WO2006012917A1 - Use of fatty alcohols as plasticizer to improve the physical-mechanical properties and processability of phb and its co-polymers - Google Patents

Use of fatty alcohols as plasticizer to improve the physical-mechanical properties and processability of phb and its co-polymers Download PDF

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Publication number
WO2006012917A1
WO2006012917A1 PCT/EP2004/008874 EP2004008874W WO2006012917A1 WO 2006012917 A1 WO2006012917 A1 WO 2006012917A1 EP 2004008874 W EP2004008874 W EP 2004008874W WO 2006012917 A1 WO2006012917 A1 WO 2006012917A1
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WO
WIPO (PCT)
Prior art keywords
phb
proviso
branched
saturated
fatty alcohols
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2004/008874
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French (fr)
Inventor
Wanderson Bueno De Almeida
Pablo Silva Bizzarri
Antônio SERTORI DURAO
Jefter Fernandes Do Nascimenti
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cognis Brasil Ltda
PHB Industrial SA
Cognis IP Management GmbH
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Brasil Ltda
PHB Industrial SA
Cognis Deutschland GmbH and Co KG
Cognis IP Management GmbH
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Application filed by Cognis Brasil Ltda, PHB Industrial SA, Cognis Deutschland GmbH and Co KG, Cognis IP Management GmbH filed Critical Cognis Brasil Ltda
Priority to PCT/EP2004/008874 priority Critical patent/WO2006012917A1/en
Priority to CN200480043761XA priority patent/CN101035902B/en
Priority to AT04763902T priority patent/ATE469977T1/en
Priority to US11/573,278 priority patent/US20080139702A1/en
Priority to CA2575273A priority patent/CA2575273C/en
Priority to JP2007524183A priority patent/JP4787830B2/en
Priority to MX2007001297A priority patent/MX2007001297A/en
Priority to EP04763902A priority patent/EP1781798B1/en
Priority to DE602004027554T priority patent/DE602004027554D1/en
Priority to BRPI0418990-6A priority patent/BRPI0418990B1/en
Priority to AU2004322084A priority patent/AU2004322084B2/en
Priority to PT04763902T priority patent/PT1781798E/en
Priority to ES04763902T priority patent/ES2344951T3/en
Publication of WO2006012917A1 publication Critical patent/WO2006012917A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08K5/05—Alcohols; Metal alcoholates
    • 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
    • C08K5/10—Esters; Ether-esters

Definitions

  • Fatty alcohols as plasticizer to improve the physical-mechanical properties and processability of PHB and its co-polymers.
  • Fatty alcohols with or without glycerol fatty esters are used as plasticizers in PHB and its co ⁇ polymer compositions to improve the processability and physical-mechanical properties.
  • the plasticizers are incorporated in the PHB and its co-polymers by mixing in a dry blend system.
  • PHAs Polyhydroxyalcanoates
  • PHAs are: the PHB (poly-3-hydroxybutyrate), PHB-V (poly(hydroxybutyrate-co-hydroxyvalerate)), P4HB (poly-4-hydroxybutyrate), P3HB4HB (poly(3-hydroxybutyrate-co-4-hydroxybutyrate)) and any PHAmcl (middle chain polyhy- droxyalcanoates), and the PHHx (polyhydroxyhexanoate) are a typical biopolymer these last family.
  • the PHAs Chemical structure can be described as a polymeric chain made for unit repetition below:
  • R is a variable length chain alkyl group.
  • PHAs can be processed on extruders, common injection molding without too big modifiers for a good processability. Also, there is a possibility to process these polymers in cast and coating film system for application like food industrial packs.
  • these polymers can be used to make packs for personal hygiene of high-speed discharge and low thickness. Even where intrinsically the biodegrad ⁇ able properties were required, the PHAs has technical and commercial basements application aspects very clear, like compostage packs, golf tops, fishing articles and other things directly at the plastics materials handle in open field.
  • PHAs can be applied in flowerpot, reforesting little tubes, plantation coating films and principally, in controlling liberation system for nutrients, herbicides, insecticides and others.
  • PHAs can be used in microencapsulating for compounds control- ling liberation, medical sutures and osseous fracture fixation pins.
  • biopolymer extraction and purification process of biomass employing halogenated sol ⁇ vents are absolutely prohibitive today. They are extremely aggressive for the human health and the environment. Therefore, a solvent for PHA extraction and purification must be in the first place, environment friendly. Therefore, the use of resources damaging for the environment in any production step must be avoided. Also the energy source used in production process must come of renewable source. Where senseless have a low environmental impact plastic; if in your productio only non ⁇ renewable resources were utilized, for example.
