【作者】 李建文；

【导师】 詹怀宇；

【作者基本信息】 华南理工大学 ， 制浆造纸工程， 2008， 博士

【摘要】 造纸工业在我国国民经济中占有重要地位。近年来,造纸工业得到了迅速发展,相应的原料结构、产品指标、生产能耗及环保要求等也都有了较大变化,如废纸浆回用增多、产品表面性能要求提高、生产成本增加等,造纸化学品的应用已成为解决这些问题的重要途径,其中,表面施胶剂由于可应用于多种造纸产品、显著提高纸张的表面性能、降低纸张生产成本、减少环境污染等特点,为造纸工业提供了一种更加有效的解决方法。为研制高效价廉、环境友好型的无皂乳液表面施胶剂,以苯乙烯（St）、丙烯酸丁酯（BA）、丙烯酸（AA）等为主要原料,引入功能单体乙烯基磺酸钠（HS-1）进行无皂乳液共聚,采用连续滴加方式,设计核壳层组成,合成了核壳型阴离子无皂乳液。得到合成优化条件:m（St）:m（BA）=42:47,w（MMA）=4%,w（AA）=3%,w（HS-1）=3%,w（B130）=5%,w（MA）=1%,m（核）:m（壳）=2:8,反应温度78℃,w（APS）=0.5%,单体滴加时间2.5h,反应总时间6h。IR、DSC、TEM分析表明优化产物符合预期设计结构和形态。其体积平均粒径为280nm,表面张力为50.588mN/m,质均相对分子量为229338。阴离子核壳型表面施胶剂中试产品SSTOP的实验室和纸厂试验,均取得了良好的应用效果。铜版原纸试用结果:与只用表面施胶淀粉相比,0.78kg/t的SSTOP和淀粉共用施胶,纸张的正反面Cobb值分别降低28.6%和40.8%,表面强度、抗张指数和耐折度分别提高14.2%、7.4%和16.7%。白纸板试用结果:SSTOP用量为0.15kg/t纸板时,纸板正反面Cobb值分别降到26.5 g/m²和31.5 g/m²。相同条件下,SSTOP与进口BK-350产品使用效果相当,优于国产BJ-25和DZ-10产品。双胶纸试用结果:SSTOP用量为0.75kg/t纸时,双胶纸正反面Cobb值分别达到22 g/m²和24 g/m²,表面强度分别为2.9m/s和2.3m/s。相同条件下,SSTOP与DZ-10相比,纸张正反面Cobb值分别降低10.2%和14.2%,表面强度分别提高20.8%和21.0%。采用自制阳离子高分子表面活性剂EM,以St、BA和甲基丙烯酰氧乙基三甲基氯化铵（CM）为主单体进行无皂乳液聚合,合成了阳离子纳米无皂乳液。EM表面活性研究表明其临界聚集浓度约为12g/L。得到了阳离子无皂乳液聚合的反应动力学方程:Rp∝[EM]^0.34[APS]^0.45[CM]^0.77,体系表观活化能Ea=64.3kJ.mol^-1。得到了优化产物的合成条件:m（St）:m（BA）=117:100、w（CM）=3.4%、w（EM）=8%、w（APS）=0.5%、反应时间4h。IR、ATR-IR、DSC、TEM分析表明优化产物符合预期的结构和形态,体积平均粒径为77.4nm,表面张力为46.886mN/m,Zeta电位为+30mv。采用Modde 7软件建立了理想的阳离子表面施胶剂合成数学模型。阳离子无皂型表面施胶剂中试产品CPSS-1的实验室和纸厂试用效果良好。白纸板试用结果:当CPSS-1用量为0.6kg/t纸板时,无需浆内施胶,纸板产品的反面Cobb值可降到44g/m²。与进口产品相比效果更好。瓦楞纸试用结果:当CPSS-1用量为2.5kg/t纸时,瓦楞纸正面Cobb值达到42 g/m²,横向环压指数为7.8m/s,纵向裂断长为4.3km,耐破指数为2.2 kPa.m²/g,横向耐折度达14次,达到A级瓦楞纸质量指标。苯丙共聚物表面施胶剂成膜吸水率与施胶纸张的Cobb值成正比关系。实验条件下,苯丙共聚物表面施胶剂的成膜吸水率（x）与施胶纸张Cobb值（y）之间的关系为:y=3.49561n（x）+10.504,R=0.9906。在此基础上,建立了评价苯丙共聚物施胶效果的新方法:根据产品成膜吸水率,由二者关系式计算其Cobb值来评价其施胶效果,或新产品与纸厂现用产品对比成膜吸水率的大小,数值越小则施胶效果越好。在本实验条件下,当玻璃化温度Tg在7.95—33.91℃时,Tg与施胶纸张Cobb值和表面强度性能存在较理想的反比关系式:y（Cobb值）=—1.16521n（Tg）+18.878,R=0.9518;y（表面强度）=—0.3288ln（Tg）+4.31,R=0.9831。产品表面张力（x）与表面施胶液的泡沫体积（y）的近似关系式:y=1.1389x²—114.01x+2878.6,R=0.9893。对施胶前后纸张的接触角分析表明:表面施胶剂的应用,既增大了水滴在纸张表面的初始接触角,又限制了水滴向纸张表面的渗透速率,从而改善纸张的抗水性。DSC-TGA分析表明:CPSS-1和氧化淀粉（OS）表面施胶时,CPSS-1与OS或纸张纤维形成氢键或共价键结合,使得纸页的失重率明显减小,热稳定性提高,纸页中CPSS-1的构象转变温度升高。XPS分析表明:CPSS-1和OS表面施胶时在原纸表面上均匀成膜。其亲水基团与纸张纤维吸附结合,而疏水基团向外迁移到纸张表面,应用CPSS-1后,这种趋势更加明显。经CPSS-1施胶后纸张表面产生了新的共价键或氢键结合,共价键结合有利于纸张抗水性和表面强度等性能的提高,氢键结合有利于纸张强度的改善。AFM分析表明:CPSS-1与OS软硬段相容性好,形成氢键结合,均匀分布在纸张表面,使得施胶纸张表面凹凸程度明显减弱,粗糙度减小。SEM和CLSM分析表明:CPSS-1和OS可吸附缠绕在纤维表面,与纤维组成网络结构,使纸张纤维结合更加紧密、孔隙度减小、匀度提高,有助于纸样抗水性、表面强度、平滑度等性能的改善。更多还原

【Abstract】 Paper industry is one of the most important components of national economy system in China.Recently,paper industry has been rapidly developed,and related raw materials,product properties,production cost and environment requirement also changed,such as increase use of recycled paper,upgrading of paper surface properties,raising of production cost,and so on.In order to solve the problems mentioned above,application of paper chemicals had been one of the important methods.Due to the advangtages of suiting paper various species, improving paper surface obviously,decreasing paper