° C / min.
PLA and PHA materials
Petition 870190136302, of 12/19/2019, p. 58/88
54/68 [00151] The PLA material used in the following examples was 5040D from NatureWorks LLC. Four different PHA materials were mixed with PLA. Its ID and composition were as follows:
[00152] PHA A: P3HB homopolymer [00153] PHA B: Mix of 55 to 65% P3HB and 35 to 45% P3HB-4HB copolymer with 8-14% by weight 4HB [00154] PHA C: Mixture 34 to 38% P3HB, 22 to 26% P3HB-4HB copolymer with 8 to 14% by weight 4HB and 38 to 42% P3HB-4HB copolymer with 25 to 33% by weight 4HB [00155] PHA D: Mixture of 10 to 14% P3HB, 46 to 50% P3HB copolymer to 4HB with 8 to 14% by weight of 4HB and 38 to 42% of P3HB to 4HB copolymer with 25 to 33% by weight of 4HB [00156] The amorphous rubber phase in these PHA mixtures refers to the P3HB-4HB copolymer which has 25 to 33% by weight of 4HB. The high 4HB content of this copolymer suppresses the crystallinity of the 3HB component which produces a completely amorphous copolymer that has a Tg in the range of -15 to -40 ° C. Figure 1 shows a DSC thermogram of the PHA rubber phase with Tg measured at -15 ° C. Note that there was no Tm detected by DSC in this copolymer of P3HB-4HB which indicates that this is a completely amorphous material. According to the above description, A and B of the PHA have no rubber phase component present, while C and D of PHA have 38 to 42% by weight of the rubber phase component present (or total rubber phase). As will be shown in the following examples, increasing the overall 4HB% content in mixtures does not promote increased toughness in PLA / PHA mixtures. Only when PHA has a high rubber phase content, the toughness properties of the PLA / PHA mixture are enhanced.
Example 1. Preparation of 70/30 PLA / PHA Mixtures Using
Petition 870190136302, of 12/19/2019, p. 59/88
55/68 PHAs with 0 and 25 to 33% by weight of PHA Rubber Phase. [00157] In this example, the mechanical properties of four PLA / PHA mixtures (all at a ratio of 70/30 PLA / PHA on a weight basis) are compared to those of pure PLA (5040D by Natureworks) which is designated as the control. The PHA composition of these blend formulations are listed in the table below. The mechanical properties of particular interest were tensile strength at break and tensile strength. Formulations 1 to 4 were 70/30 PLA / PHA mixtures that were formulated in a 27 mm Leistritz double screw extruder using the following temperature profile: 190/190/190/180/180/180 / 175/175/165/165 (° C). The formulation was carried out at a thread speed of 150 rpm and a rate of about 40.8 kg (90 lbs) / h. For these mixtures, it was observed that the melt pressure was in the range of 5.9 to 8.1 MPa (860 to 1,180 psi). Table 1 summarizes the four formulation compositions and the results of tensile tests.
Table 1. Summary of 70/30 PLA / PHA mix formulations with 0 and 25 to 33% PHA rubber phase and their tensile properties.
Control Formulation1 Formulation2 Formulation3 Formulation4 Mixture Composition PLA 100 70 70 70 70 PHA A0% phase 0 30 0 0 0
eraser
PHA B 0% rubber phase 0 0 30 0 PHA C25 to 33% of phase 0 0 0 30
Petition 870190136302, of 12/19/2019, p. 60/88
56/68 rubber
PHA D
25 to 33% of phase 0 0 0 0 30 rubberTotal (% by weight) 100 100 100 100 100 Continuation... Mechanical properties Module (MPa) 2700 2365 2378 1908 1879 Resistance toTraction (MPa) 60.8 22.0 19.1 39.4 36.7 Elongation by Traction (%) 4 130 84 215 204 Resistance toTraction (J) 0.05 1.11 0.65 1.65 1.50
[00158] PHA A: P3HB homopolymer [00159] PHA B: Mixture of 55 to 65% P3HB and 35 to 45% P3HB-4HB copolymer with 8-14% by weight of 4HB [00160] PHA C: Mixture 34 to 38% P3HB, 22 to 26% P3HB-4HB copolymer with 8 to 14% by weight 4HB and 38 to 42% P3HB-4HB copolymer with 25 to 33% by weight 4HB [00161] PHA D: Mixture of 10 to 14% P3HB, 46 to 50% P3HB copolymer to 4HB with 8 to 14% by weight of 4HB and 38 to 42% of P3HB to 4HB copolymer with 25 to 33% by weight of 4HB
Table 2. Improvements in strength and relative tensile elongation of PLA / PHA mixtures at 70/30 with 0 and 25 to 33% rubber phase.
Mechanical Properties- Formulation Formulation FormulationRelative cases * 1 2 3 Formulation4 Stretching by33 21 54dogTensile Strength 22 13 33 5130
Petition 870190136302, of 12/19/2019, p. 61/88
57/68 * Relative Traction Property defined as Control PLA values / PLA mix value.
[00162] As shown in Tables 1 and 2, the addition of PHA containing 0% rubber phase has already resulted in considerable improvements in toughness for PLA, that is, a 21 to 33-fold increase in tensile elongation at break and a 13 to 22-fold increase in tensile strength. While these improvements are considerable, they were not as significant as the improvements reported for PLA / PBSA mixtures in U.S. Patent No. 5,883,199. However, as seen in Tables 1 and 2, the addition of a PHA with 25 to 33% rubber phase to the PLA resulted in an even greater improvement, that is, a 51 to 54-fold increase in tensile elongation at break and a 30 to 33-fold increase in toughness. The level of improvement achieved was recorded as more significant compared to the values recorded for PLA / PBSA mixtures. This indicated that a P3HB-4HB copolymer with 25 to 33% 4HB, completely amorphous rubber phase was a considerably more efficient impact modifier for PLA compared to P3HB homopolymer or P3HB-4HB copolymer with no rubber phase or PBSA present.
Example 2. Preparation of PLA / PHA compositions Reactively Mixed with Peroxides and Coagents using PHAs with 25 to 33% by weight of Rubber Phase.
[00163] The reactive extrusion of PLA and PHA in the presence of a reactive portion such as an organic peroxide improves the interaction between the two polymers so that a more tenacified mixture is produced. These examples demonstrate a more tenacified PLA / PHA blend using the reactive extrusion approach.
