In Situ Preparation of a Compatibilized Poly(cis‐1,4‐butadiene)/Poly(ε‐caprolactone) Blend

The ternary Ziegler‐Natta‐type catalyst system based on neodymium versatate (NdV), diisobutylaluminium hydride (DIBAH) and ethylaluminium sesquichloride (EASC) was used for the in situ preparation of a compatibilized blend consisting of poly(cis‐1,4‐butadiene) (BR = butadiene rubber) and poly(ε‐caprolactone) (PCL). Poly(cis‐1,4‐butadiene)‐block‐poly(ε‐caprolactone) which acts as compatibilizer for the two immiscible polymers BR and PCL was obtained by a two step sequential polymerization with the preparation of a living cis‐1,4‐BR building block in the first stage and the subsequent polymerization of CL during the second stage. This preparation method resulted in a polymer blend comprising the homopolymers BR and PCL as well as the block copolymer BR‐block‐PCL. For detailed characterization the block copolymer was separated from the respective homopolymers BR and PCL by means of fractionation with the binary solvent mixture dimethylformamide/methylcyclohexane (DMF/MCH) which mixes well at elevated temperature and exhibits phase separation at ambient temperature. ¹H NMR, IR, SEC and TEM were used for characterization of the block copolymer.

TEM of BR‐block‐PCL.     

Synthesis and characterization of poly(ϵ‐caprolactone)–poly(L‐lactide) diblock copolymers with an organic amino calcium catalyst

The quasiliving characteristics of the ring‐opening polymerization of ?‐caprolactone (CL) catalyzed by an organic amino calcium were demonstrated. Taking advantage of this feature, we synthesized a series of poly(?‐caprolactone) (PCL)–poly(L ‐lactide) (PLA) diblock copolymers with the sequential addition of the monomers CL and L ‐lactide. The block structure was confirmed by ¹H‐NMR, ¹³C‐NMR, and gel permeation chromatography analysis. The crystalline structure of the copolymers was investigated by differential scanning calorimetry and wide‐angle X‐ray diffraction analysis. When the molecular weight of the PLA block was high enough, phase separation took place in the block copolymer to form PCL and PLA domains, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2654–2660, 2006     

Synthesis and characterization of ABA triblock and novel multiblock copolymers from ethylene glycol,L‐lactide,and ϵ‐caprolactone

Three types of copolymers were synthesized and characterized. First, triblock ABA copolymers [where A is a homopolymer of ?‐caprolactone and B is poly(ethylene glycol)] were prepared by the ring‐opening polymerization of poly(ethylene glycol) with ?‐caprolactone in the presence of stannous octoate (Sn(Oct)₂). The spectral, thermal, and mechanical properties of one sample of these copolymers were studied, and it was discovered that these types of copolymers were more hydrophilic, possessed lower melting points, and had superior mechanical properties (greater toughness) than poly(?‐caprolactone). Second, triblock ABA copolymers [where A is a homopolymer of L ‐lactide and B is poly(ethylene glycol)] were prepared by the ring‐opening polymerization of poly(ethylene glycol) with L ‐lactide in the presence of Sn(Oct)₂. The mechanical properties of these copolymers were studied, and it was found that they were tougher and softer than poly(L ‐lactide). Third, novel ABA triblock copolymers [where A is a copolymer of ?‐caprolactone and L ‐lactide and B is poly(ethylene glycol)] were prepared, and ¹H‐NMR and ¹³C‐NMR spectra of these copolymers indicated a microblock structure for the two end blocks. The stress–strain behavior revealed low yields and high toughness for these copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2072–2081, 2002     

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     

Butadiene polymerization in the presence of VOCl3–dialkylmagnesium catalytic system

The butadiene polymerization in toluene at 25°C on VOCl₃? (n‐C₄H₉)Mg(iso‐C₈H₁₇) catalytic system was investigated. The kinetic parameters of polymerization and molecular characteristics of polybutadiene were determined. It was shown that substitution of traditional organoaluminum cocatalysts in trans‐regulating vanadium systems does not have an effect on its stereospecificity, but significantly influences on the active centers reaction ability. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 596–600, 2003     

Liquid Pool Copolymerization of Propylene/1‐Butene with a MgCl2‐Supported Ziegler‐Natta Catalyst

