The effect of reactive plasticizer on viscoelastic and mechanical properties of solid rocket propellants based on different types of HTPB resin

Conventional plasticizers deteriorate mechanical and viscoelastic properties of the propellants due to their migration upon aging and long-term storage,which affects reliability and safety properties during exploitation.To address this issue,conventional plasticizer,dioctyl adipate(DOA),is replaced by reactive one,castor oil(CO).In addition,three different types of HTPB were used to obtain propellants with designed viscoelastic and mechanical properties.The CO increased propellants viscosity,without a significant impact on the propellant processability,regardless to the type of prepolymer.Conversely,mechanical properties were different depending on the type of resin,which were further analyzed by gel permeation chromatography(GPC).Addition of CO formed a denser polymer network and shifted T_(g) to higher values,compared to the compositions with DOA.The tensile strength of CO-containing propellants was lower at +20℃ and +50℃ compared to the reference compositions,while the strain at maximum load and strain at break were significantly increased with pronounced plastic deformation,especially for samples at -30℃.The inclusion of CO in the propellants composition gives more room for adjusting a wide range of mechanical properties.

Research Progress of Environment Friendly Plasticizers for Cellulose Acetate Processing

Cellulose acetate(CA)is an important cellulose derivative that can undergo thermoplas-tic processing.Plasticizers can form stable hydrogen bonds with CA molecular chains,reducing intermolecular and intramolecular interactions,and play an important role in the melting processing of CA.In recent years,environmentally friendly plasticizers that are natural,non-toxic,odorless,low dissolution,and low migration have received increas-ing attention in plastic processing.This article reviews the research progress of environ-mentally friendly plasticizers such as natural plasticizers,ionic liquid plasticizers,citrate plasticizers,and polyethylene glycol plasticizers in the processing of cellulose acetate,and looks forward to the application prospects of environmentally friendly plasticizers.

Understanding the alkyl effect of geminal dinitropropyl ester energetic plasticizers on hydroxyl terminated polybutadiene(HTPB):Simultaneous tuning on low temperature behavior and processability

Geminal dinitropropyl ester plasticizers(DNPEPs) possess excellent energetic performances which provide good potentials as insensitive plasticizer. In this study, we design and synthesize DNPEPs with different alkane chain parts, and systematically investigate their structure-property relationships.Results show that DNPEPs have impact sensitivities all higher than 25.2 J, thermal decomposition temperatures all higher than 254 ℃, and glass transition temperatures(T_(g)) lower than-90 ℃.Furthermore, the effects of DNPEPs as plasticizer are studied on hydroxyl terminated polybutadiene(HTPB) in detail, including the viscosity, glass transition temperatures and others. It is noteworthy that 2,2-dinitropropyl nonanoate(DNPNc) among these DNPEPs exhibits the most expected simultaneous tuning effects on both viscosity and T_(g) of HTPB systems, providing favorable potentials to replace the conventional plastizers as dioctyl sebacate(DOS) in the HTPB based propellants and explosives.

Phosphorus Containing Rubber Seed oil as a Flame Retardant Plasticizer for Polyvinyl Chloride

The application of phthalate plasticizers has been restricted around the world due to their poor migration and potential harm to the human body.Hence,producing functional bio-based plasticizers via exploiting clean and reusable resources meets the satisfaction of current demands.In this study,flame-retardant rubber seed oil-based plasticize(FRP)was prepared via epoxidation reaction and ring opening addition reactions,which was used as a flame-resistant plasticizer for polyvinyl chloride to replace petroleum-based phthalate plasticizer.When DOP was replaced with FRP,the torque of PVC blends increased from 11.4 to 18.4 N⋅m,the LOI value increased from 24.3%for PVC-FRP-0%to 33.1%for PVC-FRP-20.The THR value diminished from 39 MJ/m^(2)(pertaining to PVC-FRC-0)to 22 MJ/m^(2)Tg increased from 23°C to 47°C,the weight loss of plasticized PVC blends significantly reduced from 22.6%to 2.8%in leaching tests.The study provided a new way to prepare flame retardant plasticizer using rubber seed oil as raw material.

