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

Controlled release of TDI and hence the cure characteristics of several blocked TDI with HTPB are reported. The reactions were followed through viscosity measurements as a function of time and temperature under the catalytic influence of triethylamine. The effect of nature of substituents present on the end capping substrate, temperature, solvent, basicity of catalyst and kinetics thereon have been studied.

Determination of toluene diisocyanate in synthetic-rubber track by ion chromatography with ultraviolet detection after alkaline suppressor

In the present work, a novel analytical method was proposed for the determination of toluene diisocyanate （TDI） in syntheticrubber track by ion chromatography （IC） coupled with an ultraviolet detector setting at 212 nm. TDI can be hydrolyzed to toluene diamine （TDA） which can be separated by cation-exchange IC easily. The optimum IC separation was performed on an IonPac CS12A column （150 mm ×4.0 mm） using 20 mmol L^-1 sodium sulfate, 10 mmol L^-1 sulfuric acid and 10% acetonitrile as eluent. It was found that a higher signal response of TDA could be obtained under alkaline condition. A suppressor was used to change the acidic eluent into alkaline one. 0.8 mol L^-1 potassium hydroxide was chosen as the optimum regeneration eluent. With the added suppressor and regenerant, signal response was magnified by about 16 times and lower limit of detection （LOD, 0.13 μg L^-1） was obtained. Within-day relative standard deviation （R.S.D.） was less than 3.6%. The recoveries of TDI spiked in synthetic-rubber track samoles were 96.4-110.6%.

Kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to1,6-hexamethylene diisocyanate

The kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate was studied. A consecutive reaction model was established and the reaction orders for the two steps were confirmed to be 1 and 1.3 by the integral test method and the numerical differential method, respectively. The activation energies of the two steps were （56.94 4±5.90） kJ·mol^-1 and （72.07±3.47） kJ·mol^-1 with the frequency factors exp（ 12.53±1.42） min^- 1 and （ 14.254±0.84） tool^-0.33. L^0.33·min^-1, respectively. Based on the kinetic model obtained, the progress of the reaction can be calculated under given conditions.

~1H NMR analysis of the tolylene-2,4-diisocyanate-methanol reaction

Tolylene-2,4-diisocyanate（2,4-TDI） 1 reacts with methanol through two simultaneous paths in the polyurethane reaction,which involve two different intermediates-tolylene-4-carbamatic-2-isocyanate 2 and tolylene-2-carbamatic-4-isocyanate 3,and the final product is tolylene-2,4-dicarbamate 4.The-CH_3 chemical shifts in benzene ring in compounds 1,2,3 and 4 can be easily tested and well distinguished,through which those four compounds are quantified and their kinetics are investigated.It shows that four rate constants for the tolylene-2,4-diisocyanate-methanol reaction in CCl_4 at 50℃are k_1=9.6×10^（-2）h^（-2）mol^（-2）min^（-1）, k_2=1.4×10^（-2）h^（-2）mol^（-2）min^（-1）,k_3=4.0×10^（-3）h^（-2）mol^（-2）min^（-1）,k_4=1.4×10^（-3）h^（-2）mol^（-2）min^（-1）.（k_1 is the reaction rate constant from compounds 1 to 2;k_2 is the reaction rate constant from compounds 1 to 3;k_3 is the reaction rate constant from compounds 3 to 4;k_4 is the reaction rate constant from compounds 2 to 4）.

DIBUTYLTIN DILAURATE-CATALYZED DIISOCYANATE COUPLING—GRAFTING OF POLY(ETHYLENE GLYCOL)ONTO NANO-SILICA SURFACE THROUGH A ONE-STEP PROCEDURE

Grafting polymer glycols onto nano-silica surface through one-step procedure was investigated.The major characteristic of this procedure is that all the materials and reagents(silica,PEG,TDI,DBTDL,solvent)required for grafting were added simultaneously into the reaction vessel.TDI and DBTDL were used as coupling agent and catalyst,respectively. The products were characterized by FTIR,TGA,elemental analyses and TEM,giving evidence for successful grafting of PEG.Possible mechanism of this grafting was studied and two grafting processes were proposed.The process through which the grafting proceeds depends on the reaction temperature.Effect of molecular weight of PEG on grafting was also investigated.

