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 acrylate polymer/silica nanocomposite particles with high silica encapsulation efficiency via miniemulsion polymerization

Acrylate polymer/silica nanocomposite particles were prepared through miniemulsion polymerization by using methyl methacrylate/butyl acrylate mixture containing the well-dispersed nano-sized silica particles coupling treated with 3-(trimethoxysilyl)propyl methacrylate (MPS). The encapsulation efficiency of silica particles was determined through the elution and hydrofluoride acid etching experiments, and the size distribution and the morphology of the composite latex particles were characterized by dynamic light scattering and transmission electron microscopy. The coupling treatment of silica with MPS can improve the encapsulation efficiency of silica and the degree of grafting of polymer onto silica. When 0.10 g MPS/g silica was used to modify silica, the encapsulation efficiency of silica was greater than 95%, and the degree of grafting of acrylate polymer onto silica was about 60%. Although the average size and the size distribution index of the composite latex particles increased as the weight fraction of silica increased, the stable latex containing the ‘guava-like’ composite particles was obtained. The grafting of polymer onto silica particles improved the dispersion of silica particles in the solvents for acrylate polymer and in the polymer matrix.     

Influence of amorphous silica on the hydration in ultra-high performance concrete

Amorphous silica particles (silica) are used in ultra-high performance concretes to densify the microstructure and accelerate the clinker hydration. It is still unclear whether silica predominantly increases the surface for the nucleation of C–S–H phases or dissolves and reacts pozzolanically. Furthermore, varying types of silica may have different and time dependent effects on the clinker hydration. The effects of different silica types were compared in this study by calorimetric analysis, scanning and transmission electron microscopy, in situ X-ray diffraction and compressive strength measurements. The silica component was silica fume, pyrogenic silica or silica synthesized by a wet-chemical route (Stoeber particles). Water-to-cement ratios were 0.23. Differences are observed between the silica for short reaction times (up to 3 days). Results indicate that silica fume and pyrogenic silica accelerate alite hydration by increasing the surface for nucleation of C–S–H phases whereas Stoeber particles show no accelerating effect.     

Preparation of nanosilica reinforced waterborne silylated polyether adhesive with high shear strength

Waterborne adhesives are extremely environment‐friendly but unfortunately deficient in mechanical properties. In this article, nanosilica, stemming from tetraethyl orthosilicate (TEOS), silica sol, and/or fumed silica powder, was employed to reinforce the waterborne silylated polyether adhesives. Effects of TEOS content, silica sol content, and the type and content of fumed silica on the shear strength of the adhesive were investigated using a scanning electronic microscope and an electronic instron tester and the strengthening mechanisms of different silica source were discussed. All the shear strengths of silylated polyether adhesives first increased and then decreased as TEOS content, silica sol content or fumed silica content increased. Colloidal silica particles was less efficient than fumed silica particles for reinforcing the polyether adhesive but can increase the shear strength of hydrophobic fumed silica embedded adhesive. Comparing the adhesives with the hydrophilic fumed silica (HS‐5) or the extremely hydrophobic fumed silica (TS‐720), the adhesive with moderate hydrophobic fumed silica (TS‐610) had the highest shear strength. The maximal shear strength of 2.5 MPa was achieved when TEOS, silica sol, and fumed silica were combined. It seemed that TEOS, silica sol, and fumed silica played crosslinking (with polyether chain), dispersing (for fumed silica), and reinforcing roles on waterborne adhesive, respectively. This reinforcing mechanism opened a new way to fabricate waterborne adhesives (or coatings) with high performances. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of fumed silica nanoparticles on glass fiber filled thermotropic liquid crystalline polymer composites

