Thermal Emulsion Polymerization without any Conventional Initiators and Emulsifiers

Stable poly（styrene-co-sodium styrene sulfonate） （P（St-NaSS） nanoparticles with broader size distribution were synthesized by thermal emulsion polymerization without any conventional initiators and emulsifiers. The obtained polymer nanoparticles have higher potential, and the particle sizes have broad distribution. The stability of polymer particles originated from the addition of small amounts of ionic comonomer, NaSS, which can act as an emulsifier in somewhat. The monomer conversion could reach up to about 28 wt% in 48 h, and did not increase by further polymerization when higher polymerization temperature （120℃） was employed. This polymerization system may be give some further understand for mechanism of emulsion polymerization.

Breaking Through Bottlenecks for Thermally Conductive Polymer Composites:A Perspective for Intrinsic Thermal Conductivity,Interfacial Thermal Resistance and Theoretics

Rapid development of energy,electrical and electronic technologies has put forward higher requirements for the thermal conductivities of polymers and their composites.However,the thermal conductivity coefficient(λ)values of prepared thermally conductive polymer composites are still difficult to achieve expectations,which has become the bottleneck in the fields of thermally conductive polymer composites.Aimed at that,based on the accumulation of the previous research works by related researchers and our research group,this paper proposes three possible directions for breaking through the bottlenecks:(1)preparing and synthesizing intrinsically thermally conductive polymers,(2)reducing the interfacial thermal resistance in thermally conductive polymer composites,and(3)establishing suitable thermal conduction models and studying inner thermal conduction mechanism to guide experimental optimization.Also,the future development trends of the three above-mentioned directions are foreseen,hoping to provide certain basis and guidance for the preparation,researches and development of thermally conductive polymers and their composites.

Hydrothermal Synthesis,Crystal Structure and Properties of a 1D Chain Copper(Ⅱ) Polymer with 3-(2-Pyridiyl)-1H-1,2,4-triazole(Hpt)

A new 1D copper（Ⅱ） polymer [Cu（Hpt）（3,5-DMBA）]n has been hydrothermally synthesized with copper acetate,3-（pyridin-2-yl）-1,2,4-triazole（Hpt） and 3,5-dimethylbenzoic acid（3,5-DMBA）. It crystallizes in triclinic space group P1,with a = 8.1974（6）,b = 8.3280（6）,c = 12.5021（9） ？,α = 84.3320（10）,β = 71.8870（10）,γ= 65.4560（10）o,V = 737.44（9） ？~3,Dc = 1.612 g/cm3,Z = 2,F（000） = 366,GOOF = 1.035,R = 0.0298 and w R = 0.0855. The crystal structure is a one-dimensional（1-D） chain in which the Cu（Ⅱ） is five-coordinated with square pyramidal geometry. The crystal structure shows that the whole molecule consists of two copper ions bridged by two μ12-η：η0-3,5-dimethylbenzoic acid anions and two 3-（pyridin-2-yl）-1,2,4-triazole molecules. The coordination environment of Cu（Ⅱ） ion is CuO＋2N_3. The luminescence and thermal properties of the complex were investigated.

Synthesis,Crystal Structure and Thermal Stability Properties of a Binuclear Copper(Ⅱ) Coordination Polymer {[Cu_2(4,4'-bipy)_2(o-ABA)_4(H_2O)_2][(H_2O)_2]}_n

One-dimensional chain copper（Ⅱ） coordination polymer has been synthesized and characterized in the solvent mixture of water and alcohol with o-acetamidobenzoic acid,4,4＇-bipyridine and copper perchlorate.It is of tetragonal,space group P41212 with a=1.57756（10）,b= 1.57756（10）,c=2.1438（3）nm,V=5.3352（8） nm^3,Dc=1.524 g/cm^3,Z=4,F（000）=2536,R= 0.0479 and wR=0.0979.The crystal structure shows two coordination modes.The copper（1） is coordinated with two nitrogen atoms of one 4,4＇-bipyridine molecule and two oxygen atoms from two o-acetamidobenzoic acid molecules,forming a distorted tetrahedral coordination geometry; the copper（2） is coordinated with two nitrogen atoms of one 4,4＇-bipyridine molecule,four oxygen atoms from two o-acetamidobenzoic acid molecules and two water molecules,generating a distorted octahedral coordination geometry.The result of TG analysis shows that the title complex is stable below 180.0 ℃.

Experimental Measurements of the Sensitivity of Fiber-optic Bragg Grating Sensors with a Soft Polymeric Coating under Mechanical Loading,Thermal and Magnetic under Cryogenic Conditions

The strain and temperature sensing performance of fiber-optic Bragg gratings （FBGs） with soft polymeric coating, which can be used to sense internal strain in superconducting coils, are evaluated under variable cryogenic field and magnetic field. The response to a temperature and strain change of coated-soft polymeric FBGs is tested by comparing with those of coated-metal FBGs. The results indicate that the coated-soft polymeric FBGs can freely detect temperature and thermal strain, their At variable magnetic field, the tested results indicate accuracy and repeatability are also discussed in detail. that the cross-coupling effects of FBGs with different matrixes are not negligible to measure electromagnetic strain during fast excitation. The present results are expected to be able to provide basis measurements on the strain of pulsed superconducting magnet/cable （cable- around-conduit conductors, cable-in-conduit conductors）, independently or utilized together with other strain measurement methods.