Non-phosgene synthesis of hexamethylene-1,6-diisocyanate from thermal decomposition of hexamethylene-1,6-dicarbamate over Zn–Co bimetallic supported ZSM-5 catalyst

A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The catalyst was characterized by FTIR and XRD analyses. Three solvents dioctyl sebacate(DOS), dibutyl sebacate(DBS) and 1-butyl-3-methylimidazolium tetrafluoroborate(BMIMBF_4) were investigated and compared; DOS gave better performance. The catalytic performances for thermal decomposition of HDC to HDI using DOS as solvent were then investigated, and the results showed that, under the optimized reaction conditions, i.e.,10 wt%concentration of HDC in DOS, 250 °C temperature, 60 min reaction time, 83.8% yield of HDI had been achieved over Zn–Co/ZSM-5. Decomposition of the intermediate hexamethylene-1-carbamate-6-isocyanate(HMI) over Zn–Co/ZSM-5 in DOS solvent was further studied and the results indicated that yield of HDI from HMI reached to 69.6%(98.6% HDI selectively) at 270 °C, which further increased the yield of the total HDI(HDI_(tol)) to as high as 95.0%. Recycling of catalyst showed that HDI and HMI yield slightly decreased, and by-product yield increased after the catalyst was reused for 4 times. At last possible reaction mechanism was proposed.

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.

The Curing for Modified Vinyl Ester Resin by Hexamethylene Diisocyanate and Its Influence on Performances

The commercial vinyl ester resins(VER)was modified by diphenylmethane diisocyanate(MDI)to enhance its toughness,which is called MVER.Hexamethylene diisocyanate(HDI),a common curing agent for polyurethane(PU),was found to be a reactive agent for MVER and can contribute to the toughness of MVER.Based on present experiment results,the crosslinking mechanism of MVER and HDI system is very similar to that of PU.The FTIR result shows the-NCO of HDI can react with the-OH of MVER.The microstructure of material prepared by MVER and HDI was characterized by NMR,and it was revealed that the unique microstructure leads to the good performances.The different content of HDI has an influence on the microstructure,and the microstructure gradually reduces the toughness and mechanical performances of the MVER cured with increasing concentration of reactive curing agent(HDI).This feature is consistent with a maximum in toughness as a function of the additive(HDI)content,followed by a rapid deterioration in toughness at higher concentrations.The toughness exhibits the maximum at such an HDI concentration(20wt%).Therefore,the special curing agent(HDI)and reactive mode is very important to the microstructure and mechanical properties of material.Furthermore,there should be other reactions which contribute to the curing and microstructure of the material,which needs the further research.

Synthesis and Properties of Organic-Inorganic Hybrid Porous Polymers Obtained with Click Addition Reactions of Thiol-Functionalized Random Type Silsesquioxane by and Diacrylate or Diisocyanate Compounds

Organic-inorganic hybrid network polymers have been synthesized by addition reaction of a thiol-functionalized random type silsesquioxane (SQ109) and alkyl diacrylate or diisocyanate compounds. Thiol-ene reaction of SQ109 and 1,4-butanediol diacrylate (BDA) successfully yield porous polymer in toluene initiated by azobis(isobutyronitrile) (AIBN) at 60°C. Morphology of the porous polymers was composed by connected globules, and the diameter of the globules decreased with increasing in the monomer concentration of the reaction system. By contrast, the reaction with 1,6-hexanediol diacrylate or 1,5-hexadiene yielded homogeneous clear gels. Thermal analyses of SQ109-BDA porous polymers indicated that thermal degradation of ester groups of BDA in the polymer network occurred at around 300°C. The porous polymer was also obtained by the reaction using a photo-initiator (Irugacure184) at room temperature, and showed higher Young’s modulus than the corresponding porous polymer obtained with the reaction with AIBN due to the small size of the globules. Young’s modulus of SQ109-BDA porous polymer increased with increasing in the monomer concentration of the reaction systems. Thiolisocyanate addition reactions between SQ109 and hexamethylene diisocyanate (HDI) or methylenediphenyl 4,4’-diisocyanate (MDI) were investigated to obtain network polymers. The reactions in toluene yielded the corresponding homogeneous clear gels. By contrast the reactions in a mixed solvent of toluene (50 vol.%) and N,N-dimethylformamide (50 vol.%) produced porous polymers. The morphology of the porous polymers was composed by connected globules or aggregated particles. The size of globules and particles in the SQ109-HDI porous polymers was larger than those in the SQ109-MDI porous polymers. Thermal degradation of SQ109-HDI and SQ109-MDI porous polymers started at round 260°C and showed endothermic peak at around 350°C derived from degradation of thio-urethane bond.

