乙丙三元胶的功能化研究

用马来酸二丁酯（ＤＢＭ）对乙丙三元胶（ＥＰＤＭ）进行了功能化，在烃链上导入极性基团，以改善ＥＰＤＭ与含极性基团聚合物的相容性．红外光谱表明功能化反应确已发生．用电子顺磁共振波谱仪（ＥＳＲ）研究了热引发的机理，产物的功能化率由皂化水解反应测定；产物交联程度由凝胶量间接表征；用凝胶渗透色谱法（ＧＰＣ）表征产物的分子量分布。研究了反应温度、反应时间、单体用量和引发剂用量等对产物功能化率和凝胶量的影响。     

甲壳胺-g-PEG的合成及医用性能的研究(Ⅰ)甲壳胺-g-PEG的合成及表征

通过官能团偶联反应，将端基改性为醛基的甲氧基聚乙二醇（分子量分别为２０００、５０００），按不同配比与甲壳胺反应，制得了甲壳胺接枝ＰＥＧ的产物（Ｃｈｉｔｏｓａｎ－ｇ－ＰＥＧ）。讨论了反应的最佳ｐＨ条件。建立了有效的产物分离方法，用红外光谱法、１Ｈ－ＮＭＲ法对产物的本体结构进行了表征，并用元素分析法和１Ｈ－ＮＭＲ法对接枝量进行了测定。     

聚环氧乙烷为支链的两亲共聚物的表征及性能

用端基带有甲基丙烯酸酯的聚环氧乙烷大分子单体（ＰＥＯ—ＭＡ）分别与小分子单体苯乙烯（Ｓ）、甲基丙烯酸甲酯（ＭＭＡ）、丙烯酸甲酯（ＭＡ）溶液自由基共聚合得到了三种具有不同主链结构的以聚环氧乙烷（ＰＥＯ）为支链的两亲接枝嵌段共聚物（分别简写为：ＰＳ─ｇ─ＰＥＯ，ＰＭＭＡ─ｇ─ＰＥＯ，ＰＭＡ─ｇ─ＰＥＯ）．用ＧＰＣ、ＩＲ、１Ｈ─ＮＭＲ、ＷＡＸＤ和ＤＳＣ对其结构进行了表征．研究了接校共聚物的结晶性能、乳化性能以及在Ｗｉｌｌｉａｍｓｏｎ反应中相转移催化作用．结果表明，不同主链结构有不同的结晶度，并随支链ＰＥＯ含量的增加，分子量的增大而提高；其乳化体积和相转移催化反应的转化率均随着共聚物浓度的增加、支链ＰＥＯ含量的增人而增大，随支链ＰＥＯ分子量的提高而减小．     

N,N—二乙基二硫代氨基甲酸聚氯乙烯酯引发甲基丙烯酸甲…

用铜试剂（Ｎ，Ｎ－二乙基二硫代氨基甲酸钠）取代聚氯乙烯中的部分氯原子制备了Ｎ，Ｎ－二乙基二硫代氨基甲酸聚氯乙烯酯（ＰＶＣ－ＳＲ），研究了紫外光照下ＰＶＣ－ＳＲ引发甲基丙烯酸甲酯（ＭＭＡ）的聚合反应，考察了光照时间、单体浓度、ＰＶＣ－ＳＲ用量及官能度的影响。结果表明，ＰＶＣ－ＳＲ能有效地引发ＭＭＡ聚合，其产物是交联型接枝聚合物，且具有高接枝率和接枝效率。     

POM／EVA共混物的研究

用力学测试、扫描电镜（ＳＥＭ）、热分析（ＤＳＣ）等手段研究了聚甲醛（ＰＯＭ）与乙烯－醋酸乙烯酯共聚物（ＥＶＡ）共混物（ＰＯＭ／ＥＶＡ）的力学性能及其微同形态；用聚甲醛与马来酸二丁酯（ＤＢＭ）的接枝物（ＰＯＭ－ｇ－ＤＢＭ）作相溶剂，能改变共的两相间的粘结力，从而提出了共混物的力学性能，ＳＥＭ观察表明接枝物的加入改变了ＰＯＭ／ＥＶＡ共混物的断裂方式，微观形态及结晶性能，对其热性能影响不大；通过改变ＰＯ     

