苯乙烯-丙烯腈-马来酸酐三元共聚物的合成及其在PC/ABS中的应用

采用本体聚合的方法,以苯乙烯、丙烯腈、马来酸酐为反应单体,加入引发剂、链转移剂合成了苯乙烯-丙烯腈-马来酸酐(SAM)三元共聚物.研究了引发剂种类、用量及链转移剂用量对三元共聚物摩尔质量的影响,寻求最优的合成条件;并以自制的SAM来增容聚碳酸酯(PC)/丙烯腈-丁二烯-苯乙烯(ABS)共混物,探讨了SAM对共混物性能的影响.通过红外(FTIR)、核磁(1H-NMR)、差示扫描量热仪(DSC)对三元聚合物结构进行了分析.研究表明:引发剂偶氮二异丁腈(AIBN)效果优于过氧化苯甲酰(BPO),苯乙烯、丙烯腈、马来酸酐物质的量之比为60:38:2,链转移剂十二硫醇(TDM)和引发剂偶氮二异丁腈(AIBN)的用量均为单体总质量的0.1%时,可获得摩尔质量为80 000g/mol左右的三元共聚物SAM;SAM对PC/ABS共混物起到了增容作用.     

可控摩尔质量窄分布受阻胺光稳定剂的合成及应用

利用自制的可聚合受阻胺光稳定剂4-丙烯酰氧基-1,2,2,6,6-五甲基哌啶(PMPA),通过可逆加成断裂链转移聚合法(RAFT)与苯乙烯进行共聚得到高分子型光稳定剂Poly(St-co-PMPA)。通过研究在不同反应条件下的RAFT聚合,发现单体/链转移剂比例、苯乙烯/PMPA比例等因素会对聚合产物摩尔质量及结构产生影响,因此,在合适的反应条件下,能够得到不同摩尔质量大小及窄摩尔质量分布的共聚物Poly(St-co-PMPA)。为了测试产物的光稳定性,将其与丙烯腈-丁二烯-苯乙烯共聚物(ABS)熔融共混。在经过800 h的紫外照射后,改性ABS的缺口冲击强度保留率为65.9%,高于纯ABS。结果表明,Poly(St-co-PMPA)是一种有效的高分子型受阻胺光稳定剂。     

AGET-ATRP法制备苯乙烯/丙烯腈共聚物

以苯乙烯(St)和丙烯腈(AN)为单体,2-溴代异丁酸乙酯(EBiB)为引发剂,三氯化铁(FeCl3)-丁二甲酸(SA)为复合催化体系,抗坏血酸为还原剂,采用电子活化再生原子转移自由基聚合(AGET-ATRP)法对苯乙烯、丙烯腈进行溶液聚合,得到了苯乙烯-丙烯腈共聚物(SAN)。采用红外、核磁表征共聚物结构;凝胶渗透色谱测定了共聚物的相对分子量及分子量分布。研究了聚合反应动力学。实验结果表明:聚合反应体系符合一级动力学规律,该聚合反应具有可控性。考察了还原剂用量、溶剂对聚合反应速率、SAN的数均相对分子质量及其分布的影响。在n(AN):n(St)=50:50、n(EBiB):n(FeCl3):n(SA):n(VC)=1:1:2:1、反应温度为75℃时,聚合反应速率最快,SAN的相对分子质量分布小于1.25(单体转化率大于30%之后),此时聚合反应的可控性较好。     

打火机专用SAN树脂生产技术开发

对国内打火机生产厂家广泛使用的进口专用苯乙烯-丙烯腈共聚物(SAN树脂)的结构和性能进行了剖析和测试,确认了该牌号SAN树脂键合丙烯腈(AN)质量分数为30.5%~31.5%,220℃、10kg时的熔融指数为15.0~18.0g/10min。根据一定转化率下进料液中2种单体的比例与共聚物组成之间的关系,参照单体组成和分子结构,模拟计算出了聚合反应进料配方和聚合工艺参数。利用中试装置对估算出的配方组成和工艺参数进行了实验验证,产品的各项指标均达到进口产品水平。     