  • the US Patent 6,127,512 discloses a polyester pellet composition
  • R2 is Cl-10 alkyl, Cl-10 alkoxy or Cl-10 alkoxyalkyl; o adipates of the formula Rl ⁇ O--C(O) ⁇ (CH2)4 ⁇ C(O) ⁇ OR2 where Rl and R2 which may be the same or different are C2-12 alkyl or C2-12 alkoxyalkyl; o sebacates of the formula Rl ⁇ C(O) ⁇ (CH2)8 -C(O)-O-Rl where Rl is C2-15 alkyl or C2- 15 alkoxyalkyl; o azelates of the formula Rl ⁇ O ⁇ C(O) ⁇ (CH2)7 -C(O)-Rl where Rl is C2-12 alkyl, benzyl, or C2-12 alkoxyalkyl;
  • alkyl ethers/esters of the formula R2 ⁇ (O) ⁇ CH2 -CH2)n --O--R1 where Rl is alkyl or — C(O)- alkyl, R2 is alkyl and n is 2 to 100; or where Rl is hydrogen and either: R2 is alkylphenyl where the alkyl is C2-12 alkyl, and n is 1 to 100; or R2 is CH3 ⁇ (CH2)10 -C(O)- and n is 5, 10, or R2 is CH3 ⁇ (CH2)7 CH CH ⁇ (CH2)7 -C(O)- and n is 5 or 15;
  • D. substituted fatty acids selected from the group consisting of sorbitan monolaurate, sorbitan monooleate, poly(oxyethylene)(20) Sorbitan monolau- rate, poly(oxyethylene)(4)lauryl ether, and butyl acetyl ricinoleate; and
  • PHB is defined as a PoIi hydroxi butirate resin, a biodegradable polymer. According to the invention this is achieved by a plasticizer composition comprising
  • PHB with the proviso that the PHB and its co-polymers of PHB are produced by a bio- polymer extraction process, characterized by the fact that the concentrated cellular material, previously dried or not, is mixed to an adequate solvent, specifically superior alcohol, prefera ⁇ bly with a chain with more than 3 carbon atoms, or any other of its acetates, preferably the isoamyl alcohol, amyl acetate, isoamyl acetate or the fusel oil as described by the Brazilian Patent PI 9302312-0 published in 04/30/2002.
  • plasticizer compositions of PHB and its co-polymer with fatty alcohols and glycerol esters used as plasticizer are easily prepared by mixing the PHB and its co-polymers in a dry blend mixer at 90 0 C for 5 minutes with slowly addition of the plasticizers under mixing.
  • the plasticizer compositions of the invention contain compounds (i) and (ii) in an amount that the weight ratio of compounds (i) and (ii) is within the range 95:5 and 50:50 and specially within the range 90:10 and 75:25.
  • compositions comprising the plasticizers (ii) with the proviso that they are composed by: a) - Fatty alcohols of chain length from 6 to 30 carbon (C6-C30) saturated or olefinically un- saturated linear or branched b) - Glycerol esters of fatty acids with 6 to 24 carbon atoms with the proviso that the fatty ac ⁇ ids can be saturated or olefinically unsaturated, linear or branched
  • the compositions preferably contain compounds (a) and (b) in an amount that the weight ratio of compounds (a) and (b) is within the range 100:0 or 95:5 or 75:25 and 50:50 and especially within the range 100:0 and 75:25.
  • plasticizer compositions which exclusively contain compounds (a) and (b) are preferred.
  • the PHB and its co-polymers provided for this invention have Mw from 300.000 to 1.000.000 with the general formula:
  • R is an alkyl group of variable length m and n are integral numbers, for PHB and its co ⁇ polymers
  • m l or 2
  • the preferably polymer used in accordance with this invention is the pure PHB with molecu ⁇ lar weight of 400.000 to 800.000.
  • the PHB and its co-polymers, according to this invention, comes from a process (Brazilian Patent PI 9302312-0) which utilize a solvent extraction process without the use of halogenated solvents.
  • the extraction process utilizes superior alcohols with chain length superior to 3 carbons atoms or the acetates derivatives.
  • the isoamyl alcohol (3 -methyl- 1-butanol), the amyl ace ⁇ tate and fusel oil or a mix of superior alcohols as by product from alcoholic fermentation process where the mainly component is the isoamyl alcohol.
