Melting temperature of trans-polyoctenamer

The effect of microstructure on crystallizability of polyoctenamers prepared by R₃Al-WCl₆ catalyst was studied. The results indicate that polyoctenamers with a broad range of trans-vinylene content do crystallize. The measured melting points are dependent on the trans-vinylene content. From the dependence of melting temperature on copolymer composition, a value of 73 ± 2°C. for the melting point and a molar heat of fusion ΔH_u of 3520 cal./mole are calculated for 100% trans-polyoctenamer. From the melting point depression in the presence of diluent, a value for ΔH_u of 4800 cal./mole is obtained.     

High-temperature aging of Halar film. II. Analysis of melting behavior

Melting behavior of an experimental Halar film, a predominantly alternating 1:1 copolymer of ethylene (E) and chlorotrifluoroethylene (CTFE), has been studied. Differential scanning calorimetry (DSC) reveals single or double melting peaks, depending upon the thermal history. The lower-temperature melting peak T_m1 is produced only by the thermal treatment and shows a strong dependence on annealing time and temperature. On the basis of the DSC and x-ray data it can be suggested that T_m1 represents the melting of relatively small crystallites formed upon annealing. The higher-temperature melting peak T_m2 is always shown at 238°C. (Note: the specification for commercial Halar product is 240°C. The slightly lower melting temperature reported in this study is probably due to the fact that we are dealing with an experimental melt-processed material.) On the basis of the heating rate study we propose that Halar crystallizes with stable crystals (T_m2 = 238°C) regardless of the crystallization conditions, i.e., quenching, slow cooling, or even annealing. Crystals of Halar have a heat of fusion of approximately 35 cal/g or 146 kJ/kg. Detailed analysis of the melting behavior of Halar is presented.     

Determination of composition of ethylene–propylene copolymers by intrinsic viscosity

Intrinsic viscosities have been measured at 25° on five ethylene–propylene copolymer samples ranging in composition from 33 to 75 mole-% ethylene. The solvents used were n-C₈ and n-C₁₆ linear alkanes and two branched alkanes, 2,2,4-trimethylpentane and 2,2,4,4,6,8,8-heptamethylnonane (br-C₁₆). This choice was based on the supposition that the branched solvent would prefer the propylene segments and the linear solvent the ethylene segments, due to similarity in shape and possibly in orientational order. It was found that [η]_n ? [η]_br ≡ Δ[η] is indeed negative for propylene-rich copolymers, zero for a 56% ethylene copolymer, and positive for ethylene-rich copolymers. The Stockmayer–Fixman relation was used to obtain from Δ[η] a molecular-weight independent function of composition. The quantities (Δ[η]/[η])(1 + aM^?1/2) and Δ[η]/M are linear with the mole percent ethylene in the range investigated with 200 ≤ a ≤ 2000. The possibility of using these results for composition determination in ethylene–propylene copolymers is discussed. Intrinsic viscosities in the same solvents are reported for two samples of a terpolymer with ethylidene norbornene.     

Stereoregular and Bernoullian copolymerization of styrene and ethylene by bridged metallocene catalysts

A stereoregular and Bernoullian copolymer of styrene and ethylene was produced by the catalyst system of rac-[isopropylidenebis(1-indenyl)]zirconium dichloride and MAO. This catalyst system yields a high molecular weight copolymer with good activity at 50°C. The copolymer consists of Et-Et, St-Et, and head to tail St-St sequences and has a highly isotactic Et-St alternating sequence. This copolymer shows a melting point (80 – 110°C), due to the isotactic alternating sequence.     

