Synthesis of multifunctional additives for solid propellants:Structure,properties and mechanism

To simplify the composite propellant formulation and address the current issue of the single-functionality present in existing additives,the multi-cyano,amine-based polybutadiene(AEHTPB-CN)was prepared based on AEHTPB by adopting appropriate synthesis strategies.By replacing 10% of HTPB binder in the propellant formulation,it can effectively enhance the interfacial bond strength between the propellant binder matrix and solid fillers(AP(ammonium perchlorate)and RDX(cyclotrimethylene-trinitramine)),the mechanical properties of the HTPB/AP/RDX/Al propellant were superior to blank control propellant with an improvement of 35.4% in tensile strength,62.0% enhancement in elongation at break,and reduce the propellant burn rate by 10.7% with any energy loss.The function mechanism of AEHTPB-CN was systematically elucidated through experiments and computer simulation techniques.The results show that the tertiary amine group in AEHTPB-CN can react with AP to form ammonium ionic bonds,and the hydroxyl and cyano groups can form hydrogen bonding interactions with AP,which enables AEHTPB-CN to be firmly adsorbed on the AP surface through chemical and physical interactions.For RDX,the interfacial bonding effect of AEHTPB-CN is attributed to their ability to form C-H···N≡C weak hydrogen bonding interaction between the cyano group and RDX methylene group.

Investigation of hydroxyl-terminated polybutadiene propellant breaking characteristics and mechanism impacted by submerged cavitation water jet

A submerged cavitation water jet(SCWJ)is an effective method to recycle solid propellant from obsolete solid engines by the breaking method.Solid propellant's breaking modes and mechanical process under SCWJ impact are unclear.This study aims to understand those impact breaking mechanisms.The hydroxyl-terminated polybutadiene(HTPB)propellant was chosen as the research material,and a self-designed test system was used to conduct impact tests at four different working pressures.The high-speed camera characterized crack propagation,and the DIC method calculated strain change during the impact process.Besides,micro and macro fracture morphologies were characterized by scanning electron microscope(SEM)and computed tomography(CT)scanning.The results reveal that the compressive strain concentration region locates right below the nozzle,and the shear strain region distributes symmetrically with the jet axis,which increases to 4% at first 16th ms,the compressive strain rises to 2% and 6% in the axial and transverse direction,respectively.The two tensile cracks formed first at the compression strain concentrate region,and there generate many shear cracks around the tensile cracks,and those shear cracks that develop and aggregate cause the cracks to become wider and cut through the tensile cracks,forming the tensile-shear cracks and the impact parts eventually fail.The HTPB propellant forms a breaking hole shaped conical after impact 10 s.The mass loss increases by 17 times at maximum,with the working pressure increasing by three times.Meanwhile,the damage value of the breaking hole remaining on the surface increases by 7.8 times while 2.9 times in the depth of the breaking hole.The breaking efficiency is closely affected by working pressures.The failure modes of HTPB impacted by SCWJ are classified as tensile crack-dominated and tensile-shear crack-dominated damage mechanisms.

Mechanical properties of thermal aged HTPB composite solid propellant under confining pressure

