过氧化苯甲酰在液态聚碳硅烷交联中的应用

聚碳硅烷热解前的交联对于提高其最终陶瓷产率至关重要.研究了过氧化苯甲酰(BPO)引发液态超支化聚碳硅烷(HBPCS)的交联反应对于陶瓷产率的影响.FT-IR和GPC证实,添加为0.5%～2.0%(质量分数,下同)的BPO,即可在80～140℃下引发HBPCS交联;在考察的实验条件下,提高交联温度、延长反应时间或增加BPO用量,均可提高HBPCS交联程度.BPO用量为2.0%时,HBPCS交联样品在1000℃下的陶瓷产率高达65%,比未加BPO的提高25%.     

Preparation of a hyperbranched polycarbosilane precursor to SiC ceramics following an efficient room-temperature cross-linking process

Room-temperature cross-linking of a hyperbranched polycarbosilane (HBPCS) with divinylbenzene (DVB) in the presence of the cyclohexanone peroxide–cobaltous naphthenate (CHP–CN) initiator system was studied. According to the Fourier transform infrared spectroscopy (FT-IR) and ¹H nuclear magnetic resonance (¹H NMR) results, the cross-linking reaction occurred via the vinyl polymerization. The GPC analysis confirmed the molecular weight of the cross-linked HBPCS significantly increased. Thermal behaviors of cross-linked HBPCS and original HBPCS were investigated by thermal gravimetric analysis-differential thermal analysis (TGA–DTA). The TGA results indicated that the ceramic yield of HBPCS remarkably increased by the cross-linking treatment. For the HBPCS/10 wt% DVB system, the maximum of reaction degree of HBPCS was obtained, which might be responsible for the highest ceramic yield of 70.1 wt% at 1000 °C. However, the ceramic yield of the non-crosslinked HBPCS was only 45 wt% at 1000 °C. The evolution of crystal structure of SiC as a function of pyrolysis temperature was traced by means of X-ray diffraction (XRD) and FT-IR. With the pyrolysis temperature increasing, the β-SiC peaks became sharper and the grain size also grew larger. As the DVB content increased, the intensity of β-SiC peaks significantly reduced, indicating smaller β-SiC grain size.     

UV电磁吸收油墨光聚合动力学研究

目的研究电磁吸收剂的加入对UV光固化体系光聚合动力学的影响。方法采用实时红外光谱技术研究光照强度、光引发剂含量、电磁吸收剂种类及其含量对光聚合动力学的影响。结果光强增加既可以提高聚合体系反应速率,又可以提高最终双键转化率。随着引发剂含量的增加,最终双键转化率从76%提高到100%,但过高的引发剂含量会降低相对反应速率。以氧化石墨烯为电磁吸收剂的油墨最终双键转化率较高,以Fe_3O_4为电磁吸收剂的油墨相对反应速率较高,达到最大相对反应速率时间在10s内。电磁吸收剂含量增大会降低油墨最终双键转化率,对油墨反应速率到达最大值的时间影响不显著。结论光照强度、光引发剂含量、电磁吸收剂种类及其含量对UV电磁吸收油墨光聚合过程均有较大影响。     

Synthesis and characterization of a novel dimethacrylate based on adamantane as possible dental resins

In this study a novel dimethacrylate based on adamantine (AB-GMA) was synthesized and proposed as possible dental monomers for dental resin mixtures. The monomer was prepared by the reaction of glycidyl methacrylate with dicarboxylic acid ester obtained from adamantanediol and maleic anhydride. The addition reaction of glycidyl methacrylate and the acidic compound was carried out in the presence of basic catalyst—tetraethylammonium bromide. AB-GMA was copolymerized with TEGDMA by varying the curing conditions: monomer composition, photoinitiator concentration and light intensity. A Real-time FTIR technique was employed to monitor the double bond conversion and the rate of polymerization. The prepared polymers were also subjected to dynamic mechanical studies (DMA). AB-GMA exhibited high degree of double bond conversion (up to 77%) and its thermo-mechanical properties were better than those of the commonly known dimethacrylates. AB-GMA showed no cytotoxicity toward growth of L929 cells and had good in vitro biocompatibility.     

