Synthesis and characterization of high molecular weight branched PBA

We prepared carboxylic acid group terminated linear polybutylene adipate (PBA) by melt polycondensation of adipic acid with 1,4‐butanediol in the presence of titanium(IV) isopropoxide (TIP) as a catalyst. High molecular weight branched PBAs were synthesized through the branching reaction between the carboxylic acid group terminated PBA and branching agent such as glycerol or pentaerythritol in the presence of TIP. The weight‐average molecular weights of the branched PBAs were found to be in the range of about 100,000–240,000 by gel permeation chromatography. Mechanical properties of the linear and branched PBAs were measured on an Instron tensile tester. The moduli of the branched PBAs had lower values of 320–450 MPa than those of the linear PBAs, whereas the elongations at break of the branched PBAs were in the range of 530–590%, which are much greater than the linear PBAs. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2143–2150, 2001     

Synthesis of high molecular weight polystyrene using AGET ATRP under high pressure

High molecular weight polystyrene (PS) was synthesized by ATRP. Under atmospheric pressure (1 bar), PS with M_n up to 200,000 was prepared using either ARGET or ICAR ATRP. Under high pressure (6 kbar), higher molecular weight PS could be obtained due to accelerated radical propagation and diminished radical termination in polymerization of styrene. Therefore, it was possible to synthesize PS with M_n > 1,000,000 and M_w/M_n < 1.25 using AGET ATRP under a pressure of 6 kbar at room temperature. This is the highest molecular weight linear PS prepared by a controlled radical polymerization.     

Rapid on-line analysis of low molecular weight hydrocarbons using glass capillary gas chromatography

Rapid analysis is important for on-line chromatography. Gaseous or vaporized samples have been injected via heated gas sampling valves of less than 500 μl dead volume. The critical sampling and split problems could be solved by temperature programming. The general analysis described could be successfully used inter alia in scouting reactions.     

Flocculation by very high molecular weight polymers

Polymer-induced flocculation in which the size of polymer molecules is much greater than that of colloidal particles is investigated. A dynamic analysis is conducted which takes the transient behaviors of the adsorption of particles to a polymer molecule and the particle-particle interactions into account. We show that the number of particles adsorbed to a polymer molecule follows approximately a binomial distribution. An approximate expression for the degree of flocculation of the system under consideration is presented.     

Semi‐perfluoroalkylated perylene diimides for conjugated polymers with high molecular weight and high electron mobility

Perylene diimides (PDIs) and their derivatives are excellent semiconductors, while conjugated polymers based on PDIs have limited applications because of their low electron mobility (μ_e) derived from low molecular weight. The reported maximum number‐average molecular weight (M_n) of related polymers is only 21 kDa because PDIs have very poor solubility due to strong π–π stacking of their big planar conjugated cores. Herein, it is found that suitable semi‐perfluoroalkyl groups could enhance the solubility of PDIs significantly, and a series of semi‐perfluoroalkyl modified conjugated polymers with high molecular weight and electron mobility were synthesized. The maximum M_n reaches 94.8 kDa [P(4C_F8C_H‐PDI‐T2)_HW]. In their space‐charge‐limited current (SCLC) devices, all polymers exhibit typical characters of electron transporting semiconductors, and the highest μ_e is up to 8.40 × 10⁻³ cm² V⁻¹ s⁻¹ [P(4C_F8C_H‐PDI‐T2)_HW], which is similar as that of widely used electron transporting semiconductor PC₆₁BM (6.41 × 10⁻³ cm² V⁻¹ s⁻¹). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 116–124     

Synthesis and characterization of multiarm star-branched polyisobutylenes: Effect of arm molecular weight

A series of star-branched polyisobutylenes with varying arm molecular weights was synthesized using the 2-chloro-2,4,4-trimethylpentane/TiCl₄/pyridine initiating system and divinylbenzene (DVB) as a core-forming comonomer (linking agent). The resulting star-branched polymers were characterized with regard to the weight-average number of arms per star molecule (N̄_w) and dilute solution viscosity behavior. As the molecular weight of the arm (M̄_{w, arm}) was increased, dramatically longer star-forming reaction times were needed to produce fully developed star polymers. It was calculated that N̄_w varied from 50 to 5 as the M̄_{w, arm} was increased from 13,000 to 54,000 g/mol. The radius of gyration, R_g, of the star polymers was observed to increase as M̄_{w, arm} was increased. The solution properties of the star polymers were evaluated in heptane using dilute solution viscometry. It was determined that the stars had a much higher [η] compared to the respective linear PIB arms, but a much lower [η] compared to a hypothetical linear analog of an equivalent molecular weight. The dependence of [η] on temperature for the stars and linear arms was very small over the temperature range 25 to 75°C, with only a very slight decrease with increasing temperature. [η]_star was also determined to increase with increasing M̄_{w, arm}, but decrease with increasing M̄_{w, star}. The branching coefficient, g′, calculated for the stars at 25°C, increased as N̄_w decreased and agre ed well with literature values for other star polymer systems. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3767–3778, 1997     

