scholarly journals A Novel Synthetic Strategy for Preparing Polyamide 6 (PA6)-Based Polymer with Transesterification

Polymers ◽  
2019 ◽  
Vol 11 (6) ◽  
pp. 978 ◽  
Author(s):  
Shengming Zhang ◽  
Jingchun Zhang ◽  
Lian Tang ◽  
Jiapeng Huang ◽  
Yunhua Fang ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Dibasic Acid ◽  
Polyamide 6 ◽  
Blocking Agent ◽  
Polymerization Process ◽  
Synthetic Route ◽  
Molecular Weights ◽  
Synthetic Strategy ◽  
Hygroscopic Properties ◽  
End Groups

In the polymerization of caprolactam, the stoichiometry of carboxyl groups and amine groups in the process of melt polycondensation needs to be balanced, which greatly limits the copolymerization modification of polyamide 6. In this paper, by combining the characteristics of the polyester polymerization process, a simple and flexible synthetic route is proposed. A polyamide 6-based polymer can be prepared by combining caprolactam hydrolysis polymerization with transesterification. First, a carboxyl-terminated polyamide 6-based prepolymer is obtained by a caprolactam hydrolysis polymerization process using a dibasic acid as a blocking agent. Subsequently, ethylene glycol is added for esterification to form a glycol-terminated polyamide 6-based prepolymer. Finally, a transesterification reaction is carried out to prepare a polyamide 6-based polymer. In this paper, a series of polyamide 6-based polymers with different molecular weight blocks were prepared by adjusting the amount and type of dibasic acid added, and the effects of different control methods on the structural properties of the final product are analyzed. The results showed that compared with the traditional polymerization method of polyamide 6, the novel synthetic strategy developed in this paper can flexibly design prepolymers with different molecular weights and end groups to meet different application requirements. In addition, the polyamide 6-based polymer maintains excellent mechanical and hygroscopic properties. Furthermore, the molecular weight increase in the polyamide 6 polymer is no longer dependent on the metering balance of the end groups, providing a new synthetic route for the copolymerization of polyamide 6 copolymer.

Structural studies of oligosilanes produced by catalytic dehydrogenative coupling of primary organosilanes

1987 ◽  
Vol 65 (8) ◽  
pp. 1804-1809 ◽  
Author(s):  
C. Aitken ◽  
J. F. Harrod ◽  
U. S. Gill
Keyword(s):  
Molecular Weight ◽  
Nuclear Magnetic Resonance ◽  
Gel Permeation Chromatography ◽  
Structural Studies ◽  
Molecular Weights ◽  
Molecular Weight Distributions ◽  
Dehydrogenative Coupling ◽  
Weight Distributions ◽  
Gel Permeation ◽  
End Groups

The structures of some poly(organosilylenes), [Formula: see text] (R = Ph, p-tolyl, n-hexyl, and benzyl), produced by catalytic dehydrogenative coupling of primary silanes have been studied by infrared, nuclear magnetic resonance, and mass spectroscopies. These results, combined with data on molecular weights and molecular weight distributions from vapour pressure osmometry and gel permeation chromatography, lead to the conclusion that the polymers are linear and have SiH2R end groups. The polymers all have degrees of polymerization of ca. 10 and very narrow molecular weight dipersions. Some possible features of the mechanism that gives rise to this behaviour are discussed.

The Study of Thermolplastic Elastomer Based on Polyamide 6: Preparation, Morphology and Mechanical Performance

2011 ◽  
Vol 332-334 ◽  
pp. 1490-1493
Author(s):  
Chun Wang Yi ◽  
Nan Fan Li ◽  
Chao Sheng Wang ◽  
Zhi Han Peng ◽  
Shi Yan Chen
Keyword(s):  
Adipic Acid ◽  
Acid Content ◽  
Ring Opening ◽  
Mechanical Performance ◽  
Thermoplastic Elastomer ◽  
Polyamide 6 ◽  
Ring Opening Polymerization ◽  
Polymerization Process ◽  
End Groups ◽  
Mechanical Performances

In this study,a new thermoplastic elastomer based on polyamid 6, and polytetrahydrofuran was prepared by continuous hydrolytic ring-opening polymerization process. The effective of adipic acid content on the number-average molecular and the content of amino end groups was investigated. The morphology deduce of TPMP, mechanical performances were also investigated.