Recent Progress in Fabrication and Structural Design of Thermal Conductive Polymer Composites

In recent years, the demand direction for electronic equipment has expanded into embedded and miniaturized devices. The heat radiation problem has become one of the most significant factors for hindering the development of electronic devices. Since heat radiation material is one of the important components in electronic devices, the demand for enhancing thermal conductivity is also increasingly urgent. Research on thermal conductive polymer composites has become a major direction for developing functional composites. This work reviewed the recent progress in the fabrication of thermal conductive polymer composites. Five different structures are presented, including the using of single fillers,hybrid fillers, double threshold percolation structure, segregated structure and other complex multiphase structures. Specifically, the preparation of high-performance thermal conductive polymer composites was introduced through the combination of various thermal conductive fillers.Finally, the development direction of high thermal conductive polymer composites was briefly explored.

SYNTHESIS AND CHARACTERIZATION OF POLY[(METHYLSILYLENE ETHYNYLENEPHENYLENEETHYNYLENE)-CO-(DIMETHYLSILYLENE ETHYNYLENEPHENYLENEETHYNYLENE)]S

A series of poly[（methylsilylene ethynylenephenyleneethynylene）-co-（dimethylsilylene ethynylenephenyleneethynylene）]s were synthesized by the incorporation of various ratios of methylsilylene to dimethylsilylene units into the polymer chain backbone. The resultant copolymers were soluble in a variety of common organic solvents at room temperature. The copolymers were characterized by FT-IR, ^1H-NMR, GPC, rheological analysis, differential scanning calorimetry （DSC） and thermogravimetric analysis （TGA）. The results showed that the copolymers exhibited good processability and cured at low temperatures like 200℃. The curing reactions involved in hydrosilylation of Si-H and alkyne groups and the polymerization of alkynes. Td5 （5% weight loss） of the cured copolymers ranged from 629℃ to 686℃, and the decomposition residues of cured copolymers at 1000℃ ranged from 88.1% to 90.9% under nitrogen. Thermal stability of the copolymers increased with the introduction of methylsilylene traits into polymer chains. The cured copolymers were sintered at 1450℃, and the results of X-ray diffraction analysis showed that β-SIC was formed in the sintered products.

Effect of Reactive Nanoclays on Performances of PMMA/Reactive Nanoclay Nanocomposites

PMMA/reactive nanoclay nanocomposites were prepared by emulsion polymerization using two different reactive nanoclays. X-ray diffraction（XRD） and thermogravimetric analysis（TGA） results confirmed that the reactive nanoclays, kaolinite and montmorillonite, were obtained by the silylation reaction and the double bonds were grafted onto the edges and surfaces of the nanoclays. The presence of reactive nanoclays could increase the average molecular weights, the glass transition temperatures（Tg） and improve the thermal properties of nanocomposite. The tensile properties, Young＇s modulus, and the aging properties of the nanocomposite films were also enhanced while the light transmittance decreased. Furthermore, the nanocomposites with the reactive kaolinite presented better performances than that with the reactive montmorillonite. Finally, the action mechanism of the reactive nanoclays to the performances of PMMA/reactive nanoclay nanocomposites was proposed.

Analysis on the Characteristic Properties of PEDOT Nano-particle Based on Reversed Micelle Method

Based on the study of a new type of conducting polymer poly （3,4-ethylenedioxythiophene） （PEDOT）,we focussed on the preparation and characteristics of PEDOT nanoparticles made by reversed micelle method.Moreover,we deeply investigated the optical,electrical and the thermal stability of PEDOT nanoparticles.The main results are as follows： the small-sized PEDOT nanoparticles were prepared and utilized by different methods,such as ultraviolet/visible （UV-Vis） spectroscopy,Fourier-transform infrared （FT- IR） spectrum,scanning electron microscopy（SEM） and so on.The results show that the amount of oxidizer,ultrasonic treatment,polymerizing temperature and doping degree can influent morphology,electrical ability and gas sensitivity of PEDOT nanoparticles.The Bragg peaks of nanoparticles at 6.7°,12.7°,25° were observed by XRD and the better orientation of molecular chain was attributed to the effective doping of toluene-p-sulfonic acid,which also resulted in an enhancement of thermal stability of nanoparticles than conventional PEDOT.