Plasticizing Effect of Camellia oleifera Seed-Oil-Based Plasticizer on PVC Material Modification

In this study,as the plasticizer,Camellia oleifera seed-oil-based cyclohexyl ester(COSOCE)was prepared by the reaction of cyclohexene oxide and refined C.oleifera seed oil(RCOSO)obtained by acidification hydrolysis after saponification.In addition,the structure of the target product was confirmed by Fourier transform infrared(FTIR)spectroscopy,nuclear magnetic resonance(NMR)spectroscopy,and Raman spectroscopy.COSOCE was used as plasticizer-modified polyvinyl chloride(PVC)membranes.The structure of the COSOCE-modified PVC membranes were characterized by Raman spectroscopy and scanning electron microscopy(SEM).The properties of the COSOCE-modified PVC membrane were characterized by contact angle measurements,universal testing machine,thermogravimetric analysis(TGA),and differential scanning calorimetry(DSC).The results revealed that(1)The COSOCE-modified PVC membranes exhibit a good microscopic morphology.Combined with energy-dispersive X-ray spectroscopy(EDS)and contact angle measurement results,the COSOCE-modified PVC membranes are confirmed to be a hydrophilic material.(2)The modified PVC membrane with 60%COSOCE exhibited the best mechanical properties.The tensile strength reached 23.56±2.94 MPa.(3)COSOCE-modified PVC material exhibited better thermal stability,with a loss rate of less than 75%at the end of the first decomposition stage.Compared with that of the dioctyl-phthalate(DOP)-modified PVC membrane,the initial decomposition temperature of PVC was increased by 1.17°C–8.17°C,and the residual rate was increased by 0.67%–5.75%.The carbon–carbon double bond in the COSOCE molecular structure can remove the free radicals generated during the degradation of PVC material and slow down the decomposition rate of PVC.In addition,the double bond can be cross-linked partially with the PVC molecular chain containing the conjugated polyene structure,thereby increasing the movement resistance of the PVC molecular chain segment.Hence,COSOCE can replace DOP as a PVC plasticizer.

Synthesis of aliphatic amidediol and used as a novel mixed plasticizer for thermoplastic starch

In this paper,aliphatic amidediol was synthesized and mixed with glycerol used as a plasticizer for preparing thermoplastic starch（AGPTPS）.The yield of aliphatic amidediol was 91%.FF-IR expressed that the mixture of aliphatic amidediol and glycerol formed stronger and stable hydrogen bond with starch molecules compared to the native cornstarch.By scanning electron microscope（SEM）native cornstarch granules were proved to transfer to a homogeneous continuous system.After being stored for a period time at room temperature,the mechanical properties of AGPTPS were also studied.As a mixed plasticizer,aliphatic amidediol and glycerol would be practical to extend TPS application scopes.

Effect of Compounding of Sodium Tripolyphosphate and Super Plasticizers on the Hydration of α-calcium Sulfate Hemihydrate

The inhibition and its mechanism of sodium tripolyphosphate （STP） composited with super plasticizers （SPs） on hydration of α-calcium sulfate hemihydrate were studied by setting time, strength, hydration heat, X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, electronic probe micro analysis （EPMA）, scanning electron microscopy （SEM） and differential scanning calorimeter （DSC） measurements. The experimental results show that compared with STP addition, compositing STP with polycarboxylate （PC） plasticizer, the final setting time is prolonged from 0.5h to 2hs. While formulating STP with naphthalene-based plasticizer （NAP） or sulfonate melamine formaldehyde plasticizer （SMF）, the final setting time is reduced to quarter of an hour. Similar changes can also be found in the rate of exothermic hydration and hydration degree. Formulating STP with suitable addition of PC can enhance the strength, while compositing STP and NAP or SMF weakens the strength. Besides, adding STP or STP and SMF, obvious movement （more than 1ev） of binding energy of Ca2p1/2 and Ca2p3/2 is detected. Compared with STP addition, content of the characteristic element （P） of STP is cut down form 1.1% to 0.49% by compositing STP with SMF. Furthermore, as hydration age increases, hydration inhibition in the presence of admixtures weakens and even disappears within 56 h.