With the purpose of investigating the effects of confining pressure and aging on the mechanical properties of Hydroxyl-terminated polybutadiene(HTPB)based composite solid propellant,tensile tests of thermal accelerated aged propellant samples under room temperature and different confining pressure conditions were performed through the use of a self-made confining pressure device and conventional testing machine.Afterwards,the maximum tensile stressσmand the corresponding strainεm for the propellant under different test conditions were obtained and analyzed.The results indicate that confining pressure and aging can significantly affect the mechanical properties of HTPB propellant,and the coupled effects are very complex.On the one hand,the stressσmincreases as a whole when confining pressure becomes higher or thermal aging time rises.Besides,this stress is more sensitive to aging with increasing confining pressure.There are almost three regions in the stress increments(σm P-σm0)/σm0and thermal aging time curves for HTPB propellant.The maximum value of the stress increment(σm P-σm0)/σm0for the propellant is about 98%at 7.0 MPa and 170 d.On the other hand,the strainεm decreases with increasing thermal aging time under the whole confining pressure conditions.However,the variation of this strain with confining pressure is more complex at various thermal aging time,which is different from that of unaged solid propellant in previous researches.In addition,this strain is slightly less sensitive to aging as the confining pressure increases.Furthermore,there is also a critical confining pressure in this investigation,whose value is between 0.15 MPa and 4.0 MPa.Beyond this critical pressure,the trends of the stressσmand the corresponding strainεm all change.Moreover,there are some critical thermal aging time for the stress increment(σm P-σm0)/σm0and strain increment(εm P-εm0)/εm0of HTPB propellant in this investigation,which are about at 35,50 and 170 d.Finally,based on the twin-shear strength theory,a new modified nonlinear strength criterion of thermal aged HTPB propellant under confining pressure was proposed.And the whole errors of fitted results are lower than 6%.Therefore,the proposed strength criterion can be selected as a failure criterion for the analysis the failure properties of aged HTPB propellant under different confining pressures,the structural integrity of solid propellant grain and the safety of solid rocket motor during ignition operation after long periods of storage.

Composite Solid Rocket Propellant Based on GAP Polyurethane Matrix with Different Binder Contents

Different GAP-based CSRP samples with different binder contents were prepared and compared with that of conventional HTPB propellant.The crosslinker mixture of trimethylol propane(TMP)and butane diol(BD)was used in the GAP matrix beside the addition of dibutyltin dilaurate(DBTDL)to ensure cross-linking and curing completion of the prepared CSRP.The viscosity and hardness of all prepared formulations were monitored continuously during the curing process.The mechanical characteristics of cured samples were tested.The burning rate at operating pressure and specific impulse were measured,while the theoretical specific impulse(I sp)was calculated by ICT code and compared with the measured results.According to the results,DOA was found to be a suitable plasticizer for GAP when using in propellant.The mechanical properties of CSRP with 25%GAP can produce the optimum mechanical behavior,which is close to that of HTPB-based CSRP.The optimum GAP-based formulation is one candidate to replace the traditional HTPB-based CSRP with high burning rate for some applications.

MORPHOLOGY OF POLYBUTADIENE “SHISH KEBABS”

Shish kebab structure of cis-1 , 4-polybutadiene has been obtained by quiescent solution crystallization at suitable temperature. The morphology and growth mechanism of formation of shish kebab structure have been studied in detail.The higher the molecular weight the faster the sample crystallizes.

CURE CHARACTERISTICS OF HYDROXYL TERMINATED POLYBUTADIENE PREPOLYMER WITH BLOCKED TOLUENE DIISOCYANATE-Ⅱ

Cure characteristics of hydroxyl terminated polybutadiene (HTPB) prepolymer with avariety of blocked toluene diisocyanate (TDI) in the presence of triethylamine (TEA) andchloroacetic acid catalyst are reported. Phenol, thiophenol, p-chloropheno1, p-nitrophenol,p-cresol, resorcinol, naphthols, caprolactam and butylated-hydroxytoluene were used as blockingagents. Viscosity measurements have been carried out using a mixture of HTPB and blocked TDIin cyclohexanone in the presence of the catalysts at 50℃ and 60℃ using Haake rotational vis-cometer. Viscosity measurements have also been carried out with 50% solids such as ammonium sulphate along with HTPB and TDI adduct.