Preparation and characterization of conducting polymer-coated thermally expandable microspheres

The thermally expandable microspheres（TEMs） were prepared via suspension polymerization with acrylonitrile（AN）, methyl methacrylate（MMA） and methyl acrylate（MA） as monomers and n-hexane as the blowing agent. Meanwhile, a novel type of functional and conductive thermal expandable microsphere was obtained through strongly covering the surface of microsphere by conductive polymers with the mass loading of 1.5%. The optimal conditions to prepare high foaming ratio and equally distributed microcapsules were investigated with AN-MMA-MA in the proportion of 70%/20%/10%（m/m/m）, and 25 wt% of n-hexane in oil phase. The further investigation results showed that the unexpanded TEMs were about 30 μm in diameter and the maximum expansion ratio was nearly 125 times of original volume. The polypyrrole（PPy） was smoothly coated on the surface of the TEMs and the expansion property of PPy-coated TEMs was almost the same as the uncoated TEMs. Moreover, the structure and expanding performance of TEMs and PPy-coated TEMs were characterized by scanning electron microscopy（SEM）, laser particle size analyzer and dilatometer（DIL）.

Self-polymerization and co-polymerization kinetics of gadolinium methacrylate

Gadolinium methacrylate（Gd（MAA）3） was synthesized by using gadolinium oxide and methacrylic acid as the starting materials and its self-polymerization kinetic was studied based on non-isothermal and isothermal analysis. Moreover, the monomer reactivity ratios of methyl methacrylate（MMA） and Gd（MAA）3 were evaluated by using Kelen-Tiidos method. The thermal neutron shielding properties of PMMA and poly（MMA-co-Gd（MAA）3） were calculated by MCNP program. The results show that the selfpolymerization of Gd（MAA）3 can be initiated by thermal and free radical and its activation energy is103.35 kJ/mol or 58.55 kJ/mol correspondingly in the solid state or aqueous solution. The polymerization rate,Rp,under low conversion at 65 ℃ is expressed as Rp = K[M]^（1.05）[I]^（0.60）. The reactivity ratios of r1（MMA） and r2（Gd（MAA）3） are 0.225 and 1.340, respectively. The ability of thermal neutron shielding of poly（MMA-co-Gd（MAA）3） is increased by gadolinium contents and is far better than PMMA.

In situ and ex situ synthesis of poly（vinyl alcohol）-Fe304 nanocomposite flame retardants

Application of flame retardants is limited because of environmental requirements. This work introduces conventional magnetic nanoparticles as a new class of nontoxic and effective flame retardant. Fe3O4 enhanced both the thermal stability and flame retardant properties of a poly（vinyl alcohol） matrix. Nanoparticles were synthesized via a simple precipitation reaction without using an inert atmosphere at room temperature. The effects of different precursors and acrylamide on the morphology of the products were investigated. Nanoparticles exhibited a ferrimagnetic behavior at room temperature. To prepare the magnetic nanocomposite, Fe3O4 nanoparticles were added to the poly（vinyl alcohol）. In the presence of a flame, the magnetic nanoparticles remained together, showed resistance to dripping and protected the polymer matrix. Dispersed nanoparticles play a role of a magnetic barrier layer, which slows product volatilization and prevents flames and oxygen from reaching the sample during decomposition of the polymer.

Novel synthesis with an atomized microemulsion technique and characterization of nano-calcium carbonate(CaCO_3)/poly(methyl methacrylate) core-shell nanoparticles

The synthesis of hard-core/soft-shell calcium carbonate （CaCO3）/poly（methyl methacrylate） （PMMA） hybrid structured nanoparticles （〈100nm） by an atomized microemulsion polymerization process is reported. The polymer chains were anchored onto the surface of nano-CaCO3 through use of a cou- pling agent, triethoxyvinyl silane （TEVS）. Ammonium persulfate （APS）, sodium dodecyl sulfate （SDS） and n-pentanol were used as the initiator, surfactant and cosurfactant, respectively. The polymeriza- tion mechanism of the core-shell latex particles is discussed. The encapsulation of nano-CaCO3 by PMMA was confirmed using a transmission electron microscope （TEM）. The grafting percentage of the core-shell particles was investigated by thermogravimetric analysis （TGA）. The nano-CaCO3/PMMA core-shell par- ticles were characterized by Fourier transform infrared （FTIR） spectroscopy and differential scanning calorimetry （DSC）. The FTIR results revealed the existence of a strong interaction at the interface of the nano-CaCO3 particle and the PMMA, which implies that the polymer chains were successfully grafted onto the surface of the nano-CaCO3 particles through the link of the coupling agent, In addition, the TGA and DSC results indicated an enhancement of the thermal stability of the core-shell materials compared with that of the pure nano-PMMA, The nano-CaCO3/PMMA particles were blended into a polypropylene （PP） matrix by melt processing. It can also be observed using scanning electron microscopy （SEM） that the PMMA chains grafted onto the CaCO3 nanoparticles interfere with the aggregation of CaCO3 in the polymer matrix （PP matrix） and thus improve the compatibility of the CaCO3 nanoparticles with the PP matrix.

Synthesis of a novel naphthyl-based self-catalyzed phthalonitrile polymer

A novel naphthyl-based self-catalyzed phthalonitrile monomer was prepared via nucleophilic displacement reaction. The structure was characterized by Fourier infrared spectrum （FT-IR） and nuclear magnetic resonance （^1H NMR）. The polymerization mechanism was explored. Thermal properties were characterized by differential scanning calorimetry （DSC） and thermogravimetric analysis （TGA）, which demonstrated self-promoted behavior and excellent heat resistance.