[00164] Mixing formulations 6 and 7 in the table below are mixtures of PLA / PHA that were formulated in a screw extruder
Petition 870190136302, of 12/19/2019, p. 62/88
58/68 Leistritz 27 mm double coil with the use of the following temperature profile: 190/190/190/180/180/180/175/175/165/165 (° C). The formulation was carried out at a thread speed of 150 rpm and a rate of about 40.8 kg (90 lbs) / h. For these mixtures, it was observed that the melting temperature was in the range of 188 to 192 ° C and the melting pressure was in the range of 5.4 to 7.7 MPa (780 to 1,120 psi). The PHA used in these mixtures has a rubber phase content of 25 to 33%. These rubber phases were completely amorphous with a Tg of around -15 ° C (see figure 1).
[00165] A small amount (approximately 5 weight percent) of a monomeric plasticizer (CITROFLEX® A4) was also included in these mixtures. While Formulation 6 was simply a physical mixture of the components, Formulation 7 was prepared in the presence of an organic peroxide (TRIGONOX® 131, Akzo Nobel) and pentaerythritol triacrylate coagent (PE3A, Sartomer). Organic peroxide / coagent additives can help to accentuate the interactions between PLA and PHA resins and thus improve PLA / PHA mixing toughness even further.
[00166] The control PLA and mixtures were molded by compacting pellets into plates measuring about 0.2 mm in thickness with the use of a mold temperature of about 200 ° C. The pellets were kept at 200 ° C for about one minute in the compaction molding machine before being abruptly cooled to room temperature. The tensile properties of these plates were measured using an Instron 3345 according to ASTM D882 at a speed of about 51 mm / min at room temperature. These properties are summarized in the table below:
Table 3. Summary of Formulations reactively mixed by PLA / PHA fusion (with 25 to 33% rubber phase) and their tensile properties.
Petition 870190136302, of 12/19/2019, p. 63/88
59/68
PLAof control Formulation6 Formulation7 Mixture Composition PLA 100 65 65 PHA C 0 30 30 CITROFLEX® A4 0 5 4.6 TRIGONOX® 131 0 0 0.2 PE3A Coagent 0 0 0.2 Total (% by weight) 100 100 100
Mechanical properties
Module (MPa) 2700 1808 1724 Resistance The Traction 60.8 29.6 38.5 (MPa) Stretching(%) per Traction 4 181 237 Tensile Strength (J) 0.05 1.10 1.74
[00167] PHA C: Mixture of 34 to 38% P3HB, 22 to 26% P3HB-4HB copolymer with 8 to 14% by weight of 4HB and 38 to 42% P3HB-4HB copolymer with 25 to 33% by weight of 4HB [00168] Elongation by tensile strength and tensile strength (area under the stress-elongation curve) are the indicators that were used to assess the toughness of the control PLA and the various mixtures. The table above shows that, with reactive mixing, the tensile strength and toughness are further improved compared to the unreacted PHA / PLA mixture. The table below lists the relative improvement (mixture property in question divided by the same property as the control PLA) in these toughness measurements for the mixture in question.
Table 4. Relative strength and tensile elongation improvements of the PLA / PHA mixture with 25 to 33% rubber phase reapetition 870190136302, from 12/19/2019, pg. 64/88
60/68 mixed by melting.
Mechanical properties Formulation Formulation Formulation Relative * 3 6 7 Traction Stretching 54 45 59 Tensile Strength 33 22 35
* Relative Traction property defined as Control PLA value / PLA mix value.
[00169] The toughness improvements over pure PLA were significant for Formulation 6 which contained PHA with 25 to 33% rubber phase and 5% by weight of CITROFLEX® A4 as a plasticizer. In comparison to the results in Table 1 for Formulation 3 (PHA C), the addition of 5% citrate ester appeared to decrease elongation at break by approximately 16% and toughness by approximately 33% as shown in Table 4. However , toughness and elongation improved as seen for Formulation 7 through reactive mixing with organic peroxide / coagent additives. This improvement over the non-reactive mixture formulation (31% increase in elongation and 60% in toughness) was attributed to the synergistic interactions between PLA and PHA during their reactive fusion mixing.
Example 3. Preparation of PLA / PHA Compositions Reactively Mixed with Peroxides, Coagents and Dendritic Polyester Using PHAs with 25 to 33% rubber phase.
[00170] This example demonstrates the effectiveness of reactive fusion mixing of PLA and PHA, resulting in a mixture that is even more toughened than the PLA / PBSA performance test.
[00171] Mixing formulations 8, 9 and 10 as shown in Table 5 were 70/30 PLA / PHA mixtures formulated in a 16 mm PRISM coil-fired twin screw extruder using the following temperature profile: 200 / 200/190/190/180/180/170/170 (° C). The formulation was carried out at a thread speed of
Petition 870190136302, of 12/19/2019, p. 65/88
61/68
150 rpm. The PHA used in these mixtures contained 25 to 33% PHA rubber phase. The rubber phase was completely amorphous with a Tg of around -15 ° C (see figure 1). A small amount of a monomeric plasticizer (CITROFLEX® A4) was also included in these mixtures. While Formulation 8 was simply a physical mixture of the components, Formulations 9 and 10 were prepared in the presence of an organic peroxide, which can help to intensify the interactions between PLA and PHA. For Formulation 10, a highly branched dendritic polyester (BOLTRON ™ H20, Perstorp) with more than 10 primary hydroxyl groups was also included to observe the effect on the ultimate PLA / PHA tensile strength.