LDPE－g－MALa离聚物的研究

详细地研究了ＬＤＰＥ熔融接枝马来酸镧（ＭＡＬａ）的反应。产物ＬＤＰＥ－ｇ－ＭＡＬａ的ＩＲ表明在波数１５４９ｃｍ－１和１６２８ｃｍ－１处出现了羧酸盐的Ｃ＝０伸缩振动峰，说明ＭＡＬａ已接枝在ＬＤＰＥ上；ＷＡＸＤ衍射结果则表明在２θ＝１７．２０°、１４．２０°处出现了新的衍射峰—离子峰。为了控制熔融接枝过程，考察了各种瓜条件对接枝率的影响。同时，ＤＳＣ的结果表明离聚物中离子微区的存在在结晶过程中可以起到较好的成核作用。     

N，N－二乙基二硫代氨基甲酸聚氯乙烯酯引发甲基丙烯酸甲酯的光接枝交联聚合反应

用铜试剂（Ｎ，Ｎ－二乙基二硫代氨基甲酸钠）取代聚氯乙烯中的部分氯原子制备了Ｎ，Ｎ－二乙基二硫代氨基甲酸聚氯乙烯酯（ＰＶＣ－ＳＲ），研究了紫外光照下ＰＶＣ－ＳＲ引发甲基丙烯酸甲酯（ＭＭＡ）的聚合反应，考察了光照时间、单体浓度、ＰＶＣ－ＳＲ用量及官能度的影响．结果表明，ＰＶＣ－ＳＲ能有效地引发ＭＭＡ聚合，其产物是交联型接枝聚合物，且具有高接枝率和接枝效率。     

接枝共聚物氯化聚乙烯—苯乙烯对聚苯乙烯的共混改性

用氯化聚乙烯接枝苯乙烯共聚物（ＣＰＥ－ｇ－Ｓｔ）和氯化聚乙烯（ＣＰＥ）对聚苯乙烯（ＰＳ）进行共混改性。当ＣＰＥ含量为２５％时，用ＣＰＥ－ｇＳｔ改性的共混物的冲击强度为１８．５ｋＪ．ｍ＾－＾２，是用ＣＰＥ改性的共混物冲击强度的２．１倍；其拉伸强度不低于３４ＭＰａ。     

肝素化聚甲基硅氧烷-聚氧乙烯接枝物的合成及其体外抗凝血性能评价

以二甲基硅油接枝端羟基聚氧乙烯（ＰＤＭＳ ｇ ＰＥＯ ＯＨ）为基材，用二环己基碳二亚胺（ＤＣＣＩ）作脱剂，研究了羟基（ＯＨ）与肝素上的羧基（—ＣＯＯＨ）之间的脱水缩合反应，制备出肝素化的抗血栓材料ＰＤＭＳ ｇ ＰＥＯ Ｈｅｐ，并对其涂覆表面的肝素含量和体外抗凝血性能进行了初步评价．实验结果表明，肝素接枝的共聚物具有优良的抗凝血性能和一定的应用前景．     

接枝共聚物氯化聚乙烯－苯乙烯对聚苯乙烯的共混改性

用氯化聚乙烯接枝苯乙烯共聚物（ＣＰＥ－ｇ－Ｓｔ）和氯比聚乙烯（ＣＰＥ）对聚苯乙烯（ＰＳ）进行共混改性．当ＣＰＥ含量为２５％时，用ＣＰＥ－ｇ－Ｓｔ改性的共混物的冲击强度为１８．５ｋＪ·ｍ￣（－２），是用ＣＰＥ改性的共混物冲击强度的２．１倍；其拉伸强度不低于３４ＭＰａ．     

自由基引发马来酸二丁酯熔融接枝低密度聚乙烯的研究

用马来酸二丁酯(DBM)为接枝单体,过氧化二枯基(DCPO)为引发剂,对低密度聚乙烯(LDPE)进行了熔融接枝功能化。样品的红外光谱表明接枝反应确已发生。通过对样品中酯基的皂化水解测定产物的接枝率,对产物进行萃取,用凝胶量间接表征产物的交联程度;用溶液的特性粘度从侧面显示样品的支化或降解情况。实验结果表明,产物的接枝率和凝胶量可以通过选择反应条件(温度、时间及反应混合物的组成)来控制;过量的DCPO是引起交联产生凝胶的主要原因;向体系中添加DMF可阻止交联反应的发生,但产物的接枝率也有所下降,以自由基机理对上述结果进行了讨论。     

