Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0016—Plasticisers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix

Definitions

• This invention relates to the field of polyhydroxyalkanoate polymers, articles made therefrom and melt processing methods. More specifically, the invention pertains to melt processing and cast film extrusion of polyhydroxyalkanoates which contain a novel combination of nucleant and plasticizer for enhancing chain mobility, crystallization rates in order to improve processibility in conventional melt processes.
• melt-spun fibers from which non-woven products can be produced for medical gowns and masks examples include melt-spun fibers from which non-woven products can be produced for medical gowns and masks, blown and cast films for compostable grocery and garbage bags, injection-molded bottles for health and personal care products and extrusion coatings on paper/paperboard for biodegradable/compostable fast-food containers.
• melt-spun fibers from which non-woven products can be produced for medical gowns and masks blown and cast films for compostable grocery and garbage bags
• injection-molded bottles for health and personal care products and extrusion coatings on paper/paperboard for biodegradable/compostable fast-food containers In the processes to produce PHA products, it is crucial to achieve line speeds, cycle times, and other processing parameters that are economically desirable.
• Polyhydroxyalkanoate copolymers are extremely sticky when melt processed due, at least in part, to extremely slow crystallization rates of their crystalline phase domains. This sticky or "tacky" behavior leads to an inability to process the polymer through any melt processing equipment, including extrusion, compounding, film and fiber operations. Unmodified polymer has a strong tendency to stick to all pieces of machinery, regardless of the material of construction. The polymer also has a strong tendency to stick to itself and to human skin when touched. The stickiness or tackiness gradually disappears in a matter of minutes to hours. However, this time frame is significantly long for any conventional processing techniques, which generally require the polymer to become non-tacky within a matter of a few seconds.
• nucleating agents include, for example, talc, micronized mica, calcium carbonate, boron nitride (see, for example, EP 0291024) and ammonium chloride (see, for example, WO 9119759).
• U.S. 5,296,521 describes polyester compositions having increased crystallization rates comprising thermoplastic polyester resins and 0.5 to about 5 weight percent of nucleating agent of the formula RO[P(O)(Ph)(CH 2 ) mO] n H where R is an alkali or alkaline earth metal; m is 1 , 2, or 3; n takes an average value within the range of 1 to 5.
• the nucleating agent can be optionally mixed with the acid or ester form providing at least 50 mole percent of the nucleating agent is in the salt form.
• the nucleating agent is preferably in the form of the sodium salt (e.g., sodium salt of hydroxymethylphenyl phosphonic acid or sodium salt of oligomethylene phenyl phosphinic acid).
• U.S. 4,536,531 describes use of carboxylic salts of metals of Group I and II in the Periodic Table as nucleating agents for polyesters exemplified by metal salts of aliphatic monocarboxylic acids such as acetic acid, propionic acid, caproic acid, palmitic acid, stearic acid, oleic acid, behenic acid and montanic acid.
• Suitable metals are sodium, potassium, lithium, magnesium, calcium, barium and zinc.
• U.S. 5,061 ,743 discloses a preferred polyhydroxyalkanoate nucleant made by dry blending cyclohexylphosphonic acid and zinc stearate with polyhydroxybutyrate-co- valerate. The nucleant is disclosed as particularly advantageous for the nucleation of polyhydroxybutyrate-co-valerate having high hydroxyvalerate content.
• WO 9905208 discloses that organophosphorous compounds having at least two phosphonic acid moieties can be used as nucleants for polyhydroxyalkanoates and other thermoplastic polyesters.
• nucleants such as boron nitride have been found to act as pigments in some situations, particularly in films and injection moldings, giving rise to opaque products where transparent products are generally desired.
• nucleant systems include constituents which may be environmentally and toxicologically undesirable.
• the polymers of the previous references tend to be copolymers that do not contain a comonomer that effectively increases the amorphous character or decreases crystallization rates of the polymer.
• the resulting polymers are often brittle and lead to undesirable properties.