本体法合成ABS树脂Ⅱ.预聚合反应动力学研究

采用本体聚合方法,以1,1-二(叔丁基过氧基)环己烷(DP275B)引发苯乙烯、丙烯腈在聚丁二烯橡胶上接枝共聚合.考察了不同聚合工艺条件下丙烯腈-丁二烯-苯乙烯三元共聚物(ABS)预聚合反应动力学行为规律,并求出相应的假一级表观增长反应速率常数.结果表明:不同工艺条件下的动力学曲线均符合一级线性关系;镍系高顺式橡胶BR9004体系的预聚合反应速率最快;增加引发剂DP275B浓度、提高引发温度、降低低顺式聚丁二烯橡胶700A用量和聚合搅拌速率均可加快ABS预聚合反应速率;当w(700A)为5.0%, w(DP275B)为0.021% 时,共聚单体的表观增长反应活化能为10.84 kJ/mol,频率因子为0.12 min-1.     

具有核壳结构的AAS接枝弹性体对聚氯乙烯树脂的共混改性

丙烯腈-丙烯酸丁酯-苯乙烯共聚物(AAS树脂)又称ASA树脂即一种耐候型丙烯腈-丁二烯-苯乙烯共聚物(ABS树脂),是一种新型树脂及高效树脂改性剂.本文采用乳液接枝——树脂共混法制备AAS树脂工艺:以丙烯酸丁酯为聚合单体,采用乳液聚合方法制备大粒径交联聚丙烯酸酯胶乳,以其作为接枝主干物,与共聚单体进行接枝聚合,再进行凝...     

甲基丙烯酸缩水甘油酯-苯乙烯-丙烯腈聚合物的合成

采用悬浮聚合方法,使甲基丙烯酸缩水甘油酯(GMA)、苯乙烯(St)和丙烯腈(AN)单体发生自由基聚合,获得数均摩尔质量M_n=7×10~4g/mol,分散度D=2.36,外观无色透明的三元共聚物珠粒.通过红外分析发现其在1727 cm~(-1)处有羰基的强烈伸缩振动吸收峰,在1253 cm~(-1)(环氧基团的对称振动吸收峰)、915 cm~(-1)和861 cm~(-1)(环氧基团的不对称振动的两个吸收峰)处的红外吸收峰,表明了环氧基团的存在;3200～3600 cm~(-1)范围没有明显的羟基吸收峰,说明聚合物中GMA的环氧基团很少或基本上没有开环,据此可以初步认定GMA单体在参与聚合反应时,是以打开双键的形式进行加成聚合反应.     

偏氯乙烯共聚物的单电子转移活性自由基聚合

以碘仿为引发剂,偏氯乙烯和丙烯酸甲酯为单体,连二亚硫酸钠/碳酸氢钠为催化剂体系,羟丙基甲基纤维素和甲基纤维素为分散剂,在水相体系中制备偏氯乙烯共聚物。研究了反应时间、反应温度以及引发剂用量对单体转化率、产物摩尔质量及分布的影响。结果表明,随着反应时间的延长和反应温度的提高,转化率和摩尔质量增加,摩尔质量分布变窄,反应具有活性聚合的特征。使用红外光谱仪(IR)和核磁共振(~1H NMR)对共聚物的结构进行表征并探讨了聚合反应的机理,说明该聚合方法符合单电子转移活性自由基聚合特征。     

α—SAN树脂的研制

α-SAN树脂是以α-甲基苯乙烯、苯乙烯和丙烯腈为原料,用悬浮共聚法制备的。本文从α-甲基苯乙烯的分子结构特点及其聚合机理考虑,选择丙烯腈和苯乙烯作为共聚单体,探讨了单体用量对共聚物性能的影响。研究了复合引发剂体系对聚合周期及共聚物单体残留量的影响。介绍了羟基磷酸钙-苯乙烯-顺丁烯二酸酐共聚物钠盐的制备方法,并以它作共聚反应的复合分散剂,减少了粘壁现象。对影响α-SAN树脂物理性能的诸因素进行了讨论。试验结果表明,α-甲基苯乙烯用量对聚合周期、产物分子量、熔体指数、玻璃化温度和冲击强度等均有显著的影响。     

苯乙烯/丙烯腈/N-苯基马来酰亚胺的乳液共聚研究

以十二烷基硫酸钠为乳化剂、过硫酸钾为引发剂,通过乳液聚合,合成了苯乙烯-丙烯腈-N-苯基马来酰亚胺三元共聚物(St-AN-PMI),并考察了各单体配比、乳化剂浓度、引发剂浓度等对聚合反应和最后产物的影响.发现该共聚物中PMI的含量是决定其性质的重要因素,而聚合时合适的乳化剂浓度和引发剂浓度分别为13～15 mmol/L和1.8～2.4 mmol/L.     

