Behavior of poly(ethylene‐co‐olefin) polymers as elastomeric materials

The properties of two new ethylene‐α‐olefin copolymers, namely, ethylene–1‐hexene copolymer (EHC) and ethylene–1‐octadecene copolymers (EOC), synthesized via metallocene catalysts were evaluated. The copolymerization was carried out in an autoclave reactor with Et(Indenyl)₂ZrCl₂/methylaluminoxane as a catalyst system. These single‐site catalysts (metallocene type) allow one to obtain very homogeneous copolymers with excellent control of the molecular weight distribution and proportion of comonomer incorporation. So, copolymers with 18 mol % comonomer in the case of EHC and 12 mol % for EOC were shaped, and activities around 100,000 kg of polymer mol^?1 of Zr bar^?1 h^?1 were reached. The properties of these copolymers were compared with other commercial elastomers, such as ethylene–propylene copolymers synthesized by Ziegler–Natta catalysts and an ethylene–octene copolymer obtained via metallocene catalysts. The results show that these new copolymers, in particular, EOC, had excellent elastomeric properties. Furthermore, they had a relatively low viscosity, which implied a good response during processing. Moreover, the effectiveness of these copolymers as impact modifiers for polyolefins was also studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3008–3015, 2004     

Model development for semicontinuous production of ethylene and norbornene copolymers having uniform composition

Terminal and penultimate models for controlling copolymer composition distribution (CCD) in ethylene and norbornene (NB) copolymerization were developed by taking into account the variation of active site concentration with the initial comonomer ratio. The models were validated by batch polymerization experimental data. The terminal model gave better correlation with the composition data whereas the penultimate model had a better fit to the rate data. The terminal model was then used to design NB feeding policies in semicontinuous processes for targeted CCD profiles. Based on the model results, a series of ethylene‐NB copolymers with various NB contents were prepared. With the same NB content, the semicontinuous process produced a uniform composition, whereas the batch process yielded broad CCD. The batch samples had lower T_g values and broader transition ranges, even yielded crystalline materials. In contrast, the semicontinuous samples overcame the disadvantages. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Emulsion copolymerization of N-phenylmaleimide with styrene

Emulsion copolymerization of N-phenylmaleimide (PMI) with styrene (St) was conducted via semibatch and batch methods. The effect of monomer mixture composition and method of copolymerization on copolymer structure-property relationships was investigated. The semibatch copolymers have a homogeneous molecular structure, exhibiting a single T_g which increases linearly with increasing PMI content. The batch copolymers have a heterogeneous molecular structure, exhibiting two T_g's, assigned to the polystyrene (PSt) and poly(PMI-co-St) components. The composition drift in the batch-copolymerized product, at different conversion levels, was examined by DSC and FTIR techniques. In general, the inherent viscosity of the semibatch copolymers is lower than that of the corresponding batch ones. The Young's modulus increases for the semibatch copolymers, with increasing PMI content, while a clear trend for the batch copolymers is not found. The tensile strength tends to decrease for both types of copolymers when PMI content increases. The thermal stability increases with increasing PMI content in the copolymers. © 1996 John Wiley & Sons, Inc.     

Semibatch RAFT polymerization for branched polyacrylamide production: Effect of divinyl monomer feeding policies

Star and hyperbranched polyacrylamides (s‐PAMs and b‐PAMs) were synthesized via semibatch RAFT copolymerization of acrylamide (AM) and N,N′‐methylenebisacrylamide (BisAM) using four monomer feeding policies. The BisAM to chain transfer agent (CTA) ratios from 1 to 40 at a constant [AM]₀/[CTA]₀ of 600 were investigated at 60°C. The s‐PAMs with the number of arms of 1.4–12.8 and 1.8–8.4 were, respectively, produced by arm‐first (AF) and core‐first (CF) approaches, whereas the b‐PAMs having the branching density of 1.34–13.1C/1000Cs were synthesized by constant BisAM feeding (semibatch polymerization, SB) and batch (batch polymerization, BA). Soluble b‐PAMs were produced with the four feeding policies at [BisAM]₀/[CTA]₀ of 5. However, when the [BisAM]₀/[CTA]₀ was increased to 30, the gelation occurred with the CF and BA approaches while the AF and SB synthesized soluble branched PAMs. The AF and SB approaches appeared to be practical in producing the respective s‐PAM and b‐PAM at high [BisAM]₀/[CTA]₀ ratios or low CTA usages. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1322–1333, 2013     

