ZHANG Hong-jie, FU Lian-she, LIN Jun, LI Huan-rong, MENG Qing-guo, LIU Feng-yi, GUO Jun-fang, WANG Jun, ZHENG You-xuan, YU Jiang-bo. Preparation and Luminescence Properties of Rare Earth/Polymer Hybrid Materials[J]. Chinese Journal of Luminescence, 2002,23(3): 228-232
ZHANG Hong-jie, FU Lian-she, LIN Jun, LI Huan-rong, MENG Qing-guo, LIU Feng-yi, GUO Jun-fang, WANG Jun, ZHENG You-xuan, YU Jiang-bo. Preparation and Luminescence Properties of Rare Earth/Polymer Hybrid Materials[J]. Chinese Journal of Luminescence, 2002,23(3): 228-232DOI:
Preparation and Luminescence Properties of Rare Earth/Polymer Hybrid Materials
Based on the difference between the inorganic composite and the organic composite
one of the softchemistry synthesis method(sol-gel process has been employed to prepare the rare earth/polymer hybrid materials.SiO
2
with good photostability and thermalstability was used as the inorganic composite and acrylic acid series e.g.methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) with the almost same refractive index as SiO
2
as the organic composite.In the presence of coupling agent 3-(trimethoxysilyl) propyl methacrylate (MSMA)
sol-gel method was used to prepare two kinds of hybrid matrix materials SiO
2
/P(MMA-MSMA) and SiO
2
/P(HEMA-MSMA).The experiment results show that inorganic network and organic network were formed in the matrix materials.Since there exists a strong chemical bond between the inorganic phase and the organic phase
no evident interface in the final materials was found.The particle size is less than 100nm
suggesting the materials belong to nanometer composites.Owing to the formation of inorganic SiO
2
and the polymer at the same time in the matrix
the materials not only have good toughness but also decrease the thermal collection and photo loss.This kind of material is a promising matrix for the inorganic/organic composite materials.In order to overcome the drawback and limitation of pre-doped and post-doped method in the traditional sol-gel method and shorten the period for the preparation of optical functional materials
a two step sol-gel method was developed with hydrochloric acid as the acid catalyst and hexamethylenetetramine (CH
2
)
6
N
4
as the base catalyst for the in situ synthesis of rare earth
c
omplex in the SiO
2
matrix based on the characteristic of the sol-gel method and synthesis rule for the rare earth
c
omplex.Since (CH
2
)
6
N
4
can generate hydroxyl groups gradually
the pH value was raised and accelerated the condensation reaction.In the meantime
this kind of reaction condition also favors the formation of rare earth
c
omplex.As a result of hydrolysis and condensation
the rare earth
c
omplex was synthesized and wrapped in the matrix.Using the two step sol-gel technique
in situ complexes of rare earth ion(Eu
3+
Tb
3+
) with organic ligands such as β diketone
aromatic carboxylic acids and phen were synthesized in SiO
2
/polymer hybrid matrix.By doping of rare earth
c
omplexes into layered compounds zirconium bis(monohydrogenphosphate) (α-ZrP) and mesoporous material MCM-41
new luminescence assemblies were prepared.Because the interlayer spacing of α-ZrP is too small to let the rare earth
c
omplex molecules intercalate
the increasing the interlayer spacing is the prerequisite for the preparation of the assemblies containing rare earth
c
omplexes.P Methoxyaniline (PMA) was used to preintercalate into the galleries of α-ZrP and the interlayer spacing was increased and confirmed by XRD.Therefore
the assemblies containing rare earth
c
omplexes were prepared and demonstrated by XRD and UV visible spectra.Since the high energy vibration of the hydroxygen group will heavily quench the luminescence of the rare earth ion
the mesoporous material MCM-41 was modified by aminopropyltriethoxysilane (APTES) and thereby the assemblies containing rare earth
c
omplexes were made.The luminescence intensity of the assembly using MCM-41 modified by APTES was as 9 times as the assembly using the MCM-41 unmodified.Novel
covalently bonded hybrid materials of rare earth
c
omplexes with silica were prepared by using bipyridine
Si as one of the precursors
which reacted with the TEOS by hydrolysis and condensation in the presence of lanthanide ions.These researches provide new possibilities for the development of new luminescence composites with high efficiency and long lifetime.