On the glass transition temperature of styrene-n-butyl methacrylate copolymers in dependence on chemical composition,molecular weight,and mixtures

For statistic copolymers of styrene and n-butyl methacrylate, the relation between the glass transition temperature and the chemical composition or molecular weight of the copolymers has been determined. Further, the dependence of the glass transition temperature on the composition of binary and ternary blends from statistical poly (styrene-co-n-butyl methacrylates) of a nearly equal chemical composition but a very different molecular weight has been studied. Among several equations considered for the correlation between glass transition temperature and composition of the mentioned copolymers with relatively low molecular weights, the Gordon/Taylor and Couchman equations gave the best agreement with the experimental results. For the glass transition temperature of poly(styrene-co-n-butyl methacrylate) with an n-butyl methacrylate content of about 30 wt % in dependence on the molecular weight, the Kanig-Ueberreiter and Fox-Flory equations proved to be useful for the examined molecular weight range. The glass transition temperatures of the polymer blends have been studied for a low/high-molecular component system, a system of two low-molecular components, as well as for systems with a third component. The glass transition temperatures of the mixtures frequently exceeded those of their individual components. © 1994 John Wiley & Sons, Inc.     

Determination of low molecular weight aliphatic amines by HPLC in environmental water samples

A high resolution liquid chromatographic method is described for determination of low molecular weight (LMW) aliphatic amines in environmental waters. The analytes after isolation are derivatized by fluram and separated with isocratic elution on octyl (C₈) column, followed by fluorimetric detection in 395/495 nm. Different isolation procedures such as octadecylsilane (ODS) and strong cation exchanger (SCX) solid phase extraction (SPE) cartridges and Amberlite CG-120 resin were evaluated. The quantitative characteristics such as recovery, linear dynamic range, correlation coefficient, limit of detection (LOD), and relative standard deviation (RSD) are presented. Using this method, aliphatic amines were analyzed in rain and tap water as well as in waste water.     

High molecular weight and low dispersity polyacrylonitrile by low temperature RAFT polymerization

High molecular weight polyacrylonitrile (PAN) with low dispersity has been successfully synthesized utilizing reversible addition‐fragmentation chain transfer (RAFT) polymerization. A comprehensive study was performed to understand the influence of reaction temperature, RAFT agent structure, and [M]₀:[CTA]₀[I]₀ on the polymerization kinetics, molecular weight, and dispersity. Enhanced control is attributed to reduction of side reactions by conducting the polymerization at lower temperature, and optimizing the radical exchange between active and dormant states via appropriate selection of RAFT agent and initiator. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 553–562     

Photo-induced bending behaviour of side-on linear liquid crystal polymers with high molecular weight

ABSTRACT

Two photoresponsive side-on linear liquid crystal polymers (SLLCPs) with different spacer lengths have been synthesised through facile ring-opening metathesis polymerisation (ROMP). For the first time, high molecular weight SLLCPs with polynorbornene backbone and azobenzene side chains are obtained and processed into films by the melt shear-induced orientation method. These SLLCP films exhibit fast and large photo-induced bending behaviour, showing bend degree up to 72° in 3 s upon UV irradiation at ambient temperature. The shape of these films remains unchanged under visible light, demonstrating good shape stability against sunlight. Moreover, owing to their linear structure, the SLLCP films are recyclable through traditional melting or solution methods. Possessing these features, these SLLCP films show application prospects in the fields of light-controllable flexible actuators.     

Crystallization behavior of disproportionately high and low molecular weight PEO blends

The crystallization behavior of PEOs with molecular weight of 1 Ok and 200k as well as their blends was studied in details. The results show that the lower molecular weight PEO crystallizes with faster crystallization rate as judged from a shorter time for completing the crystallization. On the other hand, the higher molecular weight PEO crystallizes at relatively higher temperature, indicating an early start of crystallization compared with the lower molecular weight one. The blends of these two PEOs with different blend ratios always cocrystallize during the cooling processes. It is confirmed that mixing of the 10k PEO with the 200k one is in favor of the crystallization of the system. This is not only demonstrated by the early start of the crystallization at higher crystallization temperature, and also a faster crystal growth of the blend with respect to the 200k PEO. The crystallization of the blends at higher temperature is caused by an early start of nucleation and an increment of nucleus density. This may originate from the density fluctuation of the blend and a reduction in energy barrier for nucleation. Moreover, it is found that the crystallinity of the 1 Ok PEO rich blends increases with increasing concentration of the 10k PEO. This is caused by the solvent effect of the 10k PEO toward the 200k PEO. On the other hand, the crystallinity of the 30/70 （10k/200k） PEO blend is decreased a little bit. This may be a balanced result of the improved crystallization of the 200k PEO at the expense of the high crystallization ability of the 1 Ok PEO.     