product cost and reduce the environment pollution from paper process,surface sizing agent had been used to sovle these problems as one of the most efficient chemicals in papermaking.In order to develop environment friendly soap-free surface sizing agent with excellent performance and low cost,styrene-acrylate copolymer based styrene（St）,butyl acrylate（BA）,acrylic acid（AA） and so on was prepared by introducing sodium vinyl sulfonate（HS-1） into emulsion polymerization.The core-shell type soap-free latex was obtained by charging comonomers continuously and designing the component of core and shell layer.The optimum conditions were chosen as m（St）:m（BA）=42:47,w（MMA）=4%,w（AA）=3%, w（HS-1）=3%,w（B130）=5%,w（MA）=1%,m（core）:m（shell）=2:8,temperature at 78℃,w（APS）=0.5%,charging time of 2.5h,total reaction time of 6h.The predesigned molecular structure and shape of the optimum product was obtained by analyzing its IR spectrum,DSC graph and TEM photo.Its particle average size by volume,surface tension and average molecular weight was respectively 280nm,50.588mN/m and 229338.Good effect was obtained as using pilot product SSTOP in laboratory and paper mill.The result charged with 0.78kg/t of SSTOP in art coated base paper showed that Cobb value of face and back side of the paper decreased by 28.6%and 40.8%respectively,and surface strength,tensile index and tear strength increased by 14.2%,7.4%and 16.7%in turn,compared to that of application of single surface sizing starch.The result in white paperboard showed that Cobb value of face and back side of paperboard with 0.15kg/t of SSTOP were respectively decreased to 26.5g/m² and 31.5g/m².At the same condition,the sizing effect of SSTOP was equal to that of foreign product BK-350,better than that of domestic product BJ-25 and DZ-10.The result with 0.75kg/t of SSTOP in offset printing paper showed that Cobb value and surface strength of face and back side of paper were 22g/m²,24g/m²,2.9m/s and 2.3m/s respectively.At the same application condition,Cobb value of face and back side of paper sized with SSTOP decreased by 10.2%and 14.2%,and surface strength increased by 20.8%and 21.0%,compared to that of paper sized with DZ-10.Cationic surface sizing agent was prepared on the basis of St,BA and methacryloxyethyltrimethyl ammonium chloride（CM） by introducing a macromolecule surfactant（EM） made in our lab into the soap-free emulsion copolymerization.Critical micelle concentration of EM was set up at 12g/L.The reaction dynamics equation of cationic soap-free emulsion polymerization was obtained as Rp^∝[EM]^0.34[APS]^0.45[CM]^0.77,and the apparent activation energy was 64.3kJ.mo1^-1.The optimum conditions were given as m（St）:m（BA）=117:100, w（CM）=3.4%,w（EM）=8%,w（APS）=0.5%,reaction time of 4h.The predesigned molecular structure and morphology of the optimum sample was obtained by analyzing its IR spectrum,ATR-IR spectrum,DSC graph and TEM photo.Its particle average size by volume,surface tension and Zeta potential was 77.4nm, 46.866mN/m and+30mv