In this paper, the amphiphilic random copolymers poly (styrene-co-acrylic acid) (P(St-co-AA)) were synthesized by atom transfer radical polymerization(ATRP), and the amphiphilic random copolymers P(NIPAM-co-AA-co-CEA) were synthesized by free-radical solution polymerization. Self-assembly of P(St-co-AA) and P(NIPAM-co-AA-co-CEA) were respectively researched.A series of random copolymers poly(styrene-co-tert-butyl acrylate) (P(St-co-tBA)) with different monomer ratio were synthesized by atom transfer radical polymerization (ATRP), using hydrophobic styrene(St) and tert-butyl acrylate(tBA) as monomers, ethyl-2-bromo- propionate as initiator, compound system of CuCl/ N,N,N′,N′′,N′′- penta-methyl-diethylenetri- amine as catalyst. Amphiphilic random copolymers P(St-co-AA) were obtained from hydrolyzed P(St-co-tBA) copolymers with trifluoroacetic acid as catalyst. P(St-co-tBA) and P(St-co-AA) copolymers were characterized by means of FTIR , 1H NMR, Gel Permeation Chromatography(GPC) and Differential Scanning Calorimetry(DSC). Self-assembly of P(St-co-AA) copolymers in selective solvent was characterized by means of UV, laser light scattering(LLS), laser granularity analyzer and TEM. Effect of copolymer composition, polymer concentration and water content on self-assembly were discussed.The random copolymer P(St-co-AA) was synthesized by radical solution polymerization and atom transfer radical polymerization(ATRP). The mechanism of different polymerization was different, so the inner segment sequence was different. As self-assembly was relation with the segment sequence, so effect of polymerization methods on self-assembly was researched primarily.Self-assembly of poly(N-isopropylacrylamide-co-acrylic acid-co- 2-cinnamoylethyl acrylate) [P(NIPAM-co-AA-co-CEA)], which was obtained from the radical solution polymerization was studied. At room temperature, the random copolymers self-assembly into spherical core-shell micelles with hydrophobic PCEA segment as the core, hydrophilic PNIPAM/PAA segments as the mixed shell. Increasing temperature, the diameters of micelles were reduced because of collapsed PNIPAM with PCEA as the core. Decreasing pH, PAA chains collapsed onto the core resulting in reducing of the diameters of micelles. Moreover, by UV light, the diameters of micelles reduced because of photo-crosslinking of the PCEA segment as the core.As the micelles were amphiphilic, which were similar to surfactant. Using micelles of P(NIPAM-co-AA-co-CEA) as emulisifer was studied, and effect of temperature, UV irradiation and pH were researched.

Polyhydroxyalkanoates (PHAs) are a class of biodegradable polyesters produced by microorganisms. Due to their biodegradability and biocompatibility, PHAs have received much attention as a friendly material recently. Polyethylene glycol (PEG) is a water-soluble substrate as its popular hydrophilicity. Particularly, it can be found in human blood for its good biocompatibility. In this essay, three series of poly(ester-urethane)s (PUs) were synthesized from copolymerization of different PHA members (PHB, P3/4HB and PHBHHx) which behave as a hard and hydrophobic portion and PEG functions as soft and hydrophilic moieties.The resultant products were characterized by NMR and Fourier transform infrared spectroscopy (IR), as well as gel permeation chromatography (GPC), which indicated the block copolymer architecture. Differential scanning calorimetry (DSC) revealed that PUs multiblock copolymers possess a semi-crystalline morphology with a single inner Tg due to the segments interaction. Whilst, a two phase separation was observed after placed for crystallinity equilibrium depending on its chemical composition. Thermogravimetric analysis (TGA) showed that the PUs multiblock copolymers had better thermal processability than their precursors. The morphologies of the three types PUs were controlled by the crystallinity of the PHA segments which would be potential in biomedical area. It is porous and net-like surface of crystal PHB based PUs copolymers while continuous and smooth when amorphous P3/4HB was employed. For semi-crystal block PHBHHx, the morphology changes between the two mentioned above due to the very low crystallinity rate. The differences of the aforesaid morphologies behaved novel properties and applications of the PUs. The blood compatibility of PHB-b-PEG series multiblock copolymers revealed an increasing blood clot formation time and reduced blood adhesion with increasing PEG content in the multiblock copolymers compared with the PHB only polymers. The P3/4HB and PEG block copolymers showed water dispersion behavior and the changes on hydrophilic/hydrophobic ratios led to the formation of different polymer shapes in Oil-in-Water emulsion (leaf-like and triangle). The mechanical properties assessment of the PUs based PHBHHx and PEG recorded an improved and adjustable ductility and toughness than pure PHBHHx with changing segment composition. Implantation of PU in mouse abdominal cavity indicated that tissue regeneration and tissue compatibility of PUs film was better than that of PHBHHx film. This kind of multiblock copolymer has great potential to be developed as a suitable candidate biomaterial for anti-adhesion and wound healing.To sum up, the hydrophobicity of PHA was modified successfully by copolymerization with hydrophilic PEG segments and made comparison in terms of novel properties and biomedical application between the synthesized PUs and neat PHA only materials. This would make great contributions to broaden PHA application area, especially in advanced self-assembly and biomedical materials aspects.

