Synthesis of fiber crosslinking cationic latex and its effect on surface properties of paper

Series of fiber cross-linking cationic latexes containing both epoxy and quaternary ammonium groups were synthesized in the presence of styrene/butyl acrylate/steary methacrylate/dimethyl amino ethyl methacrylate/epichlorohydrin (SBSDE). The chemical structure and composition of SBSDE were confirmed by ¹H nuclear magnetic resonance spectrum (¹H NMR), Fourier transforms infrared (FTIR), gel permeation chromatography (GPC) analyses. Latexes were subsequently used as sizing agents and surface properties (water resistance, surface strength, burst strength, whiteness, and tensile strength) of paper were examined and compared. Results revealed that SBSDE was a potential candidate for emulsion polymerization. Monomer ratio, initiator type, and SBSDE content determined the properties of latexes and strongly affected the sizing performance. The superior surface sizing agent was obtained by using 2,2-azobisisobutyronitrile as the initiator, when the concentration of SBSDE was 8.5 wt%, the butyl acrylate (BA)/styrene (St) ratio was 0.85.     

加工纸专用化学品的研究进展

介绍了造纸专用涂布黏合剂、表面施胶剂、润滑剂、分散剂、抗水剂和防水防油剂、层压纸黏合剂等。加工纸专用化学品的研究重点是绿色化学品、功能性化学品、高分子表面活性剂和特种高分子,主要产品是用以提高强度、施胶度和耐溶剂性能的表面施胶剂;提高油墨印刷性能的适印剂,无醛抗水剂,高分子分散剂及黏度调节剂,具有防水防油、润滑和剥离功能的有机硅和有机氟高分子。     

不同取代度壳聚糖季铵盐的制备及其热稳定性研究

制备了不同取代度的壳聚糖季铵盐(羟丙基三甲基氯化铵壳聚糖),利用单因素实验分析了制备条件,采用热重分析探讨了壳聚糖季铵盐的热降解温度。结果表明,壳聚糖季铵盐的最佳制备条件为环氧丙基三甲基氯化铵(ETA)与壳聚糖的比为3,水与异丙醇的比为3,反应温度为80℃,反应体系的pH值为6.0。壳聚糖季铵盐与壳聚糖相比,热稳定性下降,随着壳聚糖季铵盐取代度的增加,初始降解温度(T0)、最大降解速率温度(Tp)和终止降解温度(Tf)均逐渐降低。同时,从初始降解温度到最大降解速率温度的时间也随着取代度的增加而减少。     

生物质造纸化学品的研究进展

介绍了多种生物质造纸化学品的研究现状,重点介绍了生物质增干强剂、中性施胶剂、表面施胶剂、助留助滤剂、絮凝剂等。并对当前需要大力开发的高性能生物质造纸化学品进行了展望。特别对淀粉基、纤维素基、木质素基、壳聚糖基造纸化学品的制备及作用机理进行了论述。     

纸张表面涂料用自交联型阳离子苯丙乳液的研制

采用酮肼（DAAM-ADH）和有机硅单体A-171为交联体系,以苯乙烯（St）、丙烯酸丁酯（BA）、甲基丙烯酰氧乙基三甲基氯化铵（DMC）为主要单体原料,采用氧化还原引发体系,通过乳液聚合方法合成了一种自交联型阳离子苯丙乳液用于纸张表面涂料;通过对纸张施胶度和环压指数的测定,得出当乳化剂用量占单体总量的3％（质量分数,后同）,m（St）：m（BA）=3：1,DAAM—ADH用量占单体总量的3％,有机硅用量占单体总量的2％时,制备的阳离子树脂用于纸张表面涂料,使纸张的施胶度从24s提高到60s,环压指数从5．1N·m·g^-1提高到8．6N·m·g^-1,施胶效果显著。     

Interphases Developed from Fiber Sizings and Their Chemical-Structural Relationship to Composite Compressive Performance

The relationship between interphase microstructure produced from fiber surface chemistry and the resulting composite structural properties is not well understood. This relationship is, however, key to predicting composite performance and to the understanding of how to assemble the constituents properly for best use of the unique properties of the fibers. In this study, a significant difference in laminate compressive performance is observed for both static and dynamic loading. Two different fiber sizings, an unreacted bisphenol-A-based epoxy and the thermoplastic, polyvinylpyrrolidone (PVP), are identified as the source of these observations. The fiber, matrix and processing remained the same in both systems. However, morphological differences in the interphase region were observed. The resulting mechanical properties indicated that the PVP sizing improved static compressive strength by 51% and increased the fatigue life of notched cross ply laminates (cycled at R=-1) by at least two orders of magnitude over the bisphenol-A-sized composites. The mechanism by which PVP brought about these changes is unclear and requires further study. However, these results also indicate that the selection of interphase characteristics requires additional information about the fiber-matrix bond than merely strength.     

