含能黏合剂PAMMO的问接法合成

以3-溴甲基-3-甲基氧杂环丁烷(BrMMO)为单体,按阳离子开环聚合机理,先合成出3-溴甲基-3-甲基氧杂环丁烷均聚物(PBrMMO),接着在偶极非质子溶剂中对其进行叠氮化,最终合成出含能黏合剂3-叠氮甲基-3-甲基氧杂环丁烷均聚物(PAMMO).着重研究了BrMMO聚合过程中催化剂用量和反应体系温度对聚合的影响,确定出BrMMO聚合的最佳条件为:n(BF3OEt2):n(BDO)=0.50:1.00.0℃下加入单体,通过红外光谱确定出叠氮化反应的完成时间.用红外光谱(IR)、核磁共振(1H-NMR)、热重分析(TGA)和差示扫描量热法(DSC)对产品进行了表征.     

3-溴甲基-3-甲基氧杂环丁烷均聚物的合成及表征

以1,4-丁二醇(BDO)为引发剂,三氟化硼乙醚络合物(BF3·Et2O)为催化剂,3-溴甲基-3-甲基氧杂环丁烷(BrMMO)为单体,CH2Cl2为溶剂,按阳离子开环聚合机理,合成出有机黏合剂3-溴甲基-3-甲基氧杂环丁烷均聚物(PBrMMO).研究了低温条件下单体转化率随时间的变化情况,得出BrMMO转化率-时间曲线,考察了催化剂用量和反应体系温度对可控聚合的影响,确定出BrMMO可控聚合的最佳条件:BF3·Et2O与BDO的摩尔比为0.5∶1.0,0℃下加入单体并熟化3d.用IR、1HNMR、DSC及TGA对最终产物的结构与性能进行了表征.     

含能黏合剂BAMO-THF-GAP无规共聚醚的合成与表征

以3,3-二溴氧杂环丁烷(BBMO)、四氢呋喃(THF)和环氧氯丙烷(ECH)为单体,1,4-丁二醇(BDO)为引发剂,三氟化硼乙醚(BF3·OEt2)为催化剂,采用阳离子开环聚合法制备BBMO-THF-ECH无规共聚醚;然后将其进行叠氮化反应,制成含能黏合剂BAMO-THF-GAP(3,3-双叠氮甲基氧杂环丁烷-四氢呋喃-叠氮缩水甘油醚)无规共聚醚。研究结果表明:采用单因素试验法优选出制备无规共聚醚的最佳反应条件是w(BDO)=5%(相对于总单体质量而言)、n(BF3·OEt2)∶n(BDO)=1∶2、聚合时间为24 h、叠氮化反应时间为16 h和叠氮化反应温度为110℃。     

BAMO/AMMO基ETPE的合成与性能

以3-溴甲基-3-甲基氧杂环丁烷(BrMMO)为单体,聚合形成溴代聚醚.叠氮溴代聚醚为叠氮聚醚PAMMO;以3,3-双叠氮甲基氧杂环丁烷(BAMO)为单体,直接开环聚合形成叠氮聚醚PBAMO.以四氢呋喃为溶剂,PBAMO为硬段预聚物,PAMMO为软段预聚物,甲苯二异氰酸酯(TDI)为二异氰酸酯单体,丁二醇氨酯型齐聚醇为扩链剂,按照一步法溶液聚合工艺,制成了数均分子量在25000左右的含能热塑性弹性体(ETPE).ETPE具有可熔可溶的特点,室温抗拉强度和延伸率约为5MPa和400%.     