Glass fiber filled thermotropic liquid crystalline polymer (gLCP)/silica composites were prepared by melt compounding. The total torque of the gLCP/silica composites decreased and the melt flow index increased with increasing silica content, which indicates that the fumed silica nanoparticles act as good processing aids and enhance the processing behavior of gLCP/silica composites. The rheological properties of the gLCP/silica composites were significantly dependent on the silica content. The complex viscosity and storage modulus (G′) of the gLCP/silica composites decreased with increasing silica content. This was attributed to the ability of the silica nanoparticles to break the glass fiber–glass fiber interactions in the gLCPs. The storage modulus and loss modulus (G″) of the gLCP/silica composites increased with increasing frequency, and the increment was more significant at low frequency. Incorporation of a small quantity of silica nanoparticles improved the thermal stability and mechanical properties of gLCP/silica composites. However, at high silica nanoparticle content the mechanical properties of gLCP/silica composites decreased because of the aggregation of silica nanoparticles. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

白炭黑应用的新领域

阐述了由于白炭黑的特殊结构而具有的特殊性能，以及工业上两种主要生产白炭黑的方法，即气相法和沉淀法，综述了国外除橡胶工业外，白炭黑产品一些新的应用领域如医药、农药、日用化工等方面的应用及国内白炭黑应用开发的情况，指出白炭黑是一种有发展前景的产品。     

Dispersion of "guava-like" silica/polyacrylate nanocomposite particles in polyacrylate matrix

A series of “guava-like” silica/polyacrylate nanocomposite particles with close silica content and different grafting degrees were prepared via mini-emulsion polymerization using 3-(trimethoxysilyl)propyl methacrylate (TSPM) modified silica/acrylate dispersion. The silica/polyacrylate composite particles were melt-mixed with unfilled polyacrylate (PA) resin to prepare corresponding silica/polyacrylate molded composites and the dispersion mechanism of these silica particles from the “guava-like” composite particles into polyacrylate matrix was studied. It was calculated that about 110 silica particles were accumulated in the bulk of every silica/polyacrylate composite latex particle. Both the solubility tests of silica/polyacrylate composite latex particles in tetrahydrofuran (THF) and the section transmission electron microscope (TEM) micrographs of silica/polyacrylate molded composites indicated that the grafting degree of silica particles played a crucial role in the dispersion of silica/polyacrylate composite particles into the polyacrylate matrix. When the grafting degree of polyacrylate onto silica was in a moderate range (ca. 20%–70%), almost all of silica particles in these “guava-like” composite particles were dispersed into the polyacrylate matrix in a primaryparticle-level. However, at a lower grafting degree, massive silica aggregations were found in molded composites because of the lack of steric protection. At a greater grafting degree (i.e., 200%), a cross-linked network was formed in the silica/polyacrylate composite particles, which prevented the dispersion of composite particles in THF and polyacrylate matrix as primary particles.     

Property modulation of poly(N‐isopropylacrylamide) hydrogels by incorporation of modified silica

Poly(N‐isopropylacrylamide) (PNIPA)/silica composite hydrogels were prepared and the effects of the silica incorporation on the swelling and breaking characteristics of the hydrogels were investigated. To improve the dispersive property of silica in the PNIPA matrix via the formation of covalent bonds between the polymer and silica, vinyl groups were introduced in the silica by reacting it with a coupling agent, 3‐methacryloxypropyltrimethoxysilane. When unmodified silica was used as filler in the PNIPA‐composite hydrogel, the swelling ratio of the composite hydrogel below the critical gel transition temperature (CGTT) increased with increasing silica content. However, when the modified silica was used as the filler, the swelling ratio below CGTT decreased with increasing silica content because of the enhanced distribution and additional crosslinking. Above CGTT, the swelling ratios of the PNIPA/silica hydrogels were similar regardless of the silica modification. The gel breaking stress of the hydrogels increased with increasing silica content, and this enhancement was larger for the modified silica hydrogel. Scanning electron microscopy images showed that the modified silica particles were distributed more evenly in the PNIPA matrix than the unmodified ones were and that the size of cell‐like structure of the hydrogel decreased with increasing modified silica content. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Preparation and properties of melt‐blended polylactic acid/polyethylene glycol‐modified silica nanocomposites

