星形多臂三嵌段聚合物h-PCMS-g-PMMA-b-PBMA的合成及表征

通过对氯甲基苯乙烯(CMS)自引发ATRP技术,制备了准球形聚对氯甲基苯乙烯(h-PCMS),再以h-PCMS作为大分子引发剂,通过连续两步ATRP聚合,合成了星形多臂共聚物h-PCMS_(2700)-g-PMMA_(20000)-b-PBMA_(30000)(下标为分子量),分子量分布为2. 0。采用IR、GPC、¹H NMR及DSC等技术对聚合物的结构和性能进行确认。1H NMR定量分析证明,h-PCMS中的苄基氯能够进一步引发单体MMA进行接枝聚合,而次苄基氯由于空间位阻较大不能进一步引发MMA的接枝反应。在每一个h-PCMS表面,有接近1/3的苄基氯参与反应,平均接枝臂数为4。     

星形多臂三嵌段聚合物h-PCMS-g-PMMA-b-PBMA的合成及表征

通过对氯甲基苯乙烯(CMS)自引发ATRP技术,制备了准球形聚对氯甲基苯乙烯(h-PCMS),再以h-PCMS作为大分子引发剂,通过连续两步ATRP聚合,合成了星形多臂共聚物h-PCMS_(2700)-g-PMMA_(20000)-b-PBMA_(30000)(下标为分子量),分子量分布为2. 0。采用IR、GPC、~1H NMR及DSC等技术对聚合物的结构和性能进行确认。1H NMR定量分析证明,h-PCMS中的苄基氯能够进一步引发单体MMA进行接枝聚合,而次苄基氯由于空间位阻较大不能进一步引发MMA的接枝反应。在每一个h-PCMS表面,有接近1/3的苄基氯参与反应,平均接枝臂数为4。     

壳聚糖的自由基聚合修饰改性

综述了普通自由基聚合和原子转移自由基聚合(ATRP)反应对壳聚糖及其衍生物进行修饰改性的研究现状。着重介绍了ATRP技术在壳聚糖接枝改性方面的应用。     

对氯甲基苯乙烯共聚物引发甲基丙烯酸甲酯原子转移自由基聚合

通过偶氮二异丁氰(AIBN)引发苯乙烯(St)与对氯甲基苯乙烯(p-CMS)共聚,合成了二元共聚物P(St-co-CMS),在氯化亚铜/四甲基乙二胺(CuC l/TMEDA)催化下,以此二元共聚物为大分子引发剂引发甲基丙烯酸甲酯(MMA)的原子转移自由基聚合(ATRP),成功地合成了结构明晰的以聚苯乙烯为主链、聚甲基丙烯酸甲酯为支链的接枝共聚物P(S-g-MMA)。大分子引发剂和接枝共聚物的结构通过红外光谱(IR)、核磁共振氢谱(1HNMR)得到了确认,并测定了接枝共聚物的平均支链数目、平均支链长度、接枝率及接枝效率。结果表明,用这种方法制备的接枝共聚物相对分子质量分布较窄,支链数目及长度可控,接枝效率高达93.7%。     

原子转移自由基聚合(ATRP)的研究进展

介绍了可以实现活性聚合的ATRP、RATRP、AGET ATRP和ARGET ATRP 4种原子转移自由基聚合的机理,综述了原子转移自由基聚合技术在合成两亲性嵌段共聚物、接枝聚合物和星型共聚物等中的研究进展。     

原子转移自由基聚合原理及应用

介绍了有关原子转移自由基聚合(ATRP)的聚合原理。最新研究表明:应用ATRP法进行聚合反应可以制备接枝聚合物、嵌段聚合物、超支化聚合物和其它有机/无机混合型聚合物等。ATRP在高分子聚合反应领域具有十分广阔的应用前景。     

ATRP/RAFT技术合成刷型多元共聚物

以十二烷基三硫代碳酸酯(DDMAT)为链转移剂,通过可逆加成-断裂转移自由基聚合(RAFT)技术制备了分子量分布较窄(多分散性指数PDI为1.54)的二嵌段共聚物聚对氯甲基苯乙烯(PVBC-b-PS),再以PVBC结构中的苄基氯为引发点,借助原子转移自由基聚合(ATRP)方法在大分子主链上接枝甲基丙烯酸甲酯(MMA),得到刷型三元共聚物PVBC-b-PS-g-PMMA(PDI=3.38,分子量43 000,VBC重复单元接枝率为12.2%)。     

接枝炭黑的最新动向

1985年,笔者有幸在“炭黑月报”上以“研究”之余为题,三次发表了有关接枝炭黑的文章。至于“研究之余”——对接枝炭黑的研究,是从解释在炭黑存在的条件下,苯乙烯的热聚合受到阻碍这一现象开始的。近来,从平面状发热体到导电性油墨,接枝炭黑的用途已涉及多个方面。尤其是通过离子聚合进行的接核技术,引起了人们的关注。为此,本文试图就接枝聚合的几个问题探讨有关它的新进展。     

