Patent Grant
8981002
The present invention relates to a flame retardant composition. Specifically, the present invention is a combination of a biodegradable polymer and a branching agent to form hyper-branched polymers that possess superior flame retardant and mechanical properties.
Biodegradable polymer compositions are widely utilized in numerous applications, including automotive, home construction, electronic and consumer good products. The polymers may be composed of either bio-based polymers or petroleum-based polymers. The biodegradation of the polymer is preferred to address environmental concerns associated with disposal of the materials once they are no longer useful for their intended purpose. However, the polymers must meet certain physical and chemical characteristics in order for them to be suitable for the intended application. One frequent requirement of biodegradable polymers in certain applications is that they must be flame retardant. However, certain flame retardants, such as halogen compounds, may generate harmful gases during combustion.
The addition of conventional flame retardant materials to a polymer composition may adversely impact the physical characteristics of the composition, ultimately rendering the composition unsuitable or undesirable for its intended purpose. Highly filled flame retardant polymers are often inferior physical characteristics compared to competitive materials due to their molecular architecture. Such materials are often incapable of achieving the desired strength and impact characteristics. Other flame retardant compositions offer molecular architecture that potentially limits the subsequent processing once the multi-component composition is created.
The biodegradable compositions of this invention have an excellent balance of mechanical properties and enable the melt processing of the compositions once they are initially admixed. The combination of these attributes is a function of the molecular architecture of the compositions. In one embodiment, the hyper-branched biodegradable polymers of this invention are produced by melt processing biodegradable polymers with a branching agent at temperatures that promote free radical reactions between the biodegradable polymer and the branching agent. In one embodiment, the polymer is a biodegradable linear polyester and the branching agent is an ethylenically unsaturated compound. The composition possesses certain flame retardant characteristics without employing conventional flame retardant compounds.
The hyper-branched composition embodied in the present invention has a molecular structure that is in part created by the branching agent utilized in the composition. In one embodiment, the branching agent(s) of this invention include multifunctional compounds that can undergo free radical homolysis reactions and react with the biodegradable polyester during melt processing to form a hyper-branched biodegradable polyester. The degree of branching and interaction of the polymer chains possesses characteristics of a higher molecular weight material while still being subsequently melt processable.
The hyper-branched polymer may demonstrate flame retardant characteristics as indicated by a passing rating on UL 94 test parameters. Alternatively, a flame retardant, such as a phosphorus based compound, may be added to enhance flame retardant characteristics. Such compositions possess desired mechanical properties and the polymer is self-extinguishing.
For purposes of the present invention, the following terms used in this application are defined as follows:
“Biodegradable Polymer” means a polymeric material or resin that is capable of chemically degrading into lower molecular weight materials.
“Composite” means a mixture of a polymeric material and an additive or filler.
“Hyper-branched” means a melt processable polymer with three or more chain ends.
“Melt Processable Composition” means a formulation that is melt processed, typically at elevated temperatures, by means of a conventional polymer processing technique such as extrusion or injection molding.
“Melt Processing Techniques” means extrusion, injection molding, blow molding, rotomolding, or batch mixing.
The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the preset invention. The detailed description that follows more particularly exemplifies illustrative embodiments.
Polymers of this invention are produced by melt processing biodegradable polymers with a branching agent. The biodegradable polymers may include those polymers generally recognized by those of ordinary skill in the art to decompose into compounds having lower molecular weights. Non-limiting examples of biodegradable polymers suitable for practicing the present invention include polysaccharides, peptides, aliphatic polyesters, polyamino acids, polyvinyl alcohol, polyamides, polyalkylene glycols, and copolymers thereof.
In one aspect, the biodegradable polymer is a linear polyester. Non-limiting examples of linear polyesters include polylactic acids, poly-L-lactic acid (PLLA), and a random copolymer of L-lactic acid and D-lactic acid, and derivatives thereof. Other non-limiting examples of polyesters include polycaprolactone, polyhydroxybutyric acid, polyhydroxyvaleric acid, polyethylene succinate, polybutylene succinate, polybutylene adipate, polymalic acid, polyglycolic acid, polysuccinate, polyoxalate, polybutylene diglycolate, and polydioxanone.