The fusion of highly crystalline poly(vinyl chloride)

Low molecular weight PVC polymers of known degree of crystallinity (44% by x-ray diffraction), prepared in the presence of the chain-transfer agents n-butyraldehyde and n-butyl mercaptan, are examined by differential scanning calorimetry in order to ascertain temperatures and heats of fusion. Initial thermal scans are accompanied by large endotherms and appreciable weight losses due to the lability of the terminal groups originating from the chain-transfer agents. However, further successive scans result in approximately invariant endotherms attributable to crystalline fusion. The maximum melting point, about 265°C, exceeds the value for commercial PVC, about 210°C, but is lower than a value deduced for a hypothetical completely syndiotactic polymer, about 400°C. The average heat of fusion ΔH_u is 1180 ± 90 cal/mole, and the resultant entropy of fusion is 1.1 cal/deg/bond. The present ΔH_u value differs significantly from previously reported values of 660–785 and 2700 cal/mole, based on melting point depression theory, but appears to be concordant with known heats for a series of vinyl polymers.     

Copolymerization of ethylene with styrene catalyzed by a linked bis(phenolato) titanium catalyst

Copolymerization of ethylene with styrene, catalyzed by 1,4‐dithiabutanediyl‐linked bis(phenolato) titanium complex and methylaluminoxane, produced exclusively ethylene–styrene copolymers with high activity. Copolymerization parameters were calculated to be r_E = 1.2 for ethylene and r_S = 0.031 for styrene, with r_E r_S = 0.037 indicating preference for alternating copolymerization. The copolymer microstructure can be varied by changing the ratio between the monomers in the copolymerization feed, affording copolymers with styrene content up to 68%. The copolymer microstructure was fully elucidated by ¹³C NMR spectroscopy revealing, in the copolymers with styrene content higher than 50%, the presence of long styrene–styrene homosequences, occasionally interrupted by isolated ethylene units. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1908–1913, 2006     

Sequence distributions versus catalyst site behavior of in situ blends of polypropylene and poly(ethylene-co-propylene)

Sequential polymerizations of first propylene and then ethylene, propylene mixtures with the same Ziegler–Natta catalyst system produce in situ blends known as high-impact polypropylenes. Over 100 high-impact polypropylenes are characterized in terms of weight fractions and sequence distributions for isotactic polypropylene, atactic polypropylene, an amorphous ethylene propylene copolymer, and a crystalline ethylene propylene copolymer. The apparent r₁r₂ behaviors of the E/P copolymers suggest that the amorphous and crystalline E/P copolymers principally arise from different types of catalyst sites as opposed to originating strictly from compositional heterogeneities. The amorphous copolymers consistently have r₁r₂ values close to unity over a broad range of compositions, while the corresponding crystalline copolymers have apparent r₁r₂ values that range from 2 to over 20. An apparent r₁r₂ close to unity not only reflects random sequencing but also indicates a narrow compositional distribution. This r₁r₂ result indicates that the amorphous E/P copolymers are produced from a singular type of catalyst site. The higher r₁r₂ values shown by the crystalline E/P copolymers indicate broad compositional distributions that are produced by a different type or types of catalyst sites. The ratio of amorphous to crystalline ethylene, propylene copolymers is nominally around 80/20 over a broad range of impact copolymer compositions. The consistency of this result suggests that the two basic types of catalyst sites producing E/P copolymers are also in an approximate 80/20 ratio. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1527–1542, 1998     

Synthesis and properties of monocleavable amphiphilic comblike copolymers with alternating PEG and PCL grafts