Studies on Epoxidised Castor Oil as Co-Plasticizer with Epoxidised Soyabean Oil for PVC Processing

An acidic cation exchange resin has been used to prepare epoxidised castor oil(ECO)which was used as a co-plasticizer with epoxidised soyabean oil(ESBO)for processing polyvinyl chloride(PVC).The structure of ECO was confirmed and its physico chemical properties were evaluated.PVC/(ESBO&ECO)blends were prepared by melt mixing and compression molded into sheets.The specimens were evaluated for tensile properties,impact strength and hardness.While the tensile strength did not vary much,the elongation reduced with the replacement of ESBO with ECO.Dynamic mechanical studies revealed that the glass transition temperature increased with incorporation of ECO,however,the storage modulus was not altered much.Replacing 20%of ESBO with ECO resulted in blends with desired thermal and mechanical properties without affecting the processability of PVC.

Synthesis and Kinetics of Hydrogenated Rosin Dodecyl Ester as an Environmentally Friendly Plasticizer

The plasticizer is an important polymer material additive.Non-toxic and environmentally friendly plasticizers are developed recently in order to decrease fossil fuel reserves,serious environmental pollution and the toxicity of phthalate esters.In this study,a new,efficient and environmentally friendly plasticizer of hydrogenated rosin dodecyl ester was prepared by an esterification reaction of hydrogenated rosin and dodecanol.The influences of different reaction conditions(including different catalysts,the catalyst concentration,the ratio of the reactants,reaction temperature,and reaction time)on the esterification yield are examined and discussed.Hydrogenated rosin dodecyl ester with 71.8%yield was synthesized under the optimized reaction conditions(1:0.8 molar ratio of rosin to dodecanol,1 mol%tetrabutyl titanate concentration,and 210℃for 6 h).The esterification reaction is a second-order reaction,and kinetic calculations showed that the activation energy is 39.77 KJ·mol^(−1).The structure of the hydrogenated rosin dodecyl ester was confirmed by FT-IR spectroscopy and^(13)C NMR spectrum.Besides,the thermal stability of target product(hydrogenated rosin dodecyl ester)was also tested by thermal gravimetric analysis(TGA),which showed a good thermal stability.

Thermoplastic Starch Prepared with Different Plasticizers: Relation between Degree of Plasticization and Properties

Ethylene glycol, glycerol, sorbitol, formamide, and urea were used as plasticizers for the preparation of thermoplastic starch（TPS） from corn starch. The properties of TPS were tested by analysis method. The results showed that TPSs were more highly plasticized with amines than alcohols. For the same type of plasticizer, the degree of plasticization decreased as the molecular weight of plasticizer increased. The relationship between plasticization degree and TPS properties was characterized and described by mechanical properties and water absorption. The experimental results showed that when the degree of plasticization increased, the tensile strength decreased and the elongation at breakage and water absorption increased.

Effect of Plasticizers on Properties of Rice Straw Fiber Film

In order to improve the properties of rice straw fiber film, one factor contrast test method was employed. Plasticizer type was chosen as input variable, dry tension strength and elongation, wet tension strength and elongation, bursting strength and tearing strength were chosen as indexes. The results showed that there were significant differences among the means of dry tension strength, dry elongation and bursting strength of different plasticizers; there were not significant differences among the means of wet tension strength, wet elongation and tearing strength of different plasticizers; for dry tension strength and elongation, glycerol had a significant difference with sorbitol and PEG, no significant difference was observed between sorbitol and PEG, dry tension strength added glycerol had been reduced 6.8% compared with that added sorbitol, reduced 9.5% compared with that added PEG; elongation had been improved 6.1% and 9.4%, respectively; for bursting strength, sorbitol had a significant difference with glycerol and PEG, no significant difference was observed between glycerol and PEG; bursting strength added glycerol and added PEG had been improved 6.9% and 5.6%, respectively compared with that of the added sorbitol. The results provided a theoretical reference for further improving the straw fiber film manufacturing process.