An efficient green route for hexamethylene-1,6-diisocyanate synthesis by thermal decomposition of hexamethylene-1,6-dicarbamate over Co3O4/ZSM-5 catalyst： An indirect utilization of CO2

The utilization of CO2 as raw material for chemical synthesis has the potential for substantial economic and green benefits. Thermal decomposition of hexamethylene-1,6-dicarbamate （HDC） is a promising approach for indirect utilization of CO2 to produce hexamethylene-1,6-diisocyanate （HDI）. In this work, a green route was developed for the synthesis of HD1 by thermal decomposition of HDC over Co3O4/ZSM-5 catalyst, using chlorobenzene as low boiling point solvent. Different metal oxide supported catalysts were prepared by incipient wetness impregnation （IWI）, PEG-additive （PEG） and deposition precipitation with ammonia evaporation （DP） methods. Their catalytic performances for the thermal decomposition of HDC were tested. The catalyst screening results showed that Co3O4/ZSM-525 catalysts prepared by different methods showed different performances in the order of Co3O4/ZSM-5 25（PEG） 〉 Co3O4/ZSM-525（IWI） 〉 Co3O4/ZSM-525（DP）. The physicochemical properties of Co3O4/ZSM- 52s catalyst were characterized by XRD, FTIR, N2 adsorption-desorption measurements, NH3-TPD and XPS. The superior catalytic performance of Co3O4/ZSM-52S（PEG） catalyst was attributed to its relative surface content of Co3 ＋, surface lattice oxygen content and total acidity. Under the optimized reaction conditions： 6.5% HDC concentration in chlorobenzene, 1 wt% Co3O4/ZSM-525（PEG） catalyst, 250℃ temperature, 2.5 h time, 800 ml.min 1 nitrogen flow rate and 1.0 MPa pressure, the HDC conversion and HDI yield could reach 100% and 92.8% respectively. The Co3O4/ZSM-525（PEG） catalyst could be facilely separated from the reaction mixture, and reused without degradation in catalytic performance. Furthermore, a possible reaction mechanism was proposed based on the physicochemical properties of the Co3O4/ZSM-5 25 catalysts.

HPLC测定聚氨酯工业胶中MDI原料单体及其自聚物分布

利用HPLC测定了2种常用MDI原料单体及其自聚物分布。用甲醇或乙醇衍生MDI,以安捷伦ZORBAX Eclipse XDB-C18柱为分析柱,柱温35℃,流速1.0 mL/min,进样量10μL,流动相甲醇和水梯度洗脱,检测波长245 nm进行分析检测。结果表明:甲醇比乙醇衍生更快,溶解性更好,出峰时间更早;MDI-50衍生条件比MDI-100L温和,常温下就可以快速衍生,而MDI-100L需要烘箱加热,才可以很好地衍生并溶解。本文提出的方法满足聚氨酯工业胶中MDI原料单体及其自聚物分布的分析要求,同时为后续准确定量聚氨酯工业胶中MDI单体含量提供技术支撑。

Physical-Rheological Properties and Performances of Rejuvenated(Styrene-Butadiene-Styrene)Asphalt with Polymerized-MDI and Aromatic Oil

Traditional asphalt rejuvenators,like aromatic oil(AO),are known to be effective in improving the low-temperature properties and fatigue performances of aged SBS(styrene-butadiene-styrene)modified asphalt(SBSMA)binders and mixtures.However,these rejuvenators inevitably compromise their high-temperature properties and deformation resistances because they dilute asphalt binder but do not fix the damaged structures of aged SBS.In this study,a highly-active chemical called polymerized 4,4-diphenylmethane diisocyanate(PMDI)was used to assist the traditional AO asphalt rejuvenator.The physical and rheological characteristics of rejuvenated SBSMA binders and the moisture-induced damage and rut deformation performances of corresponding mixtures were comparatively evaluated.The results showed that the increasing proportion of AO compromises the hightemperature property and hardness of aged SBSMA binder,and an appropriate amount of PMDI works to compensate such losses;3%rejuvenator at mass ratio of AO:PMDI=70:30 can have a rejuvenated SBSMA binder with a high-temperature performance similar to that of fresh binder,approximately at 71.4°C;the use of AO can help reduce the viscosity of PMDI rejuvenated SBSMA binder for improving its workability;PMDI can help improve the resistance of AO rejuvenated SBSMA binder to deformation,especially at elevated temperatures,through its chemical reactions with aged SBS;moisture induction can enhance the resistance to damage of rejuvenated mixtures containing AO/PMDI or only PMDI;and the rejuvenator with a mass ratio of AO:PMDI=70:30 can lead the rejuvenated mixture to meet the application requirement,with a rut depth of only 2.973 mm,although more PMDI can result in a higher resistance of rejuvenated mixtures to high-temperature deformation.