Summary: Liquid pool propylene/1‐butene copolymerizations were carried out in a batch reactor with a high activity Ziegler‐Natta catalyst system. Experimental runs were performed to evaluate the effect of the 1‐butene content on the crystallinity and melt temperature of the polymer resins. According to the results, 1‐butene can be significantly incorporated into the polymer chain at high polymerization rates over the whole range of copolymer compositions, leading to a decrease in the melting temperature (T_m) of the polymer, when compared to the poly(propylene) homopolymer, allowing for reduction of the sealing initiation temperature. It was observed by GPC and MFI measurements that the average molecular weights and the polydispersity index of the copolymer significantly decreased when compared to the ones obtained from poly(propylene). Despite high polymerization rates, polymer particles with good morphological features were produced in all cases. It was also observed that the absence of an external electron donor led to low crystallinity values for both the poly(propylene) homopolymer and for copolymers with different fractions of 1‐butene, when compared to literature values frequently reported for polymer resins based on 1‐butene and propylene. The obtained results indicate that a family of bulk propylene/1‐butene copolymer grades can be successfully developed for packaging and film applications.

Surface morphology and molecular weight distribution (deconvoluted into Schulz‐Flory distributions) of the propylene/1‐butene copolymer.     

Controlled synthesis of low‐molecular‐weight polyethylene waxes by titanium–biphenolate–ethylaluminum sesquichloride based catalyst systems

Soluble complexes of titanium(IV) bearing sterically hindered biphenols, such as biphenol, 1,1′‐methylene di‐2‐naphthol, 2,2′‐methylene bis(4‐chlorophenol), 2,2′‐methylene bis(6‐tert‐butyl‐4‐ethyl phenol), and 2,2′ ethylidene bis(4,6‐di‐tert‐butyl phenol), were prepared and characterized. These catalyst precursors, formulated as [Ti(O∧O)X₂], were active in the polymerization of ethylene at high temperatures in combination with ethylaluminum sesquichloride as a cocatalyst. The ultra‐low‐molecular‐weight polyethylenes (PEs) were linear and crystalline and displayed narrow polydispersities. The catalytic polymerization leading to PE waxes in this reaction exhibited unique properties that have potential applications in surface coatings and adhesive formulations. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1531–1539, 2007     

In Situ synthesis of multiblock copolymers of poly(ϵ‐caprolactone) with different poly(ether diols) based polyurethane by reactive extrusion

Polyurethanes with multiblock copolymers of poly(?‐caprolactone) (PCL) and poly(tetramethylene oxide) glycol (PTMG) or poly(ethylene glycol) (PEG) as a soft segment were synthesized in situ via reactive extrusion from ?‐caprolactone (CL) and 4,4′‐diphenylmethane diisocyanate (MDI). The titanium alkoxide mixture generated from an ester‐exchange reaction between titanium propoxide [Ti(OPr)₄], and excessive PTMG or PEG was used as an initiator and catalyst. Compared to the reported fabrication of polycaprolactone‐based polyurethane (PCLU), the in situ reactive extrusion preparation not only explored a new rapid route for the fabrication of PCLU but also offered a simplified, controllable approach for the production of PCLU in a successive mass scale. A series of PTMG–PCLUs and PEG–PCLUs with different PCL block‐average degrees of polymerization (DP_n's) were prepared by only an adjustment of the relative concentration of CL in the reaction system, with a certain constant molar ratio of MDI to titanium alkoxide. ¹H‐NMR, gel permeation chromatography, and differential scanning calorimetry results indicate that all of the CL monomers were converted in the polymerization, and the molecular weight of the copolymers was about 8 × 10⁴ g/mol with a polydispersity index of approximate 2.4. With an increase in the PCL block‐average DP_n in PTMG–PCLU from 25 to 40, the tensile strength increased from 16.5 to 22.7 MPa, and the melting point increased from 46.1 to 49.5°C. It was also verified by PEG–PCLU prepared with organic Ti of lowered content in the initiator mixture that the mechanical properties could be greatly affected and dropped with decreasing content of organic Ti in the initiator mixture. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

AB‐ and ABC‐type di‐ and triblock copolymers of poly[styrene‐block‐(ε‐caprolactone)] and poly[styrene‐block‐(ε‐caprolactone)‐block‐lactide]: synthesis,characterization and thermal studies

Polystyrene terminated with benzyl alcohol units was employed as a macroinitiator for ring‐opening polymerization of ε‐caprolactone and L ‐lactide to yield AB‐ and ABC‐type block copolymers. Even though there are many reports on the diblock copolymers of poly(styrene‐block‐lactide) and poly(styrene‐block‐lactone), this is the first report on the poly(styrene‐block‐lactone‐block‐lactide) triblock copolymer consisting of two semicrystalline and degradable segments. The triblock copolymers exhibited twin melting behavior in differential scanning calorimetry (DSC) analysis with thermal transitions corresponding to each of the lactone and lactide blocks. The block derived from ε‐caprolactone also showed crystallization transitions upon cooling from the melt. In the DSC analysis, one of the triblock copolymers showed an exothermic transition well above the melting temperature upon cooling. Thermogravimetric analysis of these block copolymers showed a two‐step degradation curve for the diblock copolymer and a three‐step degradation for the triblock copolymer with each of the degradation steps associated with each segment of the block copolymers. The present study shows that it is possible to make pure triblock copolymers with two semicrystalline segments which also consist of degradable blocks. Copyright © 2009 Society of Chemical Industry     

