聚对苯二甲酸乙二酯—聚四亚甲基醚嵌段共聚物的玻璃化转变

<正> 对于[A—B]_n型多嵌段共聚物的结构形态和性能的研究,近年来引起了广泛的兴趣。这里“A”表示硬链段即芳族结晶性聚酯或能形成氢键的氨酯键;“B”表示软链段的脂族聚醚或聚酯。由于两链段在热力学上不相容性,而呈现出两相分离,这种不相容性特征是与两嵌段的化学结构、链段长度、链段有否形成氢键或结晶和制备方法密切相关。聚酯-聚醚多嵌段共聚物鉴于两嵌     

国内文献摘要

正一种两嵌段聚乙烯基超支化聚合物及其制备方法和应用本发明涉及高度支化聚合物的制备技术领域,具体涉及一种两嵌段聚乙烯基超支化聚合物及其制备方法和应用,其制备方法,包括两个步骤:一、制备末端羟基聚乙烯共聚物;二、制备两嵌段聚乙烯基超支化聚合物。本发明设计合成聚乙烯-超支化嵌段聚合物,一段为线性聚乙烯链,另一段为超支化聚合     

国外瞭望

陶氏化学研发出新型烯烃嵌段共聚物陶氏化学的Insite催化剂技术中心研发出一种新型烯烃嵌段共聚物(OBCs),据称可挑战EVA和苯乙烯嵌段共聚物,在某些应用方面甚至可挑战TPV。该InfuseOBC聚合物将Insite催化剂与一种新型聚合成分结合在一起,形成一种链移动剂,它能在连续工艺中把高熔点的硬段聚合物与韧性聚合物软段在单一     

有机硅-聚酰胺嵌段共聚物研究进展

综述了有机硅-聚酰胺嵌段共聚物制备及其结构-性能耦合关系的研究现状。分别采用大分子引发法可制备有机硅-聚酰胺二嵌段或三嵌段共聚物,以及聚合物-单体缩合或聚合物-聚合物缩合法可制备有机硅-聚酰胺多嵌段共聚物。分子量、组成和序列结构对有机硅-聚酰胺嵌段共聚物的微观相分离有显著影响,进而影响其宏观性能。加强对有机硅-聚酰胺嵌段共聚物"制备-结构-性质"关系的剖析,并寻找环境更友好的制备路线,将是今后研究的重点。     

三嵌段共聚物PS-b-PEG-b-PS与聚苯乙烯共混薄膜的表面形貌与性能研究

使用原子转移自由基聚合(ATRP)制备三嵌段共聚物PS-b-PEG-b-PS.通过红外光谱、核磁共振氢谱(1H-NMR)和凝胶渗透色谱(GPC)对嵌段共聚物结构及分子量进行表征.将嵌段共聚物与聚苯乙烯溶液共混成膜,使用原子力显微镜(AFM)和接触角测试仪(CA)对不同含量嵌段共聚物共混膜的表面形貌和性能进行了分析表征.PEG链段与PS链段在共混膜中发生了微相分离,由于PEG链段对PS链段的热力学排斥作用以及PS的硬链段特性,PS不能在PEG微区上方形成覆盖,因而在薄膜表面形成大量孔洞,PEG微相区位于孔洞底部.随嵌段共聚物含量增加,孔洞(PEG微区)尺寸增大.当嵌段共聚物含量增加10％以后,孔洞内出现PS微相区,导致形成“胞状”结构.嵌段共聚物含量增加使得共混薄膜的亲水性和表面张力增大.     

PS-b-P4VP的合成及其薄膜的微相分离形貌

通过原子转移自由基聚合（ATRP）方法制备了聚苯乙烯-b-聚（4-乙烯基吡啶）二嵌段共聚物（PS-b-P4VP）,使用核磁共振（1H NMR）和凝胶渗透色谱（GPC）对嵌段共聚物进行了表征。将PS-b-P4VP/三氯甲烷溶液旋涂成膜,使用原子力显微镜（AFM）观察热处理条件对薄膜微相分离形貌的影响。结果表明,PS-b-P4VP薄膜会发生微相分离,形成以PS链段为分散相、P4VP链段为连续相基体的纳米尺度微相分离形貌。热处理条件的改变使薄膜呈现不同程度的微相分离形貌结构,提高热处理温度以及延长热处理时间均有利于促进嵌段共聚物的微相分离,使微相分离程度加大。在150℃、24 h的热处理条件下,PS-b-P4VP薄膜形成了PS微相区以规则的柱状形态在薄膜表面突起的微相分离形貌,且分布均匀,界面清晰。     