Symmetric reduction‐responsive amphiphilic comblike copolymers mid‐disulfide‐functionalized comblike copolymers with alternating copolymer comprised of styrenic unit and N‐(2‐hydroxyethyl) maleimide (HEMI) unit (poly(St‐alt‐HEMI)) backbones and alternating PEG and PCL side chains (S‐CP(PEG‐alt‐PCL)) with poly(St‐alt‐HEMI) backbones and alternating poly(ε‐caprolactone) (PCL) and poly(ethylene glycol) (PEG) side chains were synthesized and used as nanocarriers for in vitro release of doxorubicin. The target copolymers with predetermined molecular weight and narrow molecular weight distribution (M_w/M_n = 1.15–1.20) were synthesized by reversible addition‐fragmentation chain transfer (RAFT) copolymerization of vinylbenzyl‐terminated PEG and N‐(2‐hydroxyethyl) maleimide mediated by a disulfide‐functionalized RAFT agent S‐CPDB, and followed by ring‐opening polymerization of ε‐caprolactone. When compared with linear block copolymer comprised of poly(ethylene glycol) (PEG) and poly(?‐caprolactone) (PCL) segments (PEG‐b‐PCL) copolymers, comblike copolymers with similar PCL contents usually exhibited decreased crystallization temperature, melting temperature, and degree of crystallinity, indicating the significant influence of copolymer architecture on physicochemical properties. Dynamic light scattering measurements revealed that comblike copolymers were liable to self‐assemble into aggregates involving vesicles and micelles with average diameter in the range of 56–226 nm and particle size distribution ranging between 0.07 and 0.20. In contrast to linear copolymer aggregates, comblike copolymer aggregates with similar compositions were of improved storage stability and enhanced drug‐loading efficiency. In vitro drug release confirmed the disulfide‐linked comblike copolymer aggregates could rapidly release the encapsulated drug when triggered by 10 mM DL ‐dithiothreitol. These reduction‐sensitive, biocompatible, and biodegradable aggregates have a potential as controlled delivery vehicles. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Melting behavior of polyethylene/α‐olefin copolymers: Narrow composition distribution copolymers and fractions from Ziegler–Natta and single‐site catalyst products

The melting temperature and heat of fusion were measured for an extensive series of compositionally uniform copolymers of ethylene with butene‐1, hexene‐1, and octene‐1. Fractions and whole polymers that exhibited minimal interchain compositional heterogeneity were from commercial copolymers made with either Ziegler–Natta (ZN) or single‐site metallocene catalysts. The present results do not support recent claims that ZN and corresponding metallocene catalyst copolymers melt at significantly different temperatures, nor the implication that comonomer incorporation is “blocky” in ZN copolymers. In five of the six comonomer/catalyst systems the dependencies of the melting temperature on comonomer type and amount were scarcely distinguishable. This common behavior is the same as that for a model random copolymer, so we conclude that most ethylene/α‐olefin copolymers have random distributions of ethylene sequences. The exception in the present study is a metallocene ethylene/butene‐1 copolymer that melts at lower temperatures and apparently has perceptibly alternating sequence distributions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3416–3427, 2004     

Synthesis of four‐armed poly(ε‐caprolactone)‐block‐poly(ethylene oxide) by diethylzinc catalyst

Biodegradable, amphiphilic, four‐armed poly(?‐caprolactone)‐block‐poly(ethylene oxide) (PCL‐b‐PEO) copolymers were synthesized by ring‐opening polymerization of ethylene oxide in the presence of four‐armed poly(?‐caprolactone) (PCL) with terminal OH groups with diethylzinc (ZnEt₂) as a catalyst. The chemical structure of PCL‐b‐PEO copolymer was confirmed by ¹H NMR and ¹³C NMR. The hydroxyl end groups of the four‐armed PCL were successfully substituted by PEO blocks in the copolymer. The monomodal profile of molecular weight distribution by gel permeation chromatography provided further evidence for the four‐armed architecture of the copolymer. Physicochemical properties of the four‐armed block copolymers differed from their starting four‐armed PCL precursor. The melting points were between those of PCL precursor and linear poly(ethylene glycol). The length of the outer PEO blocks exhibited an obvious effect on the crystallizability of the block copolymer. The degree of swelling of the four‐armed block copolymer increased with PEO length and PEO content. The micelle formation of the four‐armed block copolymer was examined by a fluorescent probe technique, and the existence of the critical micelle concentration (cmc) confirmed the amphiphilic nature of the resulting copolymer. The cmc value increased with increasing PEO length. The absolute cmc values were higher than those for linear amphiphilic block copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 950–959, 2004     

Alternating copolymerization of ethylene and 1-octene with meso-[dimethylsilylbis(2-methyl-1-indenyl)]zirconium dichloride-methylaluminoxane as catalyst system

Copolymerizations of ethylene and α-olefins with homogeneous metallocene catalysts generally give the corresponding random copolymers with narrow molecular mass distributions. In this study, we have conducted the copolymerization of ethylene and 1-octene with the meso-Me₂Si(2-Me-1-Ind)₂ZrCl₂-methylaluminoxane (MAO) catalyst system, and analyzed the microstructure of the resulting copolymers in detail. The content of the alternating [EO] sequence increases markedly with an increase in the feed ratio of 1-octene to ethylene, reaching over 95% under appropriate copolymerization conditions. We have thus succeeded in preparing the first sample of alternating olefin copolymers.     