甲基丙烯酸缩水甘油酯/苯乙烯固相接枝聚丙烯

以苯乙烯(St)为共单体，过氧化苯甲酰(BPO)为引发剂，采用固相接枝反应将甲基丙烯酸缩水甘油酯(GMA)接枝到聚丙烯(PP)大分子链上。研究了反应时间、单体用量、引发剂用量等因素对接枝率的影响。采用凝胶渗透色谱(GPE)测定了PP和接枝物PP-g-(GMA-St)的分子量和分子量分布。结果 表明固相接枝PP反应条件为[GMA／[St]=2，反应3．5h，加入GMA 10份，BPO 5份。St的加入有助于GMA与PP的接枝，同时在一定程度上抑制了PP的降解。     

Synthesis,Characterization, and Performance Evaluation of Polymeric HALS in Ethylene‐Propylene‐Diene Terpolymer (EPDM)

A polymeric hindered amine light stabilizer (HALS), wherein the hindered amine functionality was attached to the maleic anhydride graft ethylene‐propylene‐diene terpolymer (EPDM) was synthesized. This involves photoinduced grafting of maleic anhydride groups on unsaturated sites of EPDM, followed by incorporation of amino terminated HALS. The grafting and functionalization reactions were characterized by FTIR and ¹³C NMR spectroscopy. The surface changes upon degradation are studied by SEM. The photostabilizing efficiency of this polymeric HALS was studied and compared with conventional HALS under accelerated weathering conditions. The HALS grafted EPDM showed significantly improved photostabilizing efficiency.     

Preparation and characterization of vinyltriethoxysilane grafted ethylene propylene diene terpolymer/linear low density polyethylene (EPDM‐g‐VTES/LLDPE) blends

Graft polymerization of vinyltriethoxysilane (VTES) onto ethylene‐propylene‐diene terpolymer (EPDM) was carried out in toluene using dicumylperoxide (DCP) as initiator. Effects of various parameters (EPDM content, VTES content, reaction time, reaction temperature and initiator concentration) on the grafting efficiency of VTES onto EPDM were investigated. At the optimum grafting efficiency conditions, EPDM‐g‐VTES was developed by melt mixing in a twin screw extruder and then linear (l), statically vulcanized (s) and dynamically vulcanized (d) blends of EPDM‐g‐VTES with linear low‐density polyethylene (LLDPE) with varying percentage compositions were prepared by melt mixing in the twin screw extruder. The grafting of VTES onto EPDM and its crosslinking was confirmed by FT‐IR. The characterization of mechanical properties such as tensile strength, elongation at break, Young's modulus and hardness, differential scanning calorimetry (DSC) analysis and morphology were studied and compared for the EPDM‐g‐VTES/LLDPE blends. The study reveals that the dynamically vulcanized blend improves the mechanical and thermal properties due to the presence of efficient interaction between component polymers when compared with other blends. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis and characterization of anionic graft copolymers containing poly(ethylene oxide) grafts

Anionic graft copolymers were synthesized through grafting of poly(ethylene glycol) monomethyl ether (MPEG) onto terpolymers containing succicinic anhydride groups. The backbone polymers were prepared through radical terpolymerization of maleic anhydride, styrene, and one of the following monomers: methyl methacrylate, ethylhexyl methacrylate, and diethyl fumarate. MPEG of different molecular weights were grafted onto the backbone through reactions with the cyclic anhydride groups. In this reaction one carboxylic acid group is formed together with each ester bond. The molecular weights of MPEG were found to influence the rate of the grafting reaction and the final degree of conversion. The graft copolymers were characterized by IR, GPC, and ¹H-NMR. Thermal properties were examined by DSC. Graft copolymers containing 50% w/w of MPEG 2000 grafts were found to be almost completely amorphous, presumably because of crosslinking, and hydrogen bonding between carboxylic acid groups in the backbone and the ether oxygens in MPEG grafts. © 1995 John Wiley & Sons, Inc.     