Synthesis of Bio-Plasticizer from Soybean Oil and Its Application in Poly(Vinyl Chloride) Films

Herein,epoxidized soybean oil methyl ester(ESOM)plasticizer was synthesized for the preparation of plasticized poly(vinyl chloride)(PVC)films by the alcoholysis and epoxidation.The chemical structure of ESOM was investigated by infrared spectrum and 1 H nuclear magnetic resonance.The effect of content of ESOM and petroleum based plasticizer di-2-ethylhexyl phthalate(DEHP)on the performance of plasticized PVC films was studied.The result showed that substituting DEHP with ESOM can improve the thermal stability of plasticized PVC films.When the weight ratio of ESOM and PVC is fixed at 1:2,plasticized PVC film presents higher elongation at break(350.8%vs.345.1%)and lower tensile strength(14.21 MPa vs.15.8 MPa)compared with PVC plasticized with DEHP.ESOM showed less weight loss than DEHP in all solvents.The excellent migration resistance of ESOM is helpful to improve stability of plasticized PVC films.In all,the obtained bio-based plasticizer will be potential to replace petroleum based plasticizer DEHP in flexible PVC materials.

A Novel Plasticizer for the Preparation of Thermoplastic Starch

in this paper, ethylenebisformamide was synthesized and used as a novel plasticizer for cornstarch to prepare thermoplastic starch （TPS）. FT-IR expressed that ethylenebisformamide formed stronger and stable hydrogen bond with starch molecules compared to the native cornstarch. X-ray diffraction （XRD） showed that the typical A-style crystallinity in the native starch has been destructed. By scanning electron microscope （SEM） native cornstarch granules were proved to transfer to a homogeneous system. After being stored for one week at RH=33%, the mechanical properties of EPTPS was also studied. The elongation reached to 264% utmost. As a novel plasticizer, ethylenebisformamide would be practical to extend TPS application scopes.

Irradiation Effect on Photodegradation of Pure and Plasticized Poly (4-Methylstyrene) in Solid Films

The photodegradation of irradiated thin films of poly (para-methylstyrene) with 265 nm radiations in the presence of airand as a function of irradiation time has been studied using UV-VIS, fluorescence and FT-IR Spectroscopic techniques. The influence of phthalate and terephthalate plasticizers on stability of poly (para-methylstyrene) towards irradiations was also investigated. Blending with phthalate plasticizers was found to cause a higher efficiency of photodegradation than that obtained in doping with terephthalate plasticizers. The intensity of absorption was also found to increase with time of irradiation and in change in the shape of the spectra at longer wavelength, thus indicating a possibility of photodegradation of polymer chains. The analysis of the FT-IR spectra of the irradiated and non-irradiated samples, shows a predominant absorption associated with carbonyl compounds with 1740 cm-1. In addition, the observed increase in the intensities of the carbonyl and hydroxyl regions of the FT-IR spectra, have provided an evidence for the photodegradation as well as photo-oxidation of polymeric chains. The presence of the plasticizer in the polymer backbone was found to accelerate the photodegradation of polymeric chains.

EFFECT OF PLASTICIZER ON THE MICROSTRUCTURE OF PS/PVC BLENDS

In this work, controlling of the particle size of PVC in PS/PVC blends was studied. It is shown that viscosity ratio and particle size can be changed by adding a third composition, such as plasticizers, and the distribution of the third composition in two phases plays a very important role in controlling viscosity ratio and particle size. When DOP was used as the plasticizer of PVC in PS/PVC blends, the particle size of PVC could not be reduced due to the transference of DOP into PS phase. When polycaprolactone (PCL) was used as the plasticizer of PVC in the same blends, the particle size of PVC could be descreased obviously because PCL does not migrate to PS phase.