High-Throughput Synthesis of Oligo(ε-caprolactone) / Oligotetrahydrofuran Based Polyurethanes

MRS Advances ◽  
2018 ◽  
Vol 3 (49) ◽  
pp. 2965-2973
Author(s):  
M. Balk ◽  
A. Lendlein ◽  
M. Behl
Keyword(s):  
Molecular Weight ◽  
Chain Length ◽  
High Throughput ◽  
Melting Transition ◽  
Multiblock Copolymers ◽  
Molecular Weights ◽  
Melting Temperatures ◽  
End Groups ◽  
Model Components ◽  
End Group

ABSTRACTRobot assisted synthesis as part of high-throughput (HT) technology can assist in the creation of polymer libraries, e.g. polymers with a variety of molecular weights, by automatizing similar reactions. Especially for multiblock copolymers like polyurethanes (PUs) synthesized from telechels via polyaddition reaction, the adjustment of equivalent molar amounts of reactants requires a comprehensive investigation of end group functionality.In this work, PUs based on oligo(ε-caprolactone) (OCL) / oligotetrahydrofuran (OTHF) as model components were designed utilizing HT synthesis enabling the quantitative determination of the optimized ratio between reactive end-groups via fully automated syntheses without major characterization effort of end group functionality. The semi-crystalline oligomeric telechelics were connected with a diisocyanate and OCL with a molecular weight of 2, 4, or 8 kg∙mol-1 was integrated. Here, optimized molecular weights between 90 ± 10 kg∙mol-1 (in case of OCL 8 kg∙mol-1) and 260 ± 30 kg∙mol-1 (in case of OCL 2 kg∙mol-1) were obtained with an isocyanate content of 120 mol%, whereby 100 mol% of isocyanate groups resulted only in molecular weights between 60 ± 6 kg∙mol-1 (OCL 8 kg∙mol-1) and 80 ± 10 kg∙mol-1 (OCL 2 kg∙mol-1). In addition to the optimized ratio between isocyanate and hydroxy end groups, quantitative influences of the OCL chain length and overall molecular weights of PUs on thermal and mechanical properties were detected. The melting temperatures (Tms) of OCL and OTHF domains were well separated for PUs of low molecular weight, the temperature interval between the Tms decreased when the molecular weight of the PUs was increased, and were even overlapping towards one broad Tm, when OCL 2 kg∙mol-1 was incorporated. The storage modulus E’ was highly dependent on OCL chain length exhibiting an increase with increasing molecular weight of OCL from 220 MPa to 440 MPa at 0 °C and decreased with increasing chain length of PUs. The elongation at break (εb) was analyzed below and above Tm of OTHF resulting in εb = 780-870% at 0 °C and εb = 510-830% at 30 °C for PUs of high molecular weight. Accordingly, stretchability of PUs was almost independent of the state of OTHF (semi crystalline or amorphous) but correlated with the OCL precursor chain length (increasing εb with increasing chain length) and overall molecular weight of PUs (PUs at higher molecular weight exhibited higher εb). Hence, the analysis of these quantitative influences between macromolecular structure of multiblock copolymers and the resulting properties (well separated Tms versus overlapping melting transition, improvement of stretchability) would enable the design of new tailored PUs.