Ethylene/α‐olefin copolymerization by nonbridged (cyclopentadienyl)(aryloxy)titanium(IV) dichloride/AliBu3/Ph3CB(C6F5)4 catalyst systems

A series of nonbridged (cyclopentadienyl) (aryloxy)titanium(IV) complexes of the type, (η⁵‐Cp′)(OAr)TiCl₂ [OAr = O‐2,4,6‐^tBu₃C₆H₂ and Cp′ = Me₅C₅ ( 1 ), Me₄PhC₅ ( 2 ), and 1,2‐Ph₂‐4‐MeC₅H₂ ( 3 )], were prepared and used for the copolymerization of ethylene with α‐olefins (e.g., 1‐hexene, 1‐octene, and 1‐octadecene) in presence of AlⁱBu₃ and Ph₃CB(C₆F₅)₄ (TIBA/B). The effect of the catalyst structure, comonomer, and reaction conditions on the catalytic activity, comonomer incorporation, and molecular weight of the produced copolymers was examined. The substituents on the cyclopentadienyl group of the ligand in 1 – 3 play an important role in the catalytic activity and comonomer incorporation. The 1 /TIBA/B catalyst system exhibits the highest catalytic activity, while the 3 /TIBA/B catalyst system yields copolymers with the highest comonomer incorporation under the same conditions. The reactivity ratio product values are smaller than those by ordinary metallocene type, which indicates that the copolymerization of ethylene with 1‐hexene, 1‐octene, and 1‐octadecene by the 1–3/ TIBA/B catalyst systems does not proceed in a random manner. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study of the influence of the reaction parameters on the composition of the metallocene‐catalyzed ethylene copolymers using temperature rising elution fractionation and 13C nuclear magnetic resonance

Polyethylene copolymers prepared using the metallocene catalyst rac‐Et[Ind]₂ZrCl₂ were fractionated by preparative Temperature Rising Elution Fractionation (p‐TREF) and characterized by ¹³C nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), and gel permeation chromatography (GPC) to study the heterogeneity caused by experimental conditions. Two ethylene–1‐hexene copolymers with different 1‐hexene content and an ethylene–1‐octene copolymer all obtained using low (1.6 bar) ethylene pressure were compared with two ethylene–1‐hexene copolymers with different 1‐hexene content obtained at high ethylene pressure (7.0 bar). Samples obtained at low ethylene pressure and with low 1‐hexene concentration in the reactor presented narrow distributions in composition. Samples prepared with high comonomer concentration in the reactor or with high ethylene pressure showed an heterogeneous composition. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 155–163, 2002; DOI 10.1002/app.10284     

Ethylene/α‐olefin copolymerization using diphenylcyclopentadienyl‐phenoxytitanium dichloride/Al(iBu)3/[Ph3C][B(C6F5)4] catalyst systems

Copolymerization of ethylene with 1‐octene and 1‐octadecene using constrained geometry catalysts 2‐(3,4‐diphenylcyclopentadienyl)‐4,6‐di‐tert‐butylphenoxytitanium dichloride (1), 2‐(3,4‐diphenylcyclopentadienyl)‐6‐tert‐butylphenoxytitanium dichloride (2), 2‐(3,4‐diphenylcyclopentadienyl)‐6‐methylphenoxytitanium dichloride (3), and 2‐(3,4‐diphenylcyclopentadienyl)‐6‐phenylphenoxytitanium dichloride (4) was studied in the presence of Al(ⁱBu)₃ and [Ph₃C][B(C₆F₅)₄](TIBA/B). The effect of the catalyst structure, comonomer, and reaction conditions on the catalytic activity, comonomer incorporation, and molecular weight of the produced copolymers was also examined. The 1 /TIBA/B catalyst system exhibits high catalytic activity and produces high molecular weight copolymers. The melting temperature and the degree of crystallinity of the copolymers show a decrease with the increase in the comonomer incorporation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of ethylene/1‐octene copolymers from ethylene stock with tandem catalytic system