[00172] The control PLA and mixtures were molded by compacting pellets on plates measuring about 0.2 mm in thickness with the use of a molding temperature of about 200 ° C. The pellets were kept at 200 ° C for about one minute in the compaction molding machine before being abruptly cooled to room temperature. The tensile properties of these plates were then measured using an Instron 3345 according to ASTM D882 at a speed of about 51 mm / min at room temperature. A summary of the tensile properties is listed in Table 5 below:
Table 5. Summary of PLA / PHA with formulations mixed reactively by melting with 25 to 33% rubber phase and its tensile properties.
PLA ofControl Formula-tion 8 Formula-tion 9 Formulation 10 Mixture Composition PLA 100 65 65 65 PHA C 0 30 30 30 CITROFLEX® A4 0 5 4.6 2.6
Petition 870190136302, of 12/19/2019, p. 66/88
62/68
TRIGONOX® 131 0 0 0.2 0.2 PE3A Coagent 0 0 0.2 0.2 BOLTRON ™ H20 0 0 0 2 Total (% by weight) 100 100 100 100
Mechanical properties
Module (MPa) 2892 1780 1826 1789 Tensile Strength (MPa) 61.5 28.5 38.2 38.1 Elongation by Traction (%) 4 169 206 213 Tensile Strength (J) 0.04 0.95 1.35 1.45
[00173] PHA C: Mixture of 34 to 38% P3HB, 22 to 26% P3HB-4HB copolymer with 8 to 14% by weight of 4HB and 38 to 42% P3HB-4HB copolymer with 25 to 33% in weight of 4HB [00174] Elongation by tensile strength and tensile strength (area under the stress-elongation curve) are the indicators used to assess the toughness of the control PLA and the various mixtures. The table below lists the relative improvement (mixture property in question divided by the same property as the control PLA) in these toughness measurements for the mixture in question.
Table 6. Relative strength and tensile elongation improvements of the 70/30 PLA / PHA mixture with 25 to 33% rubber phase reactively mixed by melting.
Relative Mechanical Properties * Formulation8 Formulation9 Formulation10 Traction Stretching 42 52 53 Tensile Strength 24 34 36
* Relative Traction property defined as Control PLA value / PLA mix value.
[00175] The toughness improvements over PLA were significant for Formulation 8 which contained 25 to 33% PHA rubber phase and 5% by weight of A4 CITROFLEX® processing aid. As seen in Table 6, the improvement in elongation and toughness over pure PLA with the rubber phase PHA
Petition 870190136302, of 12/19/2019, p. 67/88
63/68
PHA / citrate ester with no reactive mixture was significant (42-fold increase in elongation at break and 24-fold increase in toughness). However, the addition of citrate ester plasticizer slightly decreases the overall toughness. After reactive mixing with the organic peroxide and coagent, the toughness and elongation increased additionally in relation to pure PLA even with the citrate ester present (52-fold increase in elongation and 34-fold increase in tenacity). The difference was attributed to the synergistic interactions between PLA and PHA during their reactive fusion mixing. The reactive mixture with the addition of BOLTRON ™ H2O to the mixture of PLA / PHA / peroxide / coagent did not show a marginal improvement in tensile strength compared to the mixture of PLA / PHA / peroxide / coagent, but still significantly greater than PLA pure.
Example 4. Preparation of PLA / PHA compositions Reactively Mixed with Peroxide and Coagent Using PHAs with 25 to 33% rubber phase.
[00176] In this example, PLA / PHA mixtures with 0 to 95% PLA content were prepared by reactive extrusion, similarly to those formulations in Example 2, above. A total of eleven PLA / PHA blend formulations were prepared. Table 7 shows the composition and test results of the formulation. The results for a control sample that was composed of 100% by weight of PLA without any additives or branching agents are included in the Table.
[00177] A small amount (approximately 5 weight percent) of a monomeric plasticizer (CITROFLEX® A4) was also included in the mixtures. The formulations were prepared in the presence of an organic peroxide (TRIGONOX® 131, Akzo Nobel) and pentaerythritol triacrylate coagent (PE3A, Sartomer). Organic peroxide / coagent additives help to enhance interactions between
Petition 870190136302, of 12/19/2019, p. 68/88
64/68 PLA and PHA resins and thus improve the PLA / PHA mixing toughness even further.
[00178] The eleven formulations and a control sample were processed in a 27 mm Leistritz double screw extruder using the following temperature profile: 190/190/190/180/180/180/175/175 / 165/165 (° C). The formulation was carried out at a thread speed of 150 rpm and a rate of about 40.8 kg (90 lbs) / h. The PHA C used in these mixtures had a rubber phase content of 25 to 33% by weight. This rubber phase was completely amorphous with a Tg of around -15 ° C (see figure 1).
[00179] The control PLA and mixtures were then molded by compacting pellets into plates and the tensile properties of these plates measured at room temperature. The discs were also molded by compacting the pellets and melt strength and viscosity were measured. Table 7 summarizes the results of tensile and melting properties for mixtures and control PLA.
Petition 870190136302, of 12/19/2019, p. 69/88
Table 7. Summary of tensile and rheological properties of molten material for reactively mixed PLA / PHA formulations
with 25 to 33% PHA rubber phase. 18 19 20 21 22 Formulation 11 12 13 14 15 16 17 PLA (% by weight) 85 75 65 55 45 35 25 15 5 0 95 100 PHA C (% by weight) 10 20 30 40 50 60 70 80 90 95 0 0 A4 CITROFLEX® A4 (% by weight) 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 0 Peroxide 131 TRIGANOX® (% by weight) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0 PE3A coagent (% by weight) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0 Total (% by weight) 100 100 100 100 100 100 100 100 100 100 100 100
65/68
Rheological and Mechanical Properties of Molten Material