Polyethylene glycol oligomers as siloxane modificators in consolidation of carbonate stones

2016 ◽  
Vol 88 (12) ◽  
pp. 1117-1128 ◽  
Author(s):  
Bruno Sena da Fonseca ◽  
Susana Piçarra ◽  
Ana Paula Ferreira Pinto ◽  
Maria de Fátima Montemor
Keyword(s):  
Molecular Weight ◽  
Polyethylene Glycol ◽  
Carboxylic Acid ◽  
Sol Gel ◽  
Silica Matrix ◽  
Strength Increase ◽  
Molecular Weights ◽  
Uniform Strength ◽  
End Groups ◽  
Stone Consolidants

AbstractThe overall performance of alkoxysilanes as stone consolidants is constrained by stone mineralogy (particularly in the carbonate varieties) and by their tendency to crack during drying. In an attempt to overcome these problems, polyethylene glycol “chains” with two carboxylic acid end-groups (PEG-CA) were introduced in siloxane sols obtained by sol-gel chemistry using tetraethoxysilane (TEOS) as precursor. Different pre-condensation degrees (by varying the stirring times of sol-gel reaction: 10 min, 2, and 24 h) and PEG-CA chains with different molecular weights were studied as variables affecting the initial efficacy of the consolidants when applied into a limestone. The sol containing siloxanes with the lowest pre-condensation degree (10 min stirring) was quite susceptible to the carbonate media and thus a poor consolidation was achieved. The sol with the highest pre-condensation degree (24 h stirring) together with the PEG-CA chains with intermediate molecular weight produced significant and uniform strength gains along the stone depth. The consolidation also showed to be highly dependent on the molecular weight of the PEG-CA chains, the PEG-CA with highest molecular weight produced a non-uniform strength increase with potential harmful side effects. The results confirmed the role of carboxylic acid end-groups as efficient sol-gel catalysts and their ability to be incorporated into the silica matrix in the presence of carbonate stone.

Polymerization of styrene using 1,1,2,2-tetraphenyl-1,2- ethanediol as initiator in the presence of 2,2,6,6-tetramethyl- 1-piperidinyloxy

e-Polymers ◽  
2004 ◽  
Vol 4 (1) ◽  
Author(s):  
Gang Wang ◽  
Xiulin Zhu ◽  
Dijun Hu ◽  
Zhengping Cheng ◽  
Jian Zhu
Keyword(s):  
Molecular Weight ◽  
Monomer Concentration ◽  
Bulk Polymerization ◽  
Polymerization Rate ◽  
First Order ◽  
Molecular Weights ◽  
Molecular Weight Distributions ◽  
Weight Distributions ◽  
End Groups

Abstract The bulk polymerization of styrene using 1,1,2,2-tetraphenyl-1,2-ethanediol as initiator in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) was investigated. The results show that polymerization proceeded in a controlled/ ’living’ way, i.e., polymerization rate is first order with respect to monomer concentration. Molecular weights increase linearly with conversion and molecular weight distributions are relatively low (Mw/Mn = 1.10 - 1.35). Well-defined polystyrenes with α-hydrogen and TEMPO end groups were obtained.

scholarly journals Chemically tunable mucin chimeras assembled on living cells

2015 ◽  
Vol 112 (41) ◽  
pp. 12574-12579 ◽  
Author(s):  
Jessica R. Kramer ◽  
Bibiana Onoa ◽  
Carlos Bustamante ◽  
Carolyn R. Bertozzi
Keyword(s):  
Molecular Weight ◽  
Cell Surface ◽  
Mammalian Cells ◽  
Optical Probe ◽  
Living Cells ◽  
Structure And Properties ◽  
Synthetic Route ◽  
Site Specific ◽  
Molecular Weights

Mucins are a family of secreted and transmembrane glycoproteins characterized by a massive domain of dense O-glycosylation on serine and threonine residues. Mucins are intimately involved in immunity and cancer, yet elucidation of the biological roles of their glycodomains has been complicated by their massive size, domain polymorphisms, and variable glycosylation patterns. Here we developed a synthetic route to a library of compositionally defined, high-molecular weight, dual end-functionalized mucin glycodomain constructs via N-carboxyanhydride polymerization. These glycopolypeptides are the first synthetic analogs to our knowledge to feature the native α-GalNAc linkage to serine with molecular weights similar to native mucins, solving a nearly 50-year synthetic challenge. Physical characterization of the mimics revealed insights into the structure and properties of mucins. The synthetic glycodomains were end-functionalized with an optical probe and a tetrazine moiety, which allowed site-specific bioorthogonal conjugation to an engineered membrane protein on live mammalian cells. This strategy in protein engineering will open avenues to explore the biological roles of cell surface mucins.

