苯乙烯—异戊二烯—苯乙烯热塑性嵌段共聚物

简介近年来国外SIS生产状况、生产工艺技术经济评估、SIS的基本性能和应用以及国外技术发展趋势,井对国内SIS产品开发作出预估。     

Poly(dimethylaminoethyl methacrylate) grafted natural rubber from seeded emulsion polymerization

The grafting efficiency of dimethylaminoethylmethacrylate (DMAEMA) on to natural rubber (NR) has been studied. Grafting was by ‘topology-controlled’ emulsion polymerization, whereby polymerization is initiated by a redox couple where one component (tetraethylene pentamine) is hydrophilic and the other (cumene hydroperoxide) is hydrophobic. This should promote grafting at the interface between hydrophobic natural rubber particles and the hydrophilic DMAEMA. The effects of different amounts of monomer were examined, with NMR to obtain the percent branching, transmission electron microscopy to obtain information on morphology, gel fraction measurement and dynamic mechanical analysis to obtain information on mechanical properties. Although there will be significant amounts of ungrafted polyDMAEMA present, there is good evidence for the formation of graft copolymers of NR with core-shell morphology, and significant amounts of grafting, at high concentrations of monomer.     

无规支化苯乙烯-甲基丙烯酸甲酯共聚物合成及表征

以α-溴代异丁酸叔丁酯(tBBiB)为引发剂,CuBr/2,2'-联吡啶(BPy)为催化体系,二乙烯基苯(DVB)为支化单体,经原子转移自由基聚合(ATRP),在90℃下进行了苯乙烯(St)和甲基丙烯酸甲酯(MMA)的共聚合反应,研究了不同单体组成对反应的影响.用红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)、凝胶渗透色谱(GPC)、多角激光散射仪(MALLS)分别对聚合反应过程和聚合物进行了表征和分析.结果表明:反应表现出活性聚合特征,Mw.MALLS＞3.9×105;Mw.MALLS/Mw.GPC＞1,说明反应生成了St与MMA的无规支化共聚物:当St与MMA摩尔比为3∶1时,共聚物中St单元的含量最大.     

苯乙烯—异戊二烯—苯乙烯热塑性嵌段共聚物（Ⅱ）

5 技术经济评估5.1 生产方面的评估国外某公司于1985年曾对年产量均为4.5万 t 的 SBS(S/B=30/70)和 SIS(S/IP=14/86)生产装置进行技术经济评估,现将结果列于表13。由表13可知,在生产规模相同的情况下,SIS 的投资略高于 SBS(2%),其原因在于原材料费(IP)高于 Bd30%～40%之故,其他费用和消耗均相同。每吨 SIS 的原料消耗根据推算约为1.020～1.040t,其中 IP 为     

2-乙烯基吡啶-甲基丙烯酸甲酯两嵌段共聚物的合成与表征

采用阴离子活性聚合方法合成了聚2-乙烯基吡啶(P2VP)-聚甲基丙烯酸甲酯(PMMA)两嵌段共聚物(P2VP-b-PMMA),并采用GPC、FT-IR、NMR等手段进行了结构表征.结果表明,聚合产物为数均分子量103166、多分散指数1.08的单分散P2VP-b-PMMA.     

Emulsion polymerization of styrene with amphiphilic random copolymer as surfactant: Predominant droplet nucleation

Amphiphilic random copolymer consisting of monomeric units of poly (butyl acrylate) and poly (maleic acid salt) was synthesized and characterized. The emulsion polymerization kinetics of styrene stabilized by this copolymer was investigated. The influencing factors, including polymeric surfactant concentration, initiator concentration and polymerization temperature, were systematically studied. The kinetic data show that the polymerization rate (R_P) increased with the increase of the polymeric surfactant concentration ([S]) and polymerization temperature (T). At the higher [S], droplets nucleation and micelle nucleation coexisted in the polymerization system; at the lower [S], only the droplets nucleation process existed. The polymerization did not follow Smith‐Ewart Case II kinetics. Dynamic light scatter and transmission electron microscope were utilized to measure the sizes and shapes of the particles, respectively. It would be speculated that a kind of large heterogeneous particles with multiple‐active‐sites was formed in the polymerization system. The increasing of R_P with increasing initiator concentration ([KPS]) was rapid at a medium [KPS], but the slowly increasing was observed at a lower or higher [KPS]. It was attributed to the barrier effect of the polymeric surfactant around the monomer droplets. The polymerization activation energy was 60.29 kJ/mol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