3-叠氮甲基-3-乙基氧杂环丁烷及其均聚物的合成与性能

为开发新型含能黏合剂,以三羟甲基丙烷、碳酸二乙酯、对甲苯磺酰氯、叠氮化钠为原料,合成出一种新型叠氮类氧杂环单体3-叠氮甲基-3-乙基氧杂环丁烷（AMEO）。用核磁、红外、元素分析和DSC表征了AMEO的结构与性能。以1,4-丁二醇为起始剂,三氟化硼乙醚络合物为催化剂,二氯甲烷为溶剂,AMMO为单体,借助于阳离子开环聚合,合成出聚3-叠氮甲基-3-乙基氧杂环丁烷（PAMEO）。用红外光谱、核磁共振、元素分析、羟值、数均分子质量表征和测定了聚合物的结构和性能。     

3-溴甲基-3-甲基氧杂环丁烷的合成

以2,2-二溴甲基丙醇(BBMP)为初始原料,通过与碱发生关环反应生成3-溴甲基-3-甲基氧杂环丁烷(BrMMO).讨论了碱的种类和用量对BBMP关环产率的影响以及反应体系中碱的浓度、反应温度和反应时间对合成BrMMO产率的影响.通过实验确定的最佳工艺条件为:BBMP与NaOH摩尔比为1.0∶1.1,NaOH醇溶液的质量分数为12%,反应温度为78℃,反应时间为4 h时,BrMMO产率为65%.最终产品经元素分析、IR和1HNMR检测确定为BrMMO.该试验工艺简单,原料易得,且溶剂便于回收、污染小.     

3-溴甲基-3-甲基氧杂环丁烷的合成

以2,2-二溴甲基丙醇（BBMP）为初始原料,通过与碱发生关环反应生成3-溴甲基-3-甲基氧杂环丁烷（BrMMO）。讨论了碱的种类和用量对BBMP关环产率的影响以及反应体系中碱的浓度、反应温度和反应时间对合成BrMMO产率的影响。通过实验确定的最佳工艺条件为：BBMP与NaOH摩尔比为1.0∶1.1,NaOH醇溶液的质量分数为12%,反应温度为78℃,反应时间为4h时,BrMMO产率为65%。最终产品经元素分析、IR和1HNMR检测确定为BrMMO。该试验工艺简单,原料易得,且溶剂便于回收、污染小。     

含氧杂环丁烷官能团的混杂光固化单体的合成与性能研究

为了结合自由基与阳离子两种光固化体系的优点,以解决光固化体系自由基氧气阻聚、阳离子湿气阻聚的问题。本研究将3-乙基-3-羟甲基氧杂环丁烷(TMPO)与4-甲基-1,2-环己二羧酸酐(MHHPA)进行醇解反应,得到含有甲基丙烯酸酯双键及羧基的中间体,再用中间体上的羧基通过羧基开环氧与甲基丙烯酸缩水甘油酯(GMA)反应,合成了一种同时含有甲基丙烯酸酯双键和氧杂环丁烷基团的自由基-阳离子混杂光固化单体,并通过实时红外光谱(RT-IR)、热重分析(TGA)等手段对其进行了固化性能、热性能、机械性能的研究,并将其与混合光固化体系进行了性能比较。研究结果表明:合成的自由基-阳离子混杂光固化单体拥有优良的固化性能、机械性能与热性能,且各方面性能均优于混合光固化体系。     

含能黏合剂PNIMMO的合成与性能

以1,4-丁二醇(BDO)为引发剂,三氟化硼*乙醚(BF3*Et2O)为催化剂,二氯甲烷(CH2Cl2)为溶剂,3-硝酸酯甲基-3-甲基氧杂环丁烷(NIMMO)发生阳离子开环聚合得到端羟聚3-硝酸酯甲基-3-甲基氧杂环丁烷(PNIMMO).讨论了催化剂与引发剂的摩尔比、反应温度、单体滴加速度对聚合反应的影响,得到最佳反应条件为:催化剂与引发剂的摩尔比为0.50～0.75,反应温度为10℃左右, 缓慢滴加单体.用红外光谱与核磁共振碳谱对聚合物结构进行了表征.性能测试结果表明:PNIMMO的玻璃化转变温度为-24.52 ℃,分解焓为 1212 J/g,分解峰温为221.78 ℃,与N-100固化后所得的聚氨酯胶片室温下的力学性能:δ为3.5～3.7 MPa,ε为260%～280%.     