二苯基甲烷二异氰酸酯(MDI)改性沥青及其混合料高温性能研究

制备3%MDI、5%MDI和7%MDI改性沥青及其混合料,通过动态剪切流变试验和车辙试验研究不同掺量MDI改性沥青及其混合料的高温性能。结果表明,MDI改性剂的加入增大了基质沥青的黏弹性,提高了基质沥青的软化点,降低了针入度指标;不同掺量MDI改性剂的加入均增大了基质沥青的车辙因子指标G~*/sinδ和沥青混合料的动稳定度值。其中,7%MDI改性沥青在车辙因子G~*/sinδ=2.2kPa水平对应的临界温度最高,其对沥青混合料动稳定度的提升程度亦最大,7%MDI改性沥青及其混合料可适用于相对更高温度环境中的沥青路面设计与应用。

TPP对MDI水解氯测定的影响因素的研究

二苯基甲烷二异氰酸酯(MDI)中的水解氯含量影响异氰酸酯的反应活性,是重要分析项目。为有助于样品的保存会在MDI中加入抗氧化剂亚磷酸三苯酯(TPP)。在水解氯分析过程中,MDI中的溶解性光气与HCL会与醇和水反应生成氨基甲酰氯、盐酸、二氧化碳、脲,其中生成的盐酸最终用硝酸银标准溶液进行滴定,但是TPP经过醇解和水解后的产物也会与硝酸银标准溶液反应,增加硝酸银的消耗量而造成水解氯结果偏高。

液化MDI基形状记忆聚氨酯软段组成的选择

以液化M D I和BDO(1,4-丁二醇)为硬段,分别以聚乙二醇(PEG),聚己二酸乙二醇酯(PEAG),聚己二酸丁二醇酯(PBAG),聚己二酸己二醇酯(PHAG),聚己内酯(PCL)为软段合成了聚氨酯形状记忆材料。通过FT-IR,DSC等考察了它们的结构,比较了聚乙二醇聚氨酯(EGPU),聚己二酸乙二醇酯聚氨酯(EAPU),聚己二酸丁二醇酯聚氨酯(BAPU),聚己二酸己二醇酯聚氨酯(HAPU)及聚己内酯聚氨酯(CLPU)的形状记忆性能和力学性能,研究表明,PHAG是液化M D I基形状记忆聚氨酯软段的最佳原料。

PTMG/MDI体系聚氨酯弹性体的力学性能研究

以4,4′-二苯基甲烷二异氰酸酯(MD I)和聚四氢呋喃均聚醚(PTMG)为原料合成聚氨酯(PU)预聚体,再分别与BDO、MOCA、HQEE扩链剂及混合扩链剂制备PU弹性体。讨论了预聚体NCO基含量、聚醚软段相对分子质量、三羟甲基丙烷(TMP)小分子醇含量及扩链剂类型对PU弹性体力学性能的影响。结果表明,提高预聚体NCO基含量可使PU弹性体的硬度、撕裂强度和300%模量明显提高;当预聚体NCO基含量基本相同时,软段Mn=2000比Mn=1000的PU冲击弹性高;混合扩链剂中的TMP质量分数超过30%时,弹性体的力学性能明显下降;BDO-PU的拉伸强度比HQEE-PU的强度高出70%以上,撕裂强度比HQEE-PU低了40%以上,硬度比MOCA-PU小。

纳米材料改性彩绘陶器文物保护材料MDI型聚氨酯的研究

为提高广泛应用于秦俑彩绘陶器保护中的MDI型聚氨酯（PU乳液）的耐光老化性,以物理共混方式采用超声波分散将纳米材料添加到MDI型聚氨酯中,通过UV-Vis光谱考察了分散效果,利用ATR-FTIR、漫反射光谱技术及失重分析对改性后材料的耐光老化性能进行了评价。UV-Vis分析表明,超声波分散后,当m（SP1-5702纳米SiOx）/m（PU干物质）=0.23%时,改性MDI型聚氨酯乳液对200-380 nm紫外光透过率为0,在可见光区平均透过率达到80%;光老化70 h后其FTIR表明,MDI型聚氨酯膜C=O基峰吸光度变化率由改性前的81%降低到8%;老化1.5 h后,色差ΔE由10.86减小到5.68;老化170 h的失重率由3.56%下降到2.75%。

MDI型水性聚氨酯乳液的合成及性能研究

以二苯基甲烷二异氰酸酯、聚酯二醇、二羟甲基丙酸等为原料合成了水性聚氨酯预聚体,用三乙胺中和制备了水性聚氨酯的透明乳液。通过FT-IR、TEM、拉力机等测试手段对所制水性聚氨酯进行了形貌观察、力学及耐水性测试。结果表明,当n(—NCO)∶n(—OH)比值为1.8~1.9,DMPA含量在6.5%~7%,中和度在100%~120%时可制得性能稳定的水性聚氨酯乳液,若在乳化阶段用乙二胺进行扩链,则胶膜的吸水率会进一步降低至4%。