Victrex® poly(ethersulfone) (PES) and Victrex® poly(etheretherketone) (PEEK)

Properties of two high performance engineering thermoplastics, amorphous polyethersulfone (PES) and semicrystalline polyetheretherketone (PEEK), are discussed. Both resins can be processed by conventional techniques, compounded with high performance fibers, and have high service temperature (up to 300°C). Due to the amorphous character PES can be dissolved and spray coated into metals.     

Photopyroelectric Spectroscopic Studies of ZnO-MnO(2)-Co(3)O(4)-V(2)O(5) Ceramics

Photopyroelectric (PPE) spectroscopy is a nondestructive tool that is used to study the optical properties of the ceramics (ZnO + 0.4MnO(2) + 0.4Co(3)O(4) + xV(2)O(5)), x = 0-1 mol%. Wavelength of incident light, modulated at 10 Hz, was in the range of 300-800 nm. PPE spectrum with reference to the doping level and sintering temperature is discussed. Optical energy band-gap (E(g)) was 2.11 eV for 0.3 mol% V(2)O(5) at a sintering temperature of 1025 °C as determined from the plot (ρhυ)(2)versushυ. With a further increase in V(2)O(5), the value of E(g) was found to be 2.59 eV. Steepness factor 'σ(A)' and 'σ(B)', which characterize the slope of exponential optical absorption, is discussed with reference to the variation of E(g). XRD, SEM and EDAX are also used for characterization of the ceramic. For this ceramic, the maximum relative density and grain size was observed to be 91.8% and 9.5 μm, respectively.     

(Ba_(1-α)Sr_α)_(4.8)(Sm_(0.7)La_(0.3))_(8.8)Ti_(18)O_(54)陶瓷的微波介电性能

采用固相合成法制备了(Ba(1-α)Srα)4.8(Sm0.7La0.3)8.8Ti18O54(α=0.1～0.5)系陶瓷,表征了该陶瓷的相组成和显微结构,测试了微波介电性能.结果表明:α=0.3时,(Ba(1-α)Srα)4.8(Sm0.7La0.3)8.8Ti18O54系陶瓷为单相的新钨青铜结构固溶体.α>0.3时,相继出现了第二相BaLa2Ti4O12和La0.66TiO2.993.随α的增加,(Ba(1-α)Srα)4.8(Sm0.7La0.3)8.8Ti18O54系陶瓷的相对介电常数(εr)先增大后有所波动,品质因数(Qf)先增大后减小,谐振频率温度系数(τf)单调减小.α=0.3时,在1 350℃烧结的陶瓷的微波介电性能最佳:εr=98.77,Qf=5184GHz,τf=10.9×10-6/℃,优于不掺杂的BaO-Sm2O3-TiO2陶瓷的.     

Calcium silicate hydrate (II) (“C-S-H(II)”)

This semicrystalline phase, originally named ‘calcium silicate hydrate(II)’ by Taylor (1950), has been studied with X-rays, electron optics, chemical investigation of silicate anion type, infrared spectra, and thermal methods. It is structurally related to jennite (C₉S₆H₁₁) and probably also to the fibrous CSH of cement pastes, the three phases forming a sequence of decreasing crystallinity. The specimen studied had approximate composition C₂SH_3.2 after standing over saturated CaCλ₂ at about 15°C. CSH(II) contains metasilicate chains and pyrosilicate groups and has a disordered layer structure. Much of the water can be lost reversibly without significant change in lattice parameters.     