光固化制备玻璃纤维(GF)增强不饱和聚酯树脂(UPR)复合筋材的研究

采用5种光引发剂体系,通过LED紫外光固化技术制备了玻璃纤维(GF)增强不饱和聚酯树脂(UPR)复合筋材(直径达1.5 cm),进行了热重分析以及力学性能测试,讨论了光引发剂种类及浓度(0.1％～2.0％,质量分数)、紫外光波长(365 nm、395 nm)、光照强度(30～750 mW/cm2)和光照时间对固化及制品...     

超支化聚硅氧基硅烷的合成及紫外光固化动力学

通过含硅氢键的超支化聚合物和乙烯基三烯丙基硅烷在铂炭催化剂作用下反应制备了可紫外光固化的超支化聚硅氧基硅烷。利用FT-IR,1H-NMR,13C-NMR,29Si-NMR和SEC/MALLS表征确定了聚合物的分子结构。通过UV-DSC研究了在不同温度、光强和氛围中聚合物的紫外光固化行为,给出了在这些条件下热流和转化率对时间的关系曲线。借助数学软件Matlab7.1将实验数据和动力学方程进行拟合,求得了动力学参数。     

辐射固化用聚硅氧烷的合成及表征

以端氢硅油（PHMS）和二缩三丙二醇二丙烯酸酯（TPGDA）为原料在铂催化剂的作用下,用硅氢加成反应合成了两端带有双键的辐射固化聚硅氧烷。采用红外光谱内标法测定了端氢硅油中活泼氢的转化率,通过正交试验确定了最佳反应条件：反应温度为100℃、反应时间为4h、二缩三丙二醇二丙烯酸酯与端氢硅油的物质的量比为1．2：1．0,反应催化剂氯铂酸为0．4％。产品经IR和HNMR表征,证明是所需产物。     

聚硅氧烷的紫外光固化特性及热解机理研究

通过调聚法合成了不同乙烯基含量的聚硅氧烷,利用红外光谱和凝胶渗透色谱对聚合物进行了表征.研究了光引发剂、固化氛围、乙烯基团含量对所制备聚硅氧烷紫外光固化行为的影响;并利用热失重分析仪对固化物的热解机理进行了探讨.实验表明在氮气气氛下,以IHT-PI-185为光引发剂,随着聚合物中乙烯基团含量增加,固化速率加快,且固化后聚合物的耐热性能提高.     

聚乙二醇双丙烯酸酯的紫外光聚合

以1-[4-(2-羟乙氧基)-苯基]-2-羟基-2甲基丙酮为光引发剂,通过紫外光自由基聚合制备了交联网状聚乙二醇双丙烯酸酯共聚物水凝胶。研究结果表明,随着光照时间的增加,单体共聚的转化率提高;随着引发剂浓度的增大,单体溶液中自由基增多,聚合速度增大。FI-IR结果表明PEGDA单体经30min紫外光照射后聚合完全。     

三元巯基/乙烯基硅氮烷UV固化制备聚合物陶瓷前驱体

采用差光量热扫描研究了三元巯基化合物与乙烯基硅氮烷紫外光固化特性,结果表明,随着光引发剂浓度和辐照强度的增加,体系聚合速率增大,体系终止方式以自由基双基偶合终止为主。聚合反应为一级,且聚合速率与乙烯基浓度有关,而与巯基浓度无关。对制备的聚合物陶瓷前驱体的基本性能进行分析表明,玻璃化转变温度随巯基化合物用量的减少而降低,在巯基-乙烯基硅氮烷等摩尔比时,体系的固化度最大。     

三元巯基／乙烯基硅氮烷UV固化制备聚合物陶瓷前驱体

采用差光量热扫描研究了三元巯基化合物与乙烯基硅氮烷紫外光固化特性,结果表明,随着光引发剂浓度和辐照强度的增加,体系聚合速率增大,体系终止方式以自由基双基偶合终止为主。聚合反应为一级,且聚合速率与乙烯基浓度有关,而与巯基浓度无关。对制备的聚合物陶瓷前驱体的基本性能进行了分析,结果表明,玻璃化转变温度随巯基化合物用量的减少而降低,在巯基-乙烯基硅氮烷等摩尔比时,体系的固化度最大。     