不同拓扑结构PEG-PCL嵌段共聚物的结晶研究

合成了不同拓扑结构的聚乙二醇-聚己内酯(PEG-PCL)嵌段共聚物,共聚物结构分别为AB型线性两嵌段(diblock)、ABA型线性三嵌段(triblock)、AB_2型星形(star shape)嵌段共聚物。通过表征发现嵌段共聚物的分子量与设计的分子量接近,且相对分子量分布窄。通过XRD、DSC、热台偏光显微镜(HSPOM)研究了拓扑结构对共聚物结晶的影响。ABA聚合物中间的PEG亲水链受到两端PCL链段阻碍,其结晶衍射峰最弱。三者的等温结晶速率按AB、AB_2、ABA的速率递减,形成的球晶结构规整度则逐渐增加。     

聚偏氟乙烯-b-聚甲氧基聚乙二醇甲基丙烯酸酯共聚物的合成和凝聚态结构

为了制备综合性能优异的固态聚合物电解质基材,通过碘转移活性自由基聚合(ITP)合成聚偏氟乙烯-b-聚甲氧基聚乙二醇甲基丙烯酸酯(PVDF-b-PPEGMA)共聚物。通过1H-核磁共振和凝胶渗透色谱证明了共聚物分子的合成,采用红外光谱和透射电子显微镜分析共聚物的凝聚态结构,并测试共聚物/双三氟甲基磺酰亚胺锂(LiTFSi)固态聚合物电解质的电导率。结果表明：聚甲氧基聚乙二醇甲基丙烯酸酯(PPEGMA)链段的嵌段引入可促进β相聚偏氟乙烯(PVDF)结晶的形成;PVDF和PPEGMA链段热力学不相容,嵌段共聚物存在微相分离,随着PPEGMA嵌段比增加,共聚物由“海-岛”相结构向双连续相结构转变。PPEGMA质量分数为25.5%的嵌段共聚物与锂盐混合(氧化乙烯与Li+物质的量比n(EO):n(Li+)为10:1)能达到9.4×10^-5 S·cm^-1的室温离子电导率。     

PE-b-PEO嵌段共聚物的合成及其芳烃/烷烃渗透汽化分离性能

采用阴离子聚合方法合成了具有不同环氧乙烷聚合度的聚丁二烯-b-聚环氧乙烷嵌段共聚物(PB-b-PEO嵌段共聚物),然后催化加氢得到聚乙烯-b-聚环氧乙烷嵌段共聚物(PE-b-PEO嵌段共聚物),使用凝胶渗透色谱仪(GPC)、核磁共振氢谱(1H-NMR)对共聚物进行了分析,结果表明所得聚合物具有预定的结构。通过熔融压片的方法制备PE-b-PEO嵌段共聚物均质膜,考察了PE-b-PEO嵌段共聚物分子链中聚环氧乙烷的聚合度对渗透汽化分离性能的影响。     

一步法合成聚醚酰胺嵌段共聚物及其抗静电性能研究

采用一步法合成了由聚乙二醇(PEG)链段和聚酰胺6(PA6)链段组成的聚醚酰胺嵌段共聚物,用红外光谱和核磁共振波谱等手段确证了它的化学结构。随着合成配方中己内酰胺用量的减少,聚醚酰胺嵌段共聚物相对分子质量下降,PA6链段变短。合成的聚醚酰胺嵌段共聚物具有微相分离结构,表面电阻率随着其中PEG链段含量的增加而下降。将合成的聚醚酰胺嵌段共聚物以10%的质量分数添加到ABS塑料中,其表面电阻率由1014Ω量级下降到1011Ω量级,拉伸强度变化不大,断裂伸长率有所下降。     

DPE法合成双亲性丙烯酸酯嵌段共聚物及用于颜料分散剂的研究

以1,1-二苯基乙烯（DPE）为分子量调节剂,偶氮二异丁腈（AIBN）为引发剂进行甲基丙烯酸丁酯（BMA）的可控自由基聚合（DPE法）。研究了溶剂、DPE用量及反应温度对于聚合的影响,得到分子量分布较窄（PDI=1.43）的含有DPE半醌式休眠种结构的聚甲基丙烯酸丁酯（PBMA）。以PBMA为引发剂引发甲基丙烯酸二甲氨基乙酯（DMAEMA）聚合,得到分子量分布较窄的（PDI=2.0）双亲性嵌段共聚物（PBMA-b-PDMAEMA）。核磁共振氢谱（¹H NMR）测得共聚物组成与GPC测试结果相近。差示扫描量热分析（DSC）测试表明嵌段共聚物在11℃和35℃处有两个玻璃化转变温度。色浆的流变和粒径测试及漆膜性能测试表明,将所得双亲性嵌段共聚物作为酞菁蓝颜料分散剂,可以明显提高酞菁蓝颜料在丙烯酸酯树脂中的分散效率。     