Poly(butadiene-acrylic acid(g)acrylonitrile(g)acrylic acid)

Summary In the present work we describe, the synthesis and characterization of a new gel obtained by crosslinking a cooligomer of butadiene-acrylic acid (BuAA), by reaction with acrylonitrile and acrylic acid. The purified product was characterized by FTIR, elemental analyses and scanning electronic microscopy. The thermal properties were studied and swelling indexes were determined in different solvents and at different pH values. The capacity of poly(butadiene-acrylic acid(g)acrylonitrile(g)acrylic acid) [gel A] to separate different organic substances, such as amino acids and colorants, was determined.     

Photooxidative stability of substituted poly(phenylene vinylene) (PPV) and poly(phenylene acetylene) (PPA)

The addition of side groups to improve the photooxidative stability of polymers used in polymer-based light-emitting diodes (LEDs) is explored. Infrared spectroscopy and computational chemistry techniques are used to study the effects of chemical substitution of the reactive vinylene moiety in poly(phenylene vinylene) (PPV). The bond order of the vinylene group in small oligomers is calculated using semiempirical techniques to assess the improvement in stability toward oxidants such as singlet oxygen. We find that PPV dimers allow relative comparisons across a range of possible substitutions. Experimental results correlate well with these calculations. The addition of electron-withdrawing substituents, such as nitrile groups, to the vinylene moiety is found to be particularly effective in reducing the reactivity of alkoxy-substituted PPV toward singlet oxygen. The photooxidative stability of a poly(phenylene acetylene) (PPA) derivative is also studied. It appears that this family of polymers is more stable toward photooxidation than are its PPV analogs. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2451–2458, 1998     

Chemical cross-linking of conducting poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) using poly(ethylene oxide) (PEO)

Hybrid films of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) were prepared with different molecular weights of poly(ethylene oxide) (PEO). The cross-linking reaction between PEO and PEDOT:PSS was performed at high temperature and confirmed by using differential scanning calorimeter (DSC), contact angle measurement, and solid-state ¹H NMR. The effect of chemical reaction on the conductivity and morphology of these hybrid films was studied by using 4-point probe and atomic force microscope (AFM), respectively. As-spun PEO/PEDOT:PSS films have lower electric conductivity due to the addition of nonconductive PEO, and exhibits no molecular weight dependence on conductivity. After chemical cross-linking reaction at high temperature, only PEDOT:PSS films with lowest molecular weight PEO additives show enhanced conductivity with increasing reaction time. AFM result indicates that the heat-treated PEO/PEDOT:PSS hybrid films show grain-like morphology compared to ethylene glycol treated PEDOT:PSS films which shows continuous PEDOT domain. In the present work we demonstrate that the cross-linking reaction can be used to improve the wet stability of PEDOT:PSS nanofiber, showing good water resistance and excellent dimensional stability.     

Thermal studies of blends of poly(phenylene sulfide) (PPS) with poly(phenylene sulfide sulfone) (PPSS) and with poly(phenylene sulfide ether) (PPSE)

The miscibilities of poly(phenylene) sulfide/poly(phenylene sulfide sulfone) (PPS/PPSS) and poly(phenylene) sulfide/poly(phenylene sulfide ether) (PPS/PPSE) blends were invesigated in terms of shifts of glass transition temperatures T_g of pure PPS, PPSS, a dn PPSE. The crystallization kinetics of PPS/PPSS blends was also studied as a function of molar composition. The PPS/PPSS and PPS/PPSE blends are respectively partially and fully miscible. PPSE shows a plasticizing effect on PPS as does PPS on PPSS, which necessarily improves te processibility in the respective systems. We can control T_g and melting temperature T_m of PPS by varying amounts of PPSE in blends. The melt crystallization temperature T_mc of PPS/PPSE blends was higher than that of the PPSE homopolymer. Therefore, these blends require shorter cycle times in processing than pure PPSE. The overall rate of crystallization for PPS/PPSS blends follows the Avrami equation with an exponent ?2. The maximal rate of crystallization for PPS/PPSS blends occurs at a temperatre higher by 10°C than that for PPS, while the crystallization half time t_1/2 is 4 times shorter. In the cold crystallization range, crystal growth rates increase and Avrami exponents decrease significantly as the temperature increases.