新型溴化聚醚PBrMEO的合成及表征

以1,4-丁二醇为起始剂,三氟化硼乙醚络合物为催化剂,3-溴甲基-3-乙基氧杂环丁烷为单体,二氯甲烷为溶剂,按阳离子开环聚合机理,首次合成出新型溴化聚醚(PBrMEO),用IR、1HNMR、GPC、TGA、DSC等测试方法对合成产物进行了表征.结果表明,制备出的PBrMEO均聚物Mn为3000,相对分子质量分布为1.243～1.301,Tg为32.36℃,熔程为118.96～132.84℃,热分解温度为337℃.     

NMMO齐聚物的合成与表征

以1,4-丁二醇（BDO）为引发剂,三氟化硼·乙醚（BF3·OEt2）为催化剂,二氯甲烷（CH2CI2）为溶剂,3-硝酸酯甲基-3-甲基氧杂环丁烷（NMMO）经阳离子开环聚合得到端羟基聚3-硝酸酯甲基-3-甲基氧杂环丁烷（PNMMO）,然后将PNMMO的端羟基用硝酸／醋酐硝化后得到端硝酸酯基聚3硝酸酯甲基-3-甲基氧杂环丁烷（NTPNMMO）齐聚物增塑剂。通过IR、^13C-NMR、DSC对NTPNMMO的结构和性能进行了表征。结果表明NTPNMMO的玻璃化转变温度为-45．32℃,热分解峰温为213．47℃,作为含能增塑剂具有较好的应用前景。     

1-甲基-2-溴甲基-5-乙酰氧基-6-溴-1H-吲哚-3-羧酸乙酯

1-甲基-2-溴甲基-5-乙酰氧基-6-溴-1H-吲哚-3-羧酸乙酯为合成抗病毒药物——阿比朵尔的关键中间体,以甲胺、乙酰乙酸乙酯为起始原料,经缩合反应、Nenitzescu反应、酰化反应和溴化反应合成1-甲基-2-溴甲基-5-乙酰氧基-6-溴-1H-吲哚-3-羧酸乙酯,产率为34.8%,纯度98%,产物结构经质谱、1HNMR、红外光谱确证。讨论了溶剂、反应温度以及投料量等因素对反应的影响,选择了适宜的反应条件。     

Preparation of new polymer from podophyllotoxin derivative

Summary The new monomer, 4α-acrylpodophyllotoxin(APPT) was synthesized from reaction of acryloyl chloride with the 4α-hydroxy of podophyllotoxin. The homo- and copolymer of new monomer with NIPAAm/AAm have been prepared by free radical polymerization. The new monomer and polymers have been characterized by IR, ¹H- and ¹³C-NMR spectra. The homopolymer have low the molecular weight but it is not oligomer, and the molecular weight of copolymer increased with decreasing new monomer content. The composition of copolymers was close to the original monomer composition. The distinction of antitumor activity among podophyllotoxin, new monomer and homopolymer was smaller. The copolymer with NIPAAm (The PAPPT content (mol-%) =43.7%) did not exhibit any antitumor activity at present condition of experimentation. Received: 30 July 2001/ Revised version: 3 September 2001/ Accepted: 14 September 2001     

Homopolymer of 4-chloro-3-methyl Phenyl Methacrylate and its Copolymers with Butyl Methacrylate: Synthesis, Characterization, Reactivity Ratios and Antimicrobial Activity

The methacrylate monomer 4-chloro-3‐methyl phenyl methacrylate (CMPM) was synthesized by reacting 4-chloro-3‐methyl phenol with methacryloyl chloride. The homopolymer and various copolymers of CMPM with n-butyl methacrylate were synthesized by free-radical polymerization in toluene at 70°C using 2,2′-azobis(isobutyronitrile) as the initiator. The CMPM monomer was characterized by Fourier transform IR and ¹H-NMR studies. The copolymers were characterized by IR spectroscopy. The molecular weights (M _n and M _w) and the polydispersity index were obtained from gel permeation chromatography. The solubility and intrinsic viscosity of the homopolymer and the copolymers are also discussed here. The copolymer composition obtained from UV spectra led to the determination of reactivity ratios employing Fineman-Ross and Kelen-Tudos linearization methods. Thermogravimetric analyses of the homopolymer and the copolymers were carried out under a nitrogen atmosphere. The homopolymer and the copolymers prepared were tested for their antimicrobial activity against bacteria, fungi and yeasts.     

