阻燃剂六(4-酰腙基-2-甲氧基苯氧基)环三磷腈的合成及对ABS树脂的阻燃研究

以六氯环三磷腈为原料,与香兰醛发生亲核取代制得六(4-甲酰基-2-甲氧基苯氧基)环三聚磷腈（I）,I再与取代酰肼反应得到相应的六(4-酰腙基-2-甲氧基苯氧基)环三磷腈类化合物（IIa-IIg）,利用IR、1HNMR、13CNMR、ESI-MS和元素分析对化合物的结构进行了表征;并用该化合物（IIa-IIg）对ABS树脂进行阻燃处理,测试了其限氧指数和UL 94垂直燃烧性能。结果表明,所合成的化合物（IIa-IIg）对ABS树脂均具有显著地阻燃效果,化合物IIe、IIf阻燃效果最好。     

阻燃剂六(4-酰腙基-2-甲氧基苯氧基)环三磷腈的合成及对ABS树脂的阻燃

以六氯环三磷腈为原料,与香兰醛发生亲核取代反应制得六(4-甲酰基-2-甲氧基苯氧基)环三聚磷腈(Ⅰ),Ⅰ再与取代酰肼反应得到相应的六(4-酰腙基-2-甲氧基苯氧基)环三磷腈类化合物(Ⅱa~Ⅱg),利用IR、1HNMR、13CNMR、ESI-MS和元素分析对化合物的结构进行了表征;并用化合物(Ⅱa~Ⅱg)对ABS树脂进行阻燃处理,测试了其限氧指数和UL 94垂直燃烧性能。结果表明,化合物(Ⅱa~Ⅱg)对ABS树脂均具有显著地阻燃效果,化合物Ⅱe、Ⅱf阻燃效果最好。     

六苯氧基环三磷腈的合成及对IC封装用EMC的无卤阻燃

采用滴加工艺,制备了六苯氧基环三磷腈,探索出了较佳的合成工艺,并对其进行了FT-IR表征和分析。采用自制的六苯氧基环三磷腈作为阻燃剂,制备了无卤阻燃的大规模集成电路封装用环氧树脂模塑料（EMC）。结果表明,六苯氧基环三磷腈对环氧树脂具有较好的阻燃作用,所制备的EMC可达到UL-94 V0级阻燃性能,其氧指数达到33.1%,阻燃性能大大优于传统含溴阻燃体系,可用于制备大规模集成电路封装用EMC。     

苯氧基环磷腈合成处理方法的改进及表征

苯氧基环三磷腈是一种重要的磷腈化合物,而苯氧基环磷腈（PCPZ）的制备会产生大量的副产物和过量的苯酚钠存在,使得合成实验的后处理较复杂且得很难得到纯度很高的产物。利用苯酚钠和六氯环三磷腈制备的苯氧基环三磷腈,根据产物易溶于四氢呋喃但难溶于水这一特点,找到了一种很简单的方法,使产物在大量水中结晶析出。这个方法操作方便,通...     

六(4-醛基苯氧基)环三磷腈的合成、表征及其热性能研究

通过六氯环三磷腈和4-羟基苯甲醛的亲核取代反应,成功合成出目标化合物六(4-醛基苯氧基)环三磷腈(HAPCP).并考察了溶剂和缚酸剂类型、缚酸剂粒度、原料配比及反应时间对产物收率的影响.利用红外光谱和核磁共振对目标化合物的结构进行了表征,同时用热失重分析研究了目标化合物的热稳定性.结果表明:目标化合物在400℃左右有明...     