In one embodiment, the branching agent(s) of this invention include multifunctional compounds that can undergo free radical homolysis reactions and react with the biodegradable polyester during melt processing to form a hyper-branched biodegradable polyester. Branching agents suitable for use in this invention include organic compounds that contain multiple ethylenically unsaturated sites capable of reacting with free radical species present during melt processing. Specific examples of useful ethylenically unsaturated branching agents may include multifunctional acrylate and methacrylate compounds. Non-limiting examples of multifunctional compounds include: 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, glycerol trimethacrylate, glycerol triacrylate, glycerol dimethacrylate, glycerol diacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate. Branching agents of this invention include multifunctional acrylates or methacrylates having at least three unsaturated acrylic or methacrylic moieties per molecule.
In one alternative embodiment, the materials utilized to derive the hyper-branched polymer may optionally include a free radical initiator along with the branching agent. A free radical initiator is a species that, when melt processed, forms reactive free radical moieties. Free radical initiators useful in this invention include organic peroxides and diazocompounds. Non-limiting examples of specific free radical initiators include: benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide and azoisobutrylnitrile. The free radical initiator may be included in the melt processable composition at amounts less than 0.25% by weight.
In another embodiment, impact modifying additives may be added or incorporated into the composition to address desired physical characteristics of the melt processable composition. Non-limiting examples of impact modifiers useful in this invention include elastomeric copolyesters, polyaklylene glycols and functionalized naturally occurring oils. Examples of elastomeric polyesters include, but are not limited to, those sold under the Neostar (Eastman Chemical Co., Kingsport, TN), Biomax (DuPont, Wilmington, DE) and Hytrel (DuPont) tradenames. Non-limiting examples of polyalkylene glycols include polyethylene glycols sold under the Carbowax tradename (Dow Chemical Co., Midland, MI). Non-limiting examples of functionalized naturally occurring oils include: malinated or epoxidized soybean, linseed or sunflower oils, which are commercially available from Cargill Inc.
The present invention results in hyper-branched polymers. Hyper-branching is distinct and different from certain forms of crosslinked polymers because it permits subsequent melt processing of the polymer. The use of conventional multifunctional monomers in conjunction with a free radical initiator species, such as those recognized by one of ordinary skill in the art, produces a highly crosslinked biodegradable polyester. However, the resulting materials would be difficult, if not impossible to form into an article using a secondary melt processing operation.
The hyper-branched polymer compositions of this invention have an excellent balance of mechanical properties and are melt processable. The combination of these attributes is a function of the molecular architecture of the compositions disclosed here. In one embodiment, the hyper-branched biodegradable polyesters of this invention are produced by melt processing a linear biodegradable polyester with a multifunctional monomer at temperatures that promote free radical reactions between the linear biodegradable polyester and the multifunctional monomer.
The amount of components in the melt processable, hyper-branched composition may vary depending upon the intended end use application. The polymer may comprise from about 20 to about 99 percent by weight of the final composition. The branching agent may be included at a level of up to 10 percent by weight.
In another aspect, flame retardant hyper-branched biodegradable polymer compositions are produced by melt processing a polymer, such as a linear biodegradable polyester, with a branching agent and one or more flame retardant additive(s). Any conventional halogenated or non-halogenated flame retardant additives can be utilized in this invention. The hyper-branched biodegradable polyester of this invention has improved flame retardancy when compared to a linear biodegradable polyester. In one embodiment, the flame retardant hyper-branched polyester, that includes a flame retardant additive demonstrates self extinguishing flame retardant properties. Although halogenated flame retardants can be utilized in this invention, the environmental hazards, biopersistance and toxicity associated with many of these additives make them less viable candidates in biodegradable polymer compositions. Non-halogenated flame retardants are more preferred as they do not suffer from these issues. Non-halogenated flame retardant additive materials useful in this invention include inorganic compounds (such as for example metal hydroxides, metal sulfates, metal nitrates, carbonate compounds, tin compounds, titanium compounds, zirconium compounds and molybdenum compounds) silica compounds, phosphorous compounds, boric acid containing compounds, organic compounds, and nitrogen compounds. The flame retardant additive may be included in the melt processable composition at levels of up to 80 percent by weight.