Three kinds of spherical polybenzoxazine, called P-P-B, G-A-B and P-A-B, were synthesized by changing amine and phenol resources. And three spherical polybenzoxazine resins, called S-P-P-B, S-G-A-B and S-P-A-B, were obtained by reverse-phase suspension solidification. Especially, the S-P-A-B resin was combined with a guanidine group after synthesized. What’s more, the self-assembly mechanics and process in reverse-phase suspension solidification were deduced in detail. The spherical resins were identified by SEM （scanning electronic microscope）, TGA （thermogravimetric analysis）, DSC （differential scanning calorimetry） and IR. Finally, the adsorption property was studied base on the features of the three spherical resins.The study of reverse-phase suspension solidification of P-P-B indicated that the solidification medium, the volume ratio of precursor to medium, the solidification temperature and the agitation speed played important roles in synthesizing S-P-P-B resins. The appropriate solidification medium was silicone oil, and the volume ratio of precursor to medium was 5:50. When other conditions were fixed, the size of the resin became smaller with the increasing of stir speed. Compared with conventional solidification, the reverse-phase suspension technique reduced the polymerization time to 30-40min.The G-A-B precursor which had hydrophilic and hydrophobic moieties was distributed in silicone oil and formed micelle by agitating. However, this micelle had hydrophilic core and hydrophobic shell. When the system was heated at an appropriate temperature, the ring-open reaction of G-A-B precursor was carried out in hydrophilic core which was combined by intra-and/or intermolecular interactions of hydrogen bond, while the hydrophobic shell was not polymerized. And the self-assembly S-G-A-B resin was obtained. According to SEM photograph, the S-G-A-B resin was tight and had shape of completely and perfectly round. The high decomposition temperature showed in TGA figure indicated that the thermal stability of self-assembly resin was much better than the polybenzoxazine resin obtained by conventional solidification. And according to SEM photograph and TGA figure, the existence of self-assembly process was approved.The S-P-A-B-G was obtained after the S-P-A-B resin being combined with a guanidine group. And the IR spectrogram, TGA and DSC results approved the existence of guanidine group in S-P-A-B-G.The adsorption of the S-P-P-B resin on methylene blue and the adsorption of S-G-A-B resin on vitamin C were in line with Langmuir adsorption isotherm equation. The correlation coefficient had reached more than 0.9 which indicated that the two adsorption behaviors were monolayer adsorption. The saturated adsorptive capacity （As） were 0.137 mg·g^-1, 0.114mg·g^-1 respectively.