超高分子量聚丙烯酰胺的表征

采用环己烷及乳化剂ＥＡ合成了分子量（■≥１２００万）的速溶型、粉状聚丙烯酰胺（ＰＡＡ），采用扫描电镜及透射电镜观察了其微细结构，对其速溶性作出了解释。给出了该产品的综合性能数据，与进口样品进行了对比。     

Synthesis and characterization of high molecular weight atactic polybutene‐1 with a monotitanocene/methylaluminoxane catalyst system

A novel catalyst precursor, the monotitanocene (η⁵‐pentamethylcyclopentadienyl) titanium tricinnamyloxide [Cp*Ti(OCH₂? CH?CHC₆H₅)₃], was synthesized and employed for butene‐1 polymerization in the presence of methylaluminoxane. The effects of the polymerization conditions on the catalytic activity, molecular weight, stereoregularity, and regioregularity of the polymer so obtained were investigated in detail. The results show that the monotitanocene is desirable for the production of atactic polybutene‐1 coupled with good yields under typical polymerization conditions, high molecular weight (weight‐average molecular weight = 5.3–9.6 × 10⁵), and stereoirregularity with the Bernoullian factor B equal to 0.95, which indicates that chain‐end control is predominant. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4068–4073, 2001     

低分子量聚丙烯酰胺研究进展

综述了低分子量聚丙烯酰胺的合成方法及应用研究进展,同时对其未来的发展方向进行了展望.     

Synthesis and properties of super high molecular weight polyhexene-1

TiCl₄–alkylaluminium systems have been fixed on graphite and other inorganic supports and used in hexene-1 polymerization. Kinetic studies show a decreasing polymerization rate from high initial values. High conversions (up to 99%) are reached, although retardation by a diffusion process is observed above 60%. The polymers have high molecular weights (up to 10⁷) and high isotacticity (up to 98.5% from ¹³C NMR analysis). The effects of the nature of the components (carrier, alkylaluminium), and their concentration on the polymerization kinetics and the molecular structure of the polymer are discussed. The linear chain has one alkyl group (the alkylaluminium) and one unsaturation as the chain ends. Despite the high tacticity, the polymers are amorphous and rubber-like.     

Anionic polymerization initiated by lithium amides for preparing high molecular weight polyacrylonitrile

Lithium amides have been proved to be effective anionic initiators for the anionic polymerization of acrylonitrile to get high molecular weight polyacrylonitrile in this study. Polyacrylonitrile with weightaverage molecular weight ranging from 1.02 × 10~6 g/mol to 1.23 ×10~6 g/mol (M_w/M_n= 1.9-2.2) could be prepared utilizing lithium amides derived from diisopropylamine, diethylamine, hexamethyldisilazane,dicyclohexylamine, and 2,2,6,6-tetramethylpiperidine as initiators. The polymerization of acrylonitrile proceeded in a homogeneous manner in N,N-di methyl for mamide and insignificant contribution of side reactions was confirmed.     

Fast separation of low molecular weight analytes on structurally optimized polymeric capillary monoliths

The optimization of recently introduced tetrakis(4-vinylbenzyl)silane (TVBS)-derived capillary monoliths to suit the fast separation of small molecules was accomplished by simultaneous changes in both the stoichiometry of the polymerization mixture and in the polymerization temperature. Four types of monoliths were prepared by varying the polymerization temperature within 60 and 65 °C as well as by changing the monomer content between 15.0 and 20.0 wt.%. Changes in the porosity and morphology of the capillary columns were studied applying inverse size exclusion chromatography (ISEC), nitrogen sorption (BET), and scanning electron microscopy (SEM). All monoliths were used for the reversed-phase separation of various sets of low molecular weight analytes such as alkyl benzenes, aryl amines, carboxylic acids, and a mixture of phenols and carbonyl compounds. Comparable efficiency and performance towards the different sets of analytes were observed. With optimized monolith structures, the fast separation of six-alkyl benzenes was accomplished within less than 2 min. This was made possible by a high linear solvent flow (10 mm/s) at low column pressure drops (<15 MPa).     

Analysis of low molecular weight acids by monolithic immobilized pH gradient-based capillary isoelectric focusing coupled with mass spectrometry

A novel method for the separation and detection of low molecular weight (LMW) acids was developed using monolithic immobilized pH gradient-based capillary isoelectric focusing coupled with mass spectrometry. Two main parameters, focusing conditions and delivery buffer conditions, which might affect separation efficiency, were optimized with the focusing time of 7 min at 350 V/cm and the delivery buffer of 50% (v/v) acetonitrile in 10 mmol/L ammonium formate (pH 3.0). Under these conditions, the linear correlation between the volume of delivery solvent and the pK(a) of the model components was observed. In addition, the separation mechanism of LMW acids was proposed as well. We suppose that this method may provide a useful tool for the characterization of LMW components (e.g. natural organic matter of different origins).