4，4’-（4，4’-砜基二苯氧基）二苯甲酰氯（SODBC）的合成

以对甲基苯酚、4,4’-二氯二苯砜为原料，通过亲核取代反应合成了4，4’-二（4-甲基苯氧基）二苯砜，用高锰酸钾将甲基氧化得到4，4’-（4，4’-砜基二苯氧基）二苯甲酸（SoDBA），后者在二氯亚砜和路易斯碱的催化下合成了4，4’-（4，4’-砜基二苯氧基）二苯甲酰氯（SoDBC）白色固体。用FT-IR、H—NMR、3C—NMR、DSC等对其进行了表征，实验证明该化合物具有预期的结构和较高的纯度。     

一种磷氮系阻燃剂的合成、表征及对尼龙6的阻燃性能研究

以五氯化磷、氯化铵、苯酚、氢氧化钠为原料,合成磷氮系阻燃剂六苯氧基环三磷腈,通过红外光谱、核磁、热重分析等手段对其结构进行了表征。将其与尼龙6按比例共混后测试了其氧指数和力学性能等指标。结果表明,当该化合物含量提高时,其氧指数升高,力学性能有所下降,但在一定含量范围内,对力学性能影响不大,表明六苯氧基环三磷腈可以有效改善尼龙6的阻燃性能,是一种高效的磷氮系阻燃剂。     

六苯氧基环三磷腈的合成及其在PP中的应用研究

以六氯环三膦腈和苯酚钠为原料制备了六苯氧基环三磷腈（PCPZ）,产物收率高于97％,纯度达99％以上,利用高效液相色谱（HPLC）、傅立叶红外光谱（FT—IR）31P核磁共振（叫PNMR）和‘H核磁共振（’HNMR）表征产物并确定其分子结构。将合成的PCPZ和焦磷酸蜜胺盐（MPP）、三聚氰胺（MA）、助剂（AA）复配成膨胀型阻燃剂（IFR）,并添加到聚丙烯（PP）中制备成阻燃聚丙烯（PP）。利用MINITAB软件的混料设计功能研究了复配IFR对阻燃PP体系的阻燃性能和力学性能的影响。结果表明,阻燃效果较好的IFR配方：PCPZA8．6％、MPP25．0％、MA12．5％和AA13．9％,IFF添加量为30％时,IFR—PP的LOI为33％,通过UL94V-0级测试,拉伸强度为25．98MPa,断裂伸长率为230％,缺1：7冲击强度为4．72kJ／m。。     

氰氟草酯的合成

以（S）-乳酸甲酯为原料，与对甲苯磺酰氯反应制备（S）-对甲苯磺酰乳酸甲酯，再与对苯二酚反应制备（R）-2-（4-羟基苯氧基）丙酸乙酯，然后与3，4-二氟苯腈反应制备（R）-2-[4-（4-氰基-2-氟苯氧基）苯氧基]丙酸乙酯，经水解、酯化合成氰氟草酯，总收率49％，化学纯度95％，光学纯度98％。     

环三磷腈磷酸酯衍生物的合成及结构鉴定

以六氟环三磷腈和对溴苯酚为原料、碳酸钾为催化剂、丙酮为溶剂,在氮气保护下合成六（4-溴苯氧基）环三磷腈,再与三乙氧基磷反应制得环三磷腈磷酸酯的衍生物。通过1^HNMR、13^CNMR、31^PNMR对中间化合物和目标化合物进行了结构表征。     

Synthesis and characterization of poly{hexakis[(methyl)(4‐hydroxyphenoxy)]cyclotriphosphazene}

The reaction of methylhydroquinone with hexachlorocyclotriphosphazene in the presence of a base, 4‐picoline, in cyclohexane was investigated. Nuclear magnetic resonance spectroscopy, multiangle laser light scattering, and elemental analyses were performed on the product and two other related phosphazene materials produced by analogous synthetic routes: poly[hexakis(4‐hydroxyphenoxy)cyclotriphosphazene] (1) and hexakis[(3‐tert‐butyl)(4‐hydroxyphenoxy)]cyclotriphosphazene (2) . Unlike the data for 2 where the tert‐butyl moiety enforced regiospecific nucleophilic addition, the data for the methylhydroquinone‐substituted cyclotriphosphazene product indicate that the less sterically bulky methyl group provides only limited protection for the adjacent hydroxyl group. The result is the formation of a low molecular weight oligomer, poly{hexakis[(methyl)(4‐hydroxyphenoxy)]cyclotriphosphazene} (3) , instead of a discrete cyclic trimer species. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3439–3446, 2001     