Random copolymerization of ϵ-caprolactone and trimethylene carbonate with rare earth catalysts

Random copolymerization of trimethylene carbonate (TMC) with ϵ-caprolactone (CL) catalyzed by rare earth chloride-epoxide or rare earth isopropoxide has been investigated for the first time. It was found that in the presence of epoxide, rare earth chlorides have high activities for the copolymerization, giving high-molecular-weight random copolymer P(CL-co-TMC) with a narrow molecular weight distribution. Light rare earth chloride-propylene oxide systems are more effective for the copolymerization than heavy rare earth chloride-propylene oxide systems. For the rare earth chloride-epoxide catalyst system, epoxide is the requisite component, and its amount affects the catalytic activity; while rare earth isopropoxide can catalyze the copolymerization alone. The preparative conditions of the copolymer with NdCl₃-5PO system were studied. The reactivity ratios of CL and TMC copolymerization with NdCl₃-5PO determined by Fineman-Ross method are 1.60 for r_TMC and 0.72 for r_CL, respectively. The copolymers were characterized by ¹H- and ¹³C-NMR, GPC, and DSC. The mechanism study shows that the rare earth alkoxide is the active species that initiates the ring opening copolymerization of CL and TMC with acyl-oxygen bond cleavages of the monomers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2131–2139, 1997     

A facile one‐step method for spherical support preparation of Ziegler‐Natta catalyst

This study reports a novel one‐step method to synthesize a new spherical support for Ziegler‐Natta catalyst under moderate condition. The support is obtained from a dispersion system where the particle stabilizer polyvinylpyrrolidone plays a main role to stabilize the spherical particles. The new chemical of the support is CH₃CH₂OMgOCH(CH₂Cl)₂, which is first reported here, has been approved by newly filed patents and also confirmed by solution NMR, solid state NMR, pyrolysis‐gas chromatography‐mass spectrometry (Py‐GC‐MS), and ICP‐MS. The support and catalyst particles have uniform distributions. The catalyst prepared from this support has been evaluated with high activity. The polypropylene obtained has high isotacticity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41014.     

Polymerization of 1,3‐butadiene with VO(P204)2 activated by methylaluminoxane,purified methylaluminoxane,and trimethylaluminum

The effect of different aluminum‐based cocatalysts (MAO, pMAO, and TMA) on butadiene (Bd) polymerization catalyzed by VO(P204)2 was investigated. The bimodal dependence of the polymer yield on the [MAO]/[V] molar ratio was revealed, and an highest polymer yield was achieved at a rather low [MAO]/[V] molar ratio ([MAO]/[V] = 13). The microstructures of the resulting poly(Bd)s were also significantly influenced by the ratio. In the TMA or pMAO system, the polymer yields were also very sensitive to the [Al]/[V] molar ratio. However, the microstructures of the resulting poly(Bd)s were almost independent of the ratio. In relation to the microstructures of poly(Bd)s obtained by the MAO and TMA systems at various temperatures, the 1,2‐unit contents were found to be the most abundant microstructure for both systems. In the pMAO system, the trans‐1,4‐units were the most abundant. The results of the additions of Lewis bases (THF and TPP) into Bd polyerization system comfirmed the existing of the two types of the reactions of VO(P₂₀₄)₂‐MAO catalyst and had the polymerization process controlled to some extent. The different thermal behaviors of these catalytic systems also show that multiple types of active centers were formed during the reaction between VO(P₂₀₄)₂ and MAO. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Chemical composition distribution study in ethylene/1‐hexene copolymerization to produce LLDPE material using MgCl2‐TiCl4‐based Ziegler‐Natta catalysts