Poly(ethylene glycol)-block-poly(butyl acrylate). I. Synthesis

Prepolymers of poly(ethylene oxide) (Pre-PEO) were synthesized by reacting azoisobutyronitrile (AIBN) with poly(ethylene glycol) (PEG), and their structures were characterized by IR and UV. The molecular weight of pre-PEO was related to the feed ratio and reaction time. These prepolymers can be used to prepare block copolymers—poly(ethylene oxide)-block-poly(butyl acrylate) (PEO-b-PBA) by radical polymerization in the presence of butyl acrylate (BA). Solution polymerization was a suitable technique for this step. The yield and the molecular weight of the product were related to the ratio of the prepolymer to BA, the reaction time, and temperature. GPC showed that the molecular weight increased with a higher ratio of BA to pre-PEO. The intrinsic viscosity of the copolymers was only slightly dependent on reaction time, but decreased at higher reaction temperatures, as did the amount of PBA homopolymer. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1667–1674, 1997     

Synthesis and interfacial properties of aminosilane derivative of acrylated epoxidized soybean oil

In this study silanized acrylated epoxidized soybean oil (silanized‐AESO), a multifunctional monomer, was synthesized by reacting acrylated epoxidized soybean oil with 3‐Aminopropyltriethoxysilane via a Michael addition reaction using less than equivalent amount of the silane. The characterization of silanized‐AESO was done by NMR and IR spectroscopy. Free radically initiated homopolymer of silanized‐AESO was synthesized by using the residual acrylate groups. The silanized‐AESO homopolymer was characterized by IR spectroscopy. The interfacial adhesion of the polymer on glass surface before and after moisture cure was measured according to ASTM D 4541 Pull‐Off Adhesion Test. After moisture curing process, an approximate of eightfold improvement was observed in the adhesion strength. Prolonged exposure to 92% humidity for 48 h caused to approximately 15% decrease in the adhesion strength. Silanized‐AESO was copolymerized with styrene in 1 : 1 weight ratio via radical polymerization. The effect of increased crosslink density upon moisture cure on the mechanical and physical properties of silanized‐AESO‐styrene copolymer was analyzed by DMA (Dynamic Mechanical Analysis), swelling, and surface hardness tests. Upon moisture cure 35% improvement was observed in the storage modulus because of the increase in the crosslink density. According to tan δ curves and surface hardness tests, silanized‐AESO‐styrene copolymer shows heterogeneous morphology in crosslinked areas. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2244–2253, 2007     

BAMO-AMMO三嵌段共聚物相分离及晶体结构的解析

采用DSC方法研究了3,3’-双叠氮甲基环氧丁烷-3-叠氮甲基-3’-甲基环氧丁烷(BAMO-AMMO)三嵌段共聚物的相分离程度,根据Scherrer公式和Bragg方程计算了pBAMO均聚物和BAMO-AMMO三嵌段共聚物的微晶尺寸和晶面间距,利用XRD比较了两者的结晶度.结果表明,BAMO-AMMO三嵌段共聚物形成...     

抗菌药伦氨苄西林盐酸盐合成

以3 羟基丁酮作为起始原料,经过酰氯化、成环、脱氯化氢、溴化合成4 溴甲基 5 甲基 1,3 二氧戊环 2 酮,再和氨苄青霉素反应合成伦氨苄西林盐酸盐。其含量99%,总收率(以3 羟基丁酮计)37.3%。     

丙烯酰氧乙基三甲基氯化铵-丙烯酰胺共聚物的制备研究

以丙烯酰氧乙基三甲基氯化铵(DAC)和丙烯酰胺(AM)为单体,过硫酸铵和亚硫酸氢钠为引发剂,采用水溶液聚合合成阳离子高分子聚合物P(DAC-AM)。讨论了单体质量比、引发剂用量、温度等因素对聚合反应的影响,得到了合适的制备参数:反应温度55℃,引发剂0.035g,单体质量比m(AM):m(DAC)=3:14;并对产物进行了红外光谱和热失重分析,确定了聚合物为P(DAC-AM),热分解温度为230℃。