Reactions and polymerization of hexa‐[3‐tert‐butyl‐4‐ hydroxyphenoxy]cyclotriphosphazene: A new method for the preparation of soluble cyclomatrix phosphazene polymers

Novel cyclomatrix phosphazene‐containing polyester polymers were synthesized through the reaction of a polyhydroxylated cyclotriphosphazene and a bifunctional acid chloride. To demonstrate the chemistry of the free hydroxyl of hexa‐[3‐tert‐butyl‐4‐hydroxyphenoxy]cyclotriphosphazene, nucleophilic displacement reactions were performed with both acetic anhydride and alkyl chlorides. This work compares favorably to literature data for the chemistry of hexa‐[4‐hydroxyphenoxy]cyclotriphosphazene, whose hydroxyl is not hindered by an adjacent substituent. The hindered site of hexa‐[3‐tert‐butyl‐4‐hydroxyphenoxy]cyclotriphosphazene was found to react with bidentate acid chlorides to yield new high polymers. The phosphazene‐containing polyesters were observed to have good solubility in polar organic solvents. Characterization of these new materials was performed using dilute solution laser light scattering techniques, thermal analysis, and NMR spectroscopy. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 242–251, 2001     

Novel one-component molecular glass photoresist based on cyclotriphosphazene containing t-butyloxy carbonyl group for i-line lithography

Hexakis(4-formylphenoxy) cyclotriphosphazene (HAPCP), substitution reaction product of hexachlorotriphosphazene (HCTP) with p-hydroxybenzaldehyde, was reduced by sodium borohydride to afford hexakis[4-(hydroxymethyl) phenoxyl] cyclotriphosphazene (HHPCP). The hydroxyl group of this compound was then protected by the reaction with di-tert-butyl dicarbonate ester (DBDC) in the presence of 4-dimethylaminopyridine (DMAP) as catalyst to give t-butyloxy carbonyl (tBOC) protected HHPCP. Fourier-transform infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance (¹H NMR) were employed to characterize the chemical structure, indicating that the synthesis was successful. Thermal behavior was characterized by thermogravimetric analysis (TGA), the results showed that the initial thermal decomposition temperature occurred at approximately 170 °C, X-ray diffraction analysis (XRD) results showed that the tBOC protected HHPCP derivatives had amorphous form, and performed excellent film-forming property. Upon irradiation to 365 nm exposure, the photoacid generated proton H⁺, which can catalyze the deprotection of acid labile tBOC group. This type of novel molecular glass photoresist based on hexachlorotriphosphazene showed high sensitivity, making it possible to fabricate 1 μm line and space pattern under i-line exposure.     

微波助离子液体中TiO_2/PEMA复合材料的制备及性能

在离子液体([Bmim]BF_4)中采用微波辐射加热法合成了TiO_2/PEMA复合材料,用XRD、SEM和IR对其进行表征。通过测试复合材料在乙酸乙酯中的吸光度及对甲基橙溶液的降解率,考察离子液体用量、微波功率、反应温度和反应时间等因素对复合材料分散性和光催化活性的影响。结果表明,制备TiO_2/PEMA复合材料的最佳条件:离子液体2.0 mL,钛酸丁酯3.4 mL,甲基丙烯酸乙酯1.0 mL,微波功率600 W,反应温度70℃,反应时间45 min。制备的复合材料亲油性大大提高,在乙酸乙酯中有较好的分散性,该复合材料不需要高温焙烧就具有较高的光催化活性,紫外光照射1.5 h,甲基橙降解率为99.4%。     

Thermal Behaviors of Bisazocalix[4]arene Derivatives

In this article, calix[4]arene (4) was prepared by debutylation and hydrolyses reacting from 25,27-dibenzoyl-26,28-dihydroxy-5,11,17,23-tetra(tert-butyl)calix[4]arene (2). Azocalix[4]arenes (6a-c) were coupled by linking 4-methoxy, 4-ethyl, and 4-nitroaniline to calix[4]arene (4) through a diazo-coupling reaction. Thermal behavior characteristics and decomposition routes of 25,26,27,28-tetrahydroxy-11,23-di(tert-butyl)-5,17-(p-substitue phenyl)azocalix[4]arene (6a-c) were investigated in air atmosphere by means of thermogravimetry (TG), differential thermogravimetry (DTG), and differential thermal analysis (DTA) analyses. It was found that the decomposition of all compounds complete with two exothermic stages which corresponded to removal of substitute groups (methoxy-, ethyl-, nitro-) and second stage rest of structure decomposition.     