聚(苯乙烯-co-丙烯腈)-b-聚苯乙烯两嵌段共聚物的合成

以CuBr／N，N，N’，N’，N'-五甲基二亚乙基三胺(简称NNN)为催化体系，研究了原子转移自由基聚合法(ATRP)PS-b-P(S-co-AN)两嵌段聚合物的合成。研究了聚合顺序对相对分子质量及其分布和嵌段效率的影响，并且用聚合物末端C—Br键的断裂能对实验结果进行了初步解释。     

The Conductivity of Poly(o-anisidine), Poly(o-toluidine) and Their Copolymer with Various Inorganic Dopants in the Presence of Electrolyte

ABSTRACT

An attempt has been made to prepare poly(o-anisidine) (POA), poly(o-toluidine) (POT) and copolymer poly(o-anisidine)-co-poly(o-toluidine) (POA-co-POT) thin films dopped by several inorganic salts (sulphates and chlorides) with varying size of cations using aqueous solution of H₂SO₄ as electrolyte. The effect of dopant in the presence of electrolyte is rarely studied in the field of conducting polymers. Various inorganic salts as dopants, namely, K₂SO₄, Na₂SO₄, Li₂SO₄, MgSO₄, KCl, NaCl, LiCl, and MgCl₂ are used at room temperature. The films were electropolymerized in solution containing 0.1 M monomer(s), 1 M H₂SO₄ as electrolyte and 1 M inorganic salt, by applying sequential linear potential scan rate 50 mV/sbetween ? 0.2 to 1.0 V versus Ag/AgCl electrode. The electro-synthesized films were characterized by cyclic voltammetry, UV-visible spectroscopy, and conductivity measurements. It was observed that the UV-visible peaks usually appearing at about 802–826 nm with a shoulder at 410–426 nm shows a shift in presence of doping salt for emeraldine salt (ES) phase of POA, POT, POA-co-POT. In overall study, a significant increase in conductivity is observed for all mentioned dopants and among these K₂SO₄ is found to be the best in sulphate category and KCl in chloride category. The formation of copolymer has been confirmed by differential scanning calorimetry.     

P(MMA-St)/SiO2纳米复合材料的制备及性能研究

采用硅烷偶联剂(KH-570)对纳米二氧化硅(SiO2)进行有机化处理,然后将其与甲基丙烯酸甲酯(MMA)和苯乙烯(St)按一定比例进行原位悬浮聚合,得到甲基丙烯酸甲酯苯乙烯共聚物P(MMA-St)/SiO2纳米复合材料。利用傅里叶红外光谱、凝胶渗透色谱仪、热失重分析仪、透射电子显微镜等对纳米SiO2及复合材料的结构、热稳定性、力学性能及加工流动性进行了分析和表征。结果表明,在保证良好加工性能的前提下,复合材料的热稳定性、力学性能均得到了显著提升,并且纳米SiO2的加入使聚合物相对分子质量增大,相对分子质量分布变窄。     

Poly(methylphenylphosphazene)–Graft–Poly(methyl Methacrylate) Copolymers Via Atom Transfer Radical Polymerization

Atom transfer radical polymerization (ATRP) was used to graft poly(methyl methacrylate), PMMA, onto poly(methylphenylphosphazene), [(Me)(Ph)PN] _n , PMPP. A two-step process was used to convert a portion of the methyl substituents on [(Me)(Ph)PN] _n to –CH₂C(CH₃)₂OH groups and then to bromoalkyl groups, –CH₂C(CH₃)₂OC(=O)C(CH₃)₂Br, the latter of which served as initiation sites for ATRP of methyl methacrylate (MMA) in the presence of CuCl/bipyridine. Variations in the length of the grafted chains were investigated and the graft copolymers were compared to the parent polymer and blends of similar composition. The new bromoalkyl derivatives of [(Me)(Ph)PN] _n and the PMPP–graft–PMMA copolymers were characterized by elemental analysis, ¹H and ³¹P NMR spectroscopy, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC). We dedicate this paper to Professor Harry R. Allcock for consistently maintaining the highest standards in his creative, pioneering work in inorganic rings and polymers.     

