耐水型核壳丙烯酸酯聚合物增韧剂的制备与性能研究

采用种子乳液聚合方法制备了烷基化纳米SO2/甲基丙烯酸甲酯(MMA)/甲基丙烯酸(MAA)核壳型乳液,用破乳法获得了到粉末状的核壳聚合物粒子,用TEM、FT-IR分析研究了乳液聚合产物的结构.在第三组分(含有丙烯腈的丙烯酸酯核壳聚合物)的配合下,与单一核壳聚合物粒子增韧相比,所改性的环氧树脂在水中固化的剪切强度下降幅度(相对于空气固化)由23.4%减少至8.4%,耐水性明显提高,同时力学性能也有一定的提高,而耐热性没受到影响.     

交联型丙烯酸酯核壳纳米复合涂料的制备

详细研究了核壳乳液的聚合机理、聚合工艺和软硬单体的比例、单体的滴加速度、交联单体甲基丙烯酸等对乳液性能的影响.在MMA/BA/DMMA/MAA聚合体系中,用半连续法制备出性能优越的核壳乳液,核壳乳液的性能在一定范围内随着交联单体甲基丙烯酸和DMMA的用量的增加提高,甲基丙烯酸最佳用量为单体的4%～6%,DMMA的最佳用量为2.0%.乳液中加入2%纳米二氧化硅对乳液进行改性得到纳米复合涂料.加入的纳米SiO2分散好,不产生团聚,并能显著改善复合涂料的力学性能和耐水性.     

核壳型纳米SiO2/含氟聚丙烯酸酯复合乳液的合成与表征

采用原位乳液聚合法,在可聚合阴离子乳化剂/非离子乳化剂复配体系下,以γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH-570)改性的纳米SiO2、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸(AA)等为核相组成,以MMA、BA及甲基丙烯酸十二氟庚酯(DFMA)为壳相单体,合成纳米SiO2/含氟聚丙烯酸酯复合乳液.考察了纳...     

纳米SiO_2表面接枝甲基丙烯酸甲酯的研究

为了提高纳米二氧化硅(SiO2)粒子在阻燃型聚合物基纳米复合材料中的有效利用,需要对粒子的表面进行改性。此实验采用溶液聚合法,使甲基丙烯酸甲酯单体(MMA)在烷基化预处理的纳米SiO2粒子的表面进行接枝聚合,得到以纳米SiO2粒子为核、接枝聚甲基丙烯酸甲酯为壳的复合颗粒(SiO2-g-PMMA)。结果表明,PMMA以化学键成功地接到纳米SiO2的表面,并可通过改变接枝聚合的条件来调节粒子上所接聚甲基丙烯酸甲酯的结构,改性后的纳米SiO2粒子具有良好的热稳定性及分散性。     

Ag@SiO_2核壳纳米粒子的制备与表征

以NaBH4作还原剂,TEOS为前体,采用反相微乳液法制得粒径50～100nm的Ag@SiO2核壳纳米粒子,其中Ag核为面心立方结构,壳层为无定形SiO2。考察催化剂加入的先后和微乳液R值(R=n水/n表面活性剂)对Ag@SiO2核壳纳米粒子形成的影响。用TEM、UV-Vis、XRD对纳米粒子的形貌及性质进行表征。结果表明:催化剂若先于TEOS加入,易得到Ag@SiO2核壳纳米粒子,随着R值的增加,Ag核的粒径变大,纳米粒子逐渐由单核变成多核。催化剂若后于TEOS加入,则形成负载型Ag/SiO2复合物。Ag核被SiO2壳包覆后的等离子共振吸收峰发生了微弱红移。而当壳厚80nm时,由于SiO2的散射作用,吸收峰会发生蓝移。     

纳米Si02／MMA无皂乳液聚合研究及其应用

以纳米SiO2为核。以MMA为壳层单体，进行了无皂乳液聚合。研究了单体加入方式、引发剂用量、聚合反应温度等对无皂乳液聚合的影响。核壳产物对PVC材料的力学性能有明显的提高。     

