WO2016179063A1 - Mélanges thermoplastiques renforcés - Google Patents

Mélanges thermoplastiques renforcés Download PDF

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Publication number
WO2016179063A1
WO2016179063A1 PCT/US2016/030354 US2016030354W WO2016179063A1 WO 2016179063 A1 WO2016179063 A1 WO 2016179063A1 US 2016030354 W US2016030354 W US 2016030354W WO 2016179063 A1 WO2016179063 A1 WO 2016179063A1
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WIPO (PCT)
Prior art keywords
blend
block
poly
thermoplastic polymer
polymer matrix
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PCT/US2016/030354
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English (en)
Inventor
Tuoqi LI
Liangliang GU
Lorraine FRANCIS
Frank S. Bates
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Regents Of The University Of Minnesota
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Publication of WO2016179063A1 publication Critical patent/WO2016179063A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics

Definitions

  • This invention relates to toughening thermoplastic polymers.
  • Thermoplastic polymers such as polyesters are useful in a number of applications, including packaging, textiles, and automotive parts. Although these polymers often have high strength and modulus, they are often brittle, thereby limiting their utility.
  • Various strategies have been proposed to toughen such polymers. One approach involves adding a low molecular weight plasticizer to the polymer to lower the glass transition
  • Another approach involves modifying the polymer itself by copolymerizing the monomer used to prepare the polymer with one or more toughening monomers to create a copolymer having a different molecular structure.
  • a third approach involves blending the polymer with a toughening polymer such as an elastomer. The resulting blend features a multi-phase microstructure in which the toughening polymer forms domains that are dispersed throughout a continuous polymer matrix.
  • thermoplastic blend in one aspect, includes: (a) a thermoplastic polymer matrix (“polymer C”) and (b) an amphiphilic block copolymer.
  • the block copolymer includes: (i) a first block (“polymer A”) that is miscible in the thermoplastic polymer matrix and (ii) a second block (“polymer B”) that is immiscible in the thermoplastic polymer matrix.
  • the blend A-B/C has a microstructure in the form of a continuous phase comprising the thermoplastic polymer matrix C and nanoscale-sized domains comprising the block B dispersed in the continuous phase.
  • thermoplastic polymer matrix C and block A are selected such that when the thermoplastic polymer C and a homopolymer A are combined in a melt, they exhibit a negative x ("chi") parameter, i.e., x (AC) ⁇ 0.
  • the x parameter also known as the polymer-polymer interaction parameter or Flory-Huggins (or simply Flory) parameter, reflects the exchange energy difference between molecules of different types, ⁇ is the energy needed to extract one molecule of polymer A from the undiluted melt state, one molecule of polymer C from the undiluted melt state, and exchange them, ⁇ (AA or BB or CC) equals zero, and ⁇ (BC) is a positive number.
  • a negative ⁇ parameter, ⁇ (AC) means that polymers A and C prefer to make contact with each other at the repeat unit length scale versus contact of A with A and C with C.
  • a negative ⁇ implies a negative excess Gibbs free-energy of mixing.
  • thermoplastic blend that includes: (a) a thermoplastic polyester matrix and (b) an amphiphilic block copolymer comprising (i) a first polyalkylene ether block that is miscible in the thermoplastic polymer matrix and (ii) a second polyalkylene ether block that is different from the first polyalkylene ether block and immiscible in the thermoplastic polymer matrix.
  • the blend has a microstructure in the form of a continuous phase comprising the thermoplastic polyester matrix and nanoscale-sized domains comprising the second block dispersed in the continuous phase.
  • thermoplastic polymer matrix may be a homopolymer or copolymer that includes at least two different types of monomer units.
  • the block copolymer includes at least two different blocks.
  • the thermoplastic matrix is a polyester matrix and the block copolymer includes a first polyalkylene ether block that is miscible in the polyester matrix and a second polyalkylene ether block, different from the first polyalkylene ether block, which is immiscible in the polyester matrix.
  • the polyester may include units derived from a hydroxy carboxylic acid.