Non-limiting examples of desirable non-halogenated phosphorus based flame retardant additives include: ammonium phosphate, ammonium polyphosphate, melamine phosphate, red phosphorus, phosphoric esters, tris(chloroethyl)phosphate, tris(monochloropropyl)phosphate, tris(dichloropropyl) phosphate, triallyl phosphate, tris(3-hydroxypropyl) phosphate, tris(tribromophenyl)phosphate, tris-.beta.-chloropropyl phosphate, tris(dibromophenyl) phosphate, tris(tribromoneopentyl)phosphat-e,tetrakis(2-chloroethyl)ethylenediphosphate, dimethyl methylphosphate, tris(2-chloroethyl) orthophosphate, aromatic condensed phosphates, halogen-containing condensed organophosphates, ethylenebis[tris(2-cyanoet-hyl)]phosphonium bromide, ammonium polyphosphate, .beta.-chloroethyl acid phosphate, butyl pyrophosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, melamine phosphate, halogen-containing phosphates, and phenylphosphonic acid. In one aspect ammonium polyphosphate is utilized as the flame retardant additive.
In another aspect of the invention, the melt processable composition may contain other additives. Non-limiting examples of conventional additives include antioxidants, light stabilizers, fibers, blowing agents, foaming additives, antiblocking agents, heat stabilizers, impact modifiers, biocides, compatibilizers, tackifiers, colorants, coupling agents, and pigments. The additives may be incorporated into the melt processable composition in the form of powders, pellets, granules, or in any other extrudable form. The amount and type of conventional additives in the melt processable composition may vary depending upon the polymeric matrix and the desired physical properties of the finished composition. Those skilled in the art of melt processing are capable of selecting appropriate amounts and types of additives to match with a specific polymeric matrix in order to achieve desired physical properties of the finished material.
The melt processable, hyper-branched composition of the invention can be prepared by any of a variety of ways. For example, the biodegradable polymer, branching agent, optional flame retardant and optional additives can be combined together by any of the blending means usually employed in the plastics industry, such as with a compounding mill, a Banbury mixer, or a mixing extruder. The materials may be used in the form, for example, of a powder, a pellet, or a granular product. The mixing operation is most conveniently carried out at a temperature above the melting point or softening point of the polymer. The resulting melt-blended mixture can be either extruded directly into the form of the final product shape or pelletized or otherwise comminuted into a desired particulate size or size distribution and fed to an extruder, which typically will be a twin-screw extruder, that melt-processes the blended mixture to form the final product shape. Alternatively, the composition may be molded into a desired form. The resulting composite exhibits superior performance results when the hyper-branched polymer is produced using this protocol.
In another embodiment, the flame retardant additive is melt processed with the biodegradable polymer to form a masterbatch. This masterbatch may optionally contain the branching agent. The masterbatch is then let down to the desired level of flame retardant additive in a subsequent melt processing step. This two step process can have the effect of improving the dispersion of the flame retardant additive and the chemical and mechanical properties of the final compound. In an alternative embodiment, the flame retardant masterbatch is made in the presence of the branching agent and a free radical initiator is added during a subsequent processing step. This two step process produces a particularly useful, biodegradable, hyper-branched flame retardant polymer composition. Those skilled in the art of melt processing polymer compositions are capable of selecting processing steps to achieve a desired level of intermixed components.
Melt-processing typically is performed at a temperature from 80° to 300° C., although optimum operating temperatures are selected depending upon the melting point, melt viscosity, and thermal stability of the composition. Different types of melt processing equipment, such as extruders, may be used to process the melt processable compositions of this invention. Extruders suitable for use with the present invention are described, for example, by Rauwendaal, C., “Polymer Extrusion,” Hansen Publishers, p. 11-33, 2001.
The composites of this invention are suitable for manufacturing articles in the construction, electronics, consumer goods and automotive industries. For example, articles incorporating the composition of the present invention may include: molded architectural products, forms, automotive parts, building components, household articles, or electronic hard goods.