POLYMER SCIENCE AND TECHNOLOGY IN THE PAST AND THE FUTURE:HEROISM,EXPLORATION AND ENLIGHTENMENT

The scientific and technical history of polymerization can be divided into three periods, which will be illustratedfor emulsion polymerization. The first period was when emulsion polymers were originally produced, and was developed asan attempt to copy natural rubber latex. Indeed, the natural process is quite different from the synthetic process of emulsionpolymerization, which in fact does not even need an emulsion to be present: the term is a misnomer! The results werefunctional but limited. In the second period, the first theories appeared, and a huge range of products was madefor surface coatings, adhesives, commodity polymers such as SBR, neoprene, etc. The work of the outstanding pioneers wasbased on limited types of experimental data, and some suppositions are now seen to be incorrect. Nevertheless, manyexcellent products were made and have evolved to many materials currently in everyday use. The third period of emulsionpolymerization is now dawning. The scientific efforts of many teams over previous decades, aided by the advent of newphysical techniques for investigation, have resulted in better understanding of the fundamentals of emulsion polymerizations.Some examples from the author’s group involve creating novel materials using controlled seeded emulsion polymerizationfrom natural rubber latex and other polyenes. Latex topology and controlled free-radical chemistry can be combined toproduce a) a comb polymer with hydrophobic backbone and hydrophilic "teeth", or b) with sufficient in situ compatibilizerbetween two otherwise incompatible polymers to yield a spatially uniform material down to the nanostructure level, and c) toproduce controlled nanostructures.

SYNTHESIS OF POLYBUTADIENE MACROINITIATOR AND POLYBUTADIENE/POLYACRYLAMIDE BLOCK COPOLYMERS

An azo-group containing polybutadiene macroinitiator was prepared by Pinner synthesisand characterized by IR, NMR, GPC, viscosity and elemental measurements. Themacroinitiator was further used to polymerize acrylamide (AAm) in benzene to formpolybutadiene/polyacrylamide (PBD/PAAm) block copolymers. High conversion of AAm wasobtained over a wide range of monomer/macroinitiator ratios. The PBD/PAAm blockcopolymers.were found to have excellent solvent resistance.

A NEW POLYBUTADIENE

High active catalyst systems for polymerization of butadiene may be obtained by combining MoCl,ORand proper aluminum alkyl.The conversion of 80% of butadiene can be achieved with 5x10-5 mole ofMoCl4OCH17per mole of butadiene at 70℃ in hydrogenated gasoline.The polydispersity of the polymersin the range of 1.5—2.0 is carried out with the temperature of polymerization at 30—70℃.For the purpose ofregulating molecular weight and chain structure of the polymers allyl halides is satisfactory,among othersallyl iodide is the best.With increase of amount of allyl iodide,the molecular wieght of the polymers de-crease,the 1,2-units increase and the regularity of chain structure of the polymers rises.Some of the physicalproperties of the polymers are as follows:the content of 1,2-units,88——97%;limiting viscosity number,1.8——6.2（in 30℃,toluene）;glass temperature,-27——10℃:tensile yield strength,6.5——8.5（kg/cm2）;ultimate tensile strength,12——25（kg/cm2）and elongation at break,1700—2900%.

Effects of Plasticizers,Antioxidants and Burning Rate Modifiers on Aging Performance of the HTPB/HMDI Composite Solid Propellant

The effects of plasticizers,antioxidants and burning rate modifiers on the aging performance of the composite solid propellant based on hydroxyl-terminated polybutadiene(HTPB)/hexamethylene diisocyanate(HMDI)were explored by apply-ing an accelerated aging program for 90 day at 70 ℃. The HTPB propellant matrix with the diisooctyl sebacate(DOS)as plasti-cizers and diisooctyl azelate(DOZ), antioxidants as N,N ′-Diphenyl-p-phenylenediamine(AO) and 2,2′-methylenebis(4-methyl-6-tert-butylphenol)(cyanox 2246)and burning rate modifiers as barium ferrite(BF),copper chromites(CC)and fer-ric oxide(FO)were varied. Results show that sample(S1)which based on DOS decreases the stress value and increases the strain value which considered to be an excellent start for aging program. Sample(S3)containing AO presents the higher resis-tance to oxidation showing the better performance that reflects on increasing the shelf life of the composite solid propellant mo-tor. Sample(S5)which based on BF enhances the ballistic performance among over the other tested two samples. The accelerat-ed aging program allowed us to estimate the motor in-service lifetime.