G '@ 0.25 rad / s (Pa) 3395 1431 1285 1307 1390 877 855 932 679 718 911 184 η * @ 0.25 rad / s (Pa.s) 23220 1261010680 1057010770 7686 7081 7955 6608 7054 14110 9306 Traction Module (MPa) 1877 1605 1379 1485 1026 971 798 663 573 529 2,631 2,839 Tensile Burst Stress (MPa) 18.8 28.9 29.1 32.3 15.4 18.8 23.8 22.8 19.1 22.7 46.1 54.6 Elongation by Traction (%) 22 197 232 247 157 252 397 468 456 570 5 6 Tensile Strength (J) 0.17 1.43 1.85 1.89 0.88 1.34 2.06 2.25 2.22 2.71 0.07 0.08
PHA C: Mixture of 34 to 38% P3HB, 22 to 26% P3HB-4HB copolymer with 8 to 14% by weight of 4HB and 38 to 42% P3HB-4HB copolymer with 25 to 33% of 4HB in Weight
Petition 870190136302, of 12/19/2019, p. 70/88
66/68 [00180] The data in Table 7 shows that, for PLA alone (Formulations 21 and 22), the addition of branching and coagents significantly improved melt strength and viscosity. However, the tensile properties, specifically the toughness, have not changed from that of the unbranched PLA. When PHA with 25 to 33% rubber phase was added, toughness, elongation, breaking stress, melt strength and viscosity were all significantly improved. Figures 2, 3, 4 and 5 graph the tensile properties versus the weight percentage of PHA C in the mixtures. The modulus was shown to decrease, in general, monotonically with the weight percentage of PHA C added to PLA. Tenacity, elongation and breaking stress all showed a maximum at a PLA / PHA ratio of 65/30 to 55/40 or about 32 to 42% by weight of PHA. After about 55% by weight of PHA, the elongation and toughness started to increase due to the main phase becoming essentially the rubber phase PHA. Breaking stress did not increase monotonically as did stretching and toughness. The melting properties of the mixtures, on the other hand, appeared to show a maximum at a PLA / PHA ratio of 85/10 or 10.5% PHA. The results show that, depending on the final mixing properties that are desired, different mixing ratios of PLA / PHA may be necessary.
[00181] Unlike the examples of the present invention, or unless otherwise specified, all ranges of numbers, quantities, values and percentages, such as those for material quantities, elementary contents, reaction times and temperatures, ratios of quantities, and others, in the following portion of the specification and attached claims can be read as preceded by the word about, although the term about cannot expressly appear with the value, quantity or range. Accordingly, unless
Petition 870190136302, of 12/19/2019, p. 71/88
67/68 that indicated otherwise, the numerical parameters presented in the following specification and appended claims are approximations that may vary depending on the desired properties to be obtained by the present invention. At a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in the light of the number of significant figures reported and through the application of ordinary rounding techniques.
[00182] Although the number ranges and parameters that present the broad scope of the invention are approximations, the numerical values presented in the specific examples are reported as accurately as possible. Any numerical value, however, inherently contains an error that necessarily results from the standard deviation found in its respective underlying test measurements. In addition, when numeric ranges are shown in the present invention, those ranges are inclusive of the end points of the referred range (i.e., the end points can be used). When percentages by weight are used in the present invention, the reported numerical values are relative to the total weight.
[00183] Furthermore, it should be understood that any numerical range referred to in the present invention is intended to include all the sub-ranges contained therein. For example, a range from 1 to 10 is intended to include all sub-ranges between (and including) the minimum referred value of 1 and the maximum referred value of 10, that is, that has a minimum value equal to or greater than 1 and a maximum value equal to or less than 10. The terms one or one, for use in the present invention, are intended to include at least one or one or more, except where otherwise noted.
[00184] Any patent, publication or other disclosure material, wholly or in part, that is said to be incorporated by reference.
Petition 870190136302, of 12/19/2019, p. 72/88
68/68 reference to the present invention is incorporated into the present invention only to the extent that the incorporated material does not conflict with definitions, statements or other existing disclosure material presented in that disclosure. As such, and to the extent necessary, the disclosure as explicitly described herein replaces any conflicting material incorporated herein by reference. Any material, or portion thereof, incorporated by reference to the present invention, but which conflicts with definitions, statements, or other disclosure material existing herein will be incorporated only to the extent that there is no conflict between that incorporated material and the existing disclosure material.
[00185] Unless otherwise defined, all scientific technical terms used in the present invention have the same meaning as commonly understood by the person skilled in the art to which this invention belongs. While methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents and other references mentioned in this document are hereby incorporated by reference in their entirety. In case of conflict, this specification, including definitions, will monitor. In addition, the materials, methods and examples are illustrative only and are not intended to limit.
[00186] Although this invention has been particularly shown and described with reference to preferred modalities thereof, those skilled in the art will understand that various changes in shape and details can be made there without departing from the scope of the invention covered by the appended claims.