NaCl/SDS协同作用下超声辐射引发MMA无皂乳液聚合的研究

在超声辐射下,未添加引发剂,以NaCl和小于临界胶束浓度的乳化剂（十二烷基硫酸钠,SDS）混合水溶液为介质,快速无皂乳液聚合甲基丙烯酸甲酯（MMA）,获得稳定的聚甲基丙烯酸甲酯白色乳液。讨论了超声功率、乳化剂浓度和无机盐浓度对单体转化率的影响;比较单体MMA和聚合物PMMA的红外光谱图（FT-IR）,发现聚合后1637cm-1处的C=C双键吸收峰几乎消失,这表明单体MMA在超声辐射条件下已基本上聚合;聚合物PMMA的GPC曲线为单峰,Mn=384706,Mw=529554,PDI=1.37,聚合物分子量较大,分布较窄;TEM观察发现,得到的乳胶粒大小、分布均匀,粒径较小;探讨了超声辐照无皂乳液聚合的可能过程。     

Functional copolymers of p‐cumyl phenyl methacrylate and glycidyl methacrylate: Synthesis,characterization, and reactivity ratios

Free‐radical polymerization of p‐cumyl phenyl methacrylate (CPMA) was performed in benzene using bezoyl peroxide as an initiator at 80°C. The effect of time on the molecular weight was studied. Functional copolymers of CPMA and glycidyl methacrylate (GMA) with different feed ratios were synthesized by free‐radical polymerization in methyl ethyl ketone at 70°C, and they were characterized by FTIR and ¹H‐NMR spectroscopy. The molecular weights and polydispersity indexes of the polymers and copolymers were determined by gel permeation chromatography. The copolymer composition was determined by ¹H‐NMR. The glass‐transition temperature of the polymer and the copolymers was determined by differential scanning calorimetry. The reactivity ratios of the monomers were determined by the Fineman–Ross and Kelen–Tudos methods. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 336–347, 2005     

Methyl Methacrylate-8-Quinolinyl Acrylate Copolymers-I: Synthesis and Characterization

Abstract

The monomer, 8-quinolinyl acrylate (8-QA) was synthesized and characterized by IR and ¹H-NMR spectroscopy, high performance liquid chromatography (HPLC) and elemental analysis. The homopolymer, poly (8-QA) and its copolymers with methyl methacrylate (MMA) in different monomer feed ratio were prepared by free radical polymerization using dimethyl formamide (DMF) as a solvent and 2,2′-azobis-isobutyronitrile (AIBN) as an initiator. The resulting polymers were characterized by IR spectroscopy, UV-visible spectrophotometry, gel permeation chromatography (GPC), solution viscosity and thermal analysis (TG and DSC). It was observed from the GPC results that as the 8-QA content in the copolymer increases, the molecular weight decreases whereas polydispersity increases with increasing 8-QA content in the copolymers. It was also observed from the TG data that the initial decomposition temperature (IDT) of the copolymers decreases with increasing 8-QA content in the copolymers.     

Synthesis of amphiphilic diblock copolymers by direct radical polymerization of acrylic acid via DPE method

Amphiphilic diblock copolymers, poly(methyl methacrylate)-b-poly(acrylic acid) (PMMA-b-PAA) was prepared by 1,1-diphenylethene (DPE) method. First, free radical polymerization of methyl methacrylate was carried out with AIBN as initiator in the presence of DPE, giving a DPE-containing PMMA precursor with controlled molecular weight. Amphiphilic diblock copolymer PMMA-b-PAA was then prepared by radical polymerization of acrylic acid (AA) in the presence of PMMA precursor. The formation of PMMA-b-PAA was confirmed by ¹H NMR spectrum and gel permeation chromatography. Transmission electron microscopy and dynamic light scattering were used to detect the self-assembly behavior of the amphiphilic diblock polymers in methanol.     

Block copolymers obtained by free-radical mechanism. I. Methyl methacrylate and styrene

Block copolymers were synthesized using styrene and methyl methacrylate as the monomers and a multifunctional initiator, di-t-butyl 4,4′-azobis(4-cyanoperoxyvalerate). The unique feature of this sequential initiator is the fact that the formation of the free radicals can be achieved thermally and/or by a redox system at different stages. The polymerizations for the formation of the block copolymer were carried out in two stages. First, a polymeric initiator was synthesized, which was then used in the second stage to initiate the polymerization of the second monomer. Styrene and methyl methacrylate were used as the comonomers. Selective solvent fractionation was used for the separation of the block from the homopolymers. The separation technique was found to be efficient, giving pure block copolymers which could subsequently be characterized by GPC, NMR, IR, and EM techniques.     