Poly(styrene‐co‐N‐butylmaleimide) macroinitiators by controlled autopolymerization and related block copolymers

Autopolymerization of styrene‐N‐butylmaleimide mixtures at 125 or 140°C in the presence of a stable nitroxyl radical [2,2,6,6‐tetramethylpiperidin‐1‐yloxyl (TEMPO)] was found to proceed in a pseudoliving manner. Unimolecular initiators, which were originated by trapping self‐generated radical species with TEMPO, took part in the process. Under the studied experimental conditions, the TEMPO‐controlled autopolymerization with a varying comonomer ratio provided virtually alternating copolymers of narrow molecular weight distributions. The molecular weights of the copolymers increased with conversions. The obtained styrene‐N‐butylmaleimide copolymers containing TEMPO end groups were used to initiate the polymerization of styrene. The polymerization yielded poly(styrene‐co‐N‐butylmaleimide)‐polystyrene block copolymers with various polystyrene chain lengths and narrow molecular weight distributions. The compositions, molecular weights, and molecular weight distributions of the synthesized block copolymers and the initial poly(styrene‐co‐N‐butylmaleimide) precursors were evaluated using nitrogen analysis, gel permeation chromatography, and ¹H‐ and ¹³C‐NMR spectroscopy. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2378–2385, 1999     

原位聚合改性氢氧化镁在EVA中的应用

通过苯乙烯在氢氧化镁颗粒表面的原位聚合，由化学改性法提高了颗粒表面的憎水性和亲油性，DSC和熔体流动速率等测定结果表明：经化学改性提高了氢氧化镁样品的热分解温度，使其吸水性明显下降，在乙烯一醋酸乙烯酯共聚物(EVA)基体树脂中的分散性得到改善；SEM观察发现采用原位聚合改性后的氢氧化镁与EVA基体树脂的相容性明显优于未改性氢氧化镁。将其填充EVA，明显改善了材料的力学性能和加工性能，材料的断裂伸长率提高4倍以上。     

Formation of polystyrene-poly(methyl methacrylate) block copolymers by anion to free radical transformation

This paper describes a new route for the synthesis of linear block copolymers using a combination of anionic and radical propagation reactions. Free radical polymerization of methyl methacrylate is initiated from halogen-containing end-groups incorporated into the terminal units of polystyrene produced by anionic polymerization. Gel-permeation chromatography is used to establish copolymer formation.     

Poly(aspartic acid)–tryptophan grafted copolymer and its scale‐inhibition performance

Scale deposition, which severely damages oil exploration, is a difficulty encountered in oil fields. Scale inhibitors are widely used for controlling scales. Poly(aspartic acid) (PASP) is attracting more and more attention with increasing environmental concern and discharge limitations. However, PASP's poor inhibition in a high‐temperature environment markedly limits its wide use. Thus, poly(aspartic acid)–tryptophan grafted copolymer (PASPTR) was synthesized to improve the inhibition efficiency of PASP. The results show that the reactant of PASPTR has a great effect on its inhibition performance. PASPTR was found to inhibit the precipitation of CaSO₄ close to 90% at concentrations as low as 0.4 mg/L at 50°C. The inhibition efficiency of PASPTR against CaCO₃ was close to 100% with the concentration of 2 mg/L at 50°C. Scanning electron microscopy and X‐ray diffraction analyses, which showed the morphological and crystal structural changes of CaCO₃ and CaSO₄ precipitation, verified the excellent inhibition performance of PASPTR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42739.     

SMA接枝PHBA侧链液晶高分子的合成与性质

采用溶液缩聚法合成了苯乙烯－马来酸酐共取物接枝聚对羧基苯甲酸侧链液晶高分子,讨论了反应的接枝率和液晶侧链对高聚物热性质的影响。     

Synthesis of poly(aryl ether sulfone)‐graft‐polystyrene and poly(aryl ether sulfone)‐graft‐[polystyrene‐block‐poly(methyl methacrylate)] through atom transfer radical polymerization

