Synthesis of graft copolymers from natural rubber using cumene hydroperoxide redox initiator

The graft copolymerization of 50/50 (w/w) styrene/methyl methacrylate mixtures onto natural rubber seed latex were carried out by using cumene hydroperoxide/sodium formaldehyde sulfoxylate dihydrate/EDTA‐chelated Fe²⁺ as a redox initiator. The effects of the process factors such as the amount of initiator, emulsifier, and chain‐transfer agent; monomer‐to‐rubber ratio; and temperature on the grafting efficiency (GE) and grafting level (GL) are reported. The mechanism of graft copolymerization was investigated. The synthesized graft copolymers were purified and then characterized by proton nuclear magnetic resonance (¹H‐NMR) analysis. Transmission electron microscopy (TEM) was used to study the morphology of the graft copolymers. It appears that the formation of graft copolymers occurs on the surface of the latex particles through a chain‐transfer process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2993–3001, 2002; DOI 10.1002/app.2328     

CR/MMA-AA自交联型接枝共聚物的合成与粘接性能研究

在交联单体Ｎ－羟甲基丙烯酰胺（Ｎ－ＭＡＡ）存在下,研究了氯丁橡胶（ＣＲ）／甲基丙烯酸甲酯（ＭＭＡ）－丙烯酸（ＡＡ）三元接枝共聚及产物性能,结果表明,在引发剂 为１．６￣２．０％,Ｎ－ＭＡＡ用量为２．２￣２．６％,ＡＡ（ＡＡ＋ＭＭＡ）（质量比）为１４％,反应时间为５ｈ,反应温度为８０￣８５℃时,产物的性能较优。对产物还进行了红外光谱表征和粘接性能测试。     

EPDM-g-MS/MS共混物的热性能及流变性能

用溶液聚合法合成的EPDM（乙烯／丙烯／二烯共聚物）与MMA（甲基丙烯酸甲酯）及St（苯乙烯）接枝共聚物（EP—DM—g—MS）与MS（苯乙烯-甲基丙烯酸甲酯共聚物）树脂共混制备MES（EPDM—g—MS增韧MS），通过热重分析研究了MES的热稳定性，通过测试MES的表观粘度、非牛顿指数和粘流活化能等流变参数，分析其流变性能。结果表明，MES具有较好的耐热性能，且随EPDM-g—MS含量及MMA／St配比的增加而提高。MES的非牛顿指数小于1，符合假塑性流体流动规律。其表观粘度随剪切速率和温度升高而降低，随EPDM-g—MS含量增加而提高。MES的粘流活化能小于MS树脂的。     

国产氯丁胶和MMA的接枝共聚研究

研究了国产CR - 2 4 4可接枝氯丁胶 (CR)和甲基丙烯酸甲酯 (MMA)的接枝共聚反应 ,并成功地进行了 0 .1m3和 1 .0m3的扩试生产。     

Thermal degradation behavior of PMMA synthesized by emulsifier‐free emulsion polymerization with a Cu2+/HSO3− redox system

In this study, poly(methyl methacrylate) (PMMA) latex was synthesized in an emulsifier‐free emulsion polymerization at 60°C using a Cu²⁺/HSO redox initiator system with different concentrations of Cu²⁺. The experimental results showed that the monomer conversion reached above 90% for all systems. Zeta potential was all negative due to the bonded bisulfite ion and the magnitude was greater than 30 mV, providing the stability of PMMA emulsion. The morphology of the latex observed by scanning electron microscope revealed a uniform particle size, and the average particle size increased from 181.9 to 234.2 nm as the Cu²⁺ ion concentration increased from 2.0 to 6.0 mM in 1M of MMA solution. Thermal degradation behavior of synthesized PMMA was studied by thermogravimetric analysis, in which a two‐stage degradation behavior was observed. These two stages were found to be caused by the degradation of unsaturated end group (PMMA? CR?CH₂) and saturated end group (PMMA? H), respectively. In addition, the higher the concentration of Cu²⁺ ion, the greater the proportion of PMMA? CR?CH₂ in the final product, and in turn rendering more weight loss in the first‐stage degradation. The copper ion not only played a role in the redox initiation, but also acted as a chain transfer agent to terminate growing polymer chains, thus producing PMMA? CR?CH₂. The apparent activation energies of the first stage (E_a1) and second stage (E_a2) were calculated by Ozawa's and Boswell's method. The results showed that E_a1, representing the degradation of PMMA‐CR?CH₂, was lower than E_a2 for the degradation of PMMA‐H. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

苯乙烯、丙烯腈与降解天然胶乳的共聚研究

以BPO-FeSO4为氧化还原引发体系，采用种子乳液聚合技术，在降解天然胶乳DNR粒子上接枝共聚苯乙烯(St)和丙烯腈(AN)，用正交实验法研究了较佳反应条件，考察反应温度、反应时间及投料比对单体转化率、接枝率和接枝效率的影响，并用红外光谱对共聚物进行表征。     