  • the process can be performed in a continuous or intermittent way and, in both cases, the cells containing the bio-polymer are processes by a single solvent, what characterizes a single stage process.
  • the concentrated cellular material previously dried or not, is submitted to ex ⁇ traction with an adequate solvent, superior alcohol and/or its ester.
  • the cellular resi ⁇ due is separated by conventional mechanical techniques that can be deposition, flotation, fil- tering, centrifuging or also a combination of these methods, resulting in a cake and a solution containing the polymer.
  • the later is submitted to a crystallization stage that turns the polymer not soluble in the solvent without the presence of an agent that prevents dissolution.
  • the crys ⁇ tallization may occur due to the increased concentration of the polymer in the solution, by removing the solvent (for example, evaporation), associated or not to the saturation of the solution due to the lowering of the mean's temperature.
  • the polymer will solid ⁇ ify in the solution without the addition of a dissolving prevention agent and, then, it may be recovered from the solution by conventional mechanical separation (as mentioned above). Therefore, the separated solution may be directly recycled to the extraction stage.
  • the drying and extraction of the polymer can be done in a single stage if an adequate solvent is chosen, which is not or partially not soluble in water, as, for example the isoamyl alcohol; water can be removed by distilling the mixture in its boiling point during the extraction.
  • the distilled material can then be cooled forming two phases.
  • the aqueous phase is discarded and the solvent returns directly to the extraction process.
  • appropriate pressure and temperature condi ⁇ tions must be chosen in order to prevent the thermal decomposition of the polymer.
  • the material may be sowed with selected grain that act as crystallization germs.
  • the temperature range that is more adequate for the polymer extraction is usually above 40oC and the solvent boiling point (in the case of dry cells), or at the aqueous mixture boiling point (in the case of humid cells).
  • the product precipitation occurs due to the cooling of the solution until the ambient temperature.
  • This cooling may eventually be preceded by an impurity purging.
  • the heating, cooling and purging operations are performed in the same vessel, or in two ves ⁇ sels placed in series, featuring devices to control and act upon the system's temperature.
  • the vessels can also count with a stirring system to accelerate the extraction and system of flow- directing plates to enhance deposition.
  • the cell suspension in the solvent may be heated in continuous flow through heat exchangers and, after that, transferred to a cooling and deposition vessel.
  • the quantity of solvent employed depends on the bio-polymer content in the cells and on the extraction time.
  • the ratio between the solvent mass and the mass of the cells vary between 2.5 and 200, preferably between 10 and 150.
  • thermal stabilization system consti ⁇ tuted by: primary antioxidant as Phenol hindered (in content of 0,02% and 0,5% - % in mass concerning at the totality, included the PHB and the plasticizers); secondary antioxidant as organic phosphites (in content of 0,02% and 0,5% - % in mass concerning at the totality, in ⁇ cluded the PHB and the plasticizer); thermal stabilizers as lactone (in content of 0,02% and 0,5% - % in mass concerning at the totality, included the PHB and the plasticizer).
  • This nucleants are used for the thermodynamic and kinetic process controls of the PHB crystallization (nucleating and growth) at polymeric compositions.
  • the nucleant content must be changed, of combined form with the cooling gradient imposed to the polymeric material dur ⁇ ing its final stage process.
  • the invention also relates the use of fillers in the plasticizers composition with the proviso that the fillers can be compose by starch, wood powder, cane bagasse fibers, rice pod fibers and sisal fibers. These fillers are used to concern specific process-structure-properties-cost relationship, desired for a specific product made with a polymeric composition based in PHB/plasticizer/additives.
  • Another embodiment of the invention is the use of the claimed composition as injection mol ⁇ ding pieces and/or as films for packaging.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Wrappers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates a plasticized polymeric composition comprising (i) PHB with the pro­viso that the PHB and its co-polymers of PHB are produced by a bio-polymer extraction proc­ess, characterized by the fact that the concentrated cellular material, previously dried or not, is mixed to an adequate solvent, specifically superior alcohol, preferably with a chain with more than 3 carbon atoms, or any other of its acetates, preferably the isoamyl alcohol, amyl acetate, isoamyl acetate or the fusel oil as described by the Brazilian Patent PI 9302312-0 published in 04/30/2002 (ii) a) Fatty alcohols of chain length from 6 to 30 carbon (C6-C30) with the proviso that the fatty alcohols can be saturated or olefinically unsaturated linear or branched and b) glycerol esters of fatty acids with 6 to 24 carbon atoms with the proviso that the fatty acids can be saturated or olefinically unsaturated, linear or branched and optional (iii) additives with the proviso that the additives are composed by thermal stabilization system, constituted by: primary antioxidant as Phenol hindered; secondary antioxidant as organic phosphites; thermal stabilizers as lactone; sorbitol and sodium benzoate as nucleants and starch, wood powder, cane bagasse fibers, rice pod fibers and sisal fibers as fillers.

