接枝改性无卤阻燃聚丙烯的研究

采用接枝改性手段把含有极性基团的乙烯基单体引入非极性的PP大分子骨架，将PP功能化，再与非卤阻燃剂如含NH2基的P－N膨胀型阻燃剂等进行大分子反应，制备了非卤阻燃聚丙烯母粒。着重探讨了含极性基团的乙烯基单体种类及用量等因素对PP阻燃性的影响。在PP大分子链上接枝含极性基团的乙烯基单体，可显著提高PP的阻燃性能；在双单体接枝体系中，单体A与C的配比为10／30时，最高氧指数可达32．0。     

低气味的二烯聚合物胶乳已申请专利

日本合成橡胶工业公司研制的二烯聚合物胶乳可用作纸张粘合剂及涂料。它是在pH≤7.5的条件下,由多种单体、链转移剂、松香或某种衍生物(除臭剂)等进行乳液聚合而得。采用的聚合单体有共轭二烯、不饱和羧酸及乙烯单体。如将丁:二烯、苯乙烯、甲基丙烯酸甲酯、衣康酸及丙烯酸,在松香、叔十二烷硫醇、     

正交设计在非卤阻燃ABS制备中的应用

利用正交设计法研究由Al(OH)3和Mg(OH)2为主阻燃剂,红磷等为增效剂,采用原位反应增容技术制备的阻燃ABS材料。通过方差分析,探讨了含极性基团的乙烯基单体A、B和引发剂DCP的用量以及它们之间的相互作用对阻燃ABS力学性能、阻燃性能的影响。实验结果表明,引发剂DCP和含极性基团的乙烯基单体A用量的变化对阻燃ABS各指标的影响显著,含极性基团的乙烯基单体B的用量改变对阻燃ABS的性能无明显影响,但是这3个因素之间存在相互作用,而且这些交互作用对阻燃ABS的综合性能有一定的影响,当引发剂DCP、含极性基团的乙烯基单体A和B的用量分别为1 5份、10份和30份时,制备的阻燃母粒可使阻燃ABS获得最好的综合性能。     

功能化聚烯烃接枝共聚物的制备和应用研究新进展

介绍了制备功能化聚烯烃接枝共聚物的意义及近年来功能化聚烯烃接枝共聚物的设计与合成中的应用研究新进展,重点评述了制备功能化聚烯烃接枝共聚物时所采用的3种方法,I偶合接枝法;II引发接枝法:1阴离子聚合;2硼氧自由基存在下的控制自由基聚合;3原子转移自由基聚合(ATRP);4氮氧自由基存在下的控制自由基聚合(NMRP);5可逆加成-裂解链转移活性自由基聚合(RAFT);III直接接枝法,并对上述方法进行了简单的优缺点对比。随后介绍了功能化聚烯烃接枝共聚物的应用。最后对功能化聚烯烃接枝共聚物的未来发展趋势进行了展望,认为对新型、高效、实用的制备方法的探索以及实际应用将是功能化聚烯烃接枝共聚物领域的主要研究方向。     

烯烃配位聚合的链转移反应以及应用

链转移反应在烯烃配位聚合过程中占据重要位置，不仅可以控制聚合物的分子量，甚至还可以利用链转移反应调控聚合物的拓扑结构。以均相催化剂催化烯烃配位聚合过程中的链转移反应为切入点，讨论了常见的链转移反应、向催化体系加入合适的链转移剂合成功能化基团封端的聚烯烃、配位聚合中聚合物链向溶剂甲苯转移的新颖链转移反应，以及通过链转移反应控制聚合物拓扑结构的机理，最后以氢气(H₂)为链转移剂，分别讨论了对非均相催化剂催化乙烯和丙烯聚合活性的影响机制。     

黄原酸酯调控N-乙烯基吡咯烷酮的RAFT聚合

聚(N-乙烯基吡咯烷酮)(PNVP)是一种水溶性高分子材料,广泛应用于生物医药和化妆品行业。黄原酸酯类链转移剂尤其适合于调控非共轭乙烯基单体的可逆加成-断裂链转移(RAFT)聚合。本文合成了[1-(O-乙基黄原酸)乙基]苯作为链转移剂,调控N-乙烯基吡咯烷酮(NVP)的RAFT聚合,再用正丁胺氨解得到巯基封端的PNVP,并用~1H NMR和凝胶渗透色谱(GPC)证明得到了分子量分布较窄、具有末端活性基团的PNVP。     

碳纳米管功能化的途径、机理和表面特征

由碳纳米管的功能化有共价键和非共价键两种方法。共价键功能化的机理是通过氧化或还原反应在碳纳米管表面生成极性或反应性基团(表面基团化),继而通过化学反应使碳纳米管表面有机化或聚合物化。非共价键功能化的机理是基于碳纳米管表面的?体系和疏水性可与含?电子的芳烯化合物发生?-?相互作用或与含疏水链的表面活性剂发生物理吸附。本文综述碳纳米管功能化的研究进展,完善了Kim等提出的碳纳米管功能化表面的代数表示:表面基团化的为1G,表面有机化的为2G,表面聚合物化的为3G。     