权利要求:
Claims (17)
[1]
1. Composition, characterized by the fact that it comprises a polymeric mixture of polylactic acid (PLA) and a mixture of polyhydroxyalkanoate polymer (PHA) of poly-3-hydroxybutyrate (PHB), a PHB type 1 copolymer, and a copolymer type 1 Type 2 PHB, where the PHB content in the PHA mixture is in the range of 10% to 90% by weight of the PHA in the PHA mixture, the type 1 PHB copolymer content is in the range of 5% to 90% in PHA weight in the PHA mixture and the type 2 PHB copolymer content is in the range of 5% to 90% by weight of the PHA in the PHA mixture, where the PHA mixture has a Tg, measured with a scanning colorimeter differential (DSC), between -5 ° C to -50 ° C, and the PHA mixture is a multiphase mixture featuring an amorphous rubber phase with a Tg, measured with a DSC, from -5 ° C to 40 ° C which is between 5% to 45% of the total PHA weight in the composition.
[2]
2. Composition according to claim 1, characterized by the fact that the PHA has a rubber phase with a degree of crystallinity between 0% and 5%; and / or the multiphase PHA mixture comprises three phases.
[3]
Composition according to claim 1 or 2, characterized by the fact that it also comprises a branching agent, optionally in which:
the branching agent is selected from: dicumyl peroxide, t-amyl-2-ethylhexyl peroxide carbonate, 1,1-bis (t-butylperoxy) Petition 870190136302, of 12/19/2019, p. 74/88
2/6
3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5dimethyl-2,5-di (t-amyl peroxy) hexane, 2,5-bis (t-butylperoxy) -2,5-dimethylhexane, 2,5-dimethyl-di (t-butylperoxy) hexine-3, di-t-butyl peroxide, benzoyl peroxide, di-t-amyl peroxide, peroxide t-butyl cumila, nbutyl-4,4-bis (t-butylperoxy) valerate, 1,1 -di (t-butylperoxy) -3,3,5-trimethyl-cyclohexane, 1,1 -di (t- butylperoxy) cyclohexane, 1,1 -di (t-amylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane, ethyl-3,3-di (tbutylperoxy) butyrate, 2,2-di ( t-amylperoxy) propane, ethyl-3,3-di (tamylperoxy) butyrate, t-butylperoxy-acetate, t-amylperoxyacetate, tbutilperoxybenzoate, t-amylperoxybenzoate, and di-t-butyldiperoxyphthalate or combinations thereof; and / or the branching agent concentration is between 0.001% and 0.5% by weight of the mixture composition.
[4]
Composition according to claim 3, characterized in that it further comprises a coagent to react with the polymeric mixture composition, optionally in which:
the coagent is diallyl phthalate, pentaerythritol tetra-acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol penta-acrylate, diethylene glycol dimethacrylate, bis (2-methacryloxyethyl) phosphate, or combinations thereof;
the coagent is pentaerythritol triacrylate or diethylene glycol dimethacrylate; or the coagent is a functional epoxy acrylic styrene polymer, a functional epoxy acrylic copolymer, a functional epoxy polyolefin copolymer, an oligomer comprising a glycidyl group with a functional epoxy side chain, a poly (ethylene glycidyl methacrylate-cometacrylate) functional epoxy, or an epoxy oil or combinations thereof.
[5]
Composition according to any one of claims 1 to 4, characterized by the fact that it also comprises a
Petition 870190136302, of 12/19/2019, p. 75/88
3/6 nucleating agent such as carbon black, cyanuric acid, uracil, thymine, mica talc, silica, boron nitride, barium nitride, clay, calcium carbonate, salts and synthesized silicic acid, metal salts of organophosphates, and kaolin or combinations thereof.
[6]
6. Composition according to any one of claims 1 to 5, characterized by the fact that:
the PHA comprises an amorphous rubber phase which has 3-hydroxybutyrate (3HB) and 4-hydroxybutyrate (4HB) with a 4% by weight of 25% to 50% in the PHA composition;
the PHA comprises an amorphous rubber phase that has 3-hydroxybutyrate (3HB) and 4-hydroxybutyrate (4HB) with a 4% by weight of 25% to 40% in the PHA composition;
the PHA comprises an amorphous rubber phase that has 3-hydroxybutyrate (3HB) and 4-hydroxybutyrate (4HB) with a 4% weight by weight of 25% to 35% in the PHA composition;
the PHA comprises an amorphous rubber phase which has 3-hydroxybutyrate (3HB) and 3-hydroxyhexanoate (3HH) with a 3% by weight of 3HH from 25% to 50% in the PHA composition;
the PHA comprises an amorphous rubber phase which has 3-hydroxybutyrate (3HB) and 5-hydroxyvalerate (5HV) with a weight% of 5HV from 25% to 60% in the PHA composition; or the PHA comprises an amorphous rubber phase 3hydroxybutyrate (3HB) and 3-hydroxyoctoate (HO) with a weight% HO of 15% to 60% in the PHA composition.
[7]
Composition according to any one of claims 1 to 6, characterized in that the PHA comprises an amorphous rubber phase that is free from melting point;
the amount of PHA in the polymeric composition is from 1% to 50% by weight of the total composition.
Petition 870190136302, of 12/19/2019, p. 76/88
4/6 the amount of PHA in the polymeric composition is 10% to 40% by weight of the total composition;
the amount of PHA in the polymeric composition is 20% to 30% by weight of the total composition;
the weight average molecular weight of the rubber phase or amorphous rubber phase is between 100,000 to 600,000 daltons; and / or the composition further comprises one or more additives.
[8]
Composition according to any one of claims 1 to 7, characterized by the fact that it comprises one or more additives, in which the additive is selected from pastifiers, clarifiers, nucleating agents, thermal or oxidative stabilizers, inorganic fillers, anti-slip agents , compatibilizers, blocking agents or a combination thereof, optionally wherein the compatibilizer is maleic anhydride.
[9]
Composition according to any one of claims 1 to 8, characterized in that it further comprises a dendritic or hyper-branched polyester.
[10]
10. Composition according to claim 1, characterized in that the PHA comprises an amorphous rubber phase which has 3HB and 4HB with a 4% by weight of 25% to 50% in the PHA composition, and the composition comprises 2,5-dimethyl-2,5-di (tbutylperoxy) hexane, diethylene glycol dimethacrylate, and one or more additives selected from pastifiers, clarifiers, nucleating agents, thermal or oxidative stabilizers, inorganic fillers, anti-slip agents, compatibilizers and blocking agents.
[11]
11. Multilayer laminate, characterized in that it comprises at least one layer of film comprising the composition as defined in any one of claims 1 to 10, optionally wherein the film has a thickness of 1 to 2 mm
Petition 870190136302, of 12/19/2019, p. 77/88
5/6 crons.
[12]
12. Article, characterized by the fact that it is produced with the laminate, as defined in claim 11, in which the film has a thickness of 1 to 2 microns.
[13]
13. Method of preparing a polymeric mixture of polylactic acid (PLA) / polyhydroxyalkanoate (PHA), characterized in that it comprises mixing, in a molten state, the composition as defined in any one of claims 1 to 10, forming a polymeric composition of PLA and PHA.
[14]
14. Method for preparing a polymeric composition of a polylactic acid (PLA) / polyhydroxyalkanoate (PHA) mixture, characterized in that it comprises reacting, in the molten state, a composition as defined in any one of claims 1 to 10, where a phase of the copolymeric mixture of PHA is a totally amorphous phase with a Tg, measured with a DSC, below 20 ° C and has between 5 to 45% of the total PHA, forming a branched polymeric composition of PLA and PHA with elongation improved tensile strength.
[15]
15. Film, characterized by the fact that it comprises the composition as defined in any one of claims 1 to 10, optionally in which the film has increased elongation and tensile strength according to ASTM D822 in relation to a PLA polymer blend film / Corresponding PBSA.
[16]
16. Article, characterized by the fact that it comprises the composition as defined in any one of claims 1 to 10, optionally in which the article has 31% to 58% more tensile elongation with 21 to 35% more resistance to a corresponding polymeric article consisting only of PLA polymer.
Petition 870190136302, of 12/19/2019, p. 78/88
6/6
[17]
17. Composition according to claim 1, characterized by the fact that PHA is a copolymer of multiphase PHA copolymer with 34 to 38% poly-3-hydroxybutyrate (P3HB), 22 to 26% P3HB-4HB with 8 to 14% by weight of 4HB and copolymer with 38 to 42% of P3HB-4HB with 25 to 33% by weight of 4HB, which further comprises 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, diethylene glycol dimethacrylate, and one or more additives selected from pastifiers, clarifiers, nucleating agents, thermal or oxidative stabilizers, inorganic fillers, anti-slip agents, compatibilizers and blocking agents.