Copolymerization of ethylene or propylene with α‐olefins containing hydroxyl groups with zirconocene/methylaluminoxane catalyst

Copolymerization of olefins (ethylene and propylene) and 5‐hexen‐1‐ol pretreated with alkylaluminum was performed using [dimethysilylbis(9‐fluorenyl)]zirconium dichloride/methylaluminoxane as the catalyst. The copolymerization required extra addition of alkylaluminum to prevent deactivation of the catalyst when 5‐hexen‐1‐ol was pretreated with trimethylaluminum, whereas the triisobutylaluminum‐treated system did not require any addition of alkylaluminum. The molecular weight of the copolymer depended on the kind of alkylaluminum compound (masking reagent, additive, and cocatalyst). ¹³C NMR analysis proved that poly(ethylene‐co‐5‐hexen‐1‐ol) containing 50 mol % of 5‐hexen‐1‐ol acted as an alternating copolymer, whereas the poly(propylene‐co‐5‐hexen‐1‐ol) acted as a random copolymer. The surface property of the copolymers was simply evaluated by means of water drop contact angle measurement. It was found that the copolymers containing large amounts of 5‐hexen‐1‐ol units showed good hydrophilic properties. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 52–58, 2004     

The features of syndiotactic polypropylene

The mechanism of stereoselectivity of propylene insertion in propylene-ethylene copolymerization on a C_S symmetrical zirconium complex i-Pr(Cp) (Flu) ZrCl₂ catalyst is discussed. Calculation results indicate that not only the β-carbon in the growing chain end of the polymer but also the substituent of the β-carbon play an important role in the selectivity of the prochiral face of the next-coming propylene monomer. The stereoregularity of propylene units connected to an ethylene unit (PPE) in propylene-ethylene copolymer was observed to be lower than that in propylene sequences (PPP) in the ¹³C NMR spectrum, which supports the calculation results. Furthermore, the structure and properties of propylene-olefin (ethylene, 1-butene, 1-pentene, 1-hexene, and 4-methyl-1-pentene) copolymers prepared with the i-Pr(Cp) (Flu) ZrCl₂ catalyst system were studied. Propylene-1-butene copolymer exhibits peculiarly lower melting point depression because 1-butene units enter into the unit cell of the crystal structure of syndiotactic polypropylene.     

Copolymerization of ethylene and 1-butene using a Cr—silica catalyst in a slurry reactor

A novel slurry reactor was used to investigate the copolymerization behavior of ethylene and 1-butene in the presence of 1 wt % Cr on Davison silica (Phillips-type) catalyst over the temperature range of 0–50°C, space velocity of about 0.0051 [m³ (STP)]/(g of catalyst) h, and a fixed ethylene to 1-butene feed mole ratio of 95 : 5. The effect of varying the ethylene to 1-butene feed ratios, 100 : 0, 96.5 : 3.5, 95 : 5, 93 : 7, 90 : 10, 80 : 20, and 0 : 100 mol/mol at 50°C was also studied. The addition of 1-butene to ethylene typically increased both copolymerization rates and yields relative to ethylene homopolymerization with the same catalyst, reaching a maximum yield for an ethylene: 1-butene feed ratio of 95 : 5 at 50°C. The incorporation of 1-butene within the copolymer in all cases was less than 5 mol %. The average activation energy for the apparent reaction rate constant, k_a, based on total comonomer mole fraction in the slurry liquid for the ethylene to 1-butene feed mole ratio of 95 : 5 in the temperature range of 50–30°C measured 54.2 kJ/mol. The behavior for temperatures between 30 to 0°C differed with an activation energy of 98.2 kJ/mol; thus, some diffusion limitation likely influences the copolymerization rates at temperatures above 30°C. A kinetics analysis of the experimental data at 50°C for different ethylene to 1-butene feed ratios gave the values of the reactivity ratios, r₁ = 27.3 ± 3.6 and r₂ ≅ 0, for ethylene and 1-butene, respectively. © 1996 John Wiley & Sons, Inc.     

