Abstract
Several books offer information on various aspects of polyolefin (PO) synthesis, technology, performance, as well as on the preparation, fundamentals, and degradability and recyclates of polymer alloys and blends (PAB) [Utracki and Weiss, Multiphase Polymers: Blends and Ionomers. ACS Symposium Series, vol. 395 (Washington, DC, 1989); Utracki Polymer Alloys and Blends (Hanser, Munich, 1989); J. Rheol. 35(8), 1615–1637, 1991; Encyclopaedic Dictionary of Commercial Polymer Blends (Chem Tec Pub., Toronto, 1994); Makromol. Chem. Macromol. Symp. 118, 335–345, 1997, Commercial Polymer Blends (Chapman & Hall, London, 1998); Zweifel, Stabilization of Polymeric Materials (Springer, Berlin, 1998); Moeller, Progress in Polymer Degradation and Stability Research (Nova Sci. Publ., New York, 2008); Anand (ed.), National Seminar on Emerging Trends in Plastic Recycling Technologies and Waste Management (Goa, India, 1995); Recycling and Plastics Waste Management, Proceedings of National Seminar (CIPET, Chennai, 1997); Akovali et al., Reprocessing of Commingled Polymers and Recycling of Polymer Blends. NATO ASI, vol. 351 (Kluwer, Dordrecht, 1998)]. There are also encyclopedic editions on PAB, e.g., Utracki [Encyclopaedic Dictionary of Commercial Polymer Blends (Chem Tec Pub., Toronto, 1994, 2013); Isayev (Encyclopedia of Polymer Blends (Wiley-VCH, Weinheim, 2010–2014)].
The first patent on PAB was granted to Parkes in 1846 for two natural polymers co-vulcanized during blending in the presence of CS2, i.e., a natural rubber (NR = amorphous cis-polyisoprene, IR) with gutta-percha (GP = semicrystalline trans-polyisoprene, IR). Thus, rubber PAB predates that of synthetic polymers by ca. 80 years (PMA/PVAc 1929). Notably, while the early plastics were bio-based, their usage fell to <5 wt% nowadays slowly recovering from the absolute dominance of synthetic, petroleum-based plastics.
PO is a part of the commodity resin category, where the continuous use temperature (CUT) ≤ 75 °C. Specifically, to this category belong polyethylenes (PE), polypropylenes (PP), styrenics (PS), acrylics (PMMA), and vinyls, such as poly(vinyl chloride) (PVC). The relative importance of commodity resin is evident from the data displayed in Fig. 18.1.
In the 1900s, world plastic production was about 30 kt, increasing to 300 Mt by the year 2010. Figure 18.1 shows the growth after 1960, extrapolated to 2020. Accordingly to Pardos Marketing [Pardos Marketing] plastic consumption is dominated by the commodity resins to the extent that the total consumption of plastics on the plot is indistinguishable from that of commodity resin. Notably, within the commodity resin category, PE contribution is 45–55 wt%.
The 75th anniversary of the invention of the first commercial PE seemed to be an appropriate occasion for summarizing in a (relatively) short chapter the factors that create such a vast spectrum of materials often having unexpected properties. Considering the character of the Polymer Blends Handbook – 2 (PBH-2), the Chapter provides concise, fundamental information in a historical perspective, starting with single PE resins before addressing PE blends. It also offers extensive tabulated data, useful for readers.
The chapter is divided into 19 parts, including classification of PE resin, their discovery and historical evolution, and methods and equipment of PE characterization, and then PE blends preceded by greatly abbreviated fundamentals and followed by description of various mixtures. In view of the importance of miscibility for processability and performance of PE blends, this aspect is particularly stressed.
Leszek A. Utracki: deceased.
Leszek Utracki wrote this chapter while lying in a hospital bed before he passed away in July 2012. Rather than attempt to complete what he began, out of respect for the scientist, and especially for the person that he was, and realizing that we did not know what he intended to do to complete this chapter, we have left it as he wrote it for this book. He had intended brief sections on the future evolution of PO systems and the evolution of test methods and technology. He did develop two extensive tables on the chronology of polyolefin technology, Appendix, Table 18.10, and the evolution of polymer blends, Appendix, Table 18.11.