类似技术:

---

公开号 | 公开日 | 专利标题

---

US9650513B2|2017-05-16|PHA compositions comprising PBS and PBSA and methods for their production

---

ES2724497T3|2019-09-11|Polylactic acid to achieve toughness with polyhydroxyalkanoates

---

CN109265943B|2021-08-10|Bio-based rubber modified biodegradable polymer blends

---

EP2470605B1|2019-11-27|Toughened polyhydroxyalkanoate compositions

---

BRPI0915095B1|2019-04-24|METHOD FOR RAMIFYING A DEPARTURE POLYHYDROXYL-ALKYLATE | POLYMER

---

WO2011160053A2|2011-12-22|Melt stable polyesters

---

BR122021002339B1|2021-12-21|METHOD FOR PREPARING A BRANCHED POLYMER COMPOSITION, COMPOSITION AND ARTICLE

同族专利:

---

公开号 | 公开日

---

ES2724497T3|2019-09-11|

---

CN104910599A|2015-09-16|

---

CN104910599B|2018-02-09|

---

US20130065046A1|2013-03-14|

---

EP2571936B1|2019-02-06|

---

CN102906193A|2013-01-30|

---

CA2798408A1|2011-11-24|

---

EP2571936A4|2014-05-14|

---

US9328239B2|2016-05-03|

---

WO2011146484A3|2012-03-15|

---

EP2571936A2|2013-03-27|

---

AU2011256260A1|2012-12-20|

---

CN102906193B|2015-07-01|

---

BR112012029305A2|2016-07-26|

---

WO2011146484A2|2011-11-24|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

GB9223351D0|1992-11-06|1992-12-23|Ici Plc|Polyesters|

---

US5462983A|1993-07-27|1995-10-31|Evercorn, Inc.|Biodegradable moldable products and films comprising blends of starch esters and polyesters|

---

US5756651A|1996-07-17|1998-05-26|Chronopol, Inc.|Impact modified polylactide|

---

US5973100A|1997-07-25|1999-10-26|Monsanto Company|Nucleating agents for polyhydroxyalkanoates and other thermoplastic polyesters and methods for their production and use|

---

EP1023378B1|1997-09-18|2002-06-26|Monsanto Company|Modified polyhydroxyalkanoates for production of coatings and films|

---

US6794023B1|1999-10-28|2004-09-21|The Procter & Gamble Company|Polymer products comprising soft and elastic biodegradable polyhydroxyalkanoate copolymer compositions and methods of preparing such polymer products|