Equilibrium concentration of trioxane in cationic polymerization

In the cationic polymerization of trioxane and tetraoxane near room temperature, the equilibrium trioxane concentration is not negligible during polymerization. In this work, tetraoxane was polymerized with BF₃ ? O(C₂H₅)₂ in various solvents and the equilibrium concentration of trioxane produced during the polymerization of tetraoxane and equilibrated with the growing polyoxymethylene chain was determined. The equilibrium trioxane concentrations were 0.05, 0.13, and 0.19 mole/l. in benzene, ethylene dichloride, and nitrobenzene at 30°C, respectively, and 0.20 mole/l. in thhylene dichloride at 50°C. The values in ethylene dichloride showed that the approximate values of ΔH_p and ΔS were ?4.2 kcal/mole and ?9.7 cal/mole-deg., respectively.     

Catalytic systems Me2SiCp*NtBuMX2/(CPh3)(B(C6F5)4) (MTi,XCH3, MZr,XiBu) in copolymerization of ethylene with styrene

Catalytic activity of Me₂SiCp*N^tBuMX₂/(CPh₃)(B(C₆F₅)₄) [MTi, XCH₃ (1); MZr, X=ⁱBu (2)] systems in the ethylene/styrene (E/S) feed was examined. Experimental data revealed high activity for the catalytic system (1) for copolymerization ethylene with styrene, whereas the system with enhanced catalytic activity for ethylene homopolymerization (2) was temporarily blocked in the styrene presence yielding, even at high styrene content, homopolyethylene as the final product. Properties of thus obtained polymers were analyzed. Catalytic system (1) occurred very sensitive to S/E ratio in the comonomers feed. The 10‐fold acceleration for ethylene consumption was shown in two experimental sets conducted at S/E = 1.3 ratio, 1 bar, and 7.5 bar ethylene pressure, respectively. The consequent enhancement in S/E ratio resulted in slowing down both ethylene consumption and catalyst deactivation rates. Atactic polystyrene was formed at high styrene content with the catalyst (1). Catalytic system (1) allowed design of products with the highest styrene content (20 mol %) at low ethylene pressure, moderate temperature, and high S/E ratio. The apparent activation energy estimated from the initial rates of ethylene consumption was 54.6 kJ/mol. Analysis of apparent reactivity factors (r_E = 9 and r_S = 0.04; r_E × r_S = 0.4) and ¹³C‐NMR copolymer spectra revealed an alternating tendency of the comonomers for active center incorporation. DSC measurements showed considerable decrease of melting points and crystallinity even for copolymers with low styrene content. The catalyst produced relatively high–molecular weight copolymers (140–150 kg/mol) even at 80°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1083–1093, 1999     

Alternating copolymerization of ethylene and propene with the [ethylene(1-indenyl)(9-fluorenyl)]zirconium dichloridemethylaluminoxane catalyst system

The copolymerization of ethylene and propene was conducted at −40°C with the [ethylene(1-indenyl)(9-fluorenyl)]zirconium dichloride-methylaluminoxane catalyst system, and the microstructure of the resulting copolymers was analyzed in detail by ¹³C NMR. The content of alternating [EP] sequences increased markedly with an increase in the feed ratio of propene to ethylene. A poly(ethylene-co-propene) with a proportion of [EP] sequences over 95% was thus obtained under appropriate copolymerization conditions. It was also demonstrated that the alternating ethylene-propene copolymer is stereoregular and isotactic.     

