侧氨基聚硅氧烷

中北大学的刘飞等人以八甲基环四硅氧烷（D4）和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷（HC-550）为原料、六甲基二硅氧烷（MM）为封端剂、乙醇钾为催化剂、二甲基亚砜为促进剂,通过共平衡聚合反应,合成了侧氨基聚硅氧烷。     

含硅聚酰亚胺的合成与应用研究进展

综述了含硅聚酰亚胺的合成及应用的研究进展。     

1,3-双(3-氨丙基)-1,1,3,3-四甲基二硅氧烷的合成

以二甲基一氯硅烷和γ-氯丙烯为原料,经硅氢加成得到γ-氯丙基二甲基氯硅烷,加成产物提纯后经水解缩合得到1,3-双(γ-氯丙基)四甲基二硅氧烷(简称氯丙基双封头),氯丙基双封头和液氨进行氨化反应后得到1,3-双(3-氨丙基)-1,1,3,3-四甲基二硅氧烷.对第一步硅氢加成反应的催化剂和反应条件进行优化,确定了最优合成工...     

几种含α-官能团的二硅氧烷的合成与表征

以氯甲基二甲基氯硅烷为原料制备了几种含官能团的二硅氧烷封端剂.将氯甲基二甲基氯硅烷在50%乙醇水溶液中水解,可得到85%收率的1,3-双氯甲基-1,1,3,3-四甲基二硅氧烷(产物Ⅰ);产物Ⅰ同醋酸和三乙胺在对二甲苯中回流18 h,得到90%收率的1,3-双乙酰氧甲基-1,1,3,3-四甲基二硅氧烷(产物Ⅱ);在盐酸催化下,产物Ⅱ同过量甲醇在室温下进行酯交换反应24 h,得到约80%收率的1,3-双羟甲基-1,1,3,3-四甲基二硅氧烷.用1H NMR、GC-MS、IR、元素分析等方法对产物进行了表征,以确定产物的含量、结构和主要副产物的结构,简单探讨了反应的影响因素.     

1,1,3,3-四甲基-1,3-二硅氧烷二醇的研制

分别采用3种方法(二甲基二氯硅烷于冷水中水解、D₄与氢氧化钠反应、钯催化四甲基二硅氧烷)制备1,1,3,3-四甲基-1,3-二硅氧烷二醇,以寻找有利于其工业化生产的有效路径。最终确定了以四甲基二硅氧烷为原料制备1,1,3,3-四甲基-1,3-二硅氧烷二醇的合成方法。该法操作简单,收率超过90%,易大规模生产。阐述了1,1,3,3-四甲基-1,3-二硅氧烷二醇的合成的相关机理。在钯催化下,形成的Si—PdL₂削弱了四甲基二硅氧烷中的Si—H,有利于H—OH的进攻,且随之形成的过渡态活化能大幅降低,从而实现反应速率的加快,同时较短的反应时间能够避免产物1,1,3,3-四甲基-1,3-二硅氧烷二醇发生聚合反应,进一步提高产物收率。     

1,3-二苯基-1,1,3,3-四(二甲基硅氧基)二硅氧烷的合成与表征

以苯基三甲氧基硅烷、四甲基二硅氧烷为原料,在固体酸催化下水解缩合,得到1,3-二苯基-1,1,3,3-四(二甲基硅氧基)二硅氧烷含量为42.6%的含氢低聚硅氧烷;再于0.665 kPa真空度下精馏,得到纯度为97.5%的产物。采用IR、GC-MS、1HNMR、13C NMR对其进行结构表征。结果表明,产物的结构特征与1,3-二苯基-1,1,3,3-四(二甲基硅氧基)二硅氧烷完全吻合。     

羟基保护－硅氢加成合成1,3-双(γ-羟丙基)-1,1,3,3-四甲基二硅氧烷

四乙氧基硅烷与烯丙醇在乙醇钠催化下发生酯交换反应,得到一元交换产物三乙氧基烯丙氧基硅烷(Ⅰ)。将Ⅰ与1,1,3,3-四甲基二硅氧烷在铂催化剂条件下进行硅氢加成反应,得到1,3-二(γ-三乙氧硅氧基丙基)-1,1,3,3-四甲基二硅氧烷(Ⅱ),Ⅱ在氢氧化钠水溶液和乙醇以质量比1∶1配成的混合溶液均相水解,得到1,3-双(γ-羟丙基)-1,1,3,3-四甲基二硅氧烷。以1,1,3,3-四甲基硅氧烷计算,总得率为76.4%。采用红外光谱、核磁共振、气相色谱/质谱联用等方法对中间体及产物进行了结构表征。     