Tandem catalysis offers a novel synthetic route to the production of linear low‐density polyethylene. This article reports the use of homogeneous tandem catalytic systems for the synthesis of ethylene/1‐octene copolymers from ethylene stock as the sole monomer. The reported catalytic systems involving a highly selective, bis(diphenylphosphino)cyclohexylamine/Cr(acac)₃/methylaluminoxane (MAO) catalytic systems for the synthesis of 1‐hexene and 1‐octene, and a copolymerization metallocene catalyst, rac‐Et(Ind)₂ZrCl₂/MAO for the synthesis of ethylene/1‐octene copolymer. Analysis by means of DSC, GPC, and ¹³C‐NMR suggests that copolymers of 1‐hexene and ethylene and copolymers of 1‐octene and ethylene are produced with significant selectivity towards 1‐hexene and 1‐octene as comonomers incorporated into the polymer backbone respectively. We have demonstrated that, by the simple manipulation of the catalyst molar ratio and polymerization conditions, a series of branched polyethylenes with melting temperatures of 101.1–134.1°C and density of 0.922–0.950 g cm^?3 can be efficiently produced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of molecular structure and rheology on the compression foam molding of ethylene‐α‐olefin copolymers

The morphology and mechanical properties of foams made out of a series of ethylene‐α‐olefin copolymers having well‐characterized rheological properties were investigated. A compression foaming molding technique was implemented, using azodicarbonamide as the blowing agent. The polymers differed in the amount of comonomer contained (resulting in a range of densities), type of comonomer (octene vs. butene) and molecular weight, resulting in variable thermal properties and different rheological responses under shear and extensional flow. The results showed that the majority of the octene‐based copolymers with comparable rheological properties had similar foam morphology. A distinct behaviour was observed for the butene‐based copolymer, as well as the octene‐containing one having the lowest density and lowest melting/crystallization points. The poor foamability of these grades was attributed to their differences in extensional and thermal properties, respectively. Increasing density resulted in a higher secant modulus of the foamed samples. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Copolymerization of ethylene/α‐olefins using bis(2‐phenylindenyl)zirconium dichloride metallocene catalyst: structural study of comonomer distribution

Catalysts have a major role in the polymerization of olefins and exert their influence in three ways: (1) polymerization behaviour, including polymerization activity and kinetics; (2) polymer particle morphology, including bulk density, particle size, particle size distribution and particle shape; and (3) polymer microstructure, including molecular weight regulation, chemical composition distribution and short‐ and long‐chain branching. By tailoring the catalyst structure, such as the creation of a bridge or introducing a substituent on the ligand, metallocene catalysts can play a major role in the achievement of desirable properties. Kinetic profiles of the metallocene catalyst used in this study showed decay‐type behaviour for copolymerization of ethylene/α‐olefins. It was observed that increasing the comonomer ratio in the feedstock affected physical properties such as reducing the melting temperature, crystallinity, density and molecular weight of the copolymers. It was also observed that the heterogeneity of the chemical composition distribution and the physical properties were enhanced as the comonomer molecular weight was increased. In particular, 2‐phenyl substitution on the indenyl ring reduced somewhat the melting point of the copolymers. In addition, the copolymer produced using bis(2‐phenylindenyl)zirconium dichloride (bis(2‐PhInd)ZrCl₂) catalyst exhibited a narrower distribution of lamellae (0.3–0.9 nm) than the polymer produced using bisindenylzirconium dichloride catalyst (0.5–3.6 nm). The results obtained indicate that the bis(2‐PhInd)ZrCl₂ catalyst showed a good comonomer incorporation ability. The heterogeneity of the chemical composition distribution and the physical properties were influenced by the type of comonomer and type of substituent in the catalyst. Copyright © 2010 Society of Chemical Industry     

