Extremely High Glass Transition Temperature Hydrocarbon Polymers Prepared through Cationic Cyclization of Highly 3,4‐Regulated Poly(Phenyl‐1,3‐Butadiene)

Cai, Yanfei; Lu, Jiang; Zuo, Danlin; Li, Shihui; Cui, Dongmei; Han, Bin; Yang, Wantai

doi:10.1002/marc.201800298

Cited by 14 publications

(17 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Methods. 1 H and 13 C NMR spectra were recorded on an Agilent 500-MR DD2 magnetic resonance system and Varian/Oxford AS-500 using CDCl 3 as a solvent and internal standard. Molecular weights and dispersity D of polymers and block copolymers were measured by Agilent 1260 Infinity gel permeation chromatography (GPC) system equipped with a PL gel 5 μm MiniMIX-D column (Agilent Technologies) and differential refractive index detectors.…”

Section: Methodsmentioning

confidence: 99%

“…1 H NMR analysis showed that the comonomer composition ratio in the obtained copolymer was consistent with the initial feed ratio (styrene content ∼ 54%). The isoprene units in p(St-co-Ip) displayed microstructures predominantly composed of 1,4-polymerized repeating units (1.4:1.2:3.4 = 70−73:0:27−30) along the copolymer chain (Table 1), which was identified and quantified by integrating the peaks in the 1 H and 13 C NMR spectra (Figure S1). In C 13 NMR, a decrease in the peaks (41− 42 ppm) corresponding to the main-chain α-carbon of the mid-styrene unit in the styrene sequence indicated fewer consecutive styrene units in the random copolymers (Figure S3).…”

Section: Table 1 Characteristics Of Hydrophobic and Amphiphilic Block...mentioning

confidence: 99%

“…One of the widely used methods for producing amorphous polymers consisting of cyclic units is the cationic cyclization of unsaturated hydrocarbon polymers under acidic conditions via carbocationic intermediates. − Kamigaito and co-workers reported that styrene–diene copolymer can be treated with strong Brönsted acid (CF 3 SO 3 H) to induce Friedel–Crafts alkylation between adjacent diene–styrene units to form a rigid tetrahydronaphthyl bicyclic main-chain structure. − This intramolecular cyclization in the main chain leads to a high T g and robust mechanical properties for the random copolymer. The synthesis of thermally and optically high-performance plastics from styrene (St) and isoprene (Ip) through the intramolecularly cyclized random St-Ip polymers have been studied. − Furthermore, postpolymerization modification reactions that change the main-chain structures of existing polymers can lead to new applications. − …”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Block Copolymers Composed of Main-Chain Cyclic Polymers: Morphology Transition and Covalent Stabilization of Self-Assembled Nanostructures via Intra- and Interchain Cyclization of Styrene-co-isoprene Blocks

2020

View full text Add to dashboard Cite

Amorphous saturated hydrocarbon polymers containing main-chain cyclic units have potential as novel optoelectronic materials for plastic lenses and optical storage media owing to their high glass transition temperature, nonhygroscopic nature, transparency, and low birefringence. Here, we report the synthesis of block copolymers (BCPs) incorporating a branched polyethylene glycol (PEG) hydrophilic block and randomly copolymerized styrene and isoprene units (p(St-co-Ip)) of different molecular weights as the hydrophobic component. Amorphous polymers bearing cyclic structures along with hydrophobic chains were prepared via the cationic cyclization of the unsaturated hydrocarbon polymers under acidic conditions. We suggest that the morphological transitions of self-assembled BCP structures are dependent on changes in the chain length of the hydrophobic block, which is determined by the regiospecificity of the isoprene units. The self-assembled structures could be covalently stabilized via intermolecular cyclization between the hydrophobic blocks. Notably, the cross-linked structures displayed a reversible swelling/deswelling ability in response to the type of solvent medium.