A self-assembly method was employed to synthesize water-soluble polysucrose-based nanoparticles by one step. Polysurose and acrylic acid (AA) worked as raw materials, and Cerium (IV) was used to initiate active spots onto polysucruse chains. AA was added onto polysucrose as graft-chains. Under acid condition, the nano-micelles were formed by self-assembly. Then the further addition of bi-functional cross-linker Methylenedioxymethamphetamine acrylamide (MBA) cross-linked the Poly (acrylic acid) (PAA) chains to fix the nano-micelles.Transmission electron microscope (TEM) indicated that the diameter of these nanoparticles was approximate 70 nm. IR, 13C NMR results confirmed the formation of resultant nanoparticles. The effect of reagent ratio on nanoparticles’size and diameter polydisperse index (PDI) in water was determined by Dynamics Light Scattering (DLS). From the results, the increase of AA content resulted in the increase of the dimension of resultant nanoparticles (from 209.7 nm to 293 nm) on condition that the content of other reactants were kept constant. And the PDI changed from 1.0391 to 1.0315, which indicated that the dispersion of the nanoparticles’effective diameter was very narrow in water; while the increase of initiator content resulted in the decrease of the dimension of resultant nanoparticles (from 244 nm to 281 nm) on condition that the content of other reactants were kept constant, which means the effect of initiator to the diameter was not more significant than the effect of AA. However, the PDI increased from 1.0315 to 1.0432.Bovine serum albumin (BSA) was chosen as protein model to study the protein adsorption capability of there nanoparticles. The effect of reagent ratio on this adorption capability was investigated. In addition, we also found that the protein absorption ability of the nanoparticles had a relationship with pH value of the synthesis system. The best loading efficiency was 13.6% and the lowest was 3.0%.

In this paper, triblock copolymer poly(lactic acid)-poly(ethylene glycol) -poly(lactic acid) (PLA-PEG-PLA) were synthesized from poly(ethylene glycol) and lactide. Reacted with acryloyl chloride, amphiphilic bi-acrylated poly(lactic acid)-poly(ethylene glycol) -poly(lactic acid) (AC-PLA-PEG-PLA-AC) were gain. Techniques like IR, 1H-NMR were utilized for characterization and measurement.Amphiphilic triblock copolymer AC-PLA-PEG-PLA-AC formed micelles in aqueous solution by self-assembly with a crosslinkable hydrophobic biodegradable PLA core and a hydrophilic PEG shell. The vinyl groups of the acrylated group in the micelles core were crosslinked by UV light with the photoinitiator 2, 2-dimethoxy-2-phenylacetophenone (DMPA) and crosslinker poly(ethylene glycol) diacrylate. The final crosslinked nanogels were characterized using FT-IR spectroscopy, transmission electron microscopy (TEM) and dynamic light scattering (DLS). A hydrophobic drug, Tetrandrine (TED), was encapsulated in the nanogels. This paper also investigated the effects of polymer concentration, crosslinking density, LA/EO and drug concentration on drug release.

In this paper, triblock copolymer poly(lactic acid)-poly(ethylene glycol) -poly(lactic acid) (PLA-PEG-PLA) were synthesized from poly(ethylene glycol) and lactide. Reacted with acryloyl chloride, amphiphilic bi-acrylated poly(lactic acid)-poly(ethylene glycol) -poly(lactic acid) (AC-PLA-PEG-PLA-AC) were gain. Techniques like IR, 1H-NMR were utilized for characterization and measurement.Amphiphilic triblock copolymer AC-PLA-PEG-PLA-AC formed micelles in aqueous solution by self-assembly with a crosslinkable hydrophobic biodegradable PLA core and a hydrophilic PEG shell. The vinyl groups of the acrylated group in the micelles core were crosslinked by UV light with the photoinitiator 2, 2-dimethoxy-2-phenylacetophenone (DMPA) and crosslinker poly(ethylene glycol) diacrylate. The final crosslinked nanogels were characterized using FT-IR spectroscopy, transmission electron microscopy (TEM) and dynamic light scattering (DLS). A hydrophobic drug, Tetrandrine (TED), was encapsulated in the nanogels. This paper also investigated the effects of polymer concentration, crosslinking density, LA/EO and drug concentration on drug release.