Citrus oils as chain transfer agents in the cross-metathesis degradation of polybutadiene in block copolymers using Ru-alkylidene catalysts

The cross-metathesis degradation of poly(styrene-co-butadiene) (styrene, 30 wt%) (SB-1) and poly(styrene-co-butadiene) (styrene, 21 wt%) (SB- 2) in the presence of essential oils and d-limo-nene as chain transfer agents (CTAs) using Rualkylidene catalysts (PCy3)2(Cl)2Ru = CHPh (I) and (1,3-diphenyl-4,5-dihydroimidazol-2-ylidene) (PCy3)Cl2Ru=CHPh (II) was studied. Terpene-terminated butadiene oligomers and polystyrene blocks were obtained as products of the degradation of SB-1 and SB-2. Catalysts I and II showed high activity in the degradation of SB copolymers to produce the low molecular weight products (Mn = 276 - 335 g·mol-1) and yields ranging from 91% - 95%. The cross-metathesis degradation of copolymers in organic solvents and in citrus oils (mandarin, orange and lemon oils) proceeded with similar efficiency and resulted in the same molecular weight butadiene oligomers. According to GS/MS (EI) analysis, the main products of the degradation of SB-1 copolymer with d-limonene were limonene-terminated oligomers of series Am (m = 1 - 4).

Rapid Self-healing and Strong Adhesive Elastomer via Supramolecular Aggregates from Core-shell Micelles of Silicon Hydroxyl-functionalized cis-Polybutadiene

Liquid trimethoxy silane-functionalized cis-polybutadiene(cis-PB-Si(OMe)3),possessing number-average molecular weights of cis-PB segments(Mn,PB)ranging from 1800 g/mol to 5400 g/mol,with cis-1,4 content of ca.80%and high functionality(>96%)could be synthesized by coordination copolymerization of living cis-PB chain ends with ethenyltrimethoxy-silane with neodymium-based catalytic system.The silicon hydroxyl-functionalized cis-polybutadiene(cis-PB-Si(OH)_(3))-based micelles in water have been achieved by in situ hydrolysis of cis-PB-Si(OMe)_(3)in hexane/water mixture(pH=6.8)at 70℃and by sequential removal of residue hexane.The size of the above micelles with soft elastic cis-PB cores could be remarkably enlarged by loading SiO_(2)nanoparticles on their surfaces via hydrogen bonding interaction.Giant supramolecular long chain aggregates or networks formed by hydrogen bonding interaction and possible O—Si—O chemical bonds between cis-PB-Si(OH)3-based micellar surfaces had relatively large size and thus precipitated from water after several months of storage,leading to production of cis-PB-Si(OH)_(3)solid elastomer with extremely low T_(g)at−107.0℃.The left cis-PB-Si(OH)_(3)-based micelles in water with relatively small size gradually formed the water-insoluble cis-PB-Si(OH)_(3)-based supramolecular aggregates or networks.The cis-PB-Si(OH)_(3)-based supramolecular elastomer exhibited excellent self-healing property within 60 s at 25℃.The elastomer(20 mg)in a joint of 25 mm×30 mm(2.7 mg/cm^(2))provided very strong adhesion for two pieces of glass and the bound glass keep unchanged at room temperature for 98 h even hung with 100 g of steel column below.The cis-PB-Si(OH)3-based supramolecular elastomer would have potential applications in adhesives,self-healing materials,damping materials and elastic materials.

Synthetic rubbers prepared by lanthanide coordination catalysts

China is rich in rare earth resources. Rare earth elements, also named lanthanides, are number 58 to number 81 elements in the elemental periodic table. They have unique electronic structures and may form various coordination compounds. In the early 1960s, researchers at the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences (CIAC) found the catalytic activities of lanthanide compounds in stereospecific polymerization of conjugated dienes, and published the first paper on this topic in 1964. On the basis of this finding, CIAC launched extensive research activities on lanthanide compounds as diene polymerization catalysts, from a series of fundamental research to the efforts of industrializing the rare earth catalyzed cis-1,4-polybutatine rubber and cis-1,4-polyisoprene rubber. This review aims to summarize the progress in this field in the past half century.