• Polyhydroxyalkanoate copolymers that contain more modifying comonomers, which lead to a significant amount of amorphous phase tend to be more desirable polymers because they exhibit a high level of toughness and elastic resilience.
• the large amount of amorphous phase contained in these polymers is not conducive to good crystal formation or rapid crystallization rates.
• addition of nucleants to these polymers generally does not increase the amount of crystallization or the crystallization rate enough to make melt processing of these polymers feasible.
• the invention provides a polyhydroxyalkanoate copolymer composition which can be processed into film-based products, extruded and molded articles, and coatings, comprising: (a) a polyhydroxyalkanoate copolymer; (b) a nucleant; and (c) a plasticizer, and a method of making same.
• unique combinations of either poly-3- hydroxy(butyrate-co-octanoate) or poly-3-hydroxy(butyrate-co-hexanoate) are polymerized with polyhydroxybutyrate (nucleant) and either methyl laurate or dibutylmaleate (plasticizer).
• nucleant and plasticizer to polyhydroxyalkanoate (“PHA) copolymers.
• PHA polyhydroxyalkanoate
• Addition of the nucleant and plasticizer to PHA copolymers allows crystallization processes to occur in a time frame which enables practical melt processing.
• the instant invention is applicable to any situation in which accelerated crystallization rates are desired.
• the nucleants and plasticizer are used for improved production of PHA and other thermoplastic polyester products by decreasing the cycle times normally required for producing films, extruded and molded articles, and coatings. In this disclosure, a number of terms and abbreviations are used.
• Poly(3-hydroxybutyrate-co-3-hydroxyoctanoate) which is also known as “poly-3-hydroxy(butyrate-co-octanoate)" is abbreviated P3HBO.
• Poly-3-hydroxy(butyrate-co-hexanoate) which is also known as “poly-3-hydroxy(butyrate-co-hexanoate)” is abbreviated P3HBH.
• Polyhydroxyalkanoate is abbreviated PHA.
• Polyhydroxybutyrate is abbreviated PHB. Polyhydroxyalkanoates
• Polyhydroxyalkanoates of this invention include naturally derived polymers such as polyhydroxybutyrate (PHB), including homopolymers of 3-hydroxybutyrate and 4-hydroxybutyrate. They also include copolymers of PHB with hydroxy acids, for example copolymers of PHB with 3-hydroxyhexanoate, 3-hydroxyoctanoate, or longer chain hydroxy acids (e.g. C9-C-12 hydroxy acids) and copolymers thereof. PHAs of this invention can also be synthetically derived from hydroxy carboxylic acids. Furthermore, the PHA can be predominantly of R(-) configuration, predominantly of S(+) configuration, or a random, block, or other combination of R(-) and S(+) configuration.
• R(-) and S(+) isomers refer to the ability of the repeat unit of the polymer to rotate plane polarized light in the counterclockwise or clockwise direction, respectively.
• a racemic copolymer consists of both ?(-) and S(+) repeat units within the polymer which can be arranged in any combination, including random or block configurations.
• block copolymers can be prepared having various architectures.
• an A-B diblock copolymer has a block of polymer A segments coupled to a block of B polymer segments.
• An A-B- A triblock copolymer has a block of B segments coupled to a block of A segments at each of its terminal ends.
• An -(A-B) n — multiblock copolymer has alternating sequences of A and B segments where n is a positive integer greater than 1.
• random block copolymers in which the PHB segments comprise from 85 to about 95 weight percent of the copolymer.
• PHAs have a weight average molecular weight of about 600,000 to greater than 1 ,000,000; the number average molecular weight ranges from about 280,000 to 500,000 grams/mole.
• PHAs are generally difficult to process by conventional melt processes into films, fibers, filaments, rods, tubes or other forms having physical integrity.
• Conventional melt processes include continuous melt extrusion processes, cast film extrusion, blown film extrusion, melt spinning processes and other methods generally known to those skilled in the art.
• polymer difficult to melt process it is meant that the polymer exhibits an effective melt strength and/or set time that detracts from the ability to form products having physical integrity by a conventional melt extrusion process.