The characteristic features of LLDPE polymerization with ZN catalyst are the time drift effect during polymerization and the bending effect when trying to decrease density of the copolymer by adding more comonomer to the polymerization. The time drift in LLDPE polymerization is revealed by a constant decrease of comonomer incorporation during polymerization time. The bending is revealed by difficulties in lowering the density of LLDPE material below the density of 920 kg/m³. With increasing comonomer content during polymerization, the density does not decrease, but the soluble fraction increases. To try to observe if these phenomena are connected, two types of catalysts, SiO₂ supported and precipitated MgCl₂ ZN catalysts, were studied. A short time (10 min) and an extended time (60 min) copolymerization test series where the polymerizations were performed in the presence of a gradually increasing comonomer amount. Both catalysts show a strong bending when density is presented as a function of 1‐hexene both in 10‐ and 60‐min polymerization, indicating no connection between time drift and bending. The density, melting point, and crystallinity results all indicate that both catalysts are making similar copolymer material with identical chemical composition distribution. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of unsaturated poly(ε‐caprolactone) with a new titanium alkoxide initiator

Titanium alkoxides are widely used in the ring‐opening polymerization of ε‐caprolactone. In this study, functional poly(ε‐caprolactone) was synthesized with a new titanium initiator by a two‐step procedure: First, the titanium initiator, with an unsaturated group, was prepared by a classical organic reaction between 2‐hydroxyethylmethacrylate or 2‐allyloxyethanol with titanium tetrapropoxide; then, we initiated the polymerization of the ε‐caprolactone monomer in a glass reactor or twin‐screw extruder. By means of NMR spectroscopy, the structures of the initiators and polymers were determined. When 2‐hydroxyethylmethacrylate was used, there was a side reaction (transesterification) during the preparation of the initiator, and so it was impossible to obtain the expected product. With 2‐allyloxyethanol, the designed titanium initiator was synthesized with high purity, and the allyl moiety remained intact after the polymerization of ε‐caprolactone. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ring‐opening polymerization of trimethylenecarbonate and its copolymerization with ϵ‐caprolactone by lanthanide (II) aryloxide complexes

Lanthanide metal (II) 2,6‐di‐tert‐butylphenoxide complexes (ArO)₂Ln(THF)₃ (Ln = Sm 1 , Yb 2 ) alone have been developed to catalyze the ring‐opening polymerization of trimethylenecarbonate (TMC) and random copolymerization of TMC and ε‐caprolactone (ε‐CL) for the first time. The influence of reaction conditions, such as initiator, initiator concentration, polymerization temperature, and polymerization time, on monomer conversion, molecular weight, and molecular weight distribution of the resulting PTMC was investigated. It was found that the divalent complex 1 showed higher activity for the polymerization of TMC than complex 2 . The random structure and thermal behavior of the copolymers P(TMC‐co‐CL) have been characterized by ¹H NMR, ¹³C NMR, GPC, and DSC analysis. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Polyethylene‐block‐poly(ε‐caprolactone) diblock copolymers: synthesis and compatibility

A strategy is introduced for the synthesis of polyethylene‐block‐poly(ε‐caprolactone) block copolymers by a combination of coordination polymerization and ring‐opening polymerization. First, end‐hydroxylated polyethylene (PE‐OH) was prepared with a one‐step process through ethylene/3‐buten‐1‐ol copolymerization catalyzed by a vanadium(III) complex bearing a bidentate [N,O] ligand ([PhN?C(CH₃)CHC(Ph)O]VCl₂(THF)₂). The PE‐OH was then used as macroinitiator for ring‐opening polymerization of ε‐caprolactone, leading to the desired nonpolar/polar diblock copolymers. The block structure was confirmed by spectral analysis using ¹H NMR, gel permeation chromatography and differential scanning calorimetry. The unusual topologies of the model copolymers will establish a fundamental understanding for structure–property correlations, e.g. compatibilization, of polymer blends and surface and interface modification of other polymers. © 2014 Society of Chemical Industry     

Copolymerization of ethylene and propylene catalyzed by novel magnesium chloride supported,vanadium‐based catalysts

Two novel magnesium chloride supported, vanadium‐based Ziegler–Natta catalysts with 9,9‐bis(methoxymethyl)fluorene and di‐i‐butyl phthalate as internal donors were prepared and used in the copolymerization of ethylene and propylene. The catalytic behaviors of these catalysts were investigated and compared with those of traditional magnesium chloride supported, vanadium‐based catalysts without internal donors. Differential scanning calorimetry, gel permeation chromatography, and ¹³C‐NMR spectroscopy analysis were performed to characterize the melting temperatures, molecular weights, and molecular weight distributions as well as structures and compositions of the products. The copolymerization kinetic results indicated that the novel catalyst with 9,9‐bis(methoxymethyl)fluorene as an internal donor had the highest catalytic activity and optimal kinetic behavior in ethylene–propylene copolymerization with an ethylene/propylene molar ratio of 44/56. Low‐crystallinity and high‐molecular‐weight copolymers were obtained with these novel magnesium chloride supported, vanadium‐based catalysts. The reactivity ratio data indicated that the catalytic systems had a tendency to produce random ethylene–propylene copolymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Surface chemical analysis of poly(ε‐caprolactone)–perfluoropolyether–poly(ε‐caprolactone) triblock copolymers by X‐ray photoelectron spectroscopy