A study of solid ramjet fuel containing boron–magnesium mixtures

Solid fuel ramjets (SFRJ) are known for their operational simplicity and high specific impulse. The performance of the SFRJ propulsion system is directly tied to the energy density and combustion behavior of the fuel. A typical solid fuel used in a ramjet application is a collection of metal particles suspended in a polymeric binder. Boron is the ubiquitous candidate when considering metal additives for fuels due to an impressive 122.5 kJ/cm3 energy density. However, boron requires long residence times in combustors due to its high melting and boiling points. Magnesium appears to be a natural complement to boron;while possessing a lower energy density (42.1 kJ/cm3), it burns with a high flame temperature and readily reacts in combustion with a low melting point. In this study, several HTPB–boron–magnesium fuels are studied on a small scale to evaluate performance for ramjet application. Holography experiments are conducted, as well as laser ignition tests, to study particle behavior just above the fuel surface. Small, center-perforated fuel grains are examined in a direct-connect SFRJ test stand configuration to measure ignition temperatures and performance parameters. Combustion efficiency of the HTPB–boron–magnesium fuel is found to significantly increase for one of the fuels studied.

1,3-Butadiene Polymerizations Catalyzed by Cobalt and Iron Dichloride Complexes Bearing Pyrazolylimine Ligands

A series of pyrazolylimine ligated Co(II) and Fe(II) complexes with general formula of(PhC=N(C_6H_3(R_1)2-2,6)(C_3 HN_2(R_2)2-3,5)MtCl_2(R_1 = Me, R_2 = H, Mt = Co(1 a), Fe(2 a); R_1 = Me, R_2 = Me, Mt = Co(1b), Fe(2b); R_1 = iPr, R_2 = H, Mt = Co(1 c), Fe(2 c); R_1 = i Pr, R_2 = Me, Mt = Co(1 d), Fe(2 d); R_1 = i Pr, R_2 = Ph, Mt = Co(1 e), Fe(2 e)) were synthesized and thoroughly characterized.Determined by single crystal X-ray diffraction, complexes 1 b and 2 b revealed dimeric structures, in which distorted trigonal bipyramid geometries were adopted for each metal centers. In the presence of ethylaluminum sesquichloride(EASC), all the cobalt complexes displayed high activities in 1,3-butadiene polymerization, affording polybutadienes with predominant cis-1,4 contents(up to 97.0%).Influences of ligand structure and polymerization parameters on catalytic performance were investigated systematically. For pyrazolylimine iron(II) dichloride complexes, the catalytic activities and microstructures of the resultant polybutadienes were highly dependent on ligand structures and polymerization conditions. For complex 2 a, changing cocatalyst from trialkyl aluminums to methyl aluminoxane(MAO) led to an shift of selectivity from high cis-1,4-to trans-1,4-/1,2-manner. Being activated by MAO, complexes 2 a and 2 b gave trans-1,4-/1,2-binary polybutadienes, while complexes 2 c, 2 d, and 2 e afforded cis-1,4-enriched polymers.

Radiation-induced pyrolysis of solid fuels for ramjet application

A wide variety of hydroxyl-terminated polybutadiene(HTPB)based fuels areexperimentally assessed in anaerobic reaction.In this study HTPB pyrolysis is investigatedusing a CO laser as the energy source.The formulation of the solid fuel samples issystematically changed to isolate the effects of carbon black,metal fuel additives,and smallamounts of oxidizer.In addition,chemical changes to the fuels including curative type andbase polymer are varied.Rates of pyrolysis reaction are reported for a wide range of solid fuelsapplicable to ramjet application.Processes involving the sintering together of metal particles,accumulation of carbon black,and formation of a melt layer are found to affect the reactionrate.It is determined that the surface composition is the most influential factor influencing theregression rate of HTPB based fuels.

Broadening of appropriate demulsifier dosage range for latexcontaining wastewater by sulfate addition

Investigation of demulsification of polybutadiene latex (PBL)wastewater by polyaluminum chloride (PAC)indicated that there was an appropriate dosage range for latex removal.The demulsifieation mechanism of PAC was adsorption-charge neutralization and its appropriate dosage range was controlled by zeta potential.When the zeta potential of the mixture was between -15and 15mV aider adding PAC,the demulsification effect was good.Decreasing the latex concentration in chemical oxygen demand (COD)from 8.0g/L to 0.2g/L made the appropriate PAC dosage range narrower and caused the maximum latex removal efficiency to decrease from 95%to 37%.Therefore,more accurate PAC dosage control is required.Moreover,-adding 50mg/L sulfate broadened the appropriate PAC dosage range,resulting in an increase in maximum latex removal efficiency from 37%to 91%for wastewater of 0.2g COD/L.The addition of sulfate will favor more flexible PAC dosage control in demulsification of PBL wastewater.