改性硅溶胶 /聚丙烯酸酯复合乳液的制备及性能研究

为了提高无机纳米粒子在有机聚合物中的相容性,以及无机 -有机复合材料的贮存稳定性,用硅溶胶和双丙酮丙烯酰胺（ DAAM）制备出改性硅溶胶,然后以改性硅溶胶为核,以甲基丙烯酸甲酯（ MMA）、α-甲基丙烯酸（ MAA）和丙烯酸丁酯（ BA）为原料,通过半间歇乳液聚合法制备出了核壳结构的改性硅溶胶 /聚丙烯酸酯复合乳液（ DAAM-SiO2/WPA）,并研究了硅溶胶对聚丙烯酸酯复合乳液和涂膜性能的增强作用。结果表明：用质量分数 3%的双丙酮丙烯酰胺（ DAAM）改性硅溶胶,制备的复合乳液的综合性能增强,水接触角为 77. 17°,吸水率为 11. 27%,拉伸强度为 7. 22 MPa,断裂伸长率为 431. 49%。TEM测试表明复合乳液具有核壳结构。相比较纯丙烯酸酯（ WPA）涂膜,复合乳液涂膜的耐水性、热稳定性和力学性能都有显著提高。并且与聚丙烯酸酯乳液和硅溶胶的直接物理混合溶液（ SiO2/WPA）相比,改性硅溶胶 /聚丙烯酸酯复合乳液的室温贮存稳定性超过 12个月,无机相和有机相的相容性好。     

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。     

聚丙烯酸酯原位乳液聚合包覆纳米硅溶胶的研究

首先，用水溶性聚合物羟丙基甲基纤维素（HPMC）包覆纳米二氧化硅溶胶（SiO2)，然后，通过原位乳液聚合法制成以SiO2为核，聚丙烯酸酯（ACR）为壳的复合物，实验表明，当包覆温度为60℃，且nHPMC:nSiO2等于1：16时，HPMC－SiO2/ACR复合乳液的稳定性较好；ACR的转化率及反应速率随SiO2用量的增加而下降，用HPMC－SiO2质量分数为3％－20％的HPMC－SiO2/ACR复合物改性PVC时，拉伸强度随HPMC－SiO2质量分数的增加而增大，当HPMC－SiO2质量分数达到20％后开始下降；而断裂伸长率和冲击强度在HPMC－SiO2质量分数为5％时达到最大。     

真空直镀纸用丙烯酸乳液成膜与耐温性研究

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为聚合主单体、以甲基丙烯酰氧基丙基三甲氧基硅烷(A174)为交联单体,采用核壳聚合工艺合成具有成膜性好、耐温高的真空直镀用乳液。研究了聚合物核壳比、聚合物玻璃化温度(Tg)、A174加入方式及用量等对乳液成膜性和耐温性的影响。结果表明:采用硬核软壳结构,核壳比例在75∶25,核壳聚合物的玻璃化温度设计在100/0℃、并且采用延迟滴加技术加入占单体总量2%的A174单体时,乳液具有较好的成膜性和耐温性。采用该乳液制备的涂料具有VOC气味低,成膜性好,耐温高等特点,主要应用于纸张的真空直镀,满足成膜和耐温的要求。     

Preparation of toughened PMMA through PEG-modified urethane acrylate/PMMA core–shell composite particles

Poly(urethane acrylate) (PUA)/poly(methylmethacrylate) (PMMA) core–shell composite particles were prepared by two-stage emulsion polymerization. The sizes of composite particles could be varied from 25 to 210 nm by introducing polyoxyethylene (POE) groups to the urethane acrylate molecular backbone. Core–shell morphology was identified by investigating the polarity of the surface of the core and shell polymer particles and by measuring the contact angle of the composite particles. A composite particle prepared with relatively small particles (about 20 nm) did not show the core/shell morphology, because the high polar surface of the core polymer particle and the low-stage ratio of the core to the shell cause the formation of a core/shell two-stage latex to be more thermodynamically unstable. The fracture toughness of rubber-toughened PMMA containing PUA/PMMA composite particles increased as the particle sizes decreased and the shell thickness of the composite particles increased. In particular, when the average size of the composite particle was about 43 nm and the stage ratio was 50/50, the fracture toughness of the rubber-toughened PMMA increased more than three times compared with that of pure PMMA. Furthermore, the transparency of toughened PMMA could be maintained up to 91% in the visible spectra range. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2291–2302, 1998     

Synthesis and characterization of poly(butyl acrylate)/silica and poly(butyl acrylate)/silica/poly(methyl methacrylate) composite particles