Description

Use of Fatty alcohols as plasticizer to improve the physical-mechanical properties and processability of PHB and its co-polymers.
Brief description of the invention
Fatty alcohols with or without glycerol fatty esters are used as plasticizers in PHB and its co¬ polymer compositions to improve the processability and physical-mechanical properties. The plasticizers are incorporated in the PHB and its co-polymers by mixing in a dry blend system.
State of the art
At worldwide industrial today is known the need to produce biodegradable and biocompatible materials employing renewable raw materials and energy source, through not environment aggressive process. At market, the more successfully biodegradable biopolymer applications are disposable mate¬ rials like for agrochemical and cosmetics packaging, and medicinal applications. An important biodegradable biopolymer family is the Polyhydroxyalcanoates (PHAs). They are polyesters made by many microorganisms natural synthesis. There are more than 170 microorganisms on the literature, and the commercial advantage of the PHAs is not only linked to the biodegradable qualities, but also to the thermo-mechanical properties and low production costs.
The most representatives PHAs are: the PHB (poly-3-hydroxybutyrate), PHB-V (poly(hydroxybutyrate-co-hydroxyvalerate)), P4HB (poly-4-hydroxybutyrate), P3HB4HB (poly(3-hydroxybutyrate-co-4-hydroxybutyrate)) and any PHAmcl (middle chain polyhy- droxyalcanoates), and the PHHx (polyhydroxyhexanoate) are a typical biopolymer these last family. The PHAs Chemical structure can be described as a polymeric chain made for unit repetition below:
Figure imgf000002_0001
Where R is a variable length chain alkyl group. M and n are integral numbers, in the polymers mentioned above, R and M have the following values: PHB: R=CH3, m=l PHB-V: R=CH3 or CH3-CH2-, m=l P4HB: R=H, m=2 P3HB-4HB: R=H or CH3, m=l or 2
PHHx: R=CH3-CH2-CH2-, m=l
A lot of the PHAs can be processed on extruders, common injection molding without too big modifiers for a good processability. Also, there is a possibility to process these polymers in cast and coating film system for application like food industrial packs.
Depending on the development level these polymers can be used to make packs for personal hygiene of high-speed discharge and low thickness. Even where intrinsically the biodegrad¬ able properties were required, the PHAs has technical and commercial basements application aspects very clear, like compostage packs, golf tops, fishing articles and other things directly at the plastics materials handle in open field.
At agro business, PHAs can be applied in flowerpot, reforesting little tubes, plantation coating films and principally, in controlling liberation system for nutrients, herbicides, insecticides and others. For biomedical applications, PHAs can be used in microencapsulating for compounds control- ling liberation, medical sutures and osseous fracture fixation pins.
The great development of the natural science in the last two decades, especially of the bio¬ technology, have permitted the use of the many microorganisms, natural or genetically modi¬ fied, in the commercial production of PHAs. Although many application have being made with the bacterial cells "in natura" (without the PHAs solvent agent), like moldable materials, as explain the patent US-3107172, the PHAs commercial application, in the most cases required high purity level for a good plastic proper¬ ties. It's crucial the utilization of solvents for the PHA extraction and recuperation of the re¬ sidual biomass for an adequate processability purity level. In patent EPA-01455233 A2 are described some procedures possibilities for the digestion of a cells with PHA aqueous suspension, using enzymes or surfactants agents for non-PHA sub¬ stance solubilization. This patent shows, with reference to the solvent extraction process, pos- sible limitations because of the elevated production costs. However, if desire an elevated pu¬ rity product, the solvent step isn't eliminated.
At organic solvent extraction process, frequently cited on the literature for PHA extraction and recuperation of bacterial biomass, utilize partially halogenated hydrocarbons solvents, like chloroform (patent US-3275610), the ethanol/methanol chlorine (US-3044942), chloroethane and chloropropane with the boiling point between 65 to 17O0C, 1,2-dichloroetane and 1,2,3- trichloropropane (patents EP-0014490 B 1 and EP 2446859).