---

US6821612B1|1999-10-28|2004-11-23|The Procter & Gamble Company|Methods for preparing soft and elastic biodegradable polyhydroxyalkanoate copolymer compositions and polymer products comprising such compositions|

---

ITTO20010061A1|2001-01-25|2002-07-25|Novamont Spa|BINARY MIXTURES OF BIODEGRADABLE ALIPHATIC POLYESTERS AND PRODUCTS OBTAINED FROM THESE.|

---

JP2004536897A|2001-03-27|2004-12-09|ザプロクターアンドギャンブルカンパニー|Polyhydroxyalkanoate copolymer and polylactic acid composition for laminates and films|

---

US6808795B2|2001-03-27|2004-10-26|The Procter & Gamble Company|Polyhydroxyalkanoate copolymer and polylactic acid polymer compositions for laminates and films|

---

US6774158B2|2002-03-20|2004-08-10|E. I. Du Pont De Nemours And Company|Processing of polyhydroxyalkanoates using a nucleant and a plasticizer|

---

US7781539B2|2003-02-21|2010-08-24|Metabolix Inc.|PHA blends|

---

WO2004076583A1|2003-02-21|2004-09-10|Metabolix Inc.|Pha adhesive compositions|

---

US7449510B2|2003-05-12|2008-11-11|Unitika Ltd.|Biodegradable polyester resin composition, process for producing the same and foamed article and molded article using the same|

---

US7834092B2|2003-12-12|2010-11-16|E. I. Du Pont De Nemours And Company|Article comprising poly|

---

MX282710B|2003-12-22|2011-01-10|Eastman Chem Co|Polymer blends with improved rheology and improved unnotched impact strength.|

---

US7368511B2|2003-12-22|2008-05-06|Eastman Chemical Company|Polymer blends with improved rheology and improved unnotched impact strength|

---

WO2006119020A2|2005-04-29|2006-11-09|Michigan State University|Hyperbranched polymer modified biopolymers, their biobased materials and process for the preparation thereof|

---

US20080027178A1|2006-07-27|2008-01-31|Julius Uradnisheck|Article comprising poly|

---

CN1923890A|2006-08-29|2007-03-07|天津国韵生物科技有限公司|Composition containing polyhydroxy butyrate ester copolymer and polylactic acid for foaming material|

---

CN101205356A|2006-12-22|2008-06-25|深圳市奥贝尔科技有限公司|Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid|

---

WO2009129499A1|2008-04-17|2009-10-22|Metabolix, Inc.|Nucleating agents for polyhydroxyalkanoates|

---

CA2722940A1|2008-05-06|2009-11-12|Robert S. Whitehouse|Biodegradable polyester blends|

---

CN102459462B|2009-06-26|2013-07-24|梅塔玻利克斯公司|PHA compositions comprising PBS and PBSA and methods for their production|

---

CN102648234A|2009-12-08|2012-08-22|国际纸业公司|Thermoformed articles made from reactive extrusion products of biobased materials|

---

WO2011146484A2|2010-05-17|2011-11-24|Metabolix, Inc.|Toughening polylactic acid with polyhydroxyalkanoates|

---

WO2011160053A2|2010-06-18|2011-12-22|Metabolix, Inc.|Melt stable polyesters|

---

CN109265943B|2012-06-05|2021-08-10|Cj第一制糖株式会社|Bio-based rubber modified biodegradable polymer blends|

---

CN104755538B|2012-08-17|2018-08-31|Cj 第一制糖株式会社|Bio-rubber modifying agent for blend polymer|WO2011146484A2|2010-05-17|2011-11-24|Metabolix, Inc.|Toughening polylactic acid with polyhydroxyalkanoates|

---

US11207109B2|2010-10-20|2021-12-28|206 Ortho, Inc.|Method and apparatus for treating bone fractures, and/or for fortifying and/or augmenting bone, including the provision and use of composite implants, and novel composite structures which may be used for medical and non-medical applications|

---

WO2015095745A1|2010-10-20|2015-06-25|206 Ortho, Inc.|Method and apparatus for treating bone fractures, and/or for fortifying and/or augmenting bone, including the provision and use of composite implants, and novel composite structures which may be used for medical and non-medical applications|

---

EP2629780A4|2010-10-20|2014-10-01|206 Ortho Inc|Implantable polymer for bone and vascular lesions|

---

US11058796B2|2010-10-20|2021-07-13|206 Ortho, Inc.|Method and apparatus for treating bone fractures, and/or for fortifying and/or augmenting bone, including the provision and use of composite implants, and novel composite structures which may be used for medical and non-medical applications|

---

US9320601B2|2011-10-20|2016-04-26|206 Ortho, Inc.|Method and apparatus for treating bone fractures, and/or for fortifying and/or augmenting bone, including the provision and use of composite implants|

---

US10525169B2|2010-10-20|2020-01-07|206 Ortho, Inc.|Method and apparatus for treating bone fractures, and/or for fortifying and/or augmenting bone, including the provision and use of composite implants, and novel composite structures which may be used for medical and non-medical applications|

---

SK262011A3|2011-04-11|2012-11-05|Ustav Polymerov Sav|Biologically degradable polymeric composition having improved properties|

---

KR101385879B1|2011-12-26|2014-04-16|엘지하우시스|Bio plastic composition|

---

CN109265943B|2012-06-05|2021-08-10|Cj第一制糖株式会社|Bio-based rubber modified biodegradable polymer blends|

---

GB201210800D0|2012-06-18|2012-08-01|Imerys Minerals Ltd|Compositions|

---

FR2995901B1|2012-09-21|2015-08-14|Inst Corps Gras Etudes Et Rech S Tech Iterg|NOVEL BIOSOURCES PRE-POLYMERS AND THEIR USES FOR THE PREPARATION OF USEFUL POLYMERS AS ADDITIVES IN A POLYMATRIX|