Poly(butyl acrylate)/poly(methyl methacrylate) (PBA/PMMA) core–shell particles embedded with nanometer‐sized silica particles were prepared by emulsion polymerization of butyl acrylate (BA) in the presence of silica particles preabsorbed with 2,2′‐azobis(2‐amidinopropane)dihydrochloride (AIBA) initiator and subsequent MMA emulsion polymerization in the presence of PBA/silica composite particles. The morphologies of the resulting PBA/silica and PBA/silica/PMMA composite particles were characterized, which showed that AIBA could be absorbed effectively onto silica particles when the pH of the dispersion medium was greater than the isoelectric potential point of silica. The critical amount of AIBA added to have stable dispersion of silica particles increased as the pH of the dispersion medium increased. PBA/silica composite particles prepared by in situ emulsion polymerization using silica preabsorbed with AIBA showed higher silica absorption efficiency than did the PBA/silica composite particles prepared by direct mixing of PBA latex and silica dispersion or by emulsion polymerization in which AIBA was added after the mixing of BA and silica. The PBA/silica composite particles exhibited a raspberrylike morphology, with silica particles “adhered” to the surfaces of the PBA particles, whereas the PBA/silica/PMMA composite latex particles exhibited a sandwich morphology, with silica particles mainly at the interface between the PBA core and the PMMA shell. Subsequently, the PBA/silica/PMMA composite latex obtained had a narrow particle size distribution and good dispersion stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3425–3432, 2006     

Preparation of polystyrene/poly(methyl methacrylate) core‐shell composite particles by suspension‐emulsion combined polymerization

Suspension‐emulsion combined polymerization process, in which methyl methacrylate (MMA) emulsion polymerization constituents (EPC) were drop wise added to styrene (St) suspension polymerization system, was applied to prepare polystyrene/poly(methyl methacrylate) (PS/PMMA) composite particles. The influences of the feeding condition and the composition of EPC on the particle feature of the resulting composite polymer particles were investigated. It was found that PS/PMMA core‐shell composite particles with a narrow particle size distribution and a great size would be formed when the EPC was added at the viscous energy dominated particle formation stage of St suspension polymerization with a suitable feeding rate, whereas St‐MMA copolymer particles or PS/PMMA composite particles with imperfect core‐shell structure would be formed when the EPC was added at the earlier or later stage of St suspension polymerization, respectively. It was also showed that the EPC composition affected the composite particles formation process. The individual latex particles would exist in the final product when the concentrations of MMA monomer, sodium dodecyl sulfate emulsifier, and potassium persulfate initiator were great in the EPC. Considering the feature of St suspension polymerization and the morphology of PS/PMMA composite particles, the formation mechanism of PS/PMMA particles with core‐shell structure was proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Material encapsulation in poly(methyl methacrylate) shell: A review

Material encapsulation is a relatively new technique for coating a micro/nanosize particle or droplet with polymeric or inorganic shell. Encapsulation technology has many applications in various fields including drug delivery, cosmetic, agriculture, thermal energy storage, textile, and self-healing polymers. Poly(methyl methacrylate) (PMMA) is widely used as shell material in encapsulation due to its high chemical stability, biocompatibility, nontoxicity, and good mechanical properties. The main approach for micro/nanoencapsulation of materials using PMMA as shell comprises emulsion-based techniques such as emulsion polymerization and solvent evaporation from oil-in-water emulsion. In the present review, we first focus on the encapsulation techniques of liquid materials with PMMA shell by analyzing the effective processing parameters influencing the preparation of PMMA micro/nanocapsules. We then describe the morphology of PMMA capsules in emulsion systems according to thermodynamic relations. The techniques to investigation of mechanical properties of capsule shell and the release mechanisms of core material from PMMA capsules were also investigated. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48039.     

Poly(methyl methacrylate) toughening with refractive index‐controlled core–shell composite particles

Poly(butylacrylate‐co‐styrene)/poly(methyl methacrylate) (PMMA) core–shell composite particles having different refractive indexes were prepared by a two‐stage consecutive emulsion polymerization. The refractive index of the core phase was controlled by varying the incorporated amount of divinylbenzene (DVB) which acted as a crosslinking agent as well as a refractive index enhancer. The blends of these core–shell composite particles with PMMA showed an impact strength increment of about three times compared with that of the pure PMMA. However, as the amount DVB increased, the impact strength showed a tendency toward decreasing. This was caused by the loss of the elastic property of the core phase. The toughened PMMA blended with core–shell composite particles having the core crosslinked with 1 wt % DVB showed the best transparency. However, the transparency was rather decreased, as the difference of the refractive index between the core phase and the pure PMMA increased. This suggested that in the case of using the core–shell composite particles as a toughening agent for PMMA the matching of the refractive index of the core phase with that of the pure PMMA was one of key factors in maintaining the transparency of the toughened PMMA. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1607–1614, 1999     