A new graft copolymers poly(aryl ether sulfone)‐graft‐polystyrene (PSF‐g‐PS) and poly(aryl ether sulfone)‐graft‐[polystyrene‐block‐poly(methyl methacrylate)] (PSF‐g‐(PS‐b‐PMMA)) were successfully prepared via atom transfer radical polymerisation (ATRP) catalyzed by FeCl₂/isophthalic acid in N,N‐dimethyl formamide. The products were characterized by GPC, DSC, IR, TGA and NMR. The characterization data indicated that the graft copolymerization was accomplished via conventional ATRP mechanism. The effect of chloride content of the macroinitiator on the graft copolymerization was investigated. Only one glass transition temperature (T_g) was detected by DSC for the graft copolymer PSF‐g‐PS and two glass transition temperatures were observed in the DSC curve of PSF‐g‐(PS‐b‐PMMA). The presence of PSF in PSF‐b‐PS or PSF‐g‐(PS‐b‐PMMA) was found to improve thermal stabilities. © 2002 Society of Chemical Industry     

Poly(methyl methacrylate)-block-polysulfide-block-poly(methyl methacrylate) copolymers obtained by free-radical polymerization combined with oxidative coupling

Summary Poly(methyl methacrylate)-block-polysulfide-block-poly(methyl methacrylate) copolymers were synthesized for the first time through a new method involving the free radical polymerization of MMA in the presence of a thiocol oligomer as a chain transfer agent, followed by chemical oxidation of the remaining SH end-groups. The chain transfer constant of the SH end-groups of the thiocol was estimated from the rate of consumption of the thiol groups versus the rate of consumption of the monomer (C_T=0.67). The triblock copolymers synthesized were characterized by SEC and ¹H NMR measurements.     

Effect of acrylonitrile water solubility on the suspension copolymerization of acrylonitrile and styrene

Effect of acrylonitrile water solubility on the suspension polymerization of acrylonitile and styrene was investigated. It was found that the copolymer composition produced in the suspension polymerization of acrylonitrile and styrene was significantly different from that in the bulk polymerization at the same monomer feed ratio, since acrylonitrile is partially soluble in water. To predict accurately and then control the copolymer composition in the suspension polymerization, a model to calculate the copolymer composition was proposed based on considering the phase partition of actylonitrile between monomer and aqueous phases. The results calculated by the model are in agreement with the experimental data. The real reactivity ratios in monomer phase used in the model are the same as that in the bulk polymerization, but the apparent reactivity ratios used in the classical theory for the suspension polymerization vary significantly with water/oil ratio. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4270–4274, 2006     

Non-isothermal Crystallization of Poly(ethylene terephthalate) with Poly(oxybenzoate-p-trimethylene terephthalate) Copolymer

The influence of a poly(oxybenzoate-p-trimethylene terephthalate) copolymer, designated T64, on the non-isothermal crystallization process of poly(ethylene terephthalate) (PET) was investigated. All samples were prepared by solution blending in a 60/40 by weight phenol/tetrachloroethane solvent at 50°C. The solidification process strongly depended on cooling rate and composition of system. The crystallization rate of blends was estimated by crystallization rate parameter (CRP) and crystallization rate coefficient (CRC). From these results of CRP and CRC, it was predicted that the overall non-isothermal crystallization rate of PET would be accelerated by blending with 1–15 wt% of T64. The acceleration of PET crystallization rate was most pronounced in the PET/T64 blends with 5 wt% T64. The observed changes in crystallization behavior are explained by the effect of the physical state of the copolyester during PET crystallization as well as the amount of copolymer in the blends. An Ozawa plot was used to analyze the data of non-isothermal crystallization. The obvious curvature in the plot indicated that the Ozawa model could not fit the PET/T64 blend system well, and there was an abrupt change in the slope of the Ozawa plot at a critical cooling rate.     

溶液聚合二元丁二烯-苯乙烯共聚物的研究

以正丁基锂（ｎ－ＢｕＬｉ）为引发剂,环己烷为溶剂,ＴＨＦ、２Ｇ、ＴＭＥＤＡ为结构调节剂,合成了溶液聚合二元丁二烯、苯乙烯共聚物。研究结果表明：合成的共聚物不同嵌段微观结构不同,和普通溶聚丁苯橡胶相比,该共聚物不仅具有良好的物理机械力学性能同时具有低滚动阻力和抗湿滑性能。