Production mechanism of polyzirconocarbo- silane using zirconium(IV)acetylacetonate and its conversion of the polymer into inorganic materials

The reaction of polycarbosilane with zirconium(IV)acetylacetonate proceeded at 573 K in nitrogen atmosphere by the condensation reaction of the Si–H bonds in polycarbosilane and the ligands of zirconium(IV)acetylacetonate accompanied by the evolution of acetylacetone, and then the molecular weight increased by the cross-linking reaction with a formation of Si–Zr bond. The obtained polyzirconocarbosilane showed higher ceramic yield than the polycarbosilane. Zirconium contained in the pyrolysed polyzirconocarbosilane was furthermore found to have the effect of inhibiting crystalline grain growth of -type SiC up to high temperature, so Si–Zr–C–O fibre, which was obtained by the use of polyzirconocarbosilane as precursor, showed high tensile strength up to high temperature.     

氰酸酯/环氧树脂CE-40体系的固化反应

采用差示扫描量热(DSC)方法计算得到氰酸酯/环氧树脂CE-40体系反应动力学常数,分析了温度和浓度对反应速率的影响,同时结合红外光谱对各温度段发生的反应进行了推断。研究表明,CE-40体系有两个反应温度区——低温区(150℃-180℃)和高温区(200℃-250℃)。低温区是环氧与氰酸酯直接反应,产物为三聚氰酸酯和口恶唑啉,反应速率对浓度敏感,随反应物浓度下降而降低;高温区是低温区的生成物与环氧的进一步反应,主要产物为口恶唑烷酮和异氰酸脲,反应温度决定了反应速率。     

异型(三叶型)截面碳化硅纤维制备工艺研究

以聚碳硅烷（PCS）为原料,经不熔化和烧成制得三叶型碳化硅纤维,研究了纺丝温度,压力,收丝速度对纤维异形度和当量直径的影响,研究表明,较低的纺丝温度,适当高的纺丝压力和较低的转速有利于提高纤维的异形度,抗拉强度平均提高约30％。     

聚碳硅烷制备SiC纤维的热化学交联研究

以异丙醇锆(ZIP)为交联剂、聚碳硅烷(PCS)为先驱体,在Ar气氛的保护下通过干法纺丝、热化学交联工艺使PCS从热塑性转变热固性结构.研究了该工艺对PCS纤维质量变化、Si-H反应程度、溶解性及氧含量等性能的影响.实验结果表明:在不熔化过程中,PCS结构中的Si-H键与ZIP反应,在PCS分子间形成Si-O-Zr交联结构,随着交联温度和保温时间的升高,Si-H反应程度和纤维失重率相应提高;在测试范围内最大Si-H反应程度为73.06%,失重率2.678%,氧含量低于2.0%.     

Production mechanism of polytitanocarbosilane and its conversion of the polymer into inorganic materials

The reaction of polycarbosilane with tetra-alkyltitanate proceeded at 300° C in nitrogen atmosphere by the condensation of Si-H bonds in polycarbosilane and the substituent groups of the tetra-alkyltitanate accompanied by evolution of alkan gas, and then the formation of Si-O-Ti bonds occurred. In this condensation reaction using tetra-isopropyl titanate, tetra-n-butyl titanate and tetra-2-ethylhexyl titanate, activation energies of the initial rate of the increase in molecular weight were 17.04, 20.07 and 31.07 kcal mol^–1 respectively, and thus the more bulky the substituent group of tetra-alkyltitanate, the lower the reactivity became. Of these alkyltitanates, tetra-2-ethylhexyl titanate was found to be the most advantageous reactant for obtaining polytitanocarbosilane with a narrow molecular weight distribution, low gel fraction and high titanium concentration. Polytitanocarbosilane with high titanium concentration was converted into the densified amorphous inorganic material with high Si-C bonding energy in high yield. Titanium contained in the pyrolysed polytitanocarbosilane was furthermore found to have the effect of inhibiting crystalline grain growth of -type SiC up to high temperature.     