Other resources, also halogenated, like dichloromethane, dichloroethane and dichloropropane are cited at American patents US-4.562.245 (1985), US-4.310.684 (1982), US-4.705.604 (1987) and European patent 036.699 (1981) and German 239.609 (1986).
The biopolymer extraction and purification process of biomass, employing halogenated sol¬ vents are absolutely prohibitive today. They are extremely aggressive for the human health and the environment. Therefore, a solvent for PHA extraction and purification must be in the first place, environment friendly. Therefore, the use of resources damaging for the environment in any production step must be avoided. Also the energy source used in production process must come of renewable source. Where senseless have a low environmental impact plastic; if in your productio only non¬ renewable resources were utilized, for example. A very interesting approach for this problem is the all incorporation of the bioplastic productive chain for agro industry, particularly for sugar and alcohol industry (Nonato, R.V., Mantelatto, P.E.,Rossell, C.E.V.,"Ihtegrated Pro¬ duction of Biodegradable Plastic (PHB), Sugar and Ethanol", Appl. Microbiol. Biotechnology. 57:1-5, 2001).
The US Patent 6,127,512 discloses a polyester pellet composition comprising a polyhy- droxyalkanoate (PHA) having a molecular weight (Mw) of greater than about 470,000 and a plasticizing quantity of at least one plasticizer selected from the group consisting of:
■ A. high boiling point esters selected from
o phthalates and isophthalates of the formula: [Figure 1] where Rl is C 1-20 alkyl cycloalkyl or benzyl; (ii) citrates of the formula: [Figure 2] where Rl is hydrogen or
Cl-10 alkyl, and R2 is Cl-10 alkyl, Cl-10 alkoxy or Cl-10 alkoxyalkyl; o adipates of the formula Rl ~O--C(O)~(CH2)4 ~C(O)~OR2 where Rl and R2 which may be the same or different are C2-12 alkyl or C2-12 alkoxyalkyl; o sebacates of the formula Rl ~C(O)~(CH2)8 -C(O)-O-Rl where Rl is C2-15 alkyl or C2- 15 alkoxyalkyl; o azelates of the formula Rl ~O~C(O)~(CH2)7 -C(O)-Rl where Rl is C2-12 alkyl, benzyl, or C2-12 alkoxyalkyl;
Figure Figure 2
Figure imgf000005_0002
Figure imgf000005_0001
B. alkyl ethers/esters of the formula R2 ~(O)~CH2 -CH2)n --O--R1 where Rl is alkyl or — C(O)- alkyl, R2 is alkyl and n is 2 to 100; or where Rl is hydrogen and either: R2 is alkylphenyl where the alkyl is C2-12 alkyl, and n is 1 to 100; or R2 is CH3 ~(CH2)10 -C(O)- and n is 5, 10, or R2 is CH3 ~(CH2)7 CH=CH~(CH2)7 -C(O)- and n is 5 or 15;
C. epoxy derivatives of the formula CH3 -(CH2)n ~A~(CH2)n -R in which the A is an alkene containing one or more double bonds (i.e. unsaturated fatty acids), n is 1 to 25 and R is C2-15 alky; or epoxy derivatives of triglycerides containing one or more double bonds per fatty acid chain with chain lengths from C6-26.
D. substituted fatty acids selected from the group consisting of sorbitan monolaurate, sorbitan monooleate, poly(oxyethylene)(20) Sorbitan monolau- rate, poly(oxyethylene)(4)lauryl ether, and butyl acetyl ricinoleate; and
■ E. polymeric esters of the formula -0-C(O)-Rl -C(O)~O-R2 -O- in which Rl and R2 are both independently C2-12 alkylene, or R2 may be de¬ rived from a diol. Other patents connected with this above patent are: WO9923146A1 and AU1281499A1
Description of the invention
Its is an object of the present invention to provide plasticizer compositions for PHB and its co¬ polymers, to improve the physical/ mechanical properties of the processed PHB and its co¬ polymers. PHB is defined as a PoIi hydroxi butirate resin, a biodegradable polymer. According to the invention this is achieved by a plasticizer composition comprising
(i) PHB with the proviso that the PHB and its co-polymers of PHB are produced by a bio- polymer extraction process, characterized by the fact that the concentrated cellular material, previously dried or not, is mixed to an adequate solvent, specifically superior alcohol, prefera¬ bly with a chain with more than 3 carbon atoms, or any other of its acetates, preferably the isoamyl alcohol, amyl acetate, isoamyl acetate or the fusel oil as described by the Brazilian Patent PI 9302312-0 published in 04/30/2002.
