Cyclic polymer and preparation method thereof

A cyclic polymer, cyclic technology, applied in the field of macromolecular polymers, can solve the problems of difficulty and limitations in the synthesis of linear polymers, and achieve the effects of convenient separation and application, good thermal stability, and enhanced material fluorescence.

Inactive Publication Date: 2011-02-16
SUZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] In the past few decades, as far as we know, cyclic homopolymers and copolymers, including sun-shaped, tadpole-shaped, "8"-shaped and θ-shaped cyclic polymers have been continuously reported, however, Multifunctional cyclic polymers with fluorescent and electrochemical properties have not been reported due to the difficulty of synthesizing linear polymers

Method used

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  • Cyclic polymer and preparation method thereof
  • Cyclic polymer and preparation method thereof
  • Cyclic polymer and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0030] Embodiment one: preparation of cyclic polystyrene carbazole, such as figure 1 As shown, the synthesis of cyclic polystyrene carbazole is divided into three main steps: ① Use styrene carbazole as a monomer and synthesize a bifunctional linear polystyrene carbazole with α-alkynyl-ω-bromine by ATRP. azole linear-PVBCZ-Br(a); ② use sodium azide to convert the terminal bromine of linear-PVBCZ-Br(a) into an azido group to obtain linear-PVBCZ-N 3 (b); ③ Obtain cyclic-PVBCZ (c) through intramolecular "click" cyclization reaction; the number average molecular weight and molecular weight distribution of the polymer are shown in Table 1.

[0031] Specifically include the following steps:

[0032] 1. Add 2.0 g styrene carbazole (VBCZ) (7.1×10 -3 mol), 30 μL initiator BBMP (1.8mmol), 109 μL ligand PMDETA (5.3mmol), 2.5×10 -2 g catalyst CuBr and 15mL solvent anisole, and then the reaction tube was closed-melted through the freezing-vacuum cycle three times, and placed in an oil ba...

Embodiment 2

[0038] Embodiment two: analyze the linear and cyclic polystyrene carbazole in embodiment one.

[0039] For the elution curves of GPC of linear and cyclic polystyrene carbazoles see figure 2 , it can be seen that the retention time of the three cyclic-PVBCZ elution peaks is longer than that of the corresponding linear polymer. Depend on image 3 It can be seen from the MALDI-TOF spectrum that the actual molecular weights of ring and line polymers are actually the same. According to the report of Kramers et al. and Zimm et al. (referring to: Kramers, H.A.J.Chem.Phys.1946,14,415-424; Zimm, B.H.; Stockmayer, W.H.J.Chem.Phys.1949,17,1301-1314), This phenomenon is known to be due to the smaller hydrodynamic radius of the cyclic polymer than the linear precursor.

[0040] From the FT-IR spectrum ( Figure 4 ) can also be seen, the linear polymer at 2090cm -1 The azide peak at and 3300cm -1 The alkynyl peaks at have disappeared after the cyclization reaction, proving that there...

Embodiment 3

[0042] Example 3: Thermal performance test of Cyclic-PVBCZ and Linear-PVBCZ

[0043] In Marzio's report (see: Edmund A. Di Marzio * and Charles M. Guttman Macromolecules 1987, 20, 1403-1407), since the three-dimensional structure of the ring is much smaller than that of a line of the same length, the conformational entropy ΔS of a cyclic polymer is always less than that of a linear polymer of the same molecular weight. ΔG=ΔH-TΔS, at the time of glass transition, in order to make ΔG equal to 0, under the same ΔH, the ΔS of the linear polymer is greater than that of the cyclic polymer, so T is smaller than that of the cyclic polymer. That is to say, in the case of the same molecular weight, the glass transition temperature (T g ) is always higher than linear. This phenomenon was also observed in our analysis of styrene carbazole polymers using differential scanning calorimetry. As shown in Table 2, the T of cyclic-PVBCZ(c) g It is higher than the corresponding linear-precurs...

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Abstract

The invention discloses cyclic polymer and a preparation method thereof. The cyclic polymer is cyclic polystyrene carbazole of which PDI is below 1.2 and Mn is 2,500 to 10,000. The preparation method comprises the following steps of: (1) synthesizing bifunctional linear polystyrene carbazole with alpha-alkynyl-omega-bromine by taking styrene carbazole as a monomer through atom transfer radical polymerization; (2) converting a terminal group, namely bromine, of the linear polystyrene carbazole which is obtained in the step (1) into triazo by using sodium azide to obtain the bifunctional linear polystyrene carbazole with alpha-alkynyl-omega-triazo; and (3) performing intramolecular click chemistry cyclization reaction to obtain the cyclic polystyrene carbazole. Compared with the linear polystyrene carbazole, the cyclic polystyrene carbazole prepared by the method has the advantages of higher heat stability, higher fluorescent characteristic and higher electrochemical characteristic.

Description

technical field [0001] The invention belongs to the field of macromolecular polymers, in particular to a cyclic polymer with excellent fluorescence and electrochemical properties, in particular to cyclic polystyrene carbazole and a preparation method thereof. Background technique [0002] Cyclic polymers have in some respects completely different properties from linear polymers due to the lack of end groups. For example, cyclic polymers have smaller hydrodynamic radii, reduced viscosity, larger refractive indices, and higher glass transition temperatures. In the past few decades, although the synthesis methods of cyclic polymers are much more demanding than that of linear polymers, the special properties and importance of cyclic polymers have attracted widespread attention from the polymer community. . [0003] So far, there are two main methods for the synthesis of cyclic polymers: one is the ring-expansion method of ring-type polymers obtained by continuous ring-expansio...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F112/32C08F8/48
Inventor 周年琛朱兴朱秀林张正彪程振平
Owner SUZHOU UNIV
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