Study of radical copolymerization of tetrafluoroethylene with ethylene in suspension

Radical copolymerization of tetrafluoroethylene (TFE) with ethylene (E) was initiated by 2,2′-azo-bis-isobutyronitrile in batch and semibatch operation. The effect of reaction conditions (temperature, pressure, stirring speed, molar ratio of monomers, etc.) on copolymerization rate and copolymer molecular weight was studied. The highest reaction rate was observed at TFE content over 70 mol % and was found to be proportional to initiator concentration and total monomer content by powers of 0.9 and 1.54, respectively. These dependencies were attributed to the heterophase character of the copolymerization. The monomer reactivity ratios and overall activation energy of the reaction were determined. The effect of the monomer composition on the distribution of monomer units in the copolymer chain was studied. Kinetic mechanism of the copolymerization was suggested. Some of the basic physical properties and chemical resistance of the alternating copolymers synthesized were also determined. © 1995 John Wiley & Sons, Inc.     

(Co)polymerization of ethylene via nonmetallocene catalysts with diphenyl phosphoroso schiff‐base ligand

A series of novel nonmetallocene catalysts [N, O, P] with diphenyl phosphoroso ligands were synthesized by the treatment of phthaldialdehyde, substituted phenols, chlorodiphenyl phosphine with metal halides of TiCl₄ and ZrCl₄. The catalyst microstructure was characterized by ¹H NMR and EA. After activated by methylaluminoxane (MAO), these [N, O, P] catalysts were utilized to catalyze the polymerization of ethylene and the copolymerization of ethylene with 1‐octene. The results indicated that the obtained catalysts were highly efficient for ethylene polymerization and ethylene/1‐octene copolymerization. Structures and properties of the obtained polymers were measured by WAXD, DSC, GPC, and ¹³C NMR. The results indicated that polyethylene catalyzed by Cat. 3 possessed the highest weight‐average molecular weight of 1.025 × 10⁶ g/mol and the highest melting point of 136.3°C. The copolymer of ethylene/1‐octene catalyzed by Cat. 1 exhibited the highest 1‐octene incorporation content of 0.63 mol %. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42225.     

Different behaviors of metallocene and Ziegler–Natta catalysts in ethylene/1,5‐hexadiene copolymerization

The behaviors of three different catalyst systems, TiCl₄/MgCl₂, Cp₂ZrCl₂ and Cp₂HfCl₂, were investigated in ethylene/1,5‐hexadiene copolymerization. In the Fourier transform infrared spectra of the copolymers, cyclization and branching were detected for 1,5‐hexadiene insertion in the metallocene and Ziegler–Natta systems, respectively. DSC and viscometry analyses results revealed that copolymers with lower T_m and crystallinity and higher molecular weight were obtained with metallocene catalysts. The sequence length distribution of the copolymers was investigated by using the successive self‐nucleation and annealing thermal fractionation technique. The continuous melting endotherms obtained from successive self‐nucleation and annealing analysis were employed to get information about short‐chain branching, the branching dispersity index, comonomer content and lamella thickness in the synthesized copolymers. The results established that metallocene catalysts were much more effective than Ziegler–Natta catalysts in the incorporation of 1,5‐hexadiene in the polyethylene structure. Metallocene‐based copolymers had higher short‐chain branching and comonomer content, narrower branching dispersity index and thinner lamellae. Finally, the tendency of the employed catalysts in the 1,5‐hexadiene incorporation and cyclization reaction was explored via molecular simulation. The energy results demonstrated that, in comparison to Ziegler–Natta, metallocene catalysts have a much higher tendency to 1,5‐hexadiene incorporation and cyclization. © 2018 Society of Chemical Industry     

无规共聚聚丙烯的结构与性能

利用博里叶变换红外光谱仪与差示扫描量热仪分析了五种无规共聚聚丙烯(PP)的组成和结构,测试了五种PP产品的力学与光学性能.五种无规共聚PP都是由乙烯与丙烯无规共聚合而成,在高分子链中没有乙烯结晶.PP树脂的拉伸屈服应力随着共聚单体乙烯含量的升高而降低,Izod缺口冲击强度、光学性能随着乙烯含量的增加而提高.加入乙烯的质量分数控制在2％～3％为宜.     