Side-chain liquid crystalline polymers (SLCPs), which liquid group situated on the side-chain of polymers, are new kinds of materials with broad, applied foreground and have attracted considerable attention and interest. SLCPs have been used in many kinds of fields, such as gas chromatography, the memorization and display of information. Besides, supramolecular liquid crystalline polymers have been another study focus gradually.And the supramolecular liquid crystalline polymers based on hydrogen bonds have been studied deeply, especially the side-chain supramolecular liquid crystalline polymers due to their design agility and broad functional applied foreground.In this dissertation, twelve monomers were synthesized, which include cholestery sebacate monoester(Mo),4-allyloxy-biphenyl-4-ethoxybenzonate(M1),4-(4-ethoxyl)benzocyl-4-(4-allyloxy)benzoyloxy hydroquinone diester(M2),10-(4-(4-allyloxy phenyl propionyloxy) hydroxybiphenyl)cholesterylsebacate(M3),6-(4-(4-allyloxy-phenyl-propionyloxy)hydroxyl biphenyl)cholesteryladipate(M4),4-[4-(10-undecylen-1-yloxy)]benzocyl pyridine(M5),4-(4-allyloxy)benzocyl pyridine(M6),4-(4-ethoxyl)benzocyl hydroxybiphenyl sebacate monoester (M7),4-(4-ethoxyl)benzocyl pyridine(m1),4-{4-[2-(4-allyloxy)benzocyl]ethoxyl}benzocyl pyridine(m2), cholestery pyridine sebacate(m3), cholestery pyridine adipate(m4).These monomers are liquid crystalline except m1 and m2. Different kinds of mesogenic monomers (including nematic monomers and cholesteric monomers) were grafted to linear polymethyl hydrogensiloxanes. So two series of SLCPs with different chemical structures and characters were synthesized. In addition, the complex, which were prepared by cholesteric monomers M0, nematic monomers M7 with SLCPs P6 in a single system of pyridine by self-assembly, exhibited liquid crystalline properties as P3 series of SLCPs. The structures and properties of the obtained liquid crystalline monomers and SLCPs were investigated by FT-IR spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and polarizing optical microscopy (POM). Their structure-property relationships were discussed in detail. All the obtained monomers and polymers except M0-M2, M7 were novel. The study of their synthesis and properties would enrich the fields of SLCPs materials and supramolecular LCPs, and provide academic foundation for their application in the future.Monomers M0、M3、M4、m3 and m4 were cholesteric liquid crystallines and exhibite oily streak texture and focal conic texture, which were the typical textures of cholesteric phase. The selective reflection within the range of the visible spectrum, can be easily observed by naked eye, which was the character of the cholesteric liquid crystal material. Monomers M1, M2, M5-M7 were nematic liquid crystallines and present the texture of droplets, schlieren etc. The monomers have excellent liquid crystalline properties. These three series of polymers were cholesteric liquid crystals except P1-1, P2-1, P3-1 which were nematic liquid crystallines.For P1 series, the corresponding melting point (Tm) and clearing point (Ti) decreased with increasing the content of M4. For P2 series, the corresponding glass transition temperature (Tg) decreased with increasing the content of M3. The results of TGA show that P1, P2 series of polymers have excellent stability, so they have high applied values. P3 series of polymers have wide ranges of temperature of liquid crystalline phase and present excellent liquid crystalline properties.