乙烯基聚硅氧烷乳液的制备及性能研究

以十六烷基三甲基溴化铵(CTAB)和辛基酚聚氧乙烯醚(OP-10)为复合乳化剂、KOH为催化剂、八甲基环四硅氧烷(D<,4>)和四甲基四乙烯基环四硅氧烷(D<'Vi><,4>)为单体,制备了乙烯基聚硅氧烷乳液.考察了CTAB用量、CTAB与OP-10的质量比、聚合温度对乳液性能的影响,并对制备的聚硅氧烷进行了红外(IR)与热失重(TG)表征.结果表明,D<,4>与D<'Vi><,4>发生了共聚反应;当CTAB用量为单体质量的3.2%,CTAB与OP-10的质量比为1:6,聚合温度为80℃时,可制得单体转化率为88.5%、乳胶粒粒径为74.82 nm、机械、高温、稀释与电解质稳定性都较好的乙烯基聚硅氧烷乳液.热失重分析(TGA)表明,292℃以前乙烯基聚硅氧烷的质量损失率为17.2%,然后快速分解至442℃,乙烯基聚硅氧烷的质量损失率为97.2%.     

膜用高乙烯基含量硅橡胶的合成与表征

以八甲基环四硅氧烷(D4)和四甲基四乙烯基环四硅氧烷(Dvi4)为单体、四甲基二乙烯基二硅氧烷(Mmvi)为封端剂、氢氧化钾为催化剂,合成了乙烯基摩尔分数为5%的硅橡胶PVDMS.研究了反应时间、反应温度及Mmvi加入量对产物黏度的影响,得到的最佳合成条件为反应温度140℃、反应时间180～210 min、MMvi质量分数0.9%～1.8%.用傅里叶变换红外光谱和核磁共振氢谱对其结构进行了表征,并计算了产物中的乙烯基含量,得到的结果与预期值相一致.将产物与国外牌号为184和VP7660的产品进行了膜性能比较,结果表明所得PVDMS性能良好,可替代进口硅橡胶产品.     

一种新型发用氨端基硅油的合成与表征

以八甲基环四硅氧烷（D4）为反应单体,以1,3-双（3-氨丙基）-1,1,3,3-四甲基二硅氧烷为封端剂,N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷（DL-602）为氨基硅烷偶联剂,氢氧化钾（KOH）为催化剂,二甲基亚砜（DMSO）为促进剂,采用本体聚合法合成了氨丙基封端的新型氨端基硅油,研究了反应温度、反应时间及KOH、DMSO用量对反应体系粘度及转化率的影响。结果表明,最适宜的工艺条件是：反应温度100℃,反应时间10h,KOH、DMSO用量分别为D。单体用量的0．03％,0．75％。     

端胺基聚丁二烯的合成与表征

采用阴离子聚合法合成了端羟基聚丁二烯,通过端基转化法将羟基转化成胺基,从而合成了端胺基聚丁二烯,通过红外光谱（IR）、核磁共振（1H-NMR）、凝胶渗透色谱（GPC）等对其进行了表征。结果表明,所合成的端胺基聚丁二烯相对分子质量分布较窄（≤1.10）,平均官能度接近2,且微观结构可调;通过羟基值与胺基值的测定表明,端基转化率大于98%。     

氨基聚硅氧烷改性HTPB型聚氨酯的合成与性能

以HTPB(端羟基聚丁二烯)、IPDI(异佛尔酮二异氰酸酯)和自制的NH2-PDMS(氨基聚硅氧烷)为主要原料制取NH2-PDMS改性PU(聚氨酯)预聚体;然后以MOCA(3,3′-二氯-4,4′-二苯基甲烷二胺)和硅氧烷偶联剂(DB-550)为交联固化剂,在湿态条件下交联固化,制取硅氧烷封端的HTPB型NH2-PDMS改性PU。结果表明:当R=2.5、w(NH2-PDMS)=12%和n(MOCA)∶n(DB-550)=9∶1时,采用预聚法合成的改性PU,其力学性能优异、吸水率较低以及耐老化性能较好。     