(ii) a) Fatty alcohols of chain length from 6 to 30 carbon (C6-C30) with the proviso that the fatty alcohols can be saturated or olefmically unsaturated linear or branched and b) glycerol esters of fatty acids with 6 to 24 carbon atoms with the proviso that the fatty acids can be satu- rated or olefinically unsaturated, linear or branched.
Dry blend compositions of PHB and its co-polymer with fatty alcohols and glycerol esters used as plasticizer, are easily prepared by mixing the PHB and its co-polymers in a dry blend mixer at 900C for 5 minutes with slowly addition of the plasticizers under mixing. In one embodiment the plasticizer compositions of the invention contain compounds (i) and (ii) in an amount that the weight ratio of compounds (i) and (ii) is within the range 95:5 and 50:50 and specially within the range 90:10 and 75:25.
The invention also relates to the use of compositions comprising the plasticizers (ii) with the proviso that they are composed by: a) - Fatty alcohols of chain length from 6 to 30 carbon (C6-C30) saturated or olefinically un- saturated linear or branched b) - Glycerol esters of fatty acids with 6 to 24 carbon atoms with the proviso that the fatty ac¬ ids can be saturated or olefinically unsaturated, linear or branched As also stated above the compositions preferably contain compounds (a) and (b) in an amount that the weight ratio of compounds (a) and (b) is within the range 100:0 or 95:5 or 75:25 and 50:50 and especially within the range 100:0 and 75:25. Those plasticizer compositions, which exclusively contain compounds (a) and (b) are preferred.
The PHB and its co-polymers provided for this invention have Mw from 300.000 to 1.000.000 with the general formula:
Figure imgf000007_0001
where R is an alkyl group of variable length m and n are integral numbers, for PHB and its co¬ polymers R and m have the following values: PHB: R=CH3, m=l PHB-V: R=CH3 or CH3-CH2-, m=l P4HB: R=H5 m=2 P3HB-4HB: R=H or CH3, m=l or 2 PHHx: R=CH3-CH2-CH2-, m=l
The preferably polymer used in accordance with this invention is the pure PHB with molecu¬ lar weight of 400.000 to 800.000. The PHB and its co-polymers, according to this invention, comes from a process (Brazilian Patent PI 9302312-0) which utilize a solvent extraction process without the use of halogenated solvents.
The extraction process utilizes superior alcohols with chain length superior to 3 carbons atoms or the acetates derivatives. Preferably the isoamyl alcohol (3 -methyl- 1-butanol), the amyl ace¬ tate and fusel oil or a mix of superior alcohols as by product from alcoholic fermentation process where the mainly component is the isoamyl alcohol.
The process can be performed in a continuous or intermittent way and, in both cases, the cells containing the bio-polymer are processes by a single solvent, what characterizes a single stage process. In this process, the concentrated cellular material, previously dried or not, is submitted to ex¬ traction with an adequate solvent, superior alcohol and/or its ester. After that, the cellular resi¬ due is separated by conventional mechanical techniques that can be deposition, flotation, fil- tering, centrifuging or also a combination of these methods, resulting in a cake and a solution containing the polymer. The later is submitted to a crystallization stage that turns the polymer not soluble in the solvent without the presence of an agent that prevents dissolution. The crys¬ tallization may occur due to the increased concentration of the polymer in the solution, by removing the solvent (for example, evaporation), associated or not to the saturation of the solution due to the lowering of the mean's temperature. In both cases, the polymer will solid¬ ify in the solution without the addition of a dissolving prevention agent and, then, it may be recovered from the solution by conventional mechanical separation (as mentioned above). Therefore, the separated solution may be directly recycled to the extraction stage. The drying and extraction of the polymer can be done in a single stage if an adequate solvent is chosen, which is not or partially not soluble in water, as, for example the isoamyl alcohol; water can be removed by distilling the mixture in its boiling point during the extraction. The distilled material can then be cooled forming two phases. The aqueous phase is discarded and the solvent returns directly to the extraction process. In order to operate according to the system above, appropriate pressure and temperature condi¬ tions must be chosen in order to prevent the thermal decomposition of the polymer. In order to increase the grain size and make crystallization easier, the material may be sowed with selected grain that act as crystallization germs. The temperature range that is more adequate for the polymer extraction is usually above 40oC and the solvent boiling point (in the case of dry cells), or at the aqueous mixture boiling point (in the case of humid cells).
