丙烯酸改性聚氨酯的合成与性能的研究

采用聚丙烯酸酯与聚氨酯共混、以水性聚氯酯为种子乳液进行丙烯酸种子乳液聚合以及水性聚氨酯与丙烯酸接枝共聚3种方法分别得到丙烯酸改性水性聚氯酯，通过激光散射粒径仪测定乳胶粒的粒径、乳胶膜的透明性、傅里叶变换红外光谱(FTIR)结构分析以及扫描电镜(SEM)对乳胶膜结构和表面形貌进行分析。结果表明：采用种子乳液聚合反应和接枝反应所得到的丙烯酸改性水性聚氯酯乳液乳胶粒粒径比水性聚氨酯的粒径显增大，表现出良好的相容性；由种子乳液聚合和接枝聚合制备的丙烯酸改性水性聚氯酯胶膜中颗粒与颗粒之间结合紧密，表面光亮、透明。     

丙烯酸改性氯化聚丙烯乳液的合成与性能

采用溶液法用含亲水单元的丙烯酸混合单体与氯化聚丙烯进行自由基接枝共聚反应,制得丙烯酸改性氯化聚丙烯,将其中和后加水分散即得丙烯酸改性氯化聚丙烯乳液.用傅罩叶红外光谱对产物进行了表征.研究了丙烯酸混合单体浓度、中和度和甲基丙烯酸含量对乳液性能的影响,当丙烯酸混合单体与氯化聚丙烯的质量比为0.5-1.5、甲基丙烯酸含量为15%-20%(占单体总量的质量比)、中和度为80%～120%时,制备的水性乳液具有良好的稳定性和水分散性,乳液涂膜对聚丙烯板具有很好的附着力和光泽.     

丙烯酸改性氯化聚丙烯的合成和粘接性能的研究

氯化聚丙烯是聚丙烯的氯化改性产物，通过改性，其硬度、耐磨性、耐酸性、耐盐水性能比聚丙烯都好，耐热、耐老化性也优于聚丙烯。但其性能尤其是粘接性能还不能满足其在胶粘刺等方面的需要，为了进一步提高氯化聚丙烯的粘接性能，拓宽其应用领域，需对氯化聚丙烯改性。接枝共聚法是一种很好的化学改性方法。本文以丙烯酸(AA)作为接枝单体，以过氧化苯甲酰(BPO)为引发剂，以甲苯为溶刺，采用液相接枝共聚法，将丙烯酸单体接枝到氯化聚丙烯大分子链上，得到丙烯酸改性氯化聚丙烯产物。系统研究了反应温度、反应时间、引发剂过氧化苯甲酰用量和丙烯酸单体用量等因素对丙烯酸接枝改性的氯化聚丙烯产物粘接性能的影响，得出了较佳的工艺条件是反应温度T=100℃，反应时间t=3．5h，原料质量配比为100份氯化聚丙烯、3份丙烯酸和0．3份的过氧化二苯甲酰。研究还表明，丙烯酸改性的氯化聚丙烯的粘接性能优于氯化聚丙烯的粘接性能。     

聚丙烯酸酯乳液的制备及其改性的研究

以丙烯酸酯及其衍生物作为主单体,丙烯酸为官能单体,采用乳液聚合法合成聚丙烯酸酯乳液,并用水性聚氨酯对聚丙烯酸酯乳液进行了改性。研究了搅拌速度、引发剂、丙烯酸和水性聚氨酯的含量对乳液及漆膜性能的影响。结果表明：在搅拌速度为200r／min,引发剂、丙烯酸和水性聚氨酯的含量分别为0．8％、0．3％和40％的条件下得到的乳液的稳定性、外观较好,黏度为88mPa㈦漆膜柔韧性好,附着力为一级。红外光谱分析表明合成了聚丙烯酸酯乳液,改性后的聚丙烯酸酯乳液具有聚丙烯酸酯和聚氨酯的复合结构。     