星形聚硅氧烷的合成及表征

以六苯基环三硅氮烷三锂盐和六甲基环三硅氧烷(D3)为原料，制备了环硅氧烷聚合反应引发剂“种子溶液”，并用^29Si NMR对其结构进行了表征；用“种子溶液”与聚合反应促进剂四氢呋喃或二甲基亚砜协同引发了D3或八甲基环四硅氧烷(D4)的聚合反应，并通过^1H NMR、^29Si NMR、^13C NMR及IR谱对聚合物的结构进行了表征。结果表明，“种子溶液”的结构是(Ph2SiN)3[Si(CH3)2OLi]3；“种子溶液”和促进剂可有效地引发环硅氧烷(D3或D4)的开环聚合反应，得到的聚硅氧烷具有星形结构，其主链中含有六苯基环三硅氮烷。     

Synthesis and thermal characterization of novel adamantane-based polysiloxane

Novel polysiloxane derivative having adamantyl moiety in the main chain (P1) was synthesized and characterized by differential scanning calorimetry (DSC), thermogravimetry (TG), and X-ray diffraction analysis. P1 was obtained by bulk polycondensation without catalysts as well as solution polycondensation of novel disilanol monomer, i.e., 1,3-bis[4-(dimethylhydroxysilyl)phenyl]adamantane (M1), which was prepared by the Grignard reaction using chlorodimethylsilane and 1,3-bis(4-bromophenyl)adamantane, followed by the hydrolysis catalyzed by 5% palladium on charcoal. The molecular weight of P1 was dependent on the concentration of M1 in solution polycondensation, and the high concentration of M1 would result in the high average molecular weight of P1. P1 exhibited the good solubility in common organic solvents, such as tetrahydrofuran (THF), chloroform, dichloromethane, and toluene. The glass transition temperature (T_g) of P1 determined from DSC would be dependent on the average molecular weight of P1. The highest T_g was 115 °C and much higher than that of poly(tetramethyl-1,4-silphenylenesiloxane) (−20 °C). The melting temperature (T_m) of P1 seemed to be independent of the average molecular weight of P1 and was in the range of 153-157 °C, which was comparable to the T_m of poly(tetramethyl-1,4-silphenylenesiloxane). The temperature at 5% weight loss (T_d5) of P1 determined by TG was also comparable to that of poly(tetramethyl-1,4-silphenylenesiloxane), indicating that P1 is a new polysiloxane derivative with the high T_g as well as good thermostability.     

Synthesis and characterization of hyperbranched photosensitive polysiloxane urethane acrylate

A novel hyperbranched photosensitive polysiloxane urethane acrylate (HBPSUA) based on hyperbranched polyesters (HBP-OH) has been synthesized. HBP-OH was synthesized from N,N-diethylol-3-amine methylpropionate as AB₂ monomer and trimethylolpropane (TMP) as a core molecule. The structure of the oligomer was characterized by FTIR, GPC and ¹H NMR. The molecular weight of the oligomer is about 10,000 and the viscosity is 4446 cps at room temperature. The HBPSUA possesses good compatibility with most of acrylate monomers. The effect of photoinitiators, monomers and light intensity on the photopolymerization kinetics of the oligomer HBPSUA was investigated by real-time infrared spectroscopy (RT-IR). The results show that HBPSUA can well photopolymerize under UV-irradiation in the presence of photoinitiators. Irgacure 1700 showed the highest initiating efficiency among those tested photoinitiators. The optimal concentration of photoinitiator (Darocur 1173) is determined as 0.05 wt.%. The system of HBPSUA/TPGDA has the high conversion of double bond and polymerization rate, and they are 92.38% and 22.25 s⁻¹, respectively. Compared with linear systems (PSUA), HBPSUA has the higher photopolymerization rate and lower viscosity. The cured film of HBPSUA possesses good flexibility.     