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1 Appendix
Nomenclature
- 13CNMR
-
Carbon-13 nuclear magnetic resonance
- 1HNMR
-
Hydrogen nuclear magnetic resonance
- ABC
-
Alloying–blending–compounding
- ABS
-
Acrylonitrile butadiene styrene
- AE
-
Aminoethyl
- AGR
-
Annual growth rate
- An
-
9-Anthryl
- APME
-
Association of Plastics Manufacturers in Europe
- AR
-
Autoclave reactor
- ATBN
-
Amine-terminated butadiene nitrile liquid rubber
- ATR
-
Attenuated total reflection (in FT-IR)
- a-TREF
-
Analytical temperature rising elution fractionation
- BAF
-
Tetrakis[3,5-bis(trifluoromethyl)phenyl]borate
- BC
-
Branch content
- BLCT
-
Basic lattice cluster theory (LCT)
- bPET
-
Branched polyethylene terephthalate
- BR
-
Polybutadiene, butadiene rubber
- Bu
-
Butyl
- Bz
-
Benzyl
- C2+i
-
Abbreviated notation for poly(ethylene-co- i-olefin); i = 3, 4, 6, 8, ….
- CA
-
Cellulose acetate
- CBR
-
Chlorinated butyl rubber
- CCD
-
Chemical composition distribution (or charge-coupled detector)
- CED
-
Cohesive energy density
- CEF
-
Crystallization elution fractionation
- CFC
-
Cross-fractionation chromatography
- CFT
-
Continuum field theory
- CGC
-
Constrained geometry catalyst
- CHX
-
Cyclohexyl
- CMC
-
Critical micelles concentration
- CO
-
Carbon monoxide
- COD
-
1,5-Cyclooctadiene
- COPO
-
Poly(carbon monoxide-co-polyolefin), a linear, alternating terpolymer
- CORI
-
Corotating, fully intermeshing TSE
- Cp
-
Cyclopentadienyl
- Cp=C5H5 −
-
Cyclopentadienyl anion−
- CPE
-
Chlorinated polyethylene
- CR
-
Chloroprene, or neoprene, rubber
- CRNI
-
Counterrotating, non-intermeshing TSE
- CSR
-
Chlorosulfonated polyethylene rubber
- CSTR
-
Continuously stirred tank reactor
- CTM
-
Cavity transfer mixer
- CUT
-
Continuous use temperature
- DAB
-
1,4-Diazabutadiene
- DIPP
-
2,6-Diisopropylphenyl
- DR
-
Drawdown ratio
- DSC
-
Differential scanning calorimetry
- D-W
-
Dee and Walsh theory
- EAA
-
Ethylene acrylic acid copolymer or “carboxylated PE”
- EBA
-
Ethylene butyl acrylate copolymer
- EEA
-
Elastomeric copolymer from ethylene and ethyl acrylate
- EFM
-
Extensional flow mixer
- EGMA
-
Ethylene-glycidyl methacrylate copolymer
- ELSD
-
Evaporative light-scattering detector
- EMA
-
Ethylene-maleic anhydride copolymer
- EMAc
-
Copolymer from ethylene and methacrylic acid
- EPDM
-
Ethylene-propylene-diene terpolymer
- EPR
-
Ethylene-propylene rubber
- EPR-MA
-
Maleated ethylene-propylene rubber (EPR)
- EPS
-
Polystyrene foam; expanded PS
- Et
-
Ethyl (C2H5 −)
- EVAc
-
Copolymer from ethylene and vinyl acetate
- EVAc-MA
-
Copolymer from ethylene, vinyl acetate, and methacrylic acid
- EVAL
-
Copolymer of ethylene and vinyl alcohol
- FBR
-
Fluidized bed reactor
- FOA
-
Fluorinated octyl acrylate
- FT-IR
-
Fourier transform infrared (spectroscopy)
- GF
-
Glass fiber or glass fiber-reinforced plastic
- Gi
-
The Ginsburg number
- GMA
-
Glycidyl methacrylate
- GPC
-
Gel [permeation chromatography (see SEC)
- HALS
-
Hindered amine light stabilizer
- HAS
-
Hindered amine stabilizer
- HBA
-
Hydroxybenzoic acid
- HDPE
-
High-density polyethylene
- HDPE-MA
-
Maleated high-density polyethylene
- HDXLPE
-
High-density cross-linked polyethylene
- hhPP
-
Head-to-head polypropylene
- HIPS
-
High impact polystyrene
- HMWPE
-
High-molecular-weight polyethylene
- HNA
-
Hydroxy naphthoic acid
- HTLC
-
High-temperature liquid chromatography
- Hx
-
Hexyl
- ICRR
-
Intermeshing, counterrotating TSE
- ID and OD
-
Inner and outer pipe diameters
- Ind
-
Indentyl
- i-PB
-
Isotactic polybutylene
- i- PP
-
Isotactic polypropylene
- LA
-
Lactic acid