丙烯酸改性氯化聚丙烯的合成和粘结性能的研究

氯化聚丙烯是聚丙烯的氯化改性产物，通过改性，其硬度、耐磨性、耐酸性、耐盐水性能均比聚丙烯好，耐热、耐老化性也优于聚丙烯。但其性能尤其是粘结性能还不能满足其在胶粘剂等方面的需要，为了进一步提高氯化聚丙烯的粘结性能，拓宽其应用领域，需对氯化聚丙烯改性。接枝共聚法是一种很好的化学改性方法。为此，华南理工大学化工学院化工所的傅和青等以丙烯酸作为接枝单体，以过氧化苯甲酰为引发剂，以甲苯为溶剂，采用液相接枝共聚法，将丙烯酸单体接枝到氯化聚丙烯大分子链上，得到丙烯酸改性氯化聚丙烯产物。     

丙烯酸类单体接枝改性氯化聚丙烯乳液的制备

采用溶液聚合法和相反转法合成了丙烯酸类单体改性氯化聚丙烯(CPP)乳液。正交试验表明,过氧化苯甲酰用量为丙烯酸类单体质量的0.3%、丙烯酸类单体与CPP质量比为0.8、反应时间为4.0 h、温度为95℃时,制备的丙烯酸类单体改性CPP的附着力和接枝率较好。傅里叶变换红外光谱分析表明,改性CPP在1 730 cm-1处出现了新的强吸收峰,为丙烯酸类单体的酯基和羧基中C=O的伸缩振动吸收峰;差示扫描量热法分析表明,改性CPP的玻璃化转变温度为35℃左右,比CPP升高了6℃;改性CPP乳液粒径为300～400 nm,且分布较窄。     

引发剂对醇酸-聚丙烯酸酯杂化乳液成膜性的影响

采用种子微乳液聚合法合成了醇酸-聚丙烯酸酯杂化乳液。通过不同的引发剂和用量导致所得乳液成膜性发生变化,探讨了引发剂对醇酸-聚丙烯酸酯杂化乳液成膜性的影响。结果表明:油性引发剂BPO比AIBN更适合接枝反应,以醇酸树脂与丙烯酸单体总量2%的BPO及丙烯酸单体量0.4%的APS组合体系引发聚合反应,所得杂化乳液涂膜透明、高光。     

水性光固化改性氯化聚丙烯的制备及性能

以丙烯酸(AA)和甲基丙烯酸羟乙酯(HEMA)对氯化聚丙烯(CPP)进行溶液接枝改性。考察了AA与HEMA两种单体总用量(AA与HEMA两种单体质量之和占CPP质量的百分数,下同)及引发剂用量(即引发剂质量占CPP及单体总质量的百分数,下同)对接枝率的影响,得到了最佳AA与HEMA总用量为20%,最佳引发剂用量为3%,在该条件下接枝率达到8.81%。然后以甲基丙烯酰氯对接枝改性CPP进行光固活性成分改性,研究了不同AA用量的水性光固化改性CPP乳液性能、表面张力及附着力。结果表明,AA用量占AA和HEMA总质量20%~50%,均能形成乳液,乳液粒径随AA用量增多而减小;水性化改性产物经光固活性成分改性后,以及经光固活性成分改性后的产物光固化前后,表面性能良好,表面张力均在40 m N/m以上,附着力得到提高。该材料符合环保要求,具有良好的应用前景。     

丙烯酸改性氯醚树脂乳液的合成研究

采用溶液聚合法,以丙烯酸(AA)、丙烯酸丁酯(BA)和甲基丙烯酸甲酯(MMA)为混合单体,与氯醚树脂(VC-IBVE)进行接枝共聚;用中和剂三乙胺(TEA)与接枝反应产物中和成盐,得到水性丙烯酸改性氯醚树脂乳液.讨论了引发剂浓度对该体系接枝率的影响,重点研究了丙烯酸类单体用量以及混合单体中丙烯酸和丙烯酸丁酯的含量对改性乳液性能的影响.结果表明:丙烯酸类单体用量为50％,混合单体中丙烯酸和丙烯酸丁酯的含量分别为9％～11％和40％时,制得的改性乳液具有良好的稳定性、耐盐水性和优异的附着力.并用红外光谱(FT-IR)和透射电子显微镜表征(TEM)了此改性乳液.     