  • the polyester may be selected from the group consisting of poly-L-lactic acid, poly-D-lactic acid, poly-D,L-lactic acid, and combinations thereof.
  • the first block of the block copolymer includes a polyalkylene ether selected from the group consisting of polyethylene oxide,
  • the second block of the block copolymer includes a polyalkylene ether selected from the group consisting of polybutylene oxide, polyhexylene oxide, and polydodecylene oxide.
  • the first block may include polyethylene oxide and the second block may include
  • the block copolymer may be present in an amount no greater than 20% by weight or no greater than 10% by weight based upon the weight of the blend. In some embodiments, the block copolymer is present in an amount no greater than 5% by weight based upon the weight of the blend, or no greater than 2.5% by weight based upon the weight of the blend.
  • the blend has a tensile toughness that is at least 20 MJ/m 3 .
  • the tensile toughness of the blend may be at least 10 times higher than the tensile toughness of the thermoplastic polyester matrix alone.
  • the blend has a breaking strain that is at least 2, 3, 5, or 10 times higher than the breaking strain of the thermoplastic polyester matrix alone.
  • the blend may also be transparent to visible light (i.e. the % transmission of a 1 mm thick sample of the blend is at least 84% to visible light).
  • the blends can be used to prepare blown films
  • FIG. 1 is graph of stress v. strain for blends featuring polylactic acid blended with various amounts of a poly(ethylene oxide)-b-poly(butylene oxide) block copolymer.
  • FIGS 2(a)-(d) are representative TEM images of a blend featuring polylactic acid blended with 5 wt.% of a poly(ethylene oxide)-b-poly(butylene oxide) block copolymer.
  • FIG. 3 is a graph of stress v. strain for blends featuring polylactic acid blended with 5 wt.% of a poly(ethylene oxide)-£-poly(butylene oxide) and poly(ethylene oxide)- £-poly(propylene oxide)-£-poly(ethylene oxide) block copolymers.
  • FIGS 4(a)-(d) are representative TEM images of a blend featuring polylactic acid blended with 5 wt.% of a poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) block copolymer.
  • FIG. 5 is a graph of stress v. strain for a blown film prepared from blends featuring polylactic acid blended with 2.5 wt.% of a poly(ethylene oxide)-b- poly(propylene oxide block copolymer.
  • FIGS. 6(a)-(d) are representative TEM images of a blown film prepared from blends featuring polylactic acid blended with 2.5 wt.% of a poly(ethylene oxide)-b- poly(propylene oxide block copolymer.
  • FIGS. 7(a)-(b) are representative TEM images of a blend featuring polylactic acid blended with 2.5 wt.% of a poly(ethylene oxide)-b-poly(butylene oxide) block copolymer.
  • FIGS. 7(c)-(d) are representative TEM images of a blown film along the machine direction prepared from blends featuring polylactic acid blended with 2.5 wt.% of a poly(ethylene oxide)-b-poly(propylene oxide block copolymer.
  • Like reference symbols in the various drawings indicate like elements.
  • Thermoplastic blends are prepared that feature a thermoplastic polymer (“C”) matrix and an amphiphilic block copolymer (“A-B”).
  • the block copolymer includes at least two blocks. One of the blocks (“A”) is miscible in the thermoplastic polymer matrix and one of the blocks (“B") is immiscible in the thermoplastic polymer matrix.
  • the microstructure of the blend is characterized by a continuous phase that includes the thermoplastic polymer matrix (C) and the miscible block (A), and nanoscale-sized domains dispersed in the continuous phase that include the immiscible block (B).
  • ⁇ (AC) ⁇ 0 a negative ⁇ parameter when they are combined in the melt
  • ⁇ (AC) ⁇ 0 a negative ⁇
  • the measurement of a ⁇ parameter can be conducted in several different ways. One approach is to isotopically label polymer A or C with deuterium and use Small Angle Neutron Scattering (SANS) techniques. Based on the Random Phase Approximation (RPA) theory, ⁇ (AC) can be evaluated from the intermolecular component of the scattering from binary mixtures of A and C. Russell et al.
  • suitable polyesters include polyesters prepared from hydroxy-carboxylic acid monomers, including alpha-, beta-, and gamma-hydroxy carboxylic acid monomers.
  • Specific examples include poly-L-lactic acid, poly-D-lactic acid, poly-D,L-lactic acid.
  • polyacrylates and polymethacrylates e.g., polyalkyl acrylates and