• the "effective melt strength” refers to the resistance of a molten polymer to be drawn-down to a desired dimension such as thickness (in the case of films), or diameter or denier (in the case of fibers or filaments).
• a polymer having a low effective melt strength is unable to withstand the minimum strain that is required to draw the polymer melt to a desired dimension.
• the polymeric material may exhibit instabilities such as breakage, sagging or draw resonance. The resultant products tend to be highly non-uniform in physical integrity.
• the "set time” refers to the time period required, under a given set of process conditions, for the molten polymer material to achieve a substantially non-tacky or non-sticky physical state.
• the set time is important because blocking may occur if the polymer does not set within a suitable time during processing.
• the polymeric material having residual tack may stick to itself and/or to processing equipment even after cooling to room temperature or below.
• Such residual tack may restrict the speed at which the product can be processed or prevent the product from being collected in a form of suitable quality.
• the set time is influenced by the polymer material and the processing equipment and conditions.
• the set time should be on the order of seconds under conventional process conditions.
• Such conditions typically include temperatures ranging from that of chill rolls, such as are known in the art, to the melt temperature of the material being processed, which may be up to about 150°C, (preferably 120 to 135 °C).
• longer process cycle times e.g. from the point of melt extrusion to the point of take-up of collection
• Tack or "tackiness” is known to those skilled in the art to mean sticky or the amount of stickiness. Tack is generally a subjective measurement made by touching the film surface with a finger. If the surface is “tacky”, or sticky, then it has the property of "tack”. Tack may be measured subjectively by means of many scales, but to illustrate the concept, fly paper may be considered the high point of the scale with a Teflon® sheet (polytetrafluoroethylene) (from E. I. du Pont de Nemours and Company, Wilmington, DE) as having no tack.
• Teflon® sheet polytetrafluoroethylene
• tack was subjectively measured by a single operator after pressing a film of the appropriate polymer blend between two sheets of Teflon® coated aluminum foil five times. After the fifth pressing, the sample film was cooled for 10 seconds at room temperature, and the relative force required to first remove the film from the Teflon® sheets was noted. Additionally, the force required to peel the film apart from itself after folding it over on itself was also subjectively monitored along with the force required to peel the polymer from the gloves of the operator. A result of "no tack" was recorded when no apparent additional force was required to remove the film from the Teflon® sheet or from itself after folding.
• nucleants help to compensate for the slow rate of crystallization of many PHAs due to their low nucleation density.
• the preferred amount of nucleant in the composition is from about 1% to about 10%, based on the total weight of the composition.
• the nucleant in the preferred composition is polyhydroxybutyrate and is used in an amount ranging from about 0.005% to about 20%, more preferably from about 0.05% to about 10% and most preferably from about 0.5% to about 5%, based on the total weight of the composition.
• Plasticizers are examples of plasticizers
• Plasticizers are used in the instant composition to modify the mechanical properties of products formed and to improve the processability of the composition.
• a plasticizer tends to lower the modulus and tensile strength, and to increase the ultimate elongation, impact strength, and tear strength of the polymeric product.
• the plasticizer may also be used to lower the melting point of the composition to thereby enable melt processing at lower temperatures.
• the plasticizer is used to lower the glass transition temperature as an aid to increase the rate at which a non-tacky product will be attained.
• plasticizers known in the art include glycerol, ethylene glycol, and low molecular weight polyethylene glycols.
• Preferred plasticizers for the PHAs examined include di(2- ethylhexyl)(dioctyl)maleate, paraffin, dodecanol, olive oil, soybean oil, polytetramethylene glycols, methyl oleate, n-propyl oleate, tetrahydofurfuryl oleate, epoxidized linseed oil, 2-ethylhexyl epoxytallate, glycerol triacetate, methyl linoleate, dibutyl fumarate, methyl acetyl ricinoleate, acetyl tri(n-butyl) citrate, acetyl triethyl citrate, tri(n-butyl) citrate, triethyl citrate, bis(2-hydroxyethyl) dimer
• plasticizers for the PHAs examined include methyl laurate and di-n-butyl maleate.