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Table 1 Characteristics Of Hydrophobic and Amphiphilic Block...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Block Copolymers Composed of Main-Chain Cyclic Polymers: Morphology Transition and Covalent Stabilization of Self-Assembled Nanostructures via Intra- and Interchain Cyclization of Styrene-co-isoprene Blocks

2020

View full text Add to dashboard Cite

show abstract

“…Moreover, with a phenyl group replacing methyl, Poly(2-PB) exhibits distinctive properties compared with polyisoprene. Moreover, Poly(2-PB) can also be used to produce high-temperature thermoplastics with a Tg as high as 325 • C [114]. Since the successful synthesis of 2-PB by Marvel, [115] it received much attention [116,117].…”

Section: Synthesis Of 2-phenyl-13-butadienesmentioning

confidence: 99%

Synthesis of 1,3-Butadiene and Its 2-Substituted Monomers for Synthetic Rubbers

Liu

et al. 2019

Catalysts

View full text Add to dashboard Cite

Synthetic rubbers fabricated from 1,3-butadiene (BD) and its substituted monomers have been extensively used in tires, toughened plastics, and many other products owing to the easy polymerization/copolymerization of these monomers and the high stability of the resulting material in manufacturing operations and large-scale productions. The need for synthetic rubbers with increased environmental friendliness or endurance in harsh environments has motivated remarkable progress in the synthesis of BD and its substituted monomers in recent years. We review these developments with an emphasis on the reactive routes, the products, and the synthetic strategies with a scaling potential. We present reagents that are primarily from bio-derivatives, including ethanol, C4 alcohols, unsaturated alcohols, and tetrahydrofuran; the major products of BD and isoprene; and the by-products, activities, and selectivity of the reaction. Different catalyst systems are also compared. Further, substituted monomers with rigid, polar, or sterically repulsive groups, the purpose of which is to enhance thermal, mechanical, and interface properties, are also exhaustively reviewed. The synthetic strategies using BD and its substituted monomers have great potential to satisfy the increasing demand for better-performing synthetic rubbers at the laboratory scale; the laboratory-scale results are promising, but a big gap still exists between current progress and large scalability.

show abstract

“…For example, different experimental strategies have been developed to synthesize high-temperature hydrocarbon polymers, such as (1) enhancement of the tacticity of the polymer chains, 8 , 9 (2) introduction of bulky pendant groups into the side chain, 10 , 11 , 12 and (3) incorporation of cyclic structures into the backbone chain. 13 , 14 , 15 Nevertheless, this Edisonian approach is often costly, slow, biased toward certain chemical space domains, and limited to relatively small-scale studies, which may easily miss promising compounds. 16 Thus, a robust and reliable high-throughput screening method is essential for the discovery and design of high-temperature polymers.…”

Section: Introductionmentioning

confidence: 99%

Machine learning discovery of high-temperature polymers

Tao

Chen

2021

Patterns

View full text Add to dashboard Cite

Summary To formulate a machine learning (ML) model to establish the polymer's structure-property correlation for glass transition temperature , we collect a diverse set of nearly 13,000 real homopolymers from the largest polymer database, PoLyInfo. We train the deep neural network (DNN) model with 6,923 experimental values using Morgan fingerprint representations of chemical structures for these polymers. Interestingly, the trained DNN model can reasonably predict the unknown values of polymers with distinct molecular structures, in comparison with molecular dynamics simulations and experimental results. With the validated transferability and generalization ability, the ML model is utilized for high-throughput screening of nearly one million hypothetical polymers. We identify more than 65,000 promising candidates with > 200°C, which is 30 times more than existing known high-temperature polymers (∼2,000 from PoLyInfo). The discovery of this large number of promising candidates will be of significant interest in the development and design of high-temperature polymers.

show abstract

Extremely High Glass Transition Temperature Hydrocarbon Polymers Prepared through Cationic Cyclization of Highly 3,4‐Regulated Poly(Phenyl‐1,3‐Butadiene)

Cited by 14 publications

References 36 publications

Block Copolymers Composed of Main-Chain Cyclic Polymers: Morphology Transition and Covalent Stabilization of Self-Assembled Nanostructures via Intra- and Interchain Cyclization of Styrene-co-isoprene Blocks

Block Copolymers Composed of Main-Chain Cyclic Polymers: Morphology Transition and Covalent Stabilization of Self-Assembled Nanostructures via Intra- and Interchain Cyclization of Styrene-co-isoprene Blocks

Synthesis of 1,3-Butadiene and Its 2-Substituted Monomers for Synthetic Rubbers

Machine learning discovery of high-temperature polymers

Contact Info

Product

Resources

About