- LC
-
Liquid chromatography
- LCB
-
Long-chain branching
- LCBPE
-
Long-chain branched PE
- LCP
-
Liquid crystalline polymer
- LCST
-
Lower critical solution temperature
- LCT
-
Lattice cluster theory
- LDPE
-
Low-density polyethylene
- L-J
-
Lennard–Jones (theory, potential, parameters)
- LLDPE
-
Linear low-density polyethylene
- M
-
Transition metal in a catalyst
- MA
-
Methyl acrylate
- MAH
-
Maleic anhydride
- MAO
-
Methylaluminoxane
- MBS
-
Copolymer from methyl-methacrylate-co-butadiene-co-styrene
- MC
-
Monte Carlo simulation
- MD
-
Machine direction
- MDPE
-
Medium-density polyethylene
- Me
-
Methyl (CH3-)
- Mes
-
Mesityl
- MFR
-
Melt flow rate
- m-LLDPE
-
Metallocene LLDPE
- m-LLDPO
-
Metallocene PO
- MM
-
Motionless mixer
- M n, M w
-
Number, weight average molecular weight
- MW
-
Molecular weight
- M w/M n
-
Molecular polydispersity index, MWD
- MWD
-
Molecular weight distribution usually expressed as M w/M n
- Nb
-
Norbornyl
- NDB
-
Negatively deviating blends
- NG
-
Nucleation and growth mechanism
- NIR
-
Near-infrared (spectroscopy)
- NMR
-
Nuclear magnetic resonance
- Np
-
Naphthyl
- NPDB
-
Negatively–positively deviating blends
- NR
-
Natural rubber
- ODCB
-
o-Dichlorobenzene
- OM
-
Optical microscopy
- P(HB-b-I-S)
-
Block copolymer of hydrogenated butadiene, isoprene, and styrene
- P(S-b-MMA)
-
Block copolymer of styrene and methyl methacrylate
- PA
-
Polyamide
- PA-46
-
Poly(tetramethylene adipamide)
- PA-6
-
Poly-ε-caprolactam
- PA-66
-
Poly(hexamethylene diamine-adipic acid), polyhexamethylene-adipamide
- PA-6IT6
-
Poly(caprolactam-co-hexamethylene diamine-isophthalic/terephthalic acids)
- PA-mXD6
-
Poly(m-xylylenediamine -adipic acid-co-caprolactam)
- PAr
-
Polyarylate
- PARA
-
Aromatic (mainly amorphous) polyamide
- PB1
-
Poly(butene-1)
- PB2
-
Poly(butene-2)
- PBD
-
Polybutadiene
- PBMA
-
Polybutyl methacrylate
- PBSA
-
Poly(polybutylene succinate-co-adipate)
- PBT
-
Polybutylene terephthalate
- PC
-
Polycarbonate of bisphenol-A
- PCL
-
Poly-ε-caprolactone
- PCW
-
Postconsumer waste
- PD
-
Polydispersity, M w/M n
- PDB
-
Positively deviating blends
- PE
-
Polyethylene
- PEA
-
Polyetheramide
- PEB = C2+4
-
Poly(ethylene butylene)
- PEE
-
Poly(ethylene propylene)
- PEEI
-
Polyesteretherimide
- PEEK
-
Polyetheretherketone
- PEE xx
-
Poly(ethylene-r-ethyl-ethylene); random copolymer with xx% of ethyl–ethylene (EE) units
- PEG
-
Polyethylene glycol
- PEH=C2+6
-
Polyethylene–hexene
- PEI
-
Polyetherimide
- PEi≡C2+I
-
Poly(ethylene-co-α-olefin), PEi≡C2+I; i = 3–8
- PEN
-
Poly(ethylene 2,6-naphthalene dicarboxylate), or polyethylene naphthalate
- PEP=C2+3
-
Poly(ethylene butylene)
- PEP
-
Poly(ethylene propylene)
- PEST
-
Thermoplastic polyesters such as PET, PBT, and PEN
- PET
-
Polyethylene terephthalate
- PETG
-
Polyethylene terephthalate glycol; copolymer
- PEtI
-
Polyethyleneimine
- PEX
-
Cross-linked polyethylene
- PGI
-
Polyglutarimide
- Ph
-
Phenyl
- PH1
-
Poly(hexene-1)
- PHB
-
Polyhydroxybutyrate
- PHBA
-
Poly(β-hydroxybutyric acid)
- PHBV
-
Poly(hydroxybutyrate-co-valerate)
- Phenoxy
-
Polyhydroxyether of bisphenol-A
- PHV
-
Poly(hydroxy valerate)
- p i
-
Internal pressure
- PI
-
Polyimide
- PIB
-
Polyisobutylene
- PIB
-
Polyisobutylene
- PLA
-
Polylactic acid
- PMA
-
Polymethylacrylate
- PMMA
-
Polymethylmethacrylate
- PMP
-
Poly-4-methyl-1-pentene, also TPX
- PNDB
-
Positively–negatively deviating blends
- PO
-
Polyolefin
- POM
-
Polyoxymethylene
- PP, i-PP
-
Isotactic polypropylene (a- PP – atactic; s-PP – syndiotactic)
- PPA
-
Polyphthalamide (also polypropyleneadipate)
- PPE