One commercial type of fumed silica modified with methoxy polyethylene glycol (mPEG) plasticizer was incorporated into polylactic acid (PLA) biobased polymer to improve its performance. The modification on silica was confirmed through Fourier transform infrared spectra, nuclear magnetic resonance, and TGA assessments. The grafting percentage of mPEG onto silica was about 19.8 wt %. Transmission electron microscope revealed a similar degree of dispersion for control silica and modified silica‐filled PLA nanocomposites. Not much difference in the glass transition temperatures at various silica contents was found for PLA/control silica systems from the differential scanning calorimetry measurement, but the glass transition temperature of PLA/modified silica nanocomposite at 10 phr of modified silica showed up to 11°C decrement. It was suggested that the mPEG plasticizer efficiently plasticized the PLA matrix through the enhanced segmental mobility of PLA chains. Young's modulus of PLA was about 2133 ± 53 MPa, and the value for the nanocomposite increased to 2547 ± 54 MPa at 10 of phr control silica mainly due to the reinforcing effect from nanoparticles. For modified silica, Young's modulus decreased at various silica contents. The elongation at break for modified silica‐filled cases was higher than that of control silica‐filled cases. These results were attributed to the plasticizing effect of surface modifier. Optical transmittance for pristine PLA was generally in a similar order as PLA/control silica and modified silica cases at various silica contents. The results agreed with the morphology observation as well. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

硅溶胶硅酸钾混合物微量热法研究

在25.0℃及搅拌条件下,采用等温热导微量热法研究了硅溶胶与硅酸钾的混合过程。结果表明,硅溶胶与硅酸钾混合,立刻发生了SiO2溶解和复杂的化学反应,并产生了完全不同于硅溶胶和硅酸钾的SiO2胶体粒子和化学成分以及热效应,热效应受硅溶胶所占的相对重量百分比的影响。其反应的特征是硅溶胶和硅酸钾的反应级数从低到高时刻都在快速不断交替变化;随着硅溶胶所占比例的提高,热谱曲线峰高、硅溶胶与硅酸钾的混合化学反应完全的曲线总面积(总焓变QT)和热力学焓变(ΔH)数值都表现出不断增大的趋势。     

Alkali silica reactivity of agglomerated silica fume

It is commonly accepted that replacement of a portion of cement in mortar or concrete with well-dispersed silica fume reduces expansion caused by alkali silica reaction. Recently there has been much discussion that large, agglomerated particles of silica fume may actually act as alkali silica reactive aggregates, thereby increasing expansion rather than reducing it. The data in the literature, from both field and laboratory studies, are inconsistent. This prompted an extensive laboratory investigation into the alkali silica reactivity of silica fume. Results from accelerated expansion testing and microscopic investigations are presented. It was seen that some agglomerated silica fumes participate in ASR while others do not. Factors determining the reactivity of silica fume agglomerates are suggested.     

SODIUM SILICATE,A NEW ENAMEL RAW MATERIAL1

The addition of silica to enamel in the form of a readily fusible silicate, such as sodium silicate, lowers the smelting time and temperature required to bring about complete solution of the silica. Enamels in which all the silica was introduced in the form of quartz, although apparently completely smelted, still contained large quantities of free silica, while enamels of identical analysis in which sodium silicate was the sole source of silica contained, after smelting, no free silica. The presence of this free silica in an enamel affects its workability and acid resistance.     

Preparation and dispersibility of poly(L‐lactide)‐grafted silica nanoparticle

To improve dispersibility of silica nanoparticle in organic solvents, the grafting of poly(L ‐lactide) (PLLA) onto silica nanoparticle surface by ring‐opening polymerization of L‐lactide (LA) was investigated in the presence of an amidine base catalyst. The ring‐opening polymerization of LA successfully initiated in the presence of silica having amino groups (silica‐NH₂) and an amidine base catalyst to give PLLA‐grafted silica, but not in the presence of untreated silica (silica‐OH). In the absence of the amidine base catalyst no ring‐opening polymerization of LA even in the presence of silica‐NH₂ and no grafting of PLLA onto silica were observed. It became apparent that the amidine base catalyst acts as an effective catalyst for the ring‐opening graft polymerization of LA from the surface of silica‐NH₂. In addition, it was found that the percentage of PLLA grafting onto silica could be controlled according to the reaction conditions. The average particle size of PLLA‐grafted silica was smaller than that of silica‐NH₂. Therefore, it was considered that the aggregation structure of silica nanoparticles was considerably destroyed by grafting of PLLA onto the surface. The PLLA‐grafted silica gave a stable dispersion in polar solvents, which are good solvents for PLLA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dispersion of “guava-like” silica/polyacrylate nanocomposite particles in polyacrylate matrix