可接枝型氯丁橡胶与甲基丙烯酸甲酯接枝共聚工艺剖析

从反应系统残留氧的影响,搅拌强度及溶剂３个方面分析了可接枝型氯丁橡胶与甲基丙烯酸甲酯接枝共聚的工艺控制情况,提高了接枝共聚的重现性。     

溶剂型复膜胶的改性研究

通过甲基丙烯酸甲酯接枝改性,提高SBS复膜胶的耐候性、耐老化性和粘接强度。讨论了单体、引发剂用量及反血温度、时间等对复膜胶性能的影响。     

The Effects of Different Grafted Clays on Thermal Properties of Their PMMA Composites

The poly(methyl methacrylate)/clay (PMMA/clay) composites were prepared with the different grafted clay, such as sepiolite fiber, vermiculite and Layered double hydroxides (LDH). These clays modified by grafting of vinyltriethoxysilane (VTS) with a double bond onto the clays surface were used as fillers for PMMA. The morphology of clays and composites were determined by Fourier transform infrared spectroscopy (FTIR). Moreover, the thermal degradation behavior was explained by thermogravimetric analysis (TGA). The three grafted clays improved the thermal stability of PMMA composites as a different level.     

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     

氯乙烯—甲基丙烯酸环氧丙酯共聚树脂的合成及其性能

采用甲基丙烯酸环氧丙酯（EAMA）与氯乙烯（VC）共聚以改进聚氯乙烯的加工性能。研究表明，少量EAMA与VC共聚，使聚合速率大为降低；共聚树脂的分子量随转化率增加而增大，随共聚组成中EAMA含量增加而逐渐减小；共取和树脂的热稳定性和加工性能随EAMA含量增加而提高。     

MAS胶粘剂的合成与性能

用甲基丙烯酸甲酯、丙烯酸、苯乙酸为单体，以二甲苯为溶剂合成MAS胶粘剂，改变苯乙烯用量，考查了苯乙烯用量对MAS胶粘剂的性能影响，了解MAS胶粘剂对木材、铁、瓷砖的粘接性能和MAS胶粘剂耐水，耐腐蚀性能。     

羧甲基甲壳素接枝甲基丙烯酸甲酯的制备及成膜性

通过高速搅拌,未使用乳化剂,制备了羧甲基甲壳素和甲基丙烯酸甲酯的接枝共聚物,避免了产物中引入乳化剂杂质。利用红外光谱对接枝共聚物进行了表征。考察了不同接枝率的产物在12种常见溶剂中的溶解性,结果表明,不同接枝率的接枝共聚物都有良好的水溶性,可以形成无色透明的膜,扩大了其实际应用价值。     

引发剂对纤维素接枝丙烯酰胺反应的影响

分别以硝酸铈铵、过硫酸钾和过硫酸钾/亚硫酸钠为引发剂,以马尾松漂白硫酸盐浆纸浆纤维素为骨架接枝丙烯酰胺,在单体浓度为0.75 mol/L、温度为45℃、反应时间为3 h时,得到硝酸铈铵和过硫酸钾的最佳浓度为3.0 mmol/L和5.0 mmol/L,过硫酸钾/亚硫酸钠在用量为6%时的最佳质量比为1.5,三者相应的接枝率分别为40%、48%和60%。同时比较了不同条件下三种引发剂的接枝效果,结果表明,过硫酸钾/亚硫酸钠的接枝效果最好,但均聚物含量高;硝酸铈铵作为引发剂虽然接枝效果不及前两者,但均聚物含量很低。     

Study of methyl‐methacrylate‐viscose fiber graft copolymerization and the effect of grafting on thermal properties

The graft copolymerization of methyl‐methacrylate onto viscose fibers was studied under photoactive conditions with visible light using Ce⁴⁺/Ti³⁺ combination as redox initiator in a limited aqueous medium. Polymerization conducted in the presence of light at 30 ± 1°C produced significant grafting, compared with that conducted in the dark under the same conditions. The % grafting, % total conversion, and % grafting efficiency were studied by varying time, monomer concentration, initiator concentration, and pH of the medium. The mechanism of polymerization and graft copolymer formation have been discussed. Characterization of the grafted fibers was done by Fourier transform infrared spectroscopy and scanning electron microscopy. The effect of % grafting on thermal properties was studied by thermogravimetric analysis. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 135–140, 1999     