有机硅改性聚丙烯酸酯微乳液

中科院化学所的金鲜英等人采用丙烯酸 2 -乙基己酯、丁酯等软单体为壳层 ,甲基丙烯酸甲酯、丙烯酸、苯乙烯等硬单体为核 ,在较低表面活性剂含量下 ,经核 /壳乳化法合成出半透明的有机硅改性聚丙烯酸酯微乳液 ;产品成膜性好、渗透性及亲和性较好。将其作为印花胶粘剂 ,用于整理涤纶织物 ,整理后的产品手感柔软、透湿性提高 ,同时耐洗且有增深效果。有机硅改性聚丙烯酸酯微乳液     

接枝共聚改性氯化聚丙烯乳液的研究

以丙烯酸酯单体作为接枝共聚单体,合成了无芳烃低VOC的CPP(氯化聚丙烯)乳液。以接枝率和耐水性作为衡量指标,采用单因素试验法优选出制备CPP乳液的最佳工艺条件。结果表明:当反应温度为95℃、反应时间为3.5 h、w(总引发剂)=1.0%(其中10%引发剂在滴加单体以前加入,并且间隔时间为10 min)、w(丙烯酸酯单体)=30%和w(丙烯酸)=5%时,相应CPP乳液的综合性能相对较好,并且其对聚丙烯(PP)基材的附着力相对最好。     

Synthesis of acrylate modified vinyl chloride and vinyl isobutyl ether copolymers and their properties

With acrylic acid, butyl acrylate and methyl methacrylate as the monomers, acrylate modified vinyl chloride and vinyl isobutyl ether copolymers were prepared by solution polymerization. Firstly, vinyl chloride and vinyl isobutyl ether copolymers were grafted with acrylic monomers to obtain a product containing acrylate grafted vinyl chloride and vinyl isobutyl ether copolymers and polyacrylate, which was then neutralized by triethylamine and dispersed into water to get a self-emulsified emulsion. The acrylate modified vinyl chloride and vinyl isobutyl ether copolymers were characterized by Fourier transform infrared spectroscopy. The mean molecular weight of grafted polymer was determined by gel permeation chromatography, and the particle sizes and their distributions of the dispersions were measured by laser light scattering. The influences of initiator concentration, acrylate content, acrylic acid content and neutralization degree upon the properties of the modified copolymers were discussed. The results show that the emulsion will be with good storage stability, and the modified polymer will be with high water resistance, impact resistance and excellent adhesion when initiator concentration is 1.5%, acrylate content is 50%, acrylic acid content ranges from 9% to 11%, and neutralization degree is between 80% and 100%.     

核/壳型有机硅改性苯丙乳液印花粘合剂的合成及应用

以过硫酸钠(NaPS)为引发剂,苯乙烯(St)和丙烯酸丁酯(BA)为核单体,甲基丙烯酸甲酯(MMA)、丙烯酸异辛酯(EHA)、苯乙烯(St)、丙烯酸(AA)为壳单体,采用种子乳液聚合法,制备了硬壳软核型苯丙乳液,对其进行有机硅改性,得到核壳型有机硅改性苯丙乳液(简称硅丙乳液),将其用作涂料印花粘合剂。研究了核壳单体质量比、丙烯酸用量、乙烯基硅油用量对乳液性能及印花性能的影响;并用热失重分析仪和透射电镜进行了表征。较佳配方为:核/壳单体质量比为6∶4,AA质量分数为2.5%,乙烯基硅油质量分数为10%～15%。该乳液的理化性能较好,耐热性优于核/壳苯丙乳液,将其用于涂料印花,改善了堵网性,印花织物的干、湿摩擦牢度,皂洗牢度,手感以及表观得色量可以达到工业用华润粘合剂的水平。     

Preparation of spherical nanocomposites consisting of silica core and polyacrylate shell by emulsion polymerization

Nanocomposite particles consisting of silica (inorganic core) and polyacrylate (organic shell) were prepared in a form of emulsion by a new and simple method—the emulsion polymerization of acrylic monomers in the presence of silica sol. The key technique of the present emulsion polymerization, which made the formation of the nanocomposites successful, is the usage of nonionic surfactant above its cloud point. The morphology of the composite was investigated by DLS, AFM, and TEM, which clearly showed formation of the core‐shell‐type particles. A transparent film was prepared by casting the emulsion, which showed high resistibility against organic solvents. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 659–669, 2006     

