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Pengyu Chen ; Zheyuan Zhang ; Kwang Won Park , et al. Chem. Mater.,2024,36(11):5621-5629. DOI: 10.1021/acs.chemmater.4c00658
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Abstract: Initiated chemical vapor deposition (iCVD) has revolutionized the preparation of high-quality conformal polymer films with excellent control over composition and properties at the nanoscale. It is compatible with over 70 functional monomers . Despite that chemical versatility, side reactions during iCVD are not well understood. For example, chain transfer could happen during the propagation of an important class of monomers that contain nitrogen (N), arresting the polymerization and limiting the molecular weight. Here, we use 1-vinylimidazole (1VI) to demonstrate the chain transfer reaction to the imidazole group during iCVD, which leads to unpredictable deposition kinetics, low molecular weight, and undesirable products. We further introduce a strategy that utilizes a vapor solvent to engineer monomer reactivity and suppress side reactions. By replacing the traditional patch flow, Ar, with acetic acid (AcOH), which forms hydrogen bonding with 1VI, chain transfer is suppressed, and the deposition rate is increased by as much as 280% while restoring its linear dependence on the monomer partial pressure. That linear dependence has not been achieved previously for 1VI. The tunable deposition kinetics, in turn, leads to a broader range of attainable material properties, including nearly doubling the maximum attainable molecular weight (from 8 kDa to 16 kDa) and increasing the elastic modulus (from 3.5 to 4.7 GPa). The vapor solvent is also effective at suppressing chain transfer in other N-containing monomers , like (2-dimethylamine) ethyl methacrylate (DMAEMA), leading to a considerable increase in the molecular weight (from 16 kDa to 38 kDa). The vapor solvent selectively increases the reactivity of N-containing monomers during copolymerization, demonstrated using 1VI and divinylbenzene (DVB) or 1,3,5,7-tetravinyl tetramethylcyclotetrasiloxane (V4D4), increasing the reactivity ratio of 1VI by an order of magnitude according to the Fineman–Ross equation. This robust strategy engineers monomer reactivity without the need for chemical modifications. It improves the chemical precision of iCVD polymerization, particularly for an important class of N-containing monomers , which have found broad applications as the polymer–electrolyte interphase in batteries, antifouling coatings in food and water production, and bioactive and functionalizable coatings in sensors.
Purchased from AmBeed: 2554-06-5
CAS No. : | 2554-06-5 | MDL No. : | MFCD00040293 |
Formula : | C12H24O4Si4 | Boiling Point : | No data available |
Linear Structure Formula : | (CH3(CH2CH)SiO)4 | InChI Key : | VMAWODUEPLAHOE-UHFFFAOYSA-N |
M.W : | 344.66 | Pubchem ID : | 75706 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P305+P351+P338 | UN#: | |
Hazard Statements: | H319 | Packing Group: | |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
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With platinum; In toluene; at 119 - 130℃; for 48h; | (1) taking 0.5 g of hydrosilylation catalyst platinum, diluted with 5 mL of toluene, and then added to a 250 mL three-necked flask;(2) Take 3.45 g of tetramethyltetravinylcyclotetrasiloxane (tetramethyl-)Tetravinylcyclotetrasiloxane, molecular weight MW=345g/mol), diluted with 20mL of toluene and added to the three-neckedBottle(3) Take 11.66g of <strong>[2488-01-9]1,4-bis(dimethylsilyl)benzene</strong> (1,4-Bis(dimethylsilyl)benzene,Sub-quantity = 194.42), diluted with 25 mL of toluene and added to a three-necked flask;(4) Set the oil bath temperature to 130 C, turn on the stirring, and turn on the condensed water until the temperature in the three-necked flask is 119 C.The mixture should start to reflux;(5) After refluxing for a period of time, take a small amount of the reaction mixture for IR test to determine whether the reaction is completed.all.(6) After 48 hours, the IR results showed that the carbon-free carbon double bond absorption peak indicates the end of the reaction, and the 1H NMR results showed noVinyl H, at this time, the reaction mixture was transferred to a rotary evaporator to distill off the solvent, and the product crosslinker 4 was precipitated |
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