scholarly journals Controlled (Co)Polymerization of Methacrylates Using a Novel Symmetrical Trithiocarbonate RAFT Agent Bearing Diphenylmethyl Groups

Molecules ◽  
2021 ◽  
Vol 26 (15) ◽  
pp. 4618
Author(s):  
Alvaro Leonel Robles Grana ◽  
Hortensia Maldonado-Textle ◽  
José Román Torres-Lubián ◽  
Claude St Thomas ◽  
Ramón Díaz de León ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Chain Transfer ◽  
Polymerization Process ◽  
Polymerization Reaction ◽  
Molecular Weights ◽  
Molar Ratios ◽  
Efficient Control ◽  
Raft Agent ◽  
Methacrylic Monomers ◽  
Leaving Groups

Herein, we report a novel type of symmetrical trithiocarbonate chain transfer agent (CTA) based diphenylmethyl as R groups. The utilization of this CTA in the Reversible Addition-Fragmentation chain Transfer (RAFT) process reveals an efficient control in the polymerization of methacrylic monomers and the preparation of block copolymers. The latter are obtained by the (co)polymerization of styrene or butyl acrylate using a functionalized macro-CTA polymethyl methacrylate (PMMA) previously synthesized. Data show low molecular weight dispersity values (Đ < 1.5) particularly in the polymerization of methacrylic monomers. Considering a typical RAFT mechanism, the leaving groups (R) from the fragmentation of CTA should be able to re-initiate the polymerization (formation of growth chains) allowing an efficient control of the process. Nevertheless, in the case of the polymerization of MMA in the presence of this symmetrical CTA, the polymerization process displays an atypical behavior that requires high [initiator]/[CTA] molar ratios for accessing predictable molecular weights without affecting the Đ. Some evidence suggests that this does not completely behave as a common RAFT agent as it is not completely consumed during the polymerization reaction, and it needs atypical high molar ratios [initiator]/[CTA] to be closer to the predicted molecular weight without affecting the Đ. This work demonstrates that MMA and other methacrylic monomers can be polymerized in a controlled way, and with “living” characteristics, using certain symmetrical trithiocarbonates.

Investigation by HPLC of the Catabolism of Recombinant Tissue Plasminogen Activator in the Rat

1988 ◽  
Vol 60 (01) ◽  
pp. 107-112 ◽  
Author(s):  
Roy Harris ◽  
Louis Garcia Frade ◽  
Lesley J Creighton ◽  
Paul S Gascoine ◽  
Maher M Alexandroni ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Plasminogen Activator ◽  
Tissue Plasminogen Activator ◽  
Half Life ◽  
Recombinant Tissue Plasminogen Activator ◽  
Rat Plasma ◽  
High Molecular Weight Complex ◽  
Molecular Weights ◽  
Major Activity ◽  
Tissue Plasminogen

SummaryThe catabolism of recombinant tissue plasminogen activator (rt-PA) was investigated after injection of radiolabelled material into rats. Both Iodogen and Chloramine T iodination procedures yielded similar biological activity loss in the resultant labelled rt-PA and had half lives in the rat circulation of 1 and 3 min respectively. Complex formation of rt-PA was investigated by HPLC gel exclusion (TSK G3000 SW) fractionation of rat plasma samples taken 1-2 min after 125I-rt-PA injection. A series of radiolabelled complexes of varying molecular weights were found. However, 60% of the counts were associated with a single large molecular weight complex (350–500 kDa) which was undetectable by immunologically based assays (ELISA and BIA) and showed only low activity with a functional promoter-type t-PA assay. Two major activity peaks in the HPLC fractions were associated with Tree t-PA and a complex having a molecular weight of ̴ 180 kDa. HPLC fractionation to produce these three peaks at various timed intervals after injection of 125I-rt-PA showed each to have a similar initial rate half life in the rat circulation of 4-5 min. The function of these complexes as yet is unclear but since a high proportion of rt-PA is associated with a high molecular weight complex with a short half life in the rat, we suggest that the formation of this complex may be a mechanism by which t-PA activity is initially regulated and finally cleared from the rat circulation.