  • the matrix polymer is generally brittle or has a glass transition temperature higher than 55°C. Its number average molecular weight generally exceeds 10 5 g/mol, higher than the associated entanglement molecular weight of that polymer and much higher than the block copolymer molecular weight.
  • the matrix polymer typically is amorphous. In some embodiments, the matrix polymer has a crystallinity no greater than 10% or no greater than 5% by weight.
  • the block copolymer may be a diblock, linear triblock, linear tetrablock, or higher order multi-block structure.
  • the number average molecular weight of the block copolymer generally ranges from 1,000 to 30,000 (e.g., 3,000 to 20,000) g/mol.
  • Representative examples include block copolymers in which one of the blocks is a polyalkylene ether that is miscible in the thermoplastic polymer matrix and one of the blocks is a different polyalklene ether that is immiscible in the thermoplastic polymer matrix.
  • suitable polyalkylene ether block copolymers include block copolymers in which the miscible block is polyethylene oxide, polypropylene oxide, or poly(ethylene-co-propylene oxide), and the immiscible block is polybutylene oxide, polyhexylene oxide, and polydodecylene oxide.
  • the first block may include polyethylene oxide and the second block may include
  • suitable block copolymers include block copolymers in which the matrix-immiscible block is a rubber (i.e. a homopolymer of the block has a glass transition temperature less than the use temperature).
  • suitable block copolymers include block copolymers in which the matrix-immiscible block is a rubber (i.e. a homopolymer of the block has a glass transition temperature less than the use temperature).
  • examples that are particularly useful for blends in which the polyester matrix is derived from a hydroxyl carboxylic acid, e.g., a polylactide include poly(P-methyl-valerolactone) and other substituted poly(lactones), poly(isoprene), poly(butadiene), poly(dimethylsiloxane), poly(alkyl methacrylates) such as poly(n-butyl methacrylate), poly(alkyl acrylates) such as poly(butyl acrylate), and poly(ethylene-propylene).
  • useful matrix-immiscible blocks include poly(ethylene), poly(styrene), poly(methyl methacrylate), and poly(propylene).
  • PAA/PVP Poly(acrylic acid)/poly(vinyl pyridine)
  • PAA/PEO Poly(acrylic acid)/poly(ethylene oxide)
  • PVSA/PVP Poly(vinyl sulfonic acid)/poly(vinyl pyridine)
  • the pairs can be interchanged, i.e. the first member can serve as the A block and the second member as the C matrix, or the first member can serve as the C matrix and the second member as the A block.
  • the relative amounts of matrix polymer and block copolymer are selected to maximize the toughening effect of the block copolymer while at the same time retaining a microstructure featuring a continuous phase and dispersed nanoscale domains dispersed throughout the continuous phase.
  • the block copolymer is present in an amount no greater than 10% by weight based upon the weight of the blend.
  • the block copolymer is present in an amount no greater than 5% by weight based upon the weight of the blend, or no greater than 2.5% by weight based upon the weight of the blend.
  • the blends may be prepared by either solvent blending or melt blending.
  • solvent blending the matrix polymer and block copolymer are dissolved in a mutually compatible solvent, after which the solvent is removed, e.g., by drying in a vacuum oven.
  • useful solvents for blends of polyesters and polyalkylene oxide-based block copolymers include chloroform and acetone.
  • melt blending the matrix polymer and block copolymer are combined in a twin-screw extruder under an inert atmosphere (e.g., a nitrogen atmosphere) at a temperature sufficiently high to melt the matrix polymer and block copolymer.
  • Blends featuring polylactic acid polymer (IngeoTM 2003D from Nature Works LLC) and a poly(ethylene oxide)-£-poly(butylene oxide) diblock copolymer (FortegraTM 100 from Dow Chemical) were prepared by dissolving the polylactic acid pellets and block copolymer liquid in chloroform at room temperature with stirring for 24 hours. At the end of the 24 hour period, the chloroform was removed by heating the sample in a vacuum oven at 100°C). Samples were prepared containing 2.5 wt.%, 5 wt.%, and 10 wt.% of the copolymer based upon the total weight of the blend.
  • each sample was placed in a metal mold and annealed at 190°C for 3 minutes, followed by 2000 pounds hot press for 2 minutes. Each sample was then immediately water-cooled (approximately 60-70°C/minute) to room temperature.