Once the hot dissolving is performed, the product precipitation occurs due to the cooling of the solution until the ambient temperature. This cooling may eventually be preceded by an impurity purging. The heating, cooling and purging operations are performed in the same vessel, or in two ves¬ sels placed in series, featuring devices to control and act upon the system's temperature. The vessels can also count with a stirring system to accelerate the extraction and system of flow- directing plates to enhance deposition. Alternatively, the cell suspension in the solvent may be heated in continuous flow through heat exchangers and, after that, transferred to a cooling and deposition vessel. The quantity of solvent employed depends on the bio-polymer content in the cells and on the extraction time. The ratio between the solvent mass and the mass of the cells vary between 2.5 and 200, preferably between 10 and 150.
Its is also an object of this invention to provide the use of thermal stabilization system, consti¬ tuted by: primary antioxidant as Phenol hindered (in content of 0,02% and 0,5% - % in mass concerning at the totality, included the PHB and the plasticizers); secondary antioxidant as organic phosphites (in content of 0,02% and 0,5% - % in mass concerning at the totality, in¬ cluded the PHB and the plasticizer); thermal stabilizers as lactone (in content of 0,02% and 0,5% - % in mass concerning at the totality, included the PHB and the plasticizer).
It's also another object of this invention to provide the use of the sorbitol and sodium benzo- ate as nucleants. This nucleants are used for the thermodynamic and kinetic process controls of the PHB crystallization (nucleating and growth) at polymeric compositions. In accordance with crystalline morphology and with crystallinity degree desired the nucleant content must be changed, of combined form with the cooling gradient imposed to the polymeric material dur¬ ing its final stage process.
The invention also relates the use of fillers in the plasticizers composition with the proviso that the fillers can be compose by starch, wood powder, cane bagasse fibers, rice pod fibers and sisal fibers. These fillers are used to concern specific process-structure-properties-cost relationship, desired for a specific product made with a polymeric composition based in PHB/plasticizer/additives.
Another embodiment of the invention is the use of the claimed composition as injection mol¬ ding pieces and/or as films for packaging.
Examples
A technical study was made with pure PHB and 6 different plasticizer composition. Dry blend mixtures of PHB and the plasticizer composition were produced by mixing them in a Mixer at 100°C to HO0C for 5 minutes and 5 minutes of cooling to 50°C.
The dry blend was pelletized by extrusion and the body tests were produced by injection molding as follow: Extrusion:
-Co-Rotacional double screw extruder- Werner & Pfleiderer ZSK-30 (30 mm) -Conditions:
Figure imgf000010_0001
Injection Moulding:
■ Injection Machine-ARBURG 270 V - 30 ton
- Mold (for body tests), ASTM D 638 (tensile Strength I) and ASTM D 256 (Impact Izod). Injection Moulding conditions:
Temperature profile (0C): Pressure/time profiles
Zone 1: 152 Pressure (bar): 400
Zone 2: 156 Pressurization (bar): 380
Zone 3: 172 Flow (cmJ/ s): 20
Zone 4: 172 Holding (bar): 300
Zone 5: 170 Time of holding (s): 12
Mold (0C): 35 Back pressure (bar): 40
Cooling time (s): 32 Dosage Speed (mm / min): 12
Figure imgf000011_0001
Tests results:
Figure imgf000011_0002

Claims

Claims
1. A plasticized polymeric composition comprising (i) PHB with the proviso that the PHB and its co-polymers of PHB are produced by a bio-polymer extraction process, characterized by the fact that the concentrated cel¬ lular material, previously dried or not, is mixed to an adequate solvent, specifi¬ cally superior alcohol, preferably with a chain with more than 3 carbon atoms, or any other of its acetates, preferably the isoamyl alcohol, amyl acetate, isoamyl ace- tate or the fusel oil as described by the Brazilian Patent PI 9302312-0 published in
04/30/2002.
(ii) a) Fatty alcohols of chain length from 6 to 30 carbon (C6-C30) with the proviso that the fatty alcohols can be saturated or olefmically unsaturated linear or branched and b) glycerol esters of fatty acids with 6 to 24 carbon atoms with the proviso that the fatty acids can be saturated or olefinically unsaturated, linear or branched.