The liquid crystalline state in organophosphazenes with biphenyl mesogenic groups

Hexakis[4-(4-decyloxy)biphenoxy]cyclotriphosphazene (HDBCTP), hexakis [4-(4-cyano)biphenoxy]cyclotriphosphazene (HCBCTP), poly{bis[4-(4-decyloxy) biphenoxy]phosphazene} (PDBP), and poly{bis[4-(4-cyano)biphenoxy] phosphazene} (PCBP) were synthesized from hexachlorocyclotriphosphazene or polydichlorophosphazene and the corresponding sodium alkoxide. Their phase transition and liquid crystalline state were then studied by differential scanning calorimetry (DSC) measurements and polarizing microscope observation. We found enantiotropic smectic C in HDBCTP between 431 and 457 K and monotropic nematic between 529 and 488 K in HCBCTP only in the cooling process. No mesomorphic state was found in PDBP and PCBP.     

酚氧基环磷腈阻燃环氧树脂的热解过程研究

用自制六氯环三磷腈通过亲核取代反应制备了六（酚氧基）环三磷腈（HPCP）,并将HPCP与环氧树脂（EP）以不同比例共混,固化成型,采用氧指数仪和热质联用仪对其热性能和降解机理进行分析。结果表明,在EP中加入HPCP可提高材料的热解残炭率;当添加10份HPCP时,阻燃EP的极限氧指数可达27.0 %;HPCP的阻燃机理是其所含的氮磷2种元素的协效作用与自缩合放出H2O分子2种阻燃机理的共同作用。     

Synthesis, characterization and thermal properties of hexaarmed star-shaped poly(ε-caprolactone)-b-poly(d,l-lactide-co-glycolide) initiated with hydroxyl-terminated cyclotriphosphazene

Hexakis[p-(hydroxymethyl)phenoxy]cyclotriphosphazene was prepared by the reaction of hexachlorocycltriphosphaneze with the sodium salt of 4-hydroxybenzaldehyde and subsequent reduction of aldehyde groups to alcohol groups by using sodium borohydride. Hexaarmed star-shaped hydroxyl-terminated poly(ε-caprolactone) (PCL) were successfully synthesized via ring-opening polymerization of ε-caprolactone (CL) with the above hydroxyl-terminated cyclotriphosphazene initiator and stannous octoate catalyst in bulk. The number-average molecular weight of PCL linearly increased with the molar ratio of monomer to initiator. The star-shaped PCL with hydroxy end groups could be used as a macroinitiator for block copolymerization with d,l-lactide (d,l-LA) and glycolide (GA) using stannous octoate catalyst. IR, ¹H NMR and GPC analysis showed the star-block copolymers were successfully synthesized and the molecular weights and the unit composition of the star-shaped block copolymers were controlled by the molar ratios of d,l-LA and GA monomers to CL. The copolymer presented a two-phase structure, namely, PCL crystalline and d,l-LAGA amorphous domains, which made the copolymer different from linear PCL and star-shaped PCL in crystallinity and thermal behaviors.     

一种Co~(2+)荧光探针的合成及其荧光性质

以2-甲基-6-硝基苯胺和水杨醛为原料合成了4-羟甲基-2-(4-羟甲基-1H-苯并[d]咪唑-2-基)苯酚,并进行了1H NMR结构表征和紫外、荧光性能的测定。荧光量子收率为0.21,斯托克斯位移为126。测定甲醇溶液中13种金属离子对化合物的荧光性质的影响,发现Co2+对该化合物具有明显优于其它金属离子的荧光淬灭效果,表明化合物对Co2+具有较好的选择性,可作为荧光淬灭型Co2+荧光传感器开展进一步的研究。