Synthesis and characterization of sustainable polyurethane modified by cyclic polysiloxane

In this article, a series of sustainable polyurethanes are prepared by introducing different content of cyclic polysilanol, which may act as a chain extender to replace 1, 4‐butanediol (BDO). Consequently, cyclic polysiloxanes are successfully incorporated into the molecular chains to afford organic–inorganic polyurethanes and then their effects on polyurethanes thermal properties and surface hydrophilicity are fully characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and contact angle testing. Results show that the hybrid polyurethanes display enhanced glass transition temperatures (T_g). While in terms of TGA, the effects of cyclic polysilanol on thermal properties seem complex, which would reduce the thermal stability in the first degradation process but enhance in the second process. The morphology observed by scanning electron microscopy (SEM) show that the inorganic constitutions, namely, cyclic polysilanol, may occur to self‐condensation or aggregation, which can help to explain the uncommon thermal phenomenon above. Thus, an opportunity of future applicability in the areas of sustainable polymer with improved properties can be envisioned in our research method of hybrid polyurethanes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41277.     

Synthesis and characterization of polyacrylate modified by polysiloxane latexes and films

In this paper, a new method was designed to prepare polyacrylate modified by polysiloxane latex particles, with methyl methacrylate (MMA) and butyl acrylate (BA) as main monomers, vinyltriethoxysilane (A-151) as functional monomer and octamethylcyclotetrasiloxane (D₄) as grafting agent. The chemical structure and morphology of the latexes were characterized by FTIR, TEM, and particle size analyzer. The properties of the films were tested in terms of static contact angle, water absorption and TGA. The results showed that uniform spherical structure and narrow particle size distribution could be obtained in the latexes. Furthermore, the hydrophobicity, low surface free energy and thermal stability were also noticeably increased with the content of polysiloxane. The mechanism of ring opening polymerization between D₄ and A-151 was also discussed; it turned out that it was quite important to control the pH under faintly acid conditions.     

Synthesis and characterization of alkali‐soluble photosensitive polysiloxane urethane acrylate

A new negative temperature coefficient of resistor (NTCR) thermistors based on nitrile butadiene rubber/magnetite (NBR/Fe₃O₄) nanocomposites were successfully fabricated by conventional roll milling technique. X‐ray diffraction and transmission (TEM) analysis showed that the product is mainly magnetite nanoparticles with diameter of 10‐13 nm. The microstructure of (NBR/Fe₃O₄) nanocomposites were examined by scanning electron microscopy (SEM) and FTIR spectroscopy. The dispersion of magnetite nanoparticles in the NBR rubber matrix and interfacial bonding between them were rather good. The thermal stability of nanocomposites was also obviously improved with the inclusion of the magnetite nanoparticles. The thermal conductivity, thermal diffusivity and specific heat of nanocomposites were investigated. The electrical conductivity of the NBR/Fe₃O₄ increases with the rise in temperature exhibiting a typical negative temperature coefficient of resistance (NTCR) behavior like a semiconductor. The nature of the temperature variation of electrical conductivity and values of activation and hopping energy, suggest that the transport conduction process is controlled by hopping mechanism. Values of characteristics parameters of the thermistors like thermistor constant, thermistor sensitivity and thermistor stability is quite good for practical application as NTCR devices at high temperature. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

侧基聚醚/二苯甲酮紫外吸收基聚硅氧烷的合成与表征

以H2PtCl6.6H2O为催化剂,甲苯为溶剂,通过硅氢化反应将端烯丙基聚氧乙烯聚氧丙烯醚(F6)和紫外吸收剂4-(3-烯丙氧-2-羟基)丙氧基-2-羟基二苯甲酮(AHDBP)同时引入聚甲基含氢硅氧烷(PHMS),合成了侧基聚醚/二苯甲酮紫外吸收基聚硅氧烷(PE-PUVSi),并用IR、UV和1HNMR对产物结构进行了表征。结果表明,在反应温度为80℃~100℃,甲苯用量为m(甲苯)∶m(PHMS)=1∶1,n(C=C)∶n(Si-H)=1.23∶1,n(F6)∶n(AHDBP)=2∶1的条件下可得到具有良好水溶性和对波长为243.6 nm、289.2 nm、325.0 nm处的紫外光有强吸收作用的产物。