Synthesis and micellization behavior of amphiphilic graft copolymer with 1‐octene as hydrophobic moiety

Two new kinds of amphiphilic copolymers were synthesized in this work. Poly(1‐octene‐co‐acrylic acid) copolymers were prepared through the copolymerization of 1‐octene and tert‐butyl acrylate, and the hydrolysis of tert‐butyl acrylate units. Poly(1‐octene‐co‐acrylic acid)‐g‐poly (ethylene glycol) copolymers were obtained from the esterification reaction between poly(1‐octene‐co‐acrylic acid) and poly(ethylene glycol) monomethyl ether. They were characterized by means of ¹H‐NMR, ¹³C‐NMR, GPC, and FTIR. These amphiphilic copolymers can form stable micelles in aqueous solutions. The critical micelle concentration was determined by fluorescence spectroscopy. The micellar morphology and size distribution were investigated by transmission electron microscopy and dynamic light scattering. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Comonomer effects in copolymerization of ethylene and 1‐hexene with MgCl2‐supported Ziegler‐Natta catalysts: New evidences from active center concentration and molecular weight distribution

In this article, comonomer effects in copolymerization of ethylene and 1‐hexene with four MgCl₂‐supported Ziegler‐Natta catalysts using either ethylene or 1‐hexene as the main monomer were investigated. It was found that no matter which monomer was used as the main monomer, the polymerization activity was significantly enhanced by introducing small amount of comonomer. In copolymerization with ethylene as the main monomer, the strength of comonomer effects was much stronger in active centers producing low‐molecular‐weight polymer than those producing high‐molecular‐weight polymer. In copolymerization with 1‐hexene as the main monomer, the number of active centers ([C*]/[Ti]) was determined, and the propagation rate constants (k_p) were calculated. Deconvolution of the polymer molecular weight distribution into Flory components were made to study the active center distribution. Introduction of small amount of ethylene caused marked increase in the number of active centers and decrease in average chain propagation rate constant. Introducing internal electron donor in the catalyst enhanced not only the number of active centers but also the chain propagation rate constant. In copolymerization of 1‐hexene with small amount of ethylene, the internal donor weakened the comonomer effects to some extent and changed the distribution of comonomer effects among different types of active centers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41264.     

Progress in the catalyst for ethylene/α-olefin copolymerization at high temperature

Ethylene/α-olefin copolymers are one of the most widely-used polyolefin materials. With the continuous improvement of polyolefin catalysts, high-performance polyolefin materials were synthesized by adjusting the chain microstructure, changing the comonomer type and comonomer insertion amount, among which the ethylene/α-olefin random copolymer elastomer (POE) and olefin block copolymer elastomer (OBC) are the most famous and well accepted by the market. The excellent properties of POE and OBC first depend on their polymer chain microstructure. The chain microstructure of polyolefins is fundamentally determined by the catalysts, polymerization conditions, comonomer feed policies, and reaction engineering. High-performance ethylene/α-olefin copolymer elastomers are currently prepared by high-temperature solution polymerization process, which needs to be carried out at a temperature above the melting point of the polymer and is beneficial to speed up the polymerization reaction rate and control the polyolefin chain microstructure. However, the high-temperature solution polymerization process launched more stringent requirements for the olefin coordination polymerization catalyst. Systematic reports on catalysts for high-temperature solution copolymerization of ethylene and α-olefins are lacking. In this review, we screened some catalysts suitable for the controllable copolymerization and high-temperature solution copolymerization of ethylene/α-olefin based on the catalyst's heat resistance, copolymerization activity, comonomer insertion ability, molecular weight, and distribution of the copolymer, including traditional Z–N catalysts, metallocene catalysts, and post-metallocene catalysts. And the future development of catalysts for high-temperature solution copolymerization of olefins, catalysts for precise control of polyolefin chain microstructures, and catalysts for olefin copolymerization with polar monomers at high temperature are envisaged.     