-
Poly(propylene ethylene)
- PPE
-
Polyphenylene ether
- PPG
-
Polypropylene glycol
- PP-MA
-
Maleated polypropylene
- PPS
-
Polyphenylene sulfide
- Pr
-
Propyl
- PRISM
-
Polymer reference interaction site model
- PS
-
Polystyrene
- PSF
-
Polysulfone
- PS-g-EPR
-
Styrene-grafted EPR
- PS-g-EVAc
-
Styrene-grafted EVAc
- PS-g-PP
-
Styrene-grafted PP
- p-TREF
-
Preparative temperature rising elution fractionation
- PVAc
-
Polyvinyl acetate
- PVAl
-
Polyvinyl alcohol
- PVC
-
Polyvinyl chloride
- PVDC
-
Polyvinylidene chloride
- PVDF
-
Polyvinylidene fluoride
- PVF
-
Polyvinyl fluoride
- PVME
-
Polyvinylmethylether
- PVP
-
Polyvinyl pyridine
- PVT
-
Pressure-volume-temperature
- py
-
Pyridyl
- QC
-
Quality control
- RI
-
Refractive index
- RPA
-
Random phase approximation
- R-TPO
-
Reactor-blended thermoplastic olefinic elastomer
- SAN
-
Styrene acrylonitrile
- SANS
-
Small-angle neutron scattering
- SAXS
-
Small-angle X-ray scattering
- SB
-
Styrene–butadiene copolymer
- SBR
-
Styrene–butadiene elastomer
- SBS
-
Styrene–butadiene–styrene three-block copolymer
- SCB
-
Short-chain branching
- SCBD
-
Distribution of SCB
- SCM
-
Super-condensed mode of m-LLDPE production
- SD
-
Spinodal decomposition mechanism
- SEBS
-
Styrene–ethylene/butene–styrene three-block copolymer
- SEBS-MA
-
Maleated SEBS
- SEC
-
Size exclusion chromatography
- SEM
-
Scanning electron microscopy
- SH
-
Strain hardening
- SIMS
-
Secondary ion mass spectrometry
- SIS
-
Styrene–isoprene–styrene three-block copolymer
- SLTC
-
Simplified lattice cluster theory (LCT)
- SMA
-
Styrene–maleic anhydride
- SMMA
-
Styrene–methyl methacrylate block copolymer
- sPS
-
Syndiotactic polystyrene
- S-S
-
Simha and Somcynsky cell-hole theory
- SSE
-
Single-screw extruder
- SSSE
-
Solid-state shear extrusion
- TD
-
Transverse direction
- TEM
-
Transmission electron microscopy
- T g
-
Glass transition temperature
- THF
-
Tetrahydrofuran
- TIBA
-
tri-Isobutyl aluminum
- T m (°C)
-
Melting temperature
- TMA
-
tri-Methyl aluminum
- TMS
-
Trimethylsilyl
- TO
-
Turnovers, number of moles of monomer polymerized per mole of metal in the catalyst
- TOF
-
Catalyst turnover frequency
- TPE
-
Thermoplastic elastomer
- TPO
-
Thermoplastic olefinic elastomer
- TPU
-
Thermoplastic urethanes
- TPV
-
Thermoplastic vulcanizate
- TR
-
Tubular reactor
- TREF
-
Temperature rising elution fractionation
- TSE
-
Twin-screw extruder
- t-TSP
-
Time–temperature superposition (also: t-T)
- UCST
-
Upper critical solution temperature
- UHMWPE
-
Ultrahigh-molecular-weight polyethylene (over 3 Mg mol−1)
- ULDPE
-
Ultralow-density polyethylene
- UV
-
Ultraviolet light spectroscopy (irradiation)
- UV-Vis
-
Ultraviolet–visible light spectroscopy
- VCH
-
Vinyl cyclohexane
- VLDPE
-
Very low density PE
- XLPE
-
Cross-linked polyethylene
- XRD
-
X-ray powder diffraction
- Z-N
-
Ziegler–Natta catalyst
- Z-N–LLDPE
-
Ziegler–Natta-catalyzed LLDPE
- ZN-LLDPO
-
Ziegler–Natta-catalyzed PO
- ΔG m
-
Gibbs free energy and heat of mixing
- δ
-
Solubility parameter
- ρ
-
Polymer density
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Utracki, L.A. (2014). Polyethylenes and Their Blends. In: Utracki, L., Wilkie, C. (eds) Polymer Blends Handbook. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-6064-6_21
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DOI: https://doi.org/10.1007/978-94-007-6064-6_21
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Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-007-6063-9
Online ISBN: 978-94-007-6064-6
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