respectively.Good mathematic model based on preparation of cationic soap-free surface sizing agent was built by using the software of MODDE 7.Good effect was obtained as using pilot product CPSS-1 in laboratory and paper mill.The result in white paperboard showed that Cobb value of back side of paperboard without any internal sizing agent was decreased to 44g/m² as charging CPSS-1 with 0.6kg/t,which was better than that of foreign product. The result in corrugated paper showed that Cobb value of face side of paper was 42g/m²,ring crush index of CD was 7.8m/s,breaking length of MD was 4.3km, burst index was 2.2kPa.m²/g and fold of CD was 14.The water absorbency（y） of styrene-acrylate based copolymer film was proportion to the Cobb value（x） of sized paper with the equation abbreviated as y=3.49561n（x）+10.504 at the experimental conditions.A simple way to evaluate the sizing effect of styrene-acrylate based copolymer was obtained as follows: better sizing effect was obtained as the water absorbency of copolymer film was less.As glass transition temperature（Tg） of copolymer was varied from 7.95℃to 33.91℃,relationship between Cobb value of sized paper and Tg of copolymer film was concluded as y（Cobb value）=-1.16521n（Tg）+18.878,and relationship between surface strength of sized paper and Tg of copolymer film was deducted as y（surface strength）=-0.32881n（Tg）+4.31.Relationship between product surface tension and foam volume in surface sizing liquid was given as y（foam volume）=1.1389（surface tension）²-114.01x+2878.6.For paper unsized or sized by surface sizing agent,the analysis of contact angle showed that application of surface sizing agent made initial contact angle of water in paper surface larger,and limited water drop penetrate into fibers of paper,which resulted in the improvement of water resistance of paper;The analysis of DSC-TGA showed that hydrogen bond or covalent bond among CPSS-1,oxidized starch（OS） and paper fibers were formed,leading to the improvement of the stability of paper in hot atmosphere and transition temperature of CPSS-1 in paper;The analysis of XPS showed that there existed the uniform film composed of CPSS-1 and OS,its hydrophilic group bonded to paper fibers but its hydrophobic group moved to the top paper surface,and new covalent bond and hydrogen bond were also formed by charging CPSS-1,all of which contributed to the improvement of water resistance and surface strength of paper;The analysis of AFM showed that good compatibility between soft phase and hard phase of OS and CPSS-1 was obtained,the hydrogen bond was formed and uniform distribution of CPSS-1 and OS in paper surface was observed,as a result,smoothness of paper surface increased obviously;The analysis of SEM and CLSM showed that network structure was formed by absorbing CPSS-1 and OS into paper fibers,bond among paper fibers became tighter,number of cavity in paper surface was less and uniformity of paper surface was enhanced,all of which improved the properties of paper surface.更多还原