---

CN102977563A|2012-11-15|2013-03-20|江苏天仁生物材料有限公司|Heat resistant polylactic acid and polyhydroxyalkanoates copolymer thin film and preparation method thereof|

---

KR20150120982A|2013-02-18|2015-10-28|유.에스. 퍼시픽 논우븐스 인더스트리 리미티드|Degradable recycling material|

---

FR3004188B1|2013-04-08|2016-02-05|Univ Bordeaux 1|USE OF POLYMERS AS ADDITIVES IN A POLYMER MATRIX|

---

CN105246972B|2013-04-10|2018-06-08|生物天然包装材料研究与开发有限及两合公司|Polymer composition|

---

WO2015059709A1|2013-10-27|2015-04-30|Tipa Corp. Ltd|Biodegradable sheet|

---

EP3068837B1|2013-11-11|2019-06-26|INEOS Styrolution Group GmbH|Blends of styrene butadiene copolymers with poly|

---

WO2015130602A2|2014-02-28|2015-09-03|Michigan Molecular Institute|Sustained release composition using biobased biodegradable hyperbranched polyesters|

---

CN103923268A|2014-04-02|2014-07-16|合肥杰事杰新材料股份有限公司|Long chain branched polylactic acid grafted by free radicals of melt and preparation method thereof|

---

KR20150128099A|2014-05-08|2015-11-18|엘지하우시스|Wall covering of pla and pha blended resin use and manufacturing method|

---

CN104086713B|2014-07-03|2019-04-30|合肥杰事杰新材料股份有限公司|A kind of polylactic acid and preparation method thereof of high crystalline energy|

---

CN104151536B|2014-08-04|2016-06-08|上海华谊（集团）公司|The method preparing biodegradable modified butanediol ester poly succinic acid|

---

KR102014555B1|2014-09-19|2019-08-27|엘지하우시스|Cushion flooing sheet and manufacturing method thereof|

---

KR20180050252A|2015-04-17|2018-05-14|렙솔, 에스.에이.|Polyalkylene carbonate and polyhydroxyalkanoate blend|

---

CN108463506A|2015-11-17|2018-08-28|Cj第制糖株式会社|Blend polymer with controllable biodegradable rate|

---

CN108602945B|2016-02-01|2020-05-15|汉高知识产权控股有限责任公司|Transesterification of polylactic acid with natural oils|

---

CN106147171B|2016-07-16|2017-11-24|宁波联华汽车部件有限公司|A kind of shape memory automobile baffle and preparation method thereof|

---

CN107163194A|2017-04-29|2017-09-15|成都博美实润科技有限公司|A kind of high-ductility lactic acid composite material and preparation method thereof|

---

US20210077667A1|2017-08-31|2021-03-18|University Of Westminster|Stents|

---

EP3676330A1|2017-08-31|2020-07-08|University of Westminster|Nerve conduits|

---

WO2019113713A1|2017-12-15|2019-06-20|University Of Guelph|Biodegradable nanostructured composites|

---

CN108676512A|2018-06-01|2018-10-19|马江嫚|A kind of viscous antiacid protective film of UV solutions|

---

CN109233229B|2018-08-13|2020-11-13|陕西理工大学|Impact-resistant ultraviolet-aging-resistant PLA wire for 3D printing and preparation method thereof|

---

CN109594144B|2018-12-13|2021-01-29|上海德福伦化纤有限公司|Melt direct spinning method of PLA fiber containing metal modified cross-shaped esterified substance|

---

CN110016729B|2018-12-13|2021-03-23|上海德福伦化纤有限公司|Hollow PLA fiber containing metal modified cross-shaped esterified substance and preparation method thereof|

---

ES2770151A1|2018-12-31|2020-06-30|Nastepur S L|BIODEGRADABLE PACKAGING, ITS PROCEDURE FOR OBTAINING AND ITS USE FOR CONTACT, TRANSPORT AND/OR STORAGE OF PERISHABLE PRODUCTS |

---

CN111170966B|2020-01-07|2021-09-07|安徽农业大学|Epoxy tea oil monomer, monomer-based polymer, pressure-sensitive adhesive and preparation method thereof|

---

CN111218727B|2020-03-04|2021-01-15|山东大学|In-situ EPDM microfiber reinforced polylactic acid composite material and preparation method and application thereof|

---

CN111234490A|2020-03-20|2020-06-05|珠海麦得发生物科技股份有限公司|High-toughness fully-degradable PHA/PLLA composite material and preparation method thereof|

---

WO2021207520A1|2020-04-09|2021-10-14|Arkema Inc.|Organic peroxide formulations for modification of bio-based and biodegradable polymers|

---

CN111349325A|2020-04-29|2020-06-30|吉林中粮生化有限公司|Modified bio-based polymer fiber composition, modified bio-based polymer fiber and preparation method thereof|

---

WO2022026362A1|2020-07-30|2022-02-03|Danimer Bioplastics, Inc.|Biobased material for consumer goods packaging|

法律状态:
2017-10-03| B25A| Requested transfer of rights approved|Owner name: CJ RESEARCH CENTER LLC (US) |

---

2018-02-20| B25A| Requested transfer of rights approved|Owner name: CJ CHEILJEDANG CORPORATION (KR) |

---

2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2020-01-28| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2020-04-07| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/05/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US34545810P| true| 2010-05-17|2010-05-17|

---

US35698610P| true| 2010-06-21|2010-06-21|

---

PCT/US2011/036808|WO2011146484A2|2010-05-17|2011-05-17|Toughening polylactic acid with polyhydroxyalkanoates|

---