ATRP法制备PVDF-g-PS共聚物及其表征

采用ATRP法制备了聚偏氟乙烯(PVDF)接枝苯乙烯共聚物(PVDF-g-PS),对产物的结构与性能进行了表征。结果表明:随着接枝率的提高,接枝共聚物的熔点和熔融焓下降,且PVDF在接枝后表面由光滑转变为凹凸不平的形貌。     

超细SiO2微粒的表面接枝聚合改性研究进展

综述了超细SiO2微粒表面接枝聚合改性技术的原理以及近年来超细SiO2微粒表面接枝聚合改性的研究进展。讨论了自由基、阳离子和阴离子接枝聚合改性的优缺点。着重介绍了一种极具发展前景的接枝聚合改性方法——ATRP技术。     

乳液法AES的研究

以歧化松香酸钾为乳化剂，过硫酸钾为引发剂，乳液接枝法合成了三元乙丙橡胶-丙烯腈-笨乙（AES）．测定了反应条件时乳胶粒直径分布、接枝率、接枝效率的影响。结果表明，该聚合体系为常规乳液聚合，而不是细乳液聚合；引发剂浓度上升．乳胶粒直径下降，但对接枝率和接枝效率影响不明显；所得AES树脂的力学性能指标优良。     

水基改性环氧树脂涂料的合成研究

研究了以环氧树脂Ｅ－ ４４（ 简称为环氧树脂） 为主要原料, 对水基改性环氧树脂涂料———环氧磷酸酯 丙烯酸接枝共聚物的合成反应, 探讨了丙烯酸及其酯, 苯乙烯和引发剂的用量,接枝反应温度, 接枝反应时间等因素对该接枝共聚物水分散稳定性的影响, 确定了较佳的工艺条件。并对该接枝共聚物进行了有关的产品性能和应用性能检测。     

Surface functionalization of Si3N4 nanoparticles by graft polymerization of glycidyl methacrylate and styrene

To improve dispersibility and interfacial interaction of nano‐Si₃N₄ particles in epoxy‐based composites, graft of glycidyl methacrylate (GMA) and styrene (St)/GMA onto the nanoparticles' surface was carried out in terms of emulsion polymerization method. The grafting polymers proved to be chemically attached to the nanoparticles via the double bonds introduced during the coupling agent pretreatment. The factors affecting the graft parameters, such as monomer concentration, initiator consumption, reaction time, etc., were investigated. It was shown that higher concentrations of monomer and initiator are favorable for the graft polymerization. When St/GMA was employed as the grafting monomer, the nanoparticles were found to play the role of polymerization loci. The grafted nanoparticles exhibit greatly improved dispersibility in cured epoxy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 992–999, 2006     

Graft copolymerization of styrene and acrylonitrile onto EPDM

Acrylonitrile–EPDM–styrene (AES) graft copolymers were synthesized by solution graft polymerization of styrene (St) and acrylonitrile (AN) onto EPDM in an n‐hexane/benzene solvent with benzoyl peroxide (BPO) as an initiator. The structure changes were studied by an FTIR spectrophotometer. The grafting parameters were calculated gravimetrically. The influence of the polymerization conditions, such as the reaction time, concentration of the initiator, EPDM content, and weight ratio of St/AN, on the structure of the products was investigated. It was found that a proper initiator concentration and EPDM content will give a high grafting ratio of the AES resin. The thermal property of the copolymer was studied using programmed thermogravimetric analysis (TGA). The results showed that the copolymer has a better heat‐resistant property than that of ABS, especially for the initial decomposition temperature (T_in) and the maximum weight loss rate temperature (T_max). Also, the mechanism of the graft reaction was discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 428–432, 2002     

A comparative study on effects of two kinds of polymerization methods on grafting of polymer onto silica surface

In this article we present the result of a comparative study of two kinds of polymerization methods—solution polymerization (sol. poly.) and dispersion polymerization (dis. poly.) for grafting polymer onto silica. As a model for the grafting polymerization reaction, styrene was chosen as the monomer and azo diisobutyronitrile (AIBN) as the initiator. The study aims at supplying theoretical reference for better selecting polymerization method to graft polymer on the silica particle surface. First, monolayers of 3‐methacryloylpropyl trimethoxysilane were chemically bonded onto the surfaces of micrometer‐sized silica gel particles, and so double bonds were immobilized onto the silica surface. Second, the copolymerizations between the immobilized double bonds and the monomer styrene were carried out, homopolymerizations of styrene followed, and finally polystyrene was grafted to the silica surfaces. Two kinds of polymerization methods, sol. poly. and dis. poly., were adopted respectively, and the effects of polymerization methods on grafting process were examined mainly. At the same time, the effects of different polymerization conditions on the grafting degree were researched. It was found that in the dis. poly. system the grafting degree is obviously higher than that in the sol. poly. system under the same polymerization conditions, and the grafting degree can go up to 47%, i.e. 47g/100g. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5808–5817, 2006     