• the preferred amount of plasticizer in the composition is from about 5% to about 35%, and more preferably from about 12% to about 20%, based on the total weight of the composition.
• melt extrusion methods are used to produce extruded and molded articles of the present invention.
• Such melt extrusion methods involve blending of polymeric components followed by extrusion of the blend.
• the strands of PHA polymer are extruded at about 120-160°C, more preferably from 130-145°C, through the die plate into a water bath having a temperature of about 30-40°C.
• pellets of the polymeric components are first prepared.
• the PHA nucleant and plasticizer can be first dry blended and then melt mixed in the film extruder itself.
• the ingredients can be first dry blended and then mixed in a pre- compounding extruder followed by pelletization prior to film melt extrusion.
• the PHA films of the present invention may be processed using conventional methods and are used for producing single or multilayer films on conventional film-making equipment. The cast or blown film extrusion methods used to make the PHA films of the present invention are more fully described in US. Patent No.
• the PHA polymer continuous film is extruded at about 120-160°C, more preferably from 120-140°C, onto rollers having a temperature of about 30-45°C, more preferably of about 40°C.
• Film refers to a continuous piece of extruded material having a high length to thickness ratio and a high width to thickness ratio. While there is no requirement for precise upper or lower limits of thickness, a preferred film thickness of the present invention is from about 0.05 to about 50 mil, and a more preferred film thickness is from about 0.5 to about 15 mil.
• the films of the present invention can comprise one, two or more layers.
• the PHA compositions of the present invention can also be made into certain selected molded articles by conventional injection molding techniques.
• Poly-3-hydroxy(butyrate-co-octanoate) (P3HBO) was obtained from Procter and Gamble Company, Inc. (Cincinnati, OH).
• Poly-3- hydroxy(butyrate-co-hexanoate) (P3HBH) was obtained from Proctor and Gamble Company, Inc. (Cincinnati, OH) (Jiangmen Center for Biotechnology Development and Tsinghua University (China).
• PHB was supplied by Aldrich Chemical Company, Inc. (St. Louis, MO).
• EXAMPLE 1 Identification of "Active" Nucleant and Plasticizer Combinations Screening of nucleant and plasticizer combinations was conducted as follows: a melt blend of the nucleant PHB and a PHA, specifically, either P3HBO or P3HBH were prepared by first tumble blending powders of the appropriate amounts of PHB and either P3HBO or P3HBH. Generally, 1 wt % PHB (0.75 g) was added to the P3HBO (74.25 g) polymer and 3 wt % PHB (2.25 g) was added to the P3HBH (72.75 g) polymer.
• the pellets were then pressed into film under the following conditions,: press temperature (140°C); pressure (1000 psi); minutes in press (2 min); cooling temperature (25°C).
• press temperature 140°C
• pressure 1000 psi
• minutes in press 2 min
• cooling temperature 25°C
• the resulting film was then cut into 2 to 5 mm wide strips to be used in the screening process.
• the resulting polymer blend was removed from the test tube (breaking the tube if necessary).
• the resulting polymer and any liquid contents were put onto a Teflon® coated aluminum foil sheet (commercially available from E. I. du Pont de Nemours and Company, Wilmington, DE) and pressed into a film.
• the film was then removed from the sheet, folded over onto itself and pressed again into a film.
• the film pressing process was repeated 5 times to ensure good blending of the three ingredients and to evaluate the effectiveness of the nucleant plasticizer combination.
• Film processing conditions were generally as follows: press temperature (140°C); press pressure (1000 psi); press time (2 min); cool temperature (room temperature); cool pressure (5 lb plate); and cool time (10 sec).
• the sample was peeled from the Teflon® coated sheet and evaluated for tack to the Teflon® coated sheet, to itself, and to the operator's gloves. If the sample exhibited no stickiness or tackiness, as defined herein, to any of the surfaces to which it was exposed, it was given a rating of "no tackiness". All other ratings indicate some level of tack.