The air‐side surface composition of a series of poly(ε‐caprolactone)–perfluoropolyether–poly(ε‐caprolactone) triblock copolymers with different compositions and block lengths have been studied by angle‐dependent X‐ray photoelectron spectroscopy (XPS). The weight percentage of the perfluoropolyether (PFPE) and polycaprolactone (PCL) blocks, and ethylene oxide linker (R_H) has been calculated in different ways: from C1s, O1s and F1s photoemission peaks and by line fitting of the C1s and O1s envelopes. The atomic sensitivity factors and the parameters used to fit the peak envelopes have been experimentally determined using some reference materials. A critical discussion of the different methods used in the surface characterization and the degradation of PFPE segments, induced by irradiation beam, have been also reported. A large excess of PFPE with respect to the bulk composition was observed in all samples, and the angular dependence of the XPS signal demonstrated that the content of the fluorinated block segment increased by decreasing the sampling depth. The PFPE surface concentration was also decreased by increasing the PCL/PFPE ratio, but the surfaces of the samples were still dominated by PFPE segments for copolymers with a bulk PFPE composition lower than 10%. Moreover, copolymers with similar PCL/PFPE bulk ratios but with different PFPE block lengths, showed similar PFPE surface composition when the number‐average molecular weight (M_n) was 2000 and 3200 g mol^?1, while that observed for copolymers containing PFPE block with M_n 900 g mol^?1 was lower. Copyright © 2003 Society of Chemical Industry     

Ring-opening polymerization of ϵ-caprolactone initiated by rare earth complex catalysts

The polymerization of caprolactone (ϵ-CL) was initiated by yttrium triisopropoxide {Y(OPⁱ_r)₃}, bimetallic isopropoxide of yttrium and aluminum {Y[Al(OPⁱ_s)₄]₃}, yttrium and tin(II) {Y[Sn(OPⁱ_r)₃]₃}, and tin(II) and yttrium {Sn[Y(OPⁱ_r)₄]₂}, respectively. The polymerization was carried out through coordinative insertion of a monomer into the free metal-oxygen bond. The molecular weight and yield of poly(ϵ-caprolactone) (PCL) were affected drastically by the mol % of the initiator to the monomer (C_o/M_o). The results showed that Y(OPⁱ_r)₃ and Sn[Y(OPⁱ_r)₄]₂ were more effective than were {Y[Al(OPⁱ_r)₄]₃} and {Y[Sn(OPⁱ_r)₃]₃} for the polymerization of ϵ-CL. When polymerization was conducted at 5°C using Y(OPⁱ_r)₃ as the initiator or at 10°C using Sn[Y(OPⁱ_r)₄]₄ as the initiator, polymers with a molecular weight of 45.9 × 10³ or 54.0 × 10³ and high yield resulted in 30 or 5 min, respectively. The polymer was characterized by FTIR, H-NMR, and GPC. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1295–1299, 1997     

Physical and thermal properties of l‐lactide/ϵ‐caprolactone copolymers: the role of microstructural design

Understanding the underlying role of microstructural design in polymers allows for the manipulation and control of properties for a wide range of specific applications. As such, this work focuses on the study of microstructure–property relationships in l‐ lactide/?‐caprolactone (LL/CL) copolymers. One‐step and two‐step bulk ring‐opening polymerization (ROP) procedures were employed to synthesize LL/CL copolymers of various compositions and chain microstructures. In the one‐step procedure, LL and CL were simultaneously copolymerized to yield P(LL‐stat‐CL) statistical copolymers. In the two‐step procedure, poly(l‐ lactide) (PLL) and poly(?‐caprolactone) (PCL) prepolymers were synthesized in the first step before CL and LL respectively were added in the second step to yield P[LL‐b‐(CL‐stat‐LL)‐b‐LL] and P[CL‐b‐(LL‐stat‐CL)‐b‐CL] block copolymers as the final products. The findings reveal that, in addition to the copolymerization procedure employed, the length and type of the prepolymer play important roles in determining the chain microstructure and thereby the overall properties of the final copolymer. Moreover, control over the degree of crystallinity and the type of crystalline domains, which is controlled during the polymer chemistry process, heavily influences the physical and mechanical properties of the final polymer. In summary, this work describes an interesting approach to the microstructural design of biodegradable copolymers of LL and CL for potential use in biomedical applications. © 2019 Society of Chemical Industry