The residue fluid catalytic cracking process (RFCC) is one of most widely used processes that can handle heavy oils with reasonable recovery of light fractions and acceptable cost, in which RFCC catalysts play a crucial role in guaranteeing good performance. It has been commonly recognized that diffusion control, often defined as accessibility, has become increasingly important for RFCC catalysts because of the short contact time operations. Several methods have been addressed to increasing the accessibility of RFCC catalysts, among which the creation of mesopores and macropores by incorporating mesoporous and macroporous zeolites into the catalyst was considered as an effective approach to improve the accessibility.While microporous zeolites such as Y are playing important roles in modern petrochemical industry for their abundant uniform microporous structures and strong intrinsic acidities, much attention is being paid to the development of a composite formed via self-assembly of precursors of microporous zeolites. The composite zeolites synthesized would have special properties, such as mutually connected microporous-mesoporous pore structure, high hydrothermal stability and graded aciditys. Unfortunately, not all types of zeloite precursors can be synthesized controllably. Naturally, it is reasonable to conceive that the degradation of waste zeolites should provide an economical route to synthesize the precursors of microporous zeolites. Different from the process of direct synthesis of precursors, degradation of waste zeolites have the advantages of reclaiming waste zeolites and thus low cost.In the present investigation, precursors were obtained by degradation of NaY zeolites. Micro/mesoporous GPZ zeolite was synthesized using P123 as the template and Y precursors as the construction units. Systemic characterization results revealed that the mesopore diameter was about 6.7 nm. BET surface area and pore volume were 595.4 m~2/g and 0.75 cm~3/g respectively. In addition, after hydrothermal treatment at 800℃for 4 h, 8 h and 12 h in 100% aqueous vapor, the remain fractions of BET surface were 95 %, 29% and 26% respectively. Micro/mesoporous GMZ zeolite was synthesized using CTMABr as the template and Y precursors as the construction units. Systemic characterization results revealed that the diameter of mesopores was about 3.2 nm. BET surface area and pore volume were 365.6 m~2/g and 0.29 cm~3 /g respectively.In the second part of this investigation, Micro/mesoporous NaY zeolite were synthesized using P123 as the template. Systemic characterization results revealed that the diameter of mesopores was about 3.8 nm. BET surface area and pore volume were 736 m~2/g and 0.37 cm~3/g respectively.In this thesis it has been shown that zeolites with graded pores and high hydrothermal stability were obtained. The successful synthesis of this material throws a light on the industrial application of meoporous zeolites.

In this work, we prepare hemoglobin-Layered double hydroxides hybrid materials, which dispersed state is different, by self-assembly of exfoliated LDH nanosheets with hemoglobin （Hb）. XRD, SEM, TEM, and FT-IR are employed to systematically analyze the resulting composite in detail. The Hb intercalated LDH and highly dispersed Hb-LDH nanohydrid materials can be synthesized by controlling the reactive conditions. The TG-DTA curves indicate the thermal stability of Hb which is assembled with LDH are improved. The ATR-FTIR spectra indicates the second structure of Hb is not changed after assembling. The fluorescence spectra indicates the environmental polarity around the Trp- and Tyr- residues are enhanced, and the changes are diminishing by the increasing of dispersed state.The catalytic activity of Hb was studied using H₂O₂ oxidation of o-phenylenediamine （OPD） to phenazine as a model reaction. Though the catalytic activiy of immobilized Hb are lower than free Hb in water at 25℃, the catalytic activity of immobilized Hb are higher than free Hb both in water at 90℃and in tolene at 25℃, and the residual acivity are higher than free Hb, too. The catalytic activiy of highly dispersed Hb-LDH is higher than Hb intercalated LDH both in water at 25℃, 90℃and in tolene at 25℃.The residual activity of unaged highly dispersed Hb-LDH is 18.57 times that of free enzyme in water at 90℃, and 5.75 times that of free enzyme in tolene at 25℃.

In this paper, dissipative particle dynamics simulations (DPD) are applied to model micellar architectures formed by comb-like copolymers in selective solvent. In order to study the effects of backbone length, side chain length and the number of grafted point on the micellar architectures, this study has been done in two parts. The first part deals with amphiphilic comb-like copolymers with hydrophobic backbone and hydrophilic grafts whereas the second part deals with amphiphilic comb-like copolymers with hydrophilic backbone and hydrophobic grafts. The simulation results demonstrated a remarkable capability of the studied comb-like copolymers to form micellar architectures such as spherical micelles, cylindrical micelles, perforated vesicles, oblate vesicles, elongated vesicles, and novel micelles such as hotdog-like micelles, staircase-like micelles, bone-like micelles, butterfly-like micelles, seahorse- like micelles, K-junction micelles and Y-junction micelles. Nevertheless, the major contribution of this study is its furthering of the understanding in chemical reactions which cannot be obtained in laboratory.