A series of “guava-like” silica/polyacrylate nanocomposite particles with close silica content and different grafting degrees were prepared via mini-emulsion polymerization using 3-(trimethoxysilyl)propyl methacrylate (TSPM) modified silica/acrylate dispersion. The silica/polyacrylate composite particles were melt-mixed with unfilled polyacrylate (PA) resin to prepare corresponding silica/polyacrylate molded composites and the dispersion mechanism of these silica particles from the “guava-like” composite particles into polyacrylate matrix was studied. It was calculated that about 110 silica particles were accumulated in the bulk of every silica/polyacrylate composite latex particle. Both the solubility tests of silica/polyacrylate composite latex particles in tetrahydrofuran (THF) and the section transmission electron microscope (TEM) micrographs of silica/polyacrylate molded composites indicated that the grafting degree of silica particles played a crucial role in the dispersion of silica/polyacrylate composite particles into the polyacrylate matrix. When the grafting degree of polyacrylate onto silica was in a moderate range (ca. 20%–70%), almost all of silica particles in these “guava-like” composite particles were dispersed into the polyacrylate matrix in a primary-particle-level. However, at a lower grafting degree, massive silica aggregations were found in molded composites because of the lack of steric protection. At a greater grafting degree (i.e., 200%), a cross-linked network was formed in the silica/polyacrylate composite particles, which prevented the dispersion of composite particles in THF and polyacrylate matrix as primary particles.     

改性接枝白炭黑填充丙烯酸酯橡胶的性能研究

主要探讨了甲基丙烯酸缩水甘油酯(GMA)接枝改性的白炭黑与橡胶的作用机理及在橡胶基体中的分散性。研究了不同种类和不同用量的白炭黑对丙烯酸酯橡胶(ACM)力学性能的影响。实验结果表明:接枝GMA的白炭黑在橡胶基体中具有较好的分散性,接枝改性的白炭黑与橡胶基体具有很好的相容性,接枝GMA的白炭黑填充的ACM力学性能较好;在白炭黑质量分数为40%时,拉伸强度达到最大值10.2MPa,而断裂伸长率在白炭黑质量分数为50%时,达到最大值345%。     

Interfacial Interactions of Silica and Natural Rubber Enhanced by Hydroxyl Telechelic Natural Rubber as Interfacial Modifier

The incompatibility between hydrophilic silica and hydrophobic rubber is an important problem on using silica in nonpolar rubber. In this study, hydroxyl telechelic natural rubber (HTNR) that contains hydroxyl‐terminated groups was introduced into silica‐reinforced natural rubber (NR) in order to improve the bonding strength between rubber and silica. The properties of silica‐reinforced NR compounds and vulcanizates as a function of varying silica contents were evaluated at a fixed HTNR concentration at 8% wt/wt of silica content. The results show that the improvement of silica dispersion and decreasing of filler–filler interactions (Payne effect) were obtained in the NR compounds and vulcanizates with HTNR addition. The enhancements in tensile properties, crosslink density, abrasion resistance, heat build‐up, and thermal properties of the silica‐reinforced NR vulcanizates with added HTNR confirmed that HTNR performed good as interfacial modifier of silica. In the study, the optimum properties of silica‐reinforced NR vulcanizate were achieved at 30 phr silica with 2.4 phr HTNR. However, HTNR still showed poorer efficiency than the synergy between commercial silane coupling agent, bis [3‐(triethoxysilyl) propyl] tetrasulphide (TESPT) and diphenylguanidine (DPG) when used in silica‐reinforced NR vulcanizate. J. VINYL ADDIT. TECHNOL., 26:291–303, 2020. © 2019 Society of Plastics Engineers     