The resulting articles produced by melt processing the inventive composition exhibit superior mechanical characteristics. For example, a hyper-branched polymer has one or more of an impact strength greater than 265 joules per meter (unnotched) and flexural modulus of greater than 2300 megapascals. Additionally, the composition exhibits self extinguishing properties under UL 94 test procedures. In certain embodiments, the hyper-branched polymer has a rating of HB on the UL 94 horizontal flame retardant test. Additionally, with the inclusion of a flame retardant compound, the hyper-branched polymer has one or more of an impact strength greater than 200 joules/meter (unnotched) and flexural modulus of greater than 3000 megapascals. The hyper-branched polymer with a flame retardant composition is capable of achieving a Classl/A rating under the ASTM E84-08 test or the comparable ANSI/UL 723 test. The hyper-branched polymer with a flame retardant composition is also capable of achieving a rating of V2, V1 or V0 on the UL 94 vertical flame retardant test.
Materials used to generate the following examples include:
Biodegradable polymer compositions were prepared using the following protocol. PLA, Branching Agent and optionally FR were dry mixed in a plastic bag and gravity fed into a 26 mm co-rotating twin screw extruder (40:1, L:D) fitted with a four strand die (commercially available from Labtech Engineering, Samutprakarn, Thailand). All samples were processed at 200 rpm screw speed using the following temperature profile: Zone 1-2=130° C., Zone 3-4=150° C., Zone 5-6=170° C., Zone 7-8=170° C., Die=170° C. The resulting strands were subsequently cooled in a water bath and pelletized into 0.64 cm pellets. The resulting pellets were injection molded into test specimens following ASTM D638 (tensile) and D790 (flexural) specifications. Injection molding on biodegradable polymer formulations was performed using an 85 ton machine (commercially available from Engel Corporation, York, PA) having a barrel and nozzle temperature of 175° C. The flexural and impact properties were subsequently tested as specified in ASTM D790 and D256; respectively. The flame retardant properties were tested following either the UL-94 Horizontal or Vertical Burning Test Methods. Melt flow index was determined as specified in ASTM D1238. In all cases, the test was performed at 190° C. using a 2.1 Kg load.
Table 1 gives the formulations for biodegradable polymer compositions comparative examples CE1-CE3 and examples 1-7 that were produced. Table 2 gives the mechanical and flame retardant properties for biodegradable polymer compositions comparative examples CE1-CE3 and examples 1-7.
From the above disclosure of the general principles of the present invention and the preceding detailed description, those skilled in this art will readily comprehend the various modifications to which the present invention is susceptible. Therefore, the scope of the invention should be limited only by the following claims and equivalents thereof.
This application claims priority to U.S. Provisional Patent Application No. 61/161,546 filed Mar. 19, 2009, the disclosure of which is herein incorporated by reference in its entirety.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/US2010/027934 | 3/19/2010 | WO | 00 | 9/13/2011 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2010/108076 | 9/23/2010 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 4863538 | Deckard | Sep 1989 | A |
| 5121329 | Crump | Jun 1992 | A |
| 5132143 | Deckard | Jul 1992 | A |