Insights into biobased epoxidized fatty acid isobutyl esters from biodiesel:Preparation and application as plasticizer

Biodiesel was used to prepare epoxidized fatty acid isobutyl esters(Ep-FABEs)as a biobased plasticizer in this work.Transesterification of biodiesel with isobutanol catalyzed by tetrabutyl titanate was carried out in a gas-liquid tower reactor.The conversion achieved nearly 100%within 5 h under the reaction temperature,the mass ratio of catalyst to fatty acid methyl esters(FAMEs),and isobutanol to FAMEs total molar ratio of 180℃,0.4%(mass),and 5.4:1,respectively.In addition,kinetic model of the transesterification reaction was developed at 150–190℃.The calculated activation energy was 48.93 kJ·mol^(-1).Then,the epoxidation of obtained fatty acid isobutyl esters(FABEs)was conducted in the presence of formic acid and hydrogen peroxide.The Ep-FABEs was further analyzed for its plasticizing effectiveness to replace dioctyl phthalate(DOP)and compared with conventional epoxy plasticizer epoxidized fatty acid methyl esters(Ep-FAMEs).The results indicated that the thermal stability and mechanical properties of PVC films with Ep-FABEs plasticizer were significantly improved compared with those plasticized with DOP.In addition,the extraction resistance and migration stability of Ep-FABEs were better than those of EpFAMEs.Overall,the prepared Ep-FABEs via structural modification of biodiesel proved to be a promising biobased plasticizer.

Rheological Studies on Glycerol Plasticized Gelatin and Its Blends with Epoxidized Soybean Oil

Blends of gelatin(Ge)plasticized with varying amounts of glycerol(Gly),buffer solution pH 10 and epoxidized soybean oil(ESO)to enhance hydrophobicity were prepared by mixing and injection-molding.Blends were characterized by rheological tests and microscopy to select optimal conditions for scaling up their processing.The effect of each component on rheological response was analyzed using parallel plate geometry.Coating of gelatin specimens with PDMS during rheological tests led to reliable and reproducible results since water evaporation was prevented.A gradual increment in ESO concentration led to blends with increased degree of phase separation,as evidenced by optical and confocal microscopy.Limited compatibility between ESO and Ge increased viscosity at high ESO levels,but up to 10%Gly could be replaced with ESO without a significant variation of rheological behavior.

Synthesis of Super Plasticizer NF-30 from Coal Coking by Product Washing Oil and Performance Analysis

Super plasticizer was synthesized by using coal coking by product washing oil and industrial naphthalene. The results show that sulfonationt time （2.5 h）, sulfonation temperature （160 ℃） and condensation time （5.0 h） are key factors. Adding oxidizing agent MO in the course of synthesis can decrease the emission of SO2 in exhaust （20%）. Compared with NF, NF-30 have some advantages in lower cost, high water reducing rate （19.7%） and optimum early strengths. Moreover, TGA-DTA and SEM analysis were adopted to research the NF-30 modified concrete on hydyation mechanism. The analysis show that, compared with NF, there are a large number of hydration products such as Ca （OH）2, C-S-H, AFt etc of NF-30, the structure of NF-30 is dense and the performance is good.

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.

CHARACTERISTICS OF CATION—CONDUCTIVE BLENDS PLASTICIZED WITH PROPYLENE CARBONATE

The cation—conductive blends plasticized with propylene carbonate were prepared. The blends exhibited good mechanical strength and single—cation conduction over a wide range of plasticizer composition. The plasticizer not only increases the conductivity of the blends but also decreases the electrochemical interface resistance between the blend and lithium electrode. The carrier in the blends obviously grows in number.