胶粘剂作为施胶剂在造纸工业中的应用

胶粘剂作为施胶剂在造纸工业中的应用由来已久。简要介绍造纸过程中的2种施胶方法（浆内施胶和表面施胶）以及几种主要施胶剂。综述了施胶剂的作用及其特点,展望了施胶剂的发展趋势：     

XPS analysis of the coverage and composition of coatings on glass fibres

For a fundamental approach to glass fibres for composite applications, it is essential to develop efficient methods to analyse the composition and distribution of the sizing layer on the glass filaments. We have been investigating the use of X-ray photoelectron spectroscopy (XPS) as a tool for the rapid characterization of the sizing and interphase in glass fibre reinforcements. In this report we present and discuss a model, based on a patchy sizing overlayer hypothesis, to assist the data reduction of XPS spectra from glass fibres coated with organic sizings. We show how plots of atomic ratios can be used to estimate the surface coverage of the sizing on glass fibres and to obtain information on the stoichiometry of the sizing. The results generated using this model are in good agreement with previously published data. Using this model, we show that XPS results combined with the weight fraction of the sizing give a quantitative value for the coverage of the fibre surface by the sizing.     

Novel Paper Sizing Agents Based on Renewables. Part 6: Sizing Properties of Maleated High Oleic Sunflower Oil

Abstract

The sizing efficiency of maleated high oleic sunflower oil (MSOHO), a green reactive sizing agent, was studied in various sizing tests. MSOHO can be applied in the papermaking process according to protocols that are commonly used for the currently popular alkenyl succinic anhydride (ASA) sizing. While an adequate degree of sizing was reached with pure MSOHO, blends of MSOHO and fatty acid anhydride (FAA), another green sizing agent, gave even better results, coming close to the efficiency of pure ASA. Although both pure sizing agents - FAA as well as MSOHO - lack some efficiency when compared to ASA, blending those two sizing agents at an optimum ratio closes this gap with respect to ASA. This synergism was not caused by simply decreasing the viscosity of MSOHO. Blends of ASA-MSOHO and ASA-MSOHO-FAA were proposed for full-scale mill trials.     

季铵化改性氨基硅油的应用研究

本文采用环氧丙基十二烷基二甲基氯化铵对氨基硅油进行季铵化改性,合成了一种新型季铵化改性氨基硅油柔软剂。对氨基硅油及其改性产物进行乳化,可得到性能稳定的柔软剂乳液。将所得乳液在纯棉平纹织物和涤纶织物上进行了柔软整理。测试结果表明:该新型季铵化改性氨基硅油柔软剂可使织物的柔软性、抗黄变性和亲水性显著提高。在应用于涤纶织物时,可以获得良好的抗静电效果。     

XPS and AFM Study of Interaction of Organosilane and Sizing with E-Glass Fibre Surface

Organosilanes are often used in commercial sizings for glass fibres to provide wettability with the resin and promote strong interfacial adhesion to the matrix in a fibre reinforced polymer composite. The silane treatment is introduced as part of a complex deposition from an aqueous emulsion immediately at the spinaret and determines the optimum properties of the cured composite. To understand the interaction of organosilanes contained in sizings for glass surfaces, XPS was used to investigate the adsorption of γ-aminopropyltriethoxysilane (APS) from a simple sizing system containing a polyurethane (PU) film former. It has been found that both APS and the sizing (containing APS and PU) deposits on E-glass fibre surfaces contained components of differing hydrolytic stability. The differences observed in the AFM images of APS coated E-glass fibres before and after water extraction also confirmed that the APS deposit contained components with different water solubility.     