| 5303141 | Batchelder et al. | Apr 1994 | A |
| 5340433 | Crump | Aug 1994 | A |
| 5474719 | Fan et al. | Dec 1995 | A |
| 5503785 | Crump et al. | Apr 1996 | A |
| 5695707 | Almquist et al. | Dec 1997 | A |
| 5773510 | Kazmaier et al. | Jun 1998 | A |
| 5939008 | Comb et al. | Aug 1999 | A |
| 5952433 | Wang et al. | Sep 1999 | A |
| 5998503 | Jacobson et al. | Dec 1999 | A |
| 6004124 | Swanson et al. | Dec 1999 | A |
| 6022207 | Dahlin et al. | Feb 2000 | A |
| 6070107 | Lombardi et al. | May 2000 | A |
| 6114489 | Vicari et al. | Sep 2000 | A |
| 6129872 | Jang | Oct 2000 | A |
| 6165406 | Jang et al. | Dec 2000 | A |
| 6175422 | Penn et al. | Jan 2001 | B1 |
| 6207782 | Czech et al. | Mar 2001 | B1 |
| 6225404 | Sorensen et al. | May 2001 | B1 |
| 6228923 | Lombardi et al. | May 2001 | B1 |
| 6645412 | Priedeman, Jr. | Nov 2003 | B2 |
| 6722872 | Swanson et al. | Apr 2004 | B1 |
| 6790403 | Priedeman, Jr. et al. | Sep 2004 | B1 |
| 6814907 | Comb | Nov 2004 | B1 |
| 7236166 | Zinniel et al. | Jun 2007 | B2 |
| 7255821 | Priedeman, Jr. et al. | Aug 2007 | B2 |
| 7265160 | Oka et al. | Sep 2007 | B2 |
| 7267170 | Mang et al. | Sep 2007 | B2 |
| 7368503 | Hale | May 2008 | B2 |
| 7449510 | Ueda et al. | Nov 2008 | B2 |
| 7589151 | Aoki et al. | Sep 2009 | B2 |
| 7632897 | Matsumoto et al. | Dec 2009 | B2 |
| 7645823 | Horie et al. | Jan 2010 | B2 |
| 7666922 | Yao | Feb 2010 | B2 |
| 7754807 | Priedeman, Jr. et al. | Jul 2010 | B2 |
| 7767732 | Ueda et al. | Aug 2010 | B2 |
| 7790069 | Kiuchi et al. | Sep 2010 | B2 |
| 8246888 | Hopkins et al. | Aug 2012 | B2 |
| 20020002242 | McNamara et al. | Jan 2002 | A1 |
| 20040222561 | Hopkins | Nov 2004 | A1 |
| 20050004282 | Priedeman, Jr. et al. | Jan 2005 | A1 |
| 20050014871 | Chin | Jan 2005 | A1 |
| 20050143502 | Yamada et al. | Jun 2005 | A1 |
| 20060142421 | Ihara et al. | Jun 2006 | A1 |
| 20060211822 | Varlet et al. | Sep 2006 | A1 |
| 20060217469 | Bauer et al. | Sep 2006 | A1 |
| 20060247387 | Mohanty et al. | Nov 2006 | A1 |
| 20070066766 | Chen et al. | Mar 2007 | A1 |
| 20070176154 | Murase et al. | Aug 2007 | A1 |
| 20070244227 | Eipper et al. | Oct 2007 | A1 |
| 20070276090 | Aoki et al. | Nov 2007 | A1 |
| 20070299170 | Ozawa et al. | Dec 2007 | A1 |
| 20080071015 | Kuichi et al. | Mar 2008 | A1 |
| 20080108729 | Ueda et al. | May 2008 | A1 |
| 20080157036 | Ogawa et al. | Jul 2008 | A1 |
| 20080194739 | Yamashita et al. | Aug 2008 | A1 |
| 20080194741 | Engelmann et al. | Aug 2008 | A1 |
| 20080213419 | Skubic et al. | Sep 2008 | A1 |
| 20080221265 | Sodergard et al. | Sep 2008 | A1 |
| 20090197999 | Shen et al. | Aug 2009 | A1 |
| 20090239433 | Kurihara et al. | Sep 2009 | A1 |
| 20090326152 | Li et al. | Dec 2009 | A1 |
| 20100041831 | Chung et al. | Feb 2010 | A1 |
| 20100096072 | Hopkins et al. | Apr 2010 | A1 |
| 20100096485 | Taatjes et al. | Apr 2010 | A1 |
| 20100140849 | Comb et al. | Jun 2010 | A1 |
| Number | Date | Country |
|---|---|---|
| 2 003 158 | Dec 2008 | EP |
| 2011103479 | Aug 2011 | WO |
| Entry |
|---|
| Carsten Gottschalk et al: “Hyperbranched Polylactide Copolymers”, Macromolecules, vol. 39, No. 5, Mar. 2006, pp. 1719-1723, XP055046902, ISSN: 0024-9297, DOI: 10.1021/ma0513259. |
| Natural Fibers, Biopolymers, and Biocomposites, Chapter 16 Polylactic Acid Technology, pp. 527, 542, 543, 544, David E. Henton et al., Publication Date Mar. 2005. |
| Number | Date | Country | |
|---|---|---|---|
| 20120101198 A1 | Apr 2012 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61161546 | Mar 2009 | US |