抗氧剂对PMMA树脂热氧化稳定性的影响及动力学分析

采用热重分析,研究了抗氧剂种类及用量对聚甲基丙烯酸甲酯(PMMA)热氧化稳定性的影响,并采用Kis-singer、Flynn-Wall-Ozawa和Flynn法对其热氧化降解行为进行了动力学分析。结果表明,抗氧剂1010、1076、702和BHT的用量为0.5‰时就能够显著提高PMMA热氧化稳定性,使其起始热分解温度提高70℃左右,而抗氧剂用量进一步提高对改善PMMA的热稳定性意义不大;动力学分析表明,抗氧剂的加入能够提高PMMA质量损失率小于30%时的热降解活化能,而热分解后期由于降解温度高于抗氧剂熔点,抗氧剂气化逸出,抗氧剂不能有效提高PMMA后期热降解活化能,未能达到提高PMMA整体热稳定性的目的。     

Grafting of acrylonitrile and methyl methacrylate from their binary mixtures on cellulose using ceric ions

Ceric ion‐initiated grafting on cellulose from a binary mixture of acrylonitrile and methyl methacrylate was carried out in heterogeneous and acidic conditions at 30 ± 0.1°C in a nitrogen atmosphere. To avoid the complexation of water molecules with Ce(IV) ions, the concentration of the nitric acid was taken to be more than the concentration of ceric ions. The effect of the feed concentration, reaction time, and ceric ions concentration on grafting were investigated at a fixed composition. To investigate the effect of monomer–monomer interactions on grafting, the graft copolymerization was also studied, using different feed compositions (f_AN) ranging from 0.25 to 0.80. In this range of feed composition, the synergistic effect of methyl methacrylate molecules has shown an important effect on acrylonitrile monomer and facilitate the incorporation of the acrylonitrile monomer into the grafted chains. The reactivity ratios of acrylonitrile and methyl methacrylate were calculated using the Mayo and Lewis method and were found to be 0.74 and 1.03, respectively. The average sequence lengths of the monomers (m̄M) were found to be dependent on the feed compositions and found to be arranged in alternate fashion in the grafted chains. The probability of the addition of a monomer (P_1,1) to the growing radicals on cellulose ended with its own type of monomer was found to be dependent on the feed composition. The composition of the grafted copolymers, homocopolymers, was determined by IR and elemental analysis for nitrogen. None of the grafted chain on cellulose was found to be made of a single type of monomer. The ceric ion consumption during grafting was found to be independent of the molarity of the feed but shown an appreciable change in the initial few hours of grafting. The variation in the values of the grafting parameters as a function of the reaction conditions is suitably explained. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 767–778, 2001     

褐藻多糖硫酸酯/甲基丙烯酸甲酯接枝聚合及抗凝血性能研究

研究了Cu(Ⅱ)离子存在时,褐藻多糖硫酸酯与甲基丙烯酸甲酯(MMA)的接枝聚合反应。主要探讨了V(MMA)/V(H2O)、Cu(Ⅱ)浓度、反应时间、温度对接枝率的影响。采用FT-IR对接枝共聚物进行了表征。接枝共聚物的体外抗凝血活性采用部分凝血活酶时间(APTT)、凝血活酶时间(PT)、凝血酶时间(TT)来评价。结果表明,褐藻多糖硫酸酯的水溶液在Cu(Ⅱ)离子存在时,可以引发MMA的自由基聚合反应。当褐藻多糖硫酸酯的质量浓度为5 6g/L,V(MMA)/V(H2O)=0 20,Cu(Ⅱ)浓度为3 26mmol/L,反应温度85℃,反应时间为3h时,接枝率为197.0%。APTT、TT、PT实验证明,接枝产物的APTT、TT比空白对照物分别延长20s和5s以上,具有抗凝血性能。     

POSS增强PMMA热性能和力学性能研究

采用溶液共混法将笼形纳米粒子甲基丙烯酸甲酯基多面低聚倍半硅氧烷（MMA-POSS）与聚甲基丙烯酸甲酯（PMMA）共混制备无机/有机纳米复合材料。利用傅里叶红外光谱仪、核磁共振波谱仪和场发射扫描电子显微镜对材料进行了结构表征。场发射扫描电子显微镜观察复合物薄膜表面形态显示,当MMA-POSS含量较小时,薄膜表面均匀平整,MMA-POSS均匀地分散于PMMA基体中,复合材料的热稳定性和力学性能得到明显改善,其玻璃化转变温度（Tg）和热分解温度（Td）显著提高,POSS含量为1.0 %（质量分数,下同）时,Tg 和Td分别提高了16.9 ℃和21.0 ℃。     

氧化还原引发降解天然橡胶与丙烯酸酯共聚的研究

研究了降解天然橡胶胶乳与丙烯酸甲酯、丙烯酸丁酯的聚合，以过氧化苯甲酰—N，N—三甲基苯胺(BP0—DMA)为氧化还原引发剂，考察了不同反应温度、引发剂配比、乳化剂用量及加料方式对单体转化率和接枝率的影响；用红外光谱对共聚物进行了表征。结果表明，采用乳化还原引发剂可使聚合反应低温快速进行，过量还原剂起阻聚作用，采用复合乳化剂可提高聚合反应速度和乳液稳定性，补加料可提高接技率。