水性丙烯酸酯汽车涂料树脂的制备与粘度的研究

合成了用于配制水性汽车罩光清漆的丙烯酸酯涂料树脂,研究了丙烯酸单体、含芳香酯基团单体、引发剂、链转移剂和聚合温度对树脂水溶性和粘度的影响,并用红外光谱表征了树脂的结构。结果表明,增加丙烯酸单体的用量会提高丙烯酸酯树脂的水溶性和粘度,而增加含芳香酯基团的甲基丙烯酸苄酯（BNMA）单体、引发剂和链转移剂的用量和提高聚合温度可降低树脂的粘度。该树脂与氨基树脂（HMMM）固化剂配制的漆膜性能优良,可以用作汽车原厂漆（OEM）。     

用亲电子基团改性的偶联二烯聚合物

由德国拜耳公司申请的专利(专利号02127810．5，公开日期2003-04-02)“用亲电子基团改性的偶联二烯聚合物”，基于共轭二烯或共轭二烯与乙烯基芳香族化合物并用亲电子基团改性，通过使基于上述单体的活性阴离子聚合物与分子中含有至少3个能与其反应的基团和至少1个用于其改性的基团的官能有机物反应来制备。     

中国专利

一种聚烯烃功能化母粒及其制备方法和应用发明涉及一种聚烯烃功能化母粒及其制备方法和应用。该功能化母粒是用特定量的聚烯烃树脂和多元胺与胍盐聚合物、烯烃单体、引发剂等共混,通过溶液接枝、固相接枝或熔融接枝的方法而得到。其结构式如下:     

Living functionalization of polymethacrylates by group transfer polymerization (GTP) using low ceiling temperature monomers

A living functionalization method for group transfer polymerization (GTP) has been developed for poly(alkyl methacrylates) using the sterically hindered monomer, methyl-2-phenylpropenoate (MPHA). The end-capping reactions of MPHA with living trimethylsilyl ketene acetal-ended poly(methyl methacrylate) (PMMA) chain ends have been systematically studied and characterized by size exclusion chromatography, vapor pressure osmometry, ultraviolet-visible, ¹H and ¹³C nuclear magnetic resonance spectroscopy. Although oligomerization of MPHA is observed at - 78° C, this is reversible and only monoaddition is observed at room temperature. In principle, various functional groups can be introduced into poly(alkyl methacrylates) via substituents on the aromatic ring of MPHA and related monomers. Amino-functionalized PMMA was prepared by end-capping reactions of living trimethylsilyl ketene acetal-ended PMMA with methyl E-3-(2-dimethylaminophenyl)-2-phenylacrylate.     

Process variables and their effects on grafting reactions of styrene and methyl methacrylate onto natural rubber

The graft copolymerization of styrene and methyl methacrylate onto natural rubber latex was studied under various reaction conditions using a cumene hydroperoxide redox initiator. The monomer conversion, graft copolymer compositions, and grafting efficiency were determined. The synthesized graft copolymers were purified and then characterized by proton nuclear magnetic resonance (¹H‐NMR) analysis and differential scanning calorimetry (DSC). A 2 fractional factorial experimental design was applied to study the main effects on the grafting. The variables investigated in this work were the amount of the initiator and emulsifier, the presence or absence of a chain‐transfer agent, the styrene‐to‐methyl methacrylate ratio, the monomer‐to‐rubber ratio, and the reaction temperature. The measured response for the experimental design was the grafting efficiency. The analysis of the results from the design showed the sequence of the main effects on the observed response of the grafting of styrene and methyl methacrylate onto natural rubber, in ascending order. The amount of the chain‐transfer agent and the reaction temperature in the range of the test had significant effects and one marginally significant effect was the monomer‐to‐rubber ratio. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 63–74, 2003     

二步溶胀法制备大粒径共聚物乳胶粒子

以聚乙烯基吡咯烷酮(PVP)作为分散剂,以偶氮二异丁腈(AIBN)作为引发剂,在以水为溶剂的体系中以苯乙烯为单体制备出纳米级种子微球;然后利用二步溶胀法再分别以苯乙烯(St)和甲基丙烯酸甲酯(MMA)为单体,进而制备出微米级的核壳型微球。运用动态激光光散射仪对粒子半径的进行表征,其中以甲基丙烯酸甲酯为单体所制备核壳型微球粒子的半径为953 nm;以苯乙烯为单体所制备核壳型微球粒子的半径为808 nm。     

Investigation on preparation and property of nano‐CaCO3/PP masterbatch modified by reactive monomers

Nano‐CaCO₃/polypropylene (PP) masterbatch containing above 80 wt % nano‐CaCO₃ was prepared by nano‐CaCO₃ coated PP modified by reactive monomers. The chemical interaction, crystallization and melting behavior, thermal stability, morphology, and surface contact angle of masterbatch were investigated with IR, DSC, TEM, TGA, ESCA, and surface contact angle. The results indicated that nano‐CaCO₃ was coated by PP graft copolymers in the masterbatch modified by reactive monomers. The graft ratio and crystallization and melting behavior of PP in the masterbatch depended on the type and content of reactive monomer. The crystallization temperatures of masterbatch modified by reactive monomer is methyl methacrylate > butyl acrylate > methyl acrylate ≈ mixture of acrylic acid and styrene > unmodified ≈ maleic anhydride ≈ acrylic acid > styrene. Modification by reactive monomer increased the thermal stability and surface contact angle of masterbatch. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3907–3914, 2006     

