Functionalization And Material Preparation Of Aminopropyl-Containing Siloxane

The modification of siloxanes is essential for the development of functional silicone materials.In this passage,aminopropyl-containing siloxanes(including disiloxaneand polysiloxane)have been functionally modified(including phosphonate functionalization and nitrile functionalization);then,the performances of the functional products were researched.1,3-bis {3-[N-(1-phosphonatediethylisopropyl)-Propyl]}-1,1,3,3-tetramethyldisilo xane(DPDS)and N,N'-bis(1-phosphonate diethyl)isopropylidene-ethylenediamine(DPDN)were synthesized via Kabachnik-Fields(K-F)reaction,and confirmed their structure using 1H-NMR,31P-NMR,13C-NMR and MS.We found that DPDS had aggregation-induced emission(AIE)phenomenon in UV lamp,then,we carried fluorescence properties test on it.By the fluorescence property test of DPDS with different concentration in CHCl3 and methanol/water solution,we concluded that DPDSindeed had AIE phenomenon.By the fluorescence property test of DPDN without Si-O-Si bond and diethyl 1-decylphosphonate(DDP)without N atom,we got a conclusion that the fluorescence resource of DPDS was phosphonate.By the fluorescence property test of DPDS in methanol/glycerol solution and polar solution and gaussian fitting method,we drawn a conclusion that the AIE mechanisms of DPDS were restriction of intramolecular rotation and intramolecular charge transfer mechanism.In addition,we introduced phosphonate to poly(dimethyl-methylaminopropyl)siloxane and synthesized lateral phosphonate-containing polydimethylsiloxane(PAPMSP).We made a research on fluorescence properties of PAPMSP.Through exploring,we got that the AIE properties of PAPMSP were similar to DPDS,but the excitation wavelength?emission wavelength and fluorescence intensity of PAPMSP were all less than DPDS because of molecular structure and state of aggregation.At the same time,we found an interesting phenomenon-upconversion luminescence phenomenon when we studied the fluorescence properties of DPDS and PAPMSP.Poly(dimethyl-methyl-methyl(N-nitrilobethylaminopropyl)]siloxane(PANPMS)and poly[dimethyl-methylvinyl-methyl(N-nitrilobethylaminopropyl)]]siloxane(PVNPMS)were synthesized via amine-ene addition reaction,which put forward a new method for the synthesis of nitrile silicone oil.We confirmed their structures and molecular weights by infrared spectrum?1H-NMR and GPC.We prepared room temperature condensation type silicon rubber with good mechanical properties by using PANPMS and methyl triethoxysilane under organotin catalyzed.The tensile strength was 1.01 MPa and the tear strength was 5.06MPa.We prepared room temperature addition silicone rubber with good mechanical properties by using PVNPMS and pentaerythritol tetra(3-mercaptopropionic acid)under the condition of benzoin dicarboxylate catalyzed.The tensile strength was 2.68MPa and the tear strength was12.38MPa.The reuse property of coordination crosslinking rubber has been of benifit for the sustainable development of rubber industry.In this passage,we introduced coordination crosslinking method to silicone rubber.In this research,nitrile silicone oil(PANPMS)was prepared firstly which molecular weight wereabout 100,000 and the nitrile content of PANPMS was about 8%.Then,PANPMS was coordinatedwith CeCl3·7H20,TbCl3·6H,0 and EuCl3·6H20,respectively.And coordination crosslinked nitrile silicone rubber with good mechanical properties was successfully prepared.The vulcanization process of coordination crosslinking was at 90? for 25 minute which determined by vulcanization characteristic curve.The coordination process of PANPMS and rare earth salts was confirmed by IR and XPS.What's more,SEM,TGA,heat aging test,heat oil test and contact angle test were also conducted.The results showed that CeCl3.7H2O/PANPMS was dispersed uniformly,and it was micro-distributed in the fonn of "island".Hoxwever,the heat resistance of the CeCl3·7H2O/PANPMS needed to improve.After being broken,second and third vulcanization of CeCl3·7H20/PANPMS were carried out respectively,and we also carried out the mechanical properties test,cross-linking density test and contact angle performance test.The test results showed that the better rubber formular could achieve third vulcanization and contain a certain mechanical properties.