  • Dogbone-shaped tensile bars were prepared from each sample and aged in a room temperature vacuum oven for 2 days prior to testing. The tensile strength of each bar as a function of strain was then measured according to ASTM D1708. The results are shown graphically in Figure 1, as well as in Table 1 set forth below.
  • each value represents an average over at least five identical specimens.
  • Elastic modulus was determined by fitting the first linear region of each curve.
  • Tensile toughness was determined from the integrated area under the engineering stress-strain curve shown in Fig. 1, from the zero strain point to the breaking strain point.
  • the results demonstrate that the inclusion of the block copolymer causes large drops in both the yield stress (> 40%) and elastic modulus (> 30%) of the matrix polymer.
  • both the ductility (as measured by breaking strain) and toughness of the matrix polymer are significantly improved. For example, with a copolymer loading as low as 2.5 wt.%, the blend exhibits an approximately twenty-fold increase in breaking strain and greater than ten-fold increase in tensile toughness relative to the matrix polymer.
  • Blends featuring polylactic acid polymer (IngeoTM 2003D from Nature Works LLC) and a poly(ethylene oxide)-£-poly(propylene oxide)-£-poly(ethylene oxide) triblock copolymer (PluronicTM L10 from BASF) were prepared in a twin-screw batch mixer. The mixing process was conducted at 180°C with 200 rpm for 5 min under inert nitrogen gas. Samples were quenched in liquid nitrogen. Samples were prepared containing 5 wt.% of the copolymer based upon the total weight of the blend.
  • Each value represents an average over at least five identical specimens.
  • Elastic modulus was determined by fitting the first linear region of each curve.
  • Tensile toughness was determined from the integrated area under the engineering stress-strain curve shown in Fig. 3, from the zero strain point to the breaking strain point.
  • This example describes the preparation of blown films.
  • Poly-D,L-lactic acid (“PDLLA) homopolymer (IngeoTM 4060D from PDLLA)
  • Blends of PDDLA and the block copolymer were prepared by melt-blending.
  • large sample batches 300 - 500 g
  • PRISM, L:D 24: 1 16 mm twin-screw extruder
  • the mass flow rate and residence time distribution were measured to be 2 - 9 g/min and 2 - 7 min for all blends, respectively.
  • Outlet pressure ranged from 50 - 160 psi and torques from 3 - 10 N m.
  • a syringe pump was used to dispense liquid block copolymer modifier (diluted in acetone to reduce viscosity, roughly 50 wt.% block polymer solution) at a controlled rate.
  • Extrudate was chilled in a water bath, dried by air blower, pelletized, and stored in a vacuum oven for at least 48 h before further processing.
  • Blown films were prepared from the pellets as follows. Pellets with different loadings of block copolymer were fed into a lab scale extruder with a blown film die and attachment.
  • the single-screw extruder had a diameter of 1 inch and a length of 25 : 1, L:D.
  • the metering zone was 10: 1, L:D and had a square pitch with a depth of 0.065 inch, a flight thickness of 0.14 inch and a helix angle of 17.7 degrees.
  • the annular die had an outer diameter of 1 inch.
  • the apparatus was operated under steady state conditions to maintain a stable bubble formation. The films produced were approximately 0.2 mm in thickness.
  • FIGS. 6(a)-(d) TEM images of blown films containing 2.5 wt.% block copolymer are shown in FIGS. 6(a)-(d).
  • FIGS. 6(a) and 6(b) depict films stretched in the machine direction (MD), i.e. the direction in which the films were stretched during the blown-film process, as denoted by the arrow in FIG. 6(a).
  • FIGS. 6(c) and (d) depict films stretched in the transverse (TD) direction, i.e. the direction perpendicular to the machine direction.
  • MD machine direction
  • TD transverse
  • FIGS. 7(a)-(b) TEM images of bulk compositions containing 2.5% block copolymer are shwon in FIGS. 7(a)-(b).
  • TEM images of blown films having the same composition stretched in the machine direction are shown in FIGS. 7(c)-(d).
  • FIGS. 7(c)-(d) show features
  • a RSA-G2 solids analyzer (TA Instruments) was used for uniaxial tensile tests.
  • a punch was used to prepare dog-bone samples with a total length of 25 mm, a gauge length of 6 mm, a width of 3.2 mm, and a thickness of approximately 0.2 mm.
  • the dog- bone specimens were aged at room temperature under vacuum to remove residual moisture for 48 h before testing. Samples were pulled at a rate of 0.1 mm/s until failure.