甲基丙烯酸三氟乙酯/甲基丙烯酸缩水甘油酯共聚物乳液的制备

以甲基丙烯酸三氟乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯和苯乙烯为基本原料,用半连续滴加的方法制备了共聚物乳液。FT-IR证明了所用单体甲基丙烯酸三氟乙酯参与了共聚反应。讨论了氟单体用量对转化率的影响。讨论了乳胶膜的吸水率的影响因素。     

Radical copolymerization of methyl 2-norbornene-2-carboxylate and 2-phenyl-2-norbornene with styrene, alkyl acrylate, and methyl methacrylate: Facile incorporation of norbornane framework into polymer main chain and its effect on glass transition temperature

Radical copolymerization behavior of methyl 2-norbornene-2-carboxylate 1 and 2-phenyl-2-norbornene 2 was investigated. Radical copolymerization of 1 and 2 with styrene, alkyl acrylate, and methyl methacrylate in a variety of monomer combinations afforded copolymers, whose main chains consisted of norbornane framework. Relative monomer reactivity ratios for the copolymerization of 1 and 2 with n-butyl acrylate (n-BA) were determined by the Fineman-Ross method. Temperature-modulated DSC analysis for poly(1 or 2-co-n-BA)s revealed remarkable T_g-raising effect of incorporation of norbornane framework into the polymer main chain, compared to that effect of styrene repeating unit.     

A simple one-step synthesis of unsaturated copolyesters

Copolyesters containing pendent vinylidine groups were prepared in a one-step synthesis by reacting either chloro- or bromoacetic acid with 2-(bromomethyl)acrylic acid and triethylamine in diethyl ether. Polymers were characterized by IR, ¹H- and ¹³C-NMR, DSC, and TGA. Copolymer formation supports a mechanism involving a triethylammonium carboxylate salt acting as an active nucleophilic species in a manner analogous to that seen in phase transfer catalysis involving carboxylate anions. Comparison of ¹³C-NMR spectra intensities indicates that 2-(bromomethyl)acrylic acid is much more reactive than the haloacetic acids leading to higher copolymer incorporation than in the monomer feed. Unsaturation in the copolymers provides a site for crosslinking during radical polymerization with an added vinyl monomer, similar to the way unsaturated polyesters function in commercial fiberglass formulations. This was confirmed by polymerization of both styrene and methyl methacrylate in the presence of an unsaturated copolymer giving insoluble semi-interpenetrating networks. These unsaturated copolymers are the first examples of soluble biodegradable glycolic acid polyesters containing such reactive functionality.     

Chain transfer and molecular weight in the ionizing radiation initiated cationic polymerization of styrene derivatives

Summary A strong effect of monomer structure on molecular weight is found in the radiation initiated cationic polymerization of para substituted styrene derivatives. This effect is proposed to result from steric hindrance in the chain transfer reaction. The conclusion is reached that the predominant chain transfer reaction under the conditions employed is attack by the cation on the monomer aromatic ring rather than by intramolecular attack on the penultimate aromatic ring of the propagating chain.     

Effect of 2-Chloro-1,3,2-dioxaphospholane on the radical polymerisation of acrylonitrile,styrene and methyl methacrylate

The effect of 2-Chloro-1,3,2-dioxaphospholane on the AIBN initiated polymerisation of acrylo — nitrile , methyl methacrylate and styrene was investigated kinetically in benzene at 60 – 80°C. With acrylonitrile normal kinetic orders with respect to monomer and AIBN could be observed with the phospholane behaving as a chain transfer agent. With methyl methacrylate and styrene it was observed that the phospholane causes enhancement of the rates due to concurrent radical and ionic polymerisation besides functioning as a chain transfer agent.     

A novel copolymer of N-[(tert-butylperoxy)methyl]acrylamide and maleic anhydride for use as a reactive surfactant in emulsion polymerization

A new copolymer of N-[(tert-butylperoxy)methyl]acrylamide (tBPMAAm), containing a primary–tertiary peroxide group and maleic anhydride (MA), was synthesized and employed as a reactive surfactant (inisurf) for the emulsion polymerization of styrene to yield surface-functionalized (peroxidized) reactive latex particles. The copolymerization characteristics were analyzed to determine the monomer reactivity ratios and to provide a way to control the copolymer composition. The ability of tBPMAAm–MA to act as a reactive surfactant during emulsion polymerization was confirmed by the synthesis of monodisperse polystyrene latexes of varying particle size. In addition, peroxide groups were localized on the surface of the particles in a controllable amount (depending on the copolymer concentration), thus, providing the opportunity for further modification of the surface of the particles. This novel copolymer is expected to be a promising and efficient material in the synthesis of functional polymer nanoparticles with well-defined core–shell morphologies.