2. Compositions according to claim 1 further comprising
(iii) additives with the proviso that the additives are composed by thermal stabilization system, constituted by: primary antioxidant as Phenol hindered; secondary anti¬ oxidant as organic phosphites; thermal stabilizers as lactone; sorbitol and sodium benzoate as nucleants and starch, wood powder, cane bagasse fibers, rice pod fi¬ bers and sisal fibers as fillers.
3. Compositions according to claim 1 and/or 2 with the proviso that the weight ratio of com¬ pounds (i) and (ii) is within the range 90:10 and 75:25.
4. Compositions according to one of the claims 1 to 3 with the proviso that the compound
(i) is defined as the following formula:
Figure imgf000012_0001
where R is an alkyl group of variable length m and n are integral numbers, for PHB and its co-polymers R and m have the following values: PHB: R=CH3, m=l
PHB-V: R=CH3 ou CH3-CH2-, m=l P4HB: R=H, m=2
P3HB-4HB: R=H ou CH3, m=l ou 2
PHHx: R=CH3-CH2-CH2-, m=l
5. Compositions according to one of the claims 1 to 4 with the proviso that the PHB mo¬ lecular weight in is within the range 300.000 to 1.000.000.
6. Compositions according to claim 1 with the proviso that the plasticizers (ii) are composed by:
a) -Fatty alcohols of chain length from 6 to 30 carbon (C6-C30) saturated or olefinically unsaturated linear or branched. b) - Glycerol esters of fatty acids with 6 to 24 carbon atoms with the proviso that the fatty acids can be saturated or olefinically unsaturated, linear or branched.
7. Compositions according to claim 6 with the proviso that the weight ratio of compounds a) and b) is within the range 100:0 and 75:25.
8. The use of the composition according to any of claim 1 to 7 as injection molding pieces and/or as films for packaging.
PCT/EP2004/008874 2004-08-06 2004-08-06 Use of fatty alcohols as plasticizer to improve the physical-mechanical properties and processability of phb and its co-polymers Ceased WO2006012917A1 (en)

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CN200480043761XA CN101035902B (en) 2004-08-06 2004-08-06 Use of fatty alcohols as plasticizers for improving the physical-mechanical properties and processability of PHB and its copolymers
AT04763902T ATE469977T1 (en) 2004-08-06 2004-08-06 USE OF FAT ALCOHOLS AS PLASTICIZERS TO IMPROVE THE PHYSICAL-MECHANICAL PROPERTIES AND PROCESSABILITY OF PHB AND ITS COPOLYMERS
US11/573,278 US20080139702A1 (en) 2004-08-06 2004-08-06 Use of Fatty Alcohols as Plasticizer to Improve the Physical-Mechanical Properties and Processability of Phb and its Co-Polymers
CA2575273A CA2575273C (en) 2004-08-06 2004-08-06 Use of fatty alcohols as plasticizer to improve the physical-mechanical properties and processability of phb and its co-polymers
JP2007524183A JP4787830B2 (en) 2004-08-06 2004-08-06 Use of fatty alcohols as plasticizers to improve the physico-mechanical properties and processability of PHB and its copolymers
MX2007001297A MX2007001297A (en) 2004-08-06 2004-08-06 Use of fatty alcohols as plasticizer to improve the physical-mechanical properties and processability of phb and its co-polymers.
EP04763902A EP1781798B1 (en) 2004-08-06 2004-08-06 Use of fatty alcohols as plasticizer to improve the physical-mechanical properties and processability of phb and its co-polymers
DE602004027554T DE602004027554D1 (en) 2004-08-06 2004-08-06 USE OF FAT ALCOHOLS AS SOFTENERS FOR THE VAFTEN AND PROCESSABILITY OF PHB AND ITS COPOLYMERS
BRPI0418990-6A BRPI0418990B1 (en) 2004-08-06 2004-08-06 Plasticizer polymer composition and use of polymer composition
AU2004322084A AU2004322084B2 (en) 2004-08-06 2004-08-06 Use of fatty alcohols as plasticizer to improve the physical-mechanical properties and processability of PHB and its co-polymers
PT04763902T PT1781798E (en) 2004-08-06 2004-08-06 Use of fatty alcohols as plasticizer to improve the physical-mechanical properties and processability of phb and its co-polymers
ES04763902T ES2344951T3 (en) 2004-08-06 2004-08-06 USE OF FAT ALCOHOLS AS A PLASTIFIER TO IMPROVE PHB PHYSICAL AND PROCESSABILITY PROPERTIES OF PHB AND ITS COPOLYMERS.

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