Photocrosslinking of elastomer systems—III Ultraviolet light induced reactions in EPDM and EPR blended with or modified by grafting of derivatives of benzophenone

Photocrosslinking experiments were performed in elastomeric polymer films (EPR or EPDM) that either contained benzophenone or some of its derivatives, or had been previously modified (EPDM) by grafting of benzophenone. This latter modification was performed by a series of Friedel-Crafts reactions. The resulting materials were characterized by i.r. and u.v. spectroscopy in conjunction with physical property measurements. The results allowed relationships between the properties of the photosensitizers in their excited states and their efficiency in the crosslinking processes to be established. The results suggest that each coupled polymer-photoinitiator exhibits a particular behaviour. Thus it appeared that, in the presence of oxygen, the hexadiene branches of the terpolymer can undergo various types of reactions. Moreover, the grafting of the photosensitizer onto the elastomer backbone was shown to enhance considerably the crosslinking reaction. It is possible to conclude that oxygen plays a substantial role in the photocrosslinking. Indeed it always enhances crosslink formation. It can be assumed that the photooxidation of the polymer backbone yields alkoxy and hydroperoxy radicals which can act as crosslink sites.     

Studies on grafting of tris(2‐methoxyethoxy)vinylsilane onto ethylene‐propylene‐diene terpolymer

New graft copolymer was prepared by incorporating tris(2‐methoxyethoxy)vinylsilane (TMEVS) on ethylene‐propylene‐diene terpolymer (EPDM) by using dicumyl peroxide (DCP) as initiator, in Haake Rheocord 90 torque rheometer. The effect of EPDM concentration, TMEVS concentration, reaction time, reaction temperature and initiator concentration on the graft co polymerization was studied. The grafting efficiency of TMEVS on EPDM was confirmed by Fourier Transform infrared (FT‐IR) spectroscopy. The grafting efficiency increased with increase in the silane concentration upto 6% by weight. The grafting efficiency decreased beyond 6% by weight due to homopolymerization of TMEVS and non‐availability of carbon–carbon double bond in the EPDM terpolymer. The thermal properties of peroxide cured EPDM and hot water cured EPDM‐g‐TMEVS were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis. The results show thermal properties like degradation tempertature and glass transition temperature of the EPDM‐g‐TMEVS were increased due to introduction of TMEVS on to EPDM terpolymer as well as the formation of thermally stable three‐dimensional network. Copyright © 2004 John Wiley & Sons, Ltd.     

Photocrosslinking of elastomer systems. II. Ultraviolet light-induced reactions in an EPDM modified by grafting of benzoin derivatives

Photocrosslinking experiments were performed on elastomeric polymer films (EPDM) previously modified by grafting a photosensitive initiator (benzoin derivative) onto the macromolecular backbone. This modification was performed by a series of Friedel–Crafts reactions and the resulting materials were characterized by infrared (IR) spectroscopy in conjunction with model reactions. After ultraviolet (UV) irradiation the photocrosslinked samples were studied by IR spectroscopy in conjunction with the measurement of physical properties. It apperared that grafting the photosensitizer onto the elastomer considerably enhances the crosslinking reaction even with a limited quantity of grafted benzoin derivative. Moreover, the results obtained suggest that the structure of the resulting networks is strongly dependent on the crosslinking process used; that is, curing the elastomer with peroxide or UV irradiation either of a blend of elastomer and photosensitizer or of the same elastomer modified by grafting the chromophore.     

Graft polymerization of arcylamide onto LLDPE film by electron beam pre-irradiation in air or argon. I. Influence of dose,grafting temperature,and monomer concentration

Linear low density polyethylene (LLDPE) film was irradiated by electron beam in air or argon prior to grafting in aqueous solutions of acrylamide containing 0.05% of Mohr's salt. The grafting kinetics was studied with pre-irradiation doses in the range of 2.5–25 Mrad and in the temperature range of 40–70°C. Grafting rates and final degrees of grafting were higher for LLDPE pre-irradiated in air than for LLDPE pre-irradiated in argon. The overall activation energies for the grafting reaction were dose-dependent. Above 5 Mrad, the overall activation energies were higher for LLDPE pre-irradiated in argon which is interpreted as being due to crosslinking of the LLDPE. © 1995 John Wiley & Sons, Inc.