Cure Characteristics and Mechanical Properties of Vinyltriethoxysilane Grafted Styrene-Butadiene Rubber/Silica Blends

Graft polymerization of vinyltriethoxysilane (VTES) onto styrene-butadiene rubber (SBR) was carried out in latex using potassium peroxydisulfate as an initiator. Then SBR-g-VTES/silica, SBR/TESPT/silica and SBR-g-VTES/TESPT/silica were prepared by mechanical mixing with different silica loading. The silica particles dispersed uniformly in the SBR-g-VTES networks. Among the three composites, the SBR-g-VTES/Silica blends show the highest of all. The t₉₀ of SBR-g-VTES/TESPT/Silica composites is the shortest of all. On the other hand, the SBR-g-VTES/TESPT/silica composites exhibit highest tensile strength and hardness of all. The SBR-g-VTES/silica composites show higher tensile strength and hardness than SBR/TESPT/silica. The tanδ value (loss tangent) at ?20-0°C of SBR-g-VTES/silica is slightly higher than that of SBR/TESPT/silica.     

Use of silica from rice husk ash as an antiblocking agent in low‐density polyethylene film

In packaging applications, blocking is always found in low‐density polyethylene (LDPE) films. Practically, such problems can be solved by incorporation of antiblocking agents, for example, silica and talc. The objective of this research was to explore the possibility of using silica from rice husk ash (RHA silica) as an antiblocking agent in LDPE film. Properties of RHA silica were compared with commercial silica, Sylo‐1. The appropriate amount of silica to be used as an antiblocking agent in LDPE film was also investigated. The results indicate that RHA silica has a smaller particle size and a higher specific surface area but a higher bulk density than those of Sylo‐1 silica. In the plastic film industry, 500–1000 ppm of silica is added in LDPE films as an antiblocking agent. It was also found that LDPE film with 2000–3000 ppm RHA silica showed similar properties to LDPE film filled with commercial silica in terms of its blocking behavior, mechanical strength, and film clarity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 848–852, 2003     

硅溶胶在分子筛类催化剂制备中的应用研究进展

硅溶胶问世已有超过100 a的历史,其在分子筛的合成及催化剂的制备中具有广泛的应用。简要综述了硅溶胶的市场情况、制备方法和性质。重点介绍了硅溶胶在分子筛类催化剂制备中的应用,包括硅溶胶在硅源、黏结剂以及制备小晶粒分子筛等方面的应用。结合国内外的研究进展,详细论述了催化剂用硅溶胶作为硅源、黏结剂和载体在分子筛的合成和催化剂制备中所起到的作用和优势。结合硅溶胶的应用研究现状,提出硅溶胶在制备分子筛类催化剂过程中存在的一些问题：以硅溶胶为黏结剂制备的硅基催化剂耐磨性差;以硅溶胶为载体制备的催化剂活性组分分散性差;硅溶胶产品的批次质量稳定性差。指出,如何解决以上问题,以更有效地提高硅溶胶在分子筛类催化剂制备中的应用,将是以后研究的重点。最后,对硅溶胶的发展前景进行了展望,指出在硅溶胶可控合成的基础上,分子筛及其催化剂的可控合成和应用开发将会有更广阔的前景。     

Effects of silica particle size on the structure and properties of polypropylene/silica composites foams

In this study, we prepared organically modified silica materials with various particle sizes, in the ranges of micrometer and nanometer, and their polypropylene (PP) composites. The PP micro/nanocomposites were then molded through conventional and microcellular injection molding processes. The effects of silica particle sizes on the structure, mechanical and rheological properties were investigated. The results showed that PP/silica nanocomposites provide better tensile strength than that of foamed nanocomposites. The addition of silica also increased the tensile strength of the nanocomposites, but decreased the tensile strength of microcomposites. Therefore, the tensile strength of PP/silica nanocomposites is better than that of PP/silica microcomposites. The silica particles helped the nanocomposites to develop small cells in the foaming process. Rheological results indicated an increase in the viscosity with the addition of nano silica and micro silica to PP. The viscosity increase for the silica nanocomposites was found greater than that of microcomposites at the same filler content.