Synthesis and characterization of ABA-type block copolymer of poly(trimethylene carbonate) with poly(ethylene glycol): Bioerodible copolymer

ABA-type block copolymers of poly(trimethylene carbonate) with poly(ethylene glycol) (M_n 6820), PTMC-b-PEG-b-PTMC, were synthesized by the ring-opening polymerization of 1,3-dioxan-2-one (trimethylene carbonate) in the presence of poly-(ethylene glycol) with stannous octoate catalyst, and the copolymers with various compositions were obtained. The PTMC-b-PEG-b-PTMC copolymers were characterized with Fourier transform infrared and nuclear magnetic resonance spectroscopies. The intrinsic viscosities of resulting copolymers increased with the increase of 1,3-dioxan-2-one content in feed while the molar ratio of monomer over catalyst kept constant. It has been observed that the glass transition temperature (T_g) of the PTMC segments in copolymers, recorded from differential scanning calorimetry, was dependent on the composition of copolymers. The melting temperature (T_m) of PEG blocks in copolymer was lower than that of PEG polymer, and then disappeared as the length of PTMC blocks increased. The results of dynamic contact angle measurement clearly revealed that the hydrophilicity of resulting copolymers increased greatly with the increase of PEG content in copolymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 695–702, 1998     

RING OPENING COPOLYMERIZATION OF SUCCINIC ANHYDRIDE-ETHYLENE OXIDE BY Al(Ⅲ) ORGANOMETALLIC CATALYSTS

Ring opening copolymerization of succinic anhydride (SA) with ethylene oxide (EO)was successfully carried out by using a series of aluminum-based catalyst in 1,4-dioxane at62±2℃. The results showed that in-situ AlR_3-H_2O (R=ethyl, iso-butyl) catalysts gavehigher molecular weight (M_w～10~4), while Al(OR)_3 catalysts gave the higher alternatingcopolymer structure with slightly lower molecular weight. The in-situ AlR_3-H_2O systemshave been evaluated in more detail for the reaction which showed the optimum H_2O/Almolar ratio to be 0.5. The copolymers with different composition (F_(SA)/F_(EO)= 36/64to 45/55 mol/mol) were synthesized by using different monomer feed ratio. The melt-ing point (T_m), glass transition temperature (T_g) and enthalpy of fusion (ΔH_f) of thesecopolymers are depended on the copolymer composition and in the range of 87～102℃,-12～-18℃, and 37～66J/g, respectively. The second heating scan of DSC also in-dicated that the higher alternating copolymer was more easily recrystallized. The onsetdecomposition temperature was more than 300℃ under nitrogen and influenced by thecopolymer composition.     

Cytotoxicity of nonionic amphiphilic copolymers

The purpose of this study is to ascertain the relationship between the structure of an amphiphilic nonionic polymer and its toxicity for cells (cytotoxicity) growing in a culture. To this end, 16 polymers of different architectures and chemical structures are tested, namely, linear triblock copolymers of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (Pluronics); diblock copolymers of propylene oxide, ethylene oxide, and hyperbranched polyglycerol; alternating and diblock copolymers of ethylene oxide and dimethylsiloxane; and two surfactants containing linear (Brij-35) or branched (Triton X-100) aliphatic chains. Polymer-cell interaction is assayed in a culture medium in the absence of serum. Effective concentrations of the polymers causing 50% cell death, EC₅₀, vary within three orders of magnitude. Toxic concentrations of the alternating copolymer, Triton X-100, and Brij-35 are lower than their CMC values. In contrast, all block copolymers, regardless of their chemical structures, become toxic at concentrations above the CMC; that is, they acquire cytotoxicity only in the micellar form. The EC₅₀ values of the copolymers depend on their hydrophilic-liphophilic balance (HLB) through the following empirical formula: EC₅₀ × 10⁶ = 8.71 × HLB^2.1. This relationship makes it possible to predict the cytotoxic concentration region of a block copolymer of a known structure.