烷基烯酮二聚体施胶体系对挂面再生纸表面不良施胶的成因剖析

针对某造纸厂再生纸抄造工程实际中,烷基烯酮二聚体（AKD）表面施胶挂面再生纸耐水性能提高不明显的质量问题,采用接触角、红外光谱（FTIR）、热重（TG）、X射线光电子能谱技术（XPS）、扫描电镜（SEM）、能谱（EDS）等研究方法,对纸厂生产的AKD施胶挂面再生纸纸样进行表征研究。结果表明,纸样接触角变化表现两面性差异,施胶纸样正面初期接触角为114.5°,反面初期接触角为118.5°,正面临界润湿接触角（≥90°）时间不足9min,反面临界润湿接触角为9min,纸样不具备长效耐水性,AKD施胶体系对纸张长效耐水性的贡献不明显;施胶后AKD特征官能团β-乙烯基丙内酯消失,施胶纸样和施胶萃取纸样在不同氛围下的失重行为不同,原子组成和原子价态化学环境不同,施胶纸样中含有可被四氢呋喃（THF）抽出的可溶物（AKD水解产物酮）,水解产物酮相对含量高于99.0%。AKD不良施胶的主要原因在于施胶体系配伍不当,导致AKD与纤维素酯化接枝反应的具有长效耐水产物的量不足。     

XPS and AFM Study of Interaction of Organosilane and Sizing with E-Glass Fibre Surface

Organosilanes are often used in commercial sizings for glass fibres to provide wettability with the resin and promote strong interfacial adhesion to the matrix in a fibre reinforced polymer composite. The silane treatment is introduced as part of a complex deposition from an aqueous emulsion immediately at the spinaret and determines the optimum properties of the cured composite. To understand the interaction of organosilanes contained in sizings for glass surfaces, XPS was used to investigate the adsorption of γ-aminopropyltriethoxysilane (APS) from a simple sizing system containing a polyurethane (PU) film former. It has been found that both APS and the sizing (containing APS and PU) deposits on E-glass fibre surfaces contained components of differing hydrolytic stability. The differences observed in the AFM images of APS coated E-glass fibres before and after water extraction also confirmed that the APS deposit contained components with different water solubility.     

含马来酰亚胺环水性聚氨酯纸张表面施胶剂的制备及应用

以聚酯二元醇(PCL1000)、异佛尔酮二异氰酸酯(IPDI)、1,4-丁二醇(BDO)、二羟甲基丙酸(DMPA)、三羟甲基丙烷(TMP)、N-(4-羟基苯基)马来酰亚胺(4-HPM)为主要原料,合成了含马来酰亚胺环水性聚氨酯(MWPU)乳液,探讨了聚氨酯乳液对纸张的表面施胶性能,并优化了合成工艺条件。结果表明,当异氰酸酯指数R=1.4,w(COOH)=1.4%,w(4-HPM)=1.0%时,此时含马来酰亚胺环水性聚氨酯乳液具有优异的表面施胶性能。以质量分数为2%的含马来酰亚胺环的水性聚氨酯乳液进行表面施胶时,纸张施胶度达64 s,抗张指数达到57 N·m/g,耐折度达82次。     

Effect of Cleaning and Abrasion-Induced Damage on the Weibull Strength Distribution of Sapphire Fiber

Fractographic analysis revealed the presence of concurrent flaw populations in sapphire fibers which were tensile tested in the as-received condition (sized and unsized) and after various cleaning procedures. The following flaw populations were identified: surface flaws attributed to handling and abrasion damage (type A), volume or internal flaws attributed to shrinkage voids which form during the manufacturing process (type B), localized fiber surface reaction flaws introduced during the flame-cleaning procedure (type C), and self-abrasion surface flaws intentionally introduced on unsized fibers (type D). The strength distribution associated with each flaw type was characterized using a censored data Weibull analysis for both the least-squares and maximum-likelihood estimation methods. The strength distribution for type C (flame-cleaning) flaws exhibited an approximately 20% degradation in strength compared to the distribution for type A flaws. The strength distribution for type D (self-abrasion) flaws exhibited an approximately 35% degradation in strength compared to the strength distribution for type A flaws. This result underscores the need for fiber sizings to prevent damage during shipping and handling. However, higher purity sizings and/or improved procedures for sizing removal are required to mitigate cleaning-induced fiber strength degradation during composite fabrication.     