Atom transfer radical polymerization of styrene initiated by bromoacetylated syndiotactic polystyrene macroinitiator

Atom transfer radical polymerization of styrene was conducted with bromoacetylated syndiotactic polystyrene as macroinitiator and copper bromide combined with N,N,N′,N′,N′‐pentamethyldiethylenetriamine as catalyst. A two‐stage process has been developed to synthesize the macroinitiator. First, syndiotactic polystyrene (sPS) was functionalized in the side phenyl rings with acetyl groups using the Friedel–Crafts reaction; second, the acetyl groups were converted to bromoacetyl groups by an acid‐catalyzed halogenation reaction. The initiator was found to be active in the polymerization of styrene, leading to the production of graft chains with well‐defined structure. The molecular weight and molecular weight distribution of the graft chains were determined using gel permeation chromatography after cleaving from the sPS backbone using peroxide acid oxidation followed by hydrazine‐catalyzed hydrolysis. The results indicated that the polymerization process was characteristic of a ‘living’ nature. Copyright © 2007 Society of Chemical Industry     

碘仿对苯乙烯乳液聚合及种子接枝聚合的影响

以碘仿（CHI3）作为链转移剂进行苯乙烯的种子乳液聚合,制备出粒径分别为150 nm和30nm的2种种子乳液。然后采用间歇加料工艺进行丙烯酸甲酯的接枝共聚,由于碘代化合物发挥退化转移自由基聚合作用,所制备的核壳乳液具有很高的接枝效率。文章考察了CHI3用量、引发剂用量等因素对接枝率和接枝效率的影响。     

Synthesis and properties of styrene–EPDM–vinyl acetate graft polymer

The styrene–EPDM–vinylacetate (SEV) graft polymer, which linked respectively the styrene (St) unit and vinylacetate the (VAc) unit to the ethylene–propylene–diene terpolymer (EPDM) backbone was synthesized by two‐step graft polymerizations: First the graft polymerization of VAc onto EPDM was carried out, and then St was added successively in the prepolymerized solution and further polymerized for a given period to obtain SEV. The effects of concentration of EPDM and an initiator, mole ratio of VAc to St, polymerization time, temperature, and solvent were examined on the graft polymerizations. The synthesized graft polymers (SEVs) that have different contents of St or VAc were identified by Fourier transform IR spectrum. The highest graft ratio has been obtained by 10 wt % of EPDM, 1.0 mole ratio of VAc to St, and 1.0 wt % of BPO in toluene for 48 h at 70°C. The glass transition temperature of SEV is lower than that of poly(vinyl acetate) (PVAc) and polystyrene (PS). The thermal stability of SEV is higher than that of PVAc, PS, and the acrylonitrile–butadiene–styrene (ABS) resin. The tensile strength of SEV was improved as compared with that of EPDM. The light resistance and weatherability of SEV were better than those of ABS. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2296–2304, 2000     

35hPBL聚合技术的改进和工业应用

针对50kt/a丙烯腈－丁二烯－苯乙烯接枝共聚物（ABS）装置改造中采用35h聚丁二烯胶乳（PBL）聚合技术后出现的PBL稳定性差的现象，通过加入阻聚剂终止聚合后期反应、改变调整用碱的浓度，达到了改善胶乳稳定性的目的。PBL的机械稳定性指标由0．0086％提高到0．0035％，接枝聚合的接枝胶含量明显从未改进前的79％增加到83％－85％，使最终产品的冲击强度也明显得到提高。     

Cationic graft polymerization of polymers from carbon fiber initiated by acylium perchlorate groups introduced onto the surface

The cationic graft polymerization of several monomers initiated by acylium perchlorate groups introduced onto the carbon fiber surface was investigated to modify the surface. The introduction of acylium perchlorate groups was successfully achieved by the reaction of silver perchlorate with acyl chloride groups, which were introduced by the reaction of surface carboxyl groups with thionyl chloride. It was found that the cationic polymerization of styrene is initiated by acylium perchlorate groups on the carbon fiber. In the polymerization, polystyrene was grafted onto the carbon fiber surface through the propagation of polystyrene from the surface. Ungrafted polymer was also formed by the chain transfer reaction of growing polymer cation to the monomer. The acylium perchlorate groups have the ability to initiate cationic ring-opening polymerization of tetrahydrofuran (THF) and ε-caprolactone (CL), polyTHF and polyCL being grafted onto the carbon fiber surface, respectively. Polyacetals, such as poly(1,3-dioxolane) and polyoxymethylene, were able to graft onto the carbon fiber by cationic ring-opening polymerization of the corresponding monomers.