环氧树脂改性核壳乳胶粒子的制备

采用预乳化-半连续种子乳液聚合工艺制备了环氧树脂改性聚丙烯酸丁酯/(聚甲基丙烯酸甲酯-衣康酸)(PBA/P(MMA-ITA-DGEBA))核壳乳胶粒子。采用激光粒度仪、傅立叶变换红外光谱(FTIR)、差示扫描量热仪(DSC)、透射电子显微镜(TEM)等方法对核壳乳胶粒子进行了表征,实验结果表明:PBA/P(MMA-ITA-DGEBA)乳胶粒子确为核壳结构,双酚A型环氧树脂已经被成功接枝到核壳乳胶粒子上,由于ITA、DGEBA链段的存在,导致壳层PMMA玻璃化转变温度的(Tg)升高。     

Morphological characterization of attapulgite/poly(methyl methacrylate) particles prepared by soapless emulsion polymerization

BACKGROUND: The synthesis of core–shell inorganic/polymer nanocomposites, in which the polymer shell determines the chemical properties and the interaction with the environment, whereas their physical properties are governed by both the size and shape of the inorganic core and the surrounding organic layer, is an area of increasing research activity. RESULTS: Core–shell and bead–string shaped attapulgite/poly(methyl methacrylate) (ATP/PMMA) nanocomposite particles were prepared by soapless emulsion polymerization in an aqueous suspension of attapulgite organically modified with cetyltrimethylammonium bromide. CONCLUSION: Transmission electron microscopy analysis results showed that the amounts of the monomer added had no influence on the morphologies of the ATP/PMMA particles. The morphologies only depended on the length/diameter ratio of the attapulgite fibrillar single crystal used. Long ATP needles formed the bead–string structure while short ATP needles formed the core–shell structure. Copyright © 2007 Society of Chemical Industry     

PMMA/PAN核-壳粒子制备工艺研究

加入适量的引发剂,通过无皂乳液聚合,以聚甲基丙烯酸甲酯( PMMA)核体为种子乳液,制备了PMMA/PAN核-壳乳液.实验中分别对引发剂量、丙稀腈( AN)滴加量对PMMA/PAN壳层厚度及其粒径和粒径分布的影响进行了较详细的研究,确定了种子乳液聚合法制备PMMA/PAN核-壳结构聚合物粒子的实验方法及条件.通过激光粒度仪、扫描电镜和透射电镜对核-壳粒子的形态结构进行了表征,证明了PMMA/PAN复合粒子的核-壳结构.     

ACR中壳层PMMA相对分子质量对PVC／ACR共混物性能的影响

采用种子乳液法制备了核壳型聚丙烯酸酯(ACR),并分别采用十二烷基硫醇和正辛基硫醇作为链转移剂对 ACR壳层的聚甲基丙烯酸甲酯(PMMA)进行相对分子质量调节,并用于PVC共混改性。黏度法对PMMA的相对分子质量测定表明,正辛基硫醇的相对分子质量调节能力较强。采用差示扫描量热分析测定PMMA的玻璃化转变温度(Tg),并对共混树脂进行动态力学性能测试。当ACR壳层PMMA平均相对分子质量低于12×104时,PVC/ACR 共混树脂的缺口冲击强度大大提高。与纯PVC相比,共混树脂的Tg均略有提高,其增量随ACR壳层PMMA平均相对分子质量的降低而减小。动态力学性能测试结果表明,ACR壳层聚合物平均相对分子质量越低,共混物分子链段运动活化能提高越少。     

以PVC为外壳层的ACR抗冲改性剂的合成及其对PVC的增韧作用

以聚丙烯酸丁酯(PBA)为内核,通过种子乳液聚合制备了分别以聚甲基丙烯酸甲酯(PMMA)、聚氯乙烯(PVC)、PMMA/PVC为壳层的纯丙烯酸酯(ACR)和PVC改性ACR乳液.扫描电镜观察发现,纯ACR乳胶粒子具有明显的核-壳结构,进一步包覆PVC后形成疏松外层.考察了不同结构ACR与PVC共混物的相态结构、抗冲性能和断面形貌,发现用PVC部分或完全替代PMMA壳层的改性ACR在PVC基体分散良好,具有与纯ACR相当的增韧PVC作用,冲击断面呈现典型的韧性断裂特征.