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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)

Abstract

La présente invention concerne un mélange thermoplastique comprenant (a) une matrice polymère thermoplastique et (b) un copolymère séquencé amphiphile qui comprend : (i) un premier bloc qui est non miscible à la matrice polymère thermoplastique et (ii) un second bloc qui est miscible à la matrice polymère thermoplastique. Le mélange présente une microstructure sous la forme d'une phase continue comprenant la matrice polymère thermoplastique et des domaines de taille nanométrique dispersés dans la phase continue. La matrice polymère thermoplastique et le second bloc sont sélectionnés de manière à ce que lorsque le polymère thermoplastique et un homopolymère du premier bloc sont combinés, ils présentent un paramètre ϰ (« chi ») négatif.
PCT/US2016/030354 2015-05-04 2016-05-02 Mélanges thermoplastiques renforcés WO2016179063A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3825115A1 (fr) 2019-11-22 2021-05-26 Henkel AG & Co. KGaA Copolymères tribloc peo-ppo-peo en tant qu'additifs pour systèmes époxy/anhydride

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4753980A (en) * 1984-02-24 1988-06-28 E. I. Du Pont De Nemours & Company Toughened thermoplastic polyester compositions
US5393837A (en) * 1993-01-21 1995-02-28 Kuraray Company Ltd. Polyester composition and process for producing the same
US20070265373A1 (en) * 2004-11-10 2007-11-15 Bates Frank S Amphiphilic Block Copolymer-Toughened Epoxy Vinyl Ester and Unsaturated Poyester Resins
US20090239433A1 (en) * 2005-11-25 2009-09-24 Kuraray Co., Ltd Polylactic acid composition
US20130210983A1 (en) * 2012-02-10 2013-08-15 Kimberly-Clark Worldwide, Inc. Rigid Renewable Polyester Compositions having a High Impact Strength and Tensile Elongation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4753980A (en) * 1984-02-24 1988-06-28 E. I. Du Pont De Nemours & Company Toughened thermoplastic polyester compositions
US5393837A (en) * 1993-01-21 1995-02-28 Kuraray Company Ltd. Polyester composition and process for producing the same
US20070265373A1 (en) * 2004-11-10 2007-11-15 Bates Frank S Amphiphilic Block Copolymer-Toughened Epoxy Vinyl Ester and Unsaturated Poyester Resins
US20090239433A1 (en) * 2005-11-25 2009-09-24 Kuraray Co., Ltd Polylactic acid composition
US20130210983A1 (en) * 2012-02-10 2013-08-15 Kimberly-Clark Worldwide, Inc. Rigid Renewable Polyester Compositions having a High Impact Strength and Tensile Elongation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SINTUREL ET AL.: "Nanostructured Polymers Obtained from Polyethylene-block-poly(ethylene oxide) Block Copolymer in Unsaturated Polyester", MACROMOLECULES, vol. 40, no. Issue 7, 15 February 2007 (2007-02-15), pages 2532 - 2538, XP055328614 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3825115A1 (fr) 2019-11-22 2021-05-26 Henkel AG & Co. KGaA Copolymères tribloc peo-ppo-peo en tant qu'additifs pour systèmes époxy/anhydride
WO2021099439A1 (fr) 2019-11-22 2021-05-27 Henkel Ag & Co. Kgaa Copolymères triséquencés péo-ppo-péo à utiliser en tant qu'additifs pour des systèmes époxyde-anhydride

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