Synthesis and photopolymerization of 2-(acryloyloxy) ethyl bis (2-(acryloyloxy) ethyl)carbamate

A low viscosity urethane diacrylate monomer of 2-(acryloyloxy) ethyl bis (2-(acryloyloxy) ethyl)carbamate (AEBAC) was prepared via a nonisocyanate route. The photopolymerization kinetics of this urethane acrylate was studied by real-time FTIR. The influences of light intensity, photoinitiator type, and concentration on the polymerization kinetics were discussed. The photopolymerization kinetic results indicated that the relationship between the polymerization rate (R _p) and the incident light intensity (I ₀) was R _p∞I ₀ ^0.5 and the maximum rate of polymerization (R _p,max) was proportional to [A]^0.5 ([A] was the molar concentration of initiator). The dynamic mechanical analysis (DMA) results indicated that the glass transition temperature (T _g) of the curing product of AEBAC was about 80°C.     

Synthesis and photopolymerization kinetics of a photoinitiator containing in-chain benzophenone and amine structure

A photoinitiator HTD bearing in-chain benzophenone (BP) and coinitiator tertiary amine, based on 4-hydroxybenzophenone (HBP), toluene-2,4-diisocyanate (TDI) and N,N-dimethylethanolamine (DMEA), was synthesized and characterized by ¹H-NMR and UV-vis absorption spectroscopy. HTD had longer absorption wavelength in the UV-vis absorption spectra than the low molecular counterpart BP. The kinetics of photopolymerization was studied by real-time Fourier transformation infrared (FTIR) spectroscopy. It showed that HTD was a more effective photoinitiator than BP. When this photointiator was used to initiate polymerization of acrylates, both rate of polymerization and final conversion increased with increase of initiator concentration and light intensity. UV-vis extract analysis showed that the extractability of HTD was much lower than BP/DMEA on the same environment condition.     

Synthesis and photopolymerization kinetics of a photoinitiator containing in-chain benzophenone and amine structure

A photoinitiator HTD bearing in-chain benzophenone (BP) and coinitiator tertiary amine, based on 4-hydroxybenzophenone (HBP), toluene-2,4-diisocyanate (TDI) and N,N-dimethylethanolamine (DMEA), was synthesized and characterized by ¹H-NMR and UV-vis absorption spectroscopy. HTD had longer absorption wavelength in the UV-vis absorption spectra than the low molecular counterpart BP. The kinetics of photopolymerization was studied by real-time Fourier transformation infrared (FTIR) spectroscopy. It showed that HTD was a more effective photoinitiator than BP. When this photointiator was used to initiate polymerization of acrylates, both rate of polymerization and final conversion increased with increase of initiator concentration and light intensity. UV-vis extract analysis showed that the extractability of HTD was much lower than BP/DMEA on the same environment condition.     

Characterization of a nanoparticle-filled resin for application in scan-LED-technology

Scan-LED-technology is a new rapid prototyping technique with increasing applications in the production of custom-made medical products. The present work is dealing with the examination of a silica/urethandimethacrylate (UDMA) nanocomposite for application in scan-LED-technology. The use of specific LED in a photo-DSC unit enables the simulation of crucial parameters of nanoparticle-filled resins for their application in scan-LED-technology. The conversion of double bonds during the curing reaction and the rate of conversion were studied as a function of radiation intensity, silica nanoparticle content, and silanization of the nanoparticles with 3-methacryloyloxypropyl-trimethoxysilane (MPTMS). The conversion of double bonds is increasing with increasing radiation intensity. The increasing conversion of the nanoparticle-filled resins is discussed as a combined effect of increasing nanoparticle content, alternated initiator/double bond ratio and increasing radiation intensity. A significant dependence of the reaction rate on nanoparticle content could not be found. Only for the unfilled resin, the rate was increasing at higher radiation intensities. The influence of residual solvent on conversion and rate of reaction was also analyzed. TGA measurements combined with FTIR were used to study the silanization of the nanoparticles. The silane layer thickness on the surface of the silica nanoparticles was determined.