Study of entangled network formation in concentrated solutions of polymer by ^(13)C NMR

Information about the exact location of topological and cohesional entanglements at molecular level has been obtained by 13C NMR relaxation analysis. The results show that about 20% of the carbon atoms in the main chain are entangled in the 25% (by weight) solution, which is independent of the content of the 1,2-segment in polybutadiene and of the kind of solvent. However, the entanglement of the carbon atone on the end group of the side chain is very weak, they behave as slipping freely at the junctions.

Anti-corrosive, weatherproof and self-healing polyurethane developed from hydrogenated hydroxyl-terminated polybutadiene toward surface-protective applications

Self-healing polyurethane(PU)faces aging deterioration due to active dynamic bonds,which remain a challenging predicament for practical use.In this work,a novel strategy is developed to address this predicament by leveraging the hydrophobicity and gas barrier of hydrogenated hydroxyl-terminated polybutadiene(HHPB).The dynamic oxime-carbamate bonds derived from 2,4-pentanedione dioxime(PDO)enable the elastomer to exhibit surface self-repairability upon applied mild heat and achieve~99.5%mechanical self-healing efficiency.The mechanical properties remained nearly intact after 30-d exposure to thermal oxidation,xenon lamp,acids,bases,and salts.Gas permeability,positron annihilation lifetime spectroscopy(PALS),and contact angle measurements reveal the pivotal role of gas barrier,free volume,and hydrophobicity in blocking undesirable molecules and ions which effectively protects the elastomer from deterioration.HHPB-PU also exhibits excellent adhesion to steel substrate.The shear strength achieves(3.02±0.42)MPa after heating at 80°C for 4 h,and(3.06±0.2)MPa after heating at 130°C for 0.5 h.Regarding its outstanding anti-corrosive and weatherproof performances,this self-healable elastomer is a promising candidate in surface-protective applications.

Hydroxyl-terminated Polyethylenes Bearing Functional Side Groups:Facile Synthesis and Their Properties

A series of hydroxyl-terminated polyethylenes(HTPE)bearing various functional side groups(e.g.carboxyl,ester and butane groups)were synthesized by the combination of ring opening metathesis polymerization(ROMP)and visible light photocatalytic thiol-ene reaction.The products are named as a,w-dihydroxyl-polyllpropionyloxythio)methinetrimethylene](HTPECarboxy),a,w dihydroxy-poly(methylpropionatethio)methinetrimethylene](HTPEeser)and a,wdihydroxyl-poly[(butylthio)methinetrimethylene](HTPEbutane)respectively.The investigation of ROMP indicated that the molecular weight of resultant hydroxy-terminated polybutadiene(HTPB)can be tailored by varying the feed ratios of monomer to chain transfer agent(CTA).The exploration of the photocatalytic thiol-ene reaction between HTPB precursor and methyl-3-mercaptopropionate revealed that blue light as well as oxygen accelerated the reaction.1H-NMR and 13C-NMR results verified all the double bonds in HTPB can be modified,and the main chain of resultant polymer can be considered as polyethylene.Subsequently,relationship between the structure of side groups and the thermal properties of functional PEs was studied.And the results suggested that the Tg was in the order of HTPEbuane<HTPEester<HTPEarboxy+.Greater interaction between side groups resulted in higher Tg.Moreover,all the functional PE samples exhibited poor thermostability as compared to HTPB.Finally,the promising applications for functional PEs were explored.HTPEcarboxy1 can be utilized as a smart material with pH-responsive properties due to its pH-dependent ionization of carboxyl side groups.HTPEbutane can be employed as a macro-initiator for building the triblock copolymer due to the presence of active hydroxyl end groups.HTPEester can serve as a plasticizer for PVC which can enhance the ductilityt of PVC without obviously sacrificing strength.