Synthesis and characterization of poly[4‐(2‐thiazolylazo)phenyl methacrylate]‐co‐poly(methyl methacrylate)

A new methacrylic monomer, 4‐(2‐thiazolylazo)phenylmethacrylate (TPMA) was synthesized. Copolymerization of the monomer with methyl methacrylate (MMA) was carried out by free radical polymerization in THF solution at 70 ± 0.5°C, using azobisisobutyronitrile (AIBN) as an initiator. The monomer TPMA and the copolymer poly(TPMA‐co‐MMA) were characterized by Fourier transform infrared (FTIR), ¹H nuclear magnetic resonance (NMR), and elemental analysis methods. The polydispersity index of the copolymer was determined using gel permeation chromatography (GPC). Thermogravimetric analysis (TGA) of the copolymer performed in nitrogen revealed that the copolymer was stable to 270°C. The glass transition temperature (T_g) of the copolymer was higher than that of PMMA. The copolymer with a pendent aromatic heterocyclic group can be dissolved in common organic solvents and shows a good film‐forming ability. Both the monomer TPMA and the copolymer poly (TPMA‐co‐MMA) have bright colors: orange and yellow, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2152–2157, 2007     

ATRP法制备纳米铜／PMMA-b-PSt复合材料及其表征

在超声辐射作用下,以α-溴代丙酸乙酯为引发剂,溴化亚铜／2,2-联吡啶为催化体系,通过原子转移自由基聚合（ATRP）制备了预聚物PMMA-Br。以此预聚物为大分子引发剂,苯乙烯为共聚单体进行ATRP反应,制得PMMA-b-PSt嵌段共聚物。通过硼氢化钠还原聚合物体系中的溴化亚铜,制得纳米铜／PMMA—b—PSt复合材料。采用红外吸收光谱（IR）、核磁共振（^1H-NMR）、凝胶渗透色谱（GPC）和透射电子显微镜（TEM）等手段对样品进行表征,并用热重分析法对样品的热性能进行了研究。实验结果表明,采用超声方法成功合成了以PMMA-b-PSt为壳和纳米铜为核的复合材料,并发现这种复合材料可以形成以PMMA-b-PSt为连续相和纳米铜为分散相的圆环状组装结构,热分析结果表明纳米铜粒子的存在降低了嵌段共聚物的分解温度。     

Synthesis and thermal properties of poly(methyl methacrylate)‐poly(L‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer

Poly(methyl methacrylate)‐poly(L ‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer was prepared using atom transfer radical polymerization (ATRP). The structure and properties of the copolymer were analyzed using infrared spectroscopy, gel permeation chromatography, nuclear magnetic resonance (¹H‐NMR, ¹³C‐NMR), thermogravimetry, and differential scanning calorimetry. The kinetic plot for the ATRP of methyl methacrylate using poly(L ‐lactic acid) (PLLA) as the initiator shows that the reaction time increases linearly with ln[M]₀/[M]. The results indicate that it is possible to achieve grafted chains with well‐defined molecular weights, and block copolymers with narrowed molecular weight distributions. The thermal stability of PLLA is improved by copolymerization. A new wash‐extraction method for removing copper from the ATRP has also exhibits satisfactory results. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

ARGET-ATRP合成双亲性嵌段共聚物及对二氧化钛分散效率的影响

以CuBr2（相对于单体物质的量的0.02%或0.01%）和还原剂、配体混合物为催化体系进行甲基丙烯酸 2(N,N-二甲氨基)乙酯（DMAEMA）的电子转移再生催化剂原子转移自由基聚合（ARGET-ATRP）,研究了溶剂、配体和还原剂种类对聚合的影响,得到分子量分布较窄的（PDI=1.56）聚甲基丙烯酸 2(N,N-二甲氨基)乙酯（PDMAEMA-Br）。以PDMAEMA-Br为引发剂引发丙烯酸丁酯进行“一步法”ARGET-ATRP聚合,得到分子量分布很窄的（PDI=1.4）双亲性嵌段共聚物（PDMAEMA-bPBA)。核磁共振氢谱（1H NMR）测得共聚物组成与GPC测试结果相近。差示扫描量热分析（DSC）测试表明嵌段共聚物在-40.1℃和123.5℃处有两个玻璃化转变温度。该方法大大降低了铜盐催化剂的用量,降低了制备成本,使聚合产物的后处理更容易进行。所得双亲性嵌段共聚物可以作为分散剂,明显提高了二氧化钛在环氧树脂中的分散效率。