• the sample was then wiped of any remaining plasticizer and weighed. Percent incorporation of plasticizer was determined by comparing final polymer weight to theoretical weight and back calculating plasticizer content assuming only plasticizer loss. A sample calculation follows: Ingredients added:
• Table 1 summarizes the nucleant and plasticizer screening done with both P3HBO and P3HBH, respectively, that showed results of no tack.
• Table 2 summarizes comparative examples that do exhibit tack.
• the abbreviation Tg used in Table 1 and Table 2 represents glass transition temperature (°C);
• EXAMPLE 2 Demonstration of Continuous Melt Extrusion of Polv-3-hvdroxy(butyrate- co-hexanoate) into Strand and On-line Pelletizinq Blending of Ingredients (di-n-butylmaleate plasticizer): Into a 35 gallon fiberpak was added 15088.6 g of powdered P3HBH, and 588.5 g of powdered PHB. To this powder mixture was slowly added 3923.0 g of di-n-butylmaleate at such a rate that the liquid plasticizer was immediately imbibed into the powder. The fiberpak was then placed onto a barrel tumbler and tumbled for six h to ensure good mixing.
• Extrusion of Polymer Strand and Pelletizing (di-n-butylmaleate plasticizer): After tumbling the polymer ingredients as described, the resulting mixture was fed into a 30 mm twin screw extruder at a rate of approximately 10 Ib/h. The extruder temperatures were set to maintain a gradient barrel temperature of 120 °C to 160 °C. Screw RPM was maintained at 100. The resulting molten polymer was extruded through a 3/16 inch die into a 12-foot long water trough kept at a temperature of 34 °C to 38 °C. The polymer was cut at a rate of 6 to 8 ft min and fed directly into a Conair polymer cutter. A total of 40.9 lb of pellets were collected.
• the resulting polymer strand exhibited some tacky behavior within the first 6 feet of the quench trough. After the strand became non-tacky in the water trough, the polymer exhibited no tacky behavior at any time during the processing operation or in subsequent processing operations.
• EXAMPLE 3 Demonstration of Continuous Melt Extrusion of Polv-3-hvdroxy(butyrate- co-hexanoate) into Strand and On-line Pelletizinq Blending and Extrusion of Polymer Strand and Pelletizing (methyl laurate plasticizer): In a process similar to that described for polymer blended with di-n-butylmaleate in Example 2, the following ingredients were blended: 11 ,793 g of P3HBH, 459.5 g of PHB, and 3063 g of methyl laurate. The resulting mixture was then fed into a 30 mm extruder as previously described set to maintain a gradiated barrel temperature between 120 °C to 160 °C.
• the screw RPM was maintained at 100 and polymer was extruded through a 3/16 inch die into a 12-foot water trough maintained at 34 °C to 38°C.
• the polymer was cut at a rate of approximately 12 ft/min by a Conair polymer cutter.
• the polymer quench time (the time at which no further tackiness was observed) was approximately 25 sec.
• a total of approximately 32 lb of non-tacky pellets were collected. It was noted that methyl laurate promoted faster quench times, thus allowing faster cutting rates.
• the extruded film was taken up onto the quench rolls and then onto packaging rolls at speeds ranging from 2 ft/min to 13 ft/min to produce films of thicknesses ranging from 1 mil to 10 mil.
• the film exhibited no tack and the following properties summarized in Table 3, (measured according to ASTM D 882-95a - Standard Test Method for Tensile Properties of Thin Plastic Sheeting):

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• Crystallography & Structural Chemistry (AREA)
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• 2002
  • 2002-04-19 KR KR10-2003-7013614A patent/KR20030096324A/ko not_active Application Discontinuation
  • 2002-04-19 CA CA002441781A patent/CA2441781A1/en not_active Abandoned
  • 2002-04-19 BR BR0209118-6A patent/BR0209118A/pt not_active IP Right Cessation
  • 2002-04-19 EP EP02723928A patent/EP1379590A1/en not_active Withdrawn
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  • 2002-04-19 JP JP2002583506A patent/JP2005501927A/ja active Pending
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