Copolymerization of ethylene and 1-octadecene with the Cp2ZrCl2/MAO and Cp2HfCl2/MAO catalyst systems

Summary The comparison of the copolymers obtained with the Cp₂ZrCl₂/MAO and Cp₂HfCl₂/MAO catalyst systems showed that the catalyst having hafnocene was much more reactive towards 1-octadecene than zirconocene. The comonomer concentration had to be three times higher in the zirconocene copolymerization than in the hafnocene copolymerization when the level of 6 mol-% was reached. Although the hafnocene catalyst was more reactive towards 1-octadecene, the molecular weights were higher than in the copolymers obtained with the zirconocene catalyst.The total activity of the zirconocene was 10 times higher than with the hafnocene catalyst. With the zirconocene catalyst the activity towards ethylene was constantly increasing by increasing the comonomer concentration but stayed nearly constant with the hafnocene catalyst. It seemed that there is no rate enhancement effect upon comonomer addition with the hafnocene catalyst.     

Preparation and application of sulfonated poly(1‐octene‐co‐styrene)

In this article, 1‐octene and styrene was copolymerized by the supported catalyst (TiCl₄/ID/MgCl₂). Subsequently, by sulfonation reaction, sulfonated poly(1‐octene‐co‐styrene)s which were amphiphilic copolymers were prepared. The copolymerization behavior between 1‐octene and styrene is moderate ideal behavior. Copolymers prepared by this catalyst contain appreciable amounts of both 1‐octene and styrene. Increase in the feed ratio of styrene/1‐octene leads to increase in styrene content in copolymer and decrease in molecular weight. As the polymerization temperature increases, the styrene content in the copolymers increases, however, the molecular weight decreases. Hydrogen is an efficient regulator to lower the molecular weights of poly(1‐octene‐co‐styrene)s. The sulfonation degree of the sulfonated poly(1‐octene‐co‐styrene)s increased as the styrene content in copolymer increased or the molecular weight decreased. Thirty‐six hour is long enough for sulfonation reaction. The sulfonated poly(1‐octene‐co‐styrene)s can be used as effective and durable modifying agent to improve the wettability of polyethylene film and have potential application in emulsified fuels and for the stabilization of dispersions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Novel copolyesters containing naphthalene structure III. Copolyesters prepared from 2,6‐dimethyl naphthalate,ethylene glycol,and 2,2‐dialkyl‐1,3‐propanediols

Poly(ethylene naphthalate) (PEN) copolymers were prepared by melt polycondensation of dimethyl naphthalate and excess ethylene glycol with 5–40 mol % (in feed) of 1,3‐propanediol or 2,2‐dialkyl‐1,3‐propanediols, where the dialkyl groups are dimethyl, diethyl, and butyl‐ethyl. No significant depression of reduced specific viscosity was observed. The comonomer contents in the copolymers are considerably higher than those in the feed. The effects of the copolymer composition on the structures of the films were investigated using thermal analyses, density measurements, X‐ray diffraction methods, and other physical tests. The crystallinities and densities of heat‐treated films decreased with increasing content of comonomer and length of alkyl side chain in the comonomer. The glass transition temperature (T_g) and melting temperature (T_m) were decreased by the copolymerization, while an increase in the length of the alkyl side chain hardly affected T_ms of the heat‐treated films. Alkali resistance, moisture resistance, dye ability, and thermal shrinkage were increased by the incorporation of comonomer having an alkyl side chain. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2754–2763, 2001