Permeability Enhancing and Chemotactic Activities of Lower Molecular Weight Degradation Products of Human Fibrinogen

1981 ◽  
Vol 45 (01) ◽  
pp. 090-094 ◽  
Author(s):  
Katsuo Sueishi ◽  
Shigeru Nanno ◽  
Kenzo Tanaka
Keyword(s):  
Molecular Weight ◽  
Degradation Products ◽  
Electron Microscopic Observation ◽  
Chemotactic Activity ◽  
Lower Molecular Weight ◽  
Electron Microscopic ◽  
Human Fibrinogen ◽  
Rabbit Skin ◽  
Molecular Weights ◽  
Active Fragments

SummaryFibrinogen degradation products were investigated for leukocyte chemotactic activity and for enhancement of vascular permeability. Both activities increased progressively with plasmin digestion of fibrinogen. Active fragments were partially purified from 24 hr-plasmin digests. Molecular weights of the permeability increasing and chemotactic activity fractions were 25,000-15,000 and 25,000 respectively. Both fractions had much higher activities than the fragment X, Y, D or E. Electron microscopic observation of the small blood vessels in rabbit skin correlated increased permeability with the formation of characteristic gaps between adjoining endothelial cells and their contraction.These findings suggest that lower molecular weight degradation products of fibrinogen may be influential in contributing to granulocytic infiltration and enhanced permeability in lesions characterized by deposits of fibrin and/or fibrinogen.

Toxicity of Heparinoids, with Special Reference to the Precipitation of Fibrinogen

1964 ◽  
Vol 12 (01) ◽  
pp. 232-261 ◽  
Author(s):  
S Sasaki ◽  
T Takemoto ◽  
S Oka
Keyword(s):  
Molecular Weight ◽  
Dextran Sulfate ◽  
Anticoagulant Activity ◽  
Molecular Structures ◽  
Severe Reaction ◽  
Clinical Use ◽  
Molecular Weights ◽  
Close Relationship

SummaryTo demonstrate whether the intravascular precipitation of fibrinogen is responsible for the toxicity of heparinoid, the relation between the toxicity of heparinoid in vivo and the precipitation of fibrinogen in vitro was investigated, using dextran sulfate of various molecular weights and various heparinoids.1. There are close relationships between the molecular weight of dextran sulfate, its toxicity, and the quantity of fibrinogen precipitated.2. The close relationship between the toxicity and the precipitation of fibrinogen found for dextran sulfate holds good for other heparinoids regardless of their molecular structures.3. Histological findings suggest strongly that the pathological changes produced with dextran sulfate are caused primarily by the intravascular precipitates with occlusion of the capillaries.From these facts, it is concluded that the precipitates of fibrinogen with heparinoid may be the cause or at least the major cause of the toxicity of heparinoid.4. The most suitable molecular weight of dextran sulfate for clinical use was found to be 5,300 ~ 6,700, from the maximum value of the product (LD50 · Anticoagulant activity). This product (LD50 · Anticoagulant activity) can be employed generally to assess the comparative merits of various heparinoids.5. Clinical use of the dextran sulfate prepared on this basis gave satisfactory results. No severe reaction was observed. However, two delayed reactions, alopecia and thrombocytopenia, were observed. These two reactions seem to come from the cause other than intravascular precipitation.

Sign in / Sign up

Export Citation Format

Share Document