Intercalated clays from pentaerythritol stearate for use in polymer nanocomposites

Smectite clays treated with quaternary ammonium salts have been utilized for decades in paints, greases, cosmetics, and personal care products as rheological modifiers. They have also been used in industrial wastewater treatment extensively. In more recent times these surface modified clays have demonstrated benefits in polymer/clay nanocomposites. The use of quaternary ammonium modifiers limits the usefulness of these composites in food packaging because they are not approved for direct food contact. It would be advantageous to have surface modifying chemicals acceptable for direct food contact in these composites. This article reports research conducted on a promising surface modifier pentaerythritol stearate (PS), which is approved by the FDA for inclusion in food as a preservative. The surface modification of montmorillonite with PS is reported in detail as well as the production of nanocomposites with selected polymers made with the modified clay. Molecular modeling and purification of commercial PS samples indicate that the mono‐ and diesters are the critical surface modifiers, although the as received commercial material works well in forming intercalated clay complexes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

纸厂回收淀粉用于纸张施胶剂的制备与应用

以纸厂回收并经过处理的废淀粉作为聚合物的主链,通过接枝苯乙烯(St)、丙烯酸丁酯(BA)及甲基丙烯酸甲酯(MMA)等单体,合成出一种稳定的苯丙乳液施胶剂。结果表明:当w(引发剂)=2.5%~4%、反应温度为70~80℃和m(总单体)∶m(废淀粉)=1∶1.5时,废淀粉接枝共聚物乳液施胶剂的综合性能最好;该施胶剂能有效提高原纸张的各项性能,在同等条件下其性能略低于市售施胶剂;废淀粉回收价格较低,将其用于纸张施胶剂的制备,可达到降低污染、节约成本等目的。     

两种碳纤维上浆剂的比较

测试并比较了某国产上浆剂和进口上浆剂的黏度、表面张力、粒径等性能,研究了两种碳纤维上浆剂对聚丙烯腈基碳纤维表面形貌、耐磨性、水接触角、表面能、拉伸强度等性能的影响。结果表明,国产上浆剂固含量高、黏度高、粒径小,进口上浆剂黏度低、表面张力小、粒径分布窄。采用国产上浆剂上浆后的碳纤维,接触角为56.701°,毛丝量为0.15 mg/m,表面能为41.32 mJ/m²,耐磨次数为447次,拉伸强度为2.86 GPa;采用进口上浆剂上浆后的碳纤维表面光滑,接触角为51.063°,毛丝量为0.08 mg/m,表面能为47.26 mJ/m²,耐磨次数为461次,拉伸强度为2.95 GPa。     

The preparation of emulsion type sizing agent for carbon fiber and the properties of carbon fiber/vinyl ester resin composites

Vinyl ester resin emulsion type sizing agent (HMSA‐1) was synthesized by phase inversion emulsification method. Centrifugal sedimentation analysis, particle size analysis, Fourier transforms infrared spectroscopy (FTIR), and gel permeation chromatography were used to characterize HMSA‐1 and Japanese commercial sizing agents (JSA‐1 and JSA‐2). Meanwhile, abrasion resistance, fluffs and breakage, stiffness, scanning electron microscope (SEM) were used to analyze the workability in later process of carbon fiber and surface morphology. The results showed that HMSA‐1 could significantly improve handling characteristics of carbon fiber. SEM micrographs demonstrated that the sized carbon fiber had smooth surface. HMSA‐1 had better compatibility with vinyl ester resin. The interlaminar shear strength (ILSS) of HMSA‐1 sized carbon fiber/vinyl ester resin composite reached the maximum value of 45.96 MPa. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

阳离子型无皂苯丙乳液纸张表面施胶剂的研制

以苯乙烯(St)、丙烯酸丁酯(BA)、甲基丙烯酸二甲基氨基乙酯(DM)和丙烯酰胺(AM)等为主要原料,采用无皂乳液聚合法在丙烯腈改性淀粉分子链上接枝苯丙共聚单体,合成出一种阳离子型淀粉接枝苯丙乳液施胶剂;然后以此为基料配制纸张表面施胶液,并对文化用纸和瓦楞纸进行施胶。结果表明:在其他条件相同的前提下,各种施胶纸的施胶效果均优于原纸,并且施胶度增幅最大;文化用纸的施胶度从原来的3 s增至48 s,瓦楞纸的施胶度从原来的43 s增至154 s。