Synthesis and characterization of nanosilica/polyacrylate composite latex

The nanosilica/polyacrylate organic–inorganic composite latex was synthesized by in‐situ emulsion polymerization of methyl methacrylate (MMA) and butyl acrylate (BA) in the presence of silica nanoparticles, which were modified by silane coupling agent. The surface properties and dispersibility of silica nanoparticles modification, chemical structure, Zeta potential, diameter distribution of the composite latex prepared, surface roughness, and thermal stability of the hybrid film formed by the composite latex were investigated by fourier transform infrared spectrometer (FTIR), transmission electron microscopy (TEM), Zeta meter, ZetaPlus apparatus (dynamic light scattering method), atomic force microscopy (AFM), and thermogravimetric analysis (TGA), respectively. After modification with silane coupling agent, silane was grafted onto the surface of silica nanoparticles to form the organic layers, which was able to efficiently prevent the silica nanoparticles from aggregating to individually homogeneous disperse in the in‐situ emulsion polymerization system and improve the compatibility of silica nanoparticles with the acrylate monomers. The nanosilica/polyacrylate organic–inorganic composite latex prepared had the properties of silica nanoparticles and pure polyacrylate latex but was not simply a combination. Strong chemical bonding tethered the silica and acrylate chains to form the core/shell structural composite latex. Consequently, the hybrid film formed by nanosilica/polyacrylate composite latex exhibited a smooth surface and better thermal properties than the pure polyacrylate film. POLYM. COMPOS. 27:282–288, 2006. © 2006 Society of Plastics Engineers     

原位聚合法制备纳米TiO2/有机硅改性丙烯酸酯复合乳液

用硅烷偶联剂对纳米二氧化钛(TiO2)粒子表面进行预处理，使其表面由亲水性变为疏水性，并在其表面接枝上可反应的有机官能团。通过改性纳米TiO2表面上的原位聚合反应，制备了纳米TiO2／硅丙复合乳液。透射电子显微镜观察结果显示，乳液中存在两种结构的乳胶粒子：一种是以聚丙烯酸酯为核、有机硅聚合物为壳的核壳结构硅丙乳胶粒子；另一种是以纳米TiO2为核、有机聚合物为壳的纳米TiO2／聚合物复合结构乳胶粒子。乳胶粒子的结构形态可由乳化剂的用量控制。该复合乳液具有较好的杀菌效果，在较短时间内对细菌的杀灭率可达90％以上。     

Coating based on the modified chlorinated polypropylene emulsion for promoting printability of biaxially oriented polypropylene film

In this paper, a polymeric coating based on the modified chlorinated polypropylene (CPP) emulsion was synthesized, methyl methacrylate (MMA), butyl acrylate (BA) and acrylic acid (AA) were grafted onto CPP backbone and phase inversion was conducted to obtain waterborne emulsion. Results showed that the concentration of initiator (BPO) had the greatest effect on graft copolymerization. The concentration of emulsifier and temperature influenced the results of phase inversion. Besides, the thermal performances of modified CPP were better than untreated one. In addition, the coating obtained in optimum condition had excellent adhesion to BOPP film, and apparently improved the printing quality of the film. The printability promotion should be attributed to the different movement trend of coating’s polar and un-polar chains during the baking step, as well as the subsequent formations of new coating/substrate and coating/ink interface layer.     

有机硅改性丙烯酸酯核-壳乳液的研制

采用种子乳液聚合法,以丙烯酸异辛酯为壳,MMA为核,MMA和有机硅偶联剂(A-151)为官能性单体,合成了内硬外软的核-壳型有机硅改性丙烯酸酯乳液。讨论了官能性单体、核-壳单体结构、引发剂等对乳液性能的影响。     

改性CPP的表征及其对PP附着性能的影响

采用混合单体甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)和2-甲基丙烯酸(MAA)对氯化聚丙烯(CPP)进行接枝改性,制备了几种不同接枝率的改性CPP,并用红外光谱和热分析仪对其进行了表征,探讨了改性CPP在PP基材上的附着性能。结果表明:改性CPP在PP塑料上具有良好的附着力;随着接枝率的提高,改性CPP与丙烯酸树脂的相容性增强,其混合液在PP塑料上的附着力达到100%,可用来制备直接涂覆的PP涂料。