摘要
浆内施胶自1807年沿用至今,虽添加量有所降低,但还未完全被表面施胶所替代。主要原因是目前的聚合物表面施胶剂在应用中仍存在一些重大技术问题,主要是:涂布后仍不能保证达到浆内施胶的效果;抗水性能较差;表面强度差,掉毛掉粉现象仍较严重等。
本课题的创新之处在于:(1)可替代浆内施胶,降低湿部化学的多变性和白水循环负担,使造纸实现清洁化生产;(2)产品兼具有机/无机互穿三维网络结构,既具高分子的柔韧性,又具无机的刚性和耐磨性,大幅度提高纸张的综合性能。(3)硅溶胶可赋予纸张表面强化交联结构,产品中的疏水组分和黏结组分与纤维相互作用,增加纤维间的结合强度,改善纸张的耐溶剂性、油墨吸收性、耐洗涤性能等,解决掉毛掉粉现象,实现反应性基团与纤维反应的宏观调控。(4)产品制备过程中不使用有机溶剂和小分子乳化剂,有利于环境保护。
本课题通过对反应单体的筛选,在马来半酯可聚合乳化剂(MT)的作用下,选择丙烯酸丁酯(BA)为核单体,丙烯酸丁酯、苯乙烯及硅烷偶联剂KH-570为壳单体制得系列“软核硬壳”核壳乳液,同时引入功能性单体丙烯酸(MAA)。并对乳液的稳定性、微观形貌和流变性能进行了研究,分析了乳胶膜力学性能、耐介质性、结晶性和动态力学性能的影响因素。同时将其用于纸张表面施胶,研究了其对浆内施胶的替代作用。具体结论如下:
(1)可聚合乳化剂下核壳乳液的结构与性能
红外光谱表明马来半酯可聚合乳化剂上含有可聚合基团双键,而核壳共聚物上不饱和双键的特征吸收峰消失,表明可聚合乳化剂基本完全键合到共聚物分子链上。
透射电镜表明核壳乳胶粒呈球形结构,乳胶粒子的核壳结构明显。原子力显微镜(AFM)显示当有机硅含量为0.0%时,胶膜表面相对舒展,平展;而当有机硅含量为2.0%时,胶膜纵断面轮廓线起伏较大。
稳定性研究表明当w(MT)＞1.5%,w(ODA)=0.5%,乳液pH值介于7-9,乳液固含量＜40%,分子量调节剂正十二硫醇用量＞1%,w(KH-570)＜2.5%,w(硅溶胶)＜8%时,体系的稳定性较佳。
光散射研究表明随着KH-570用量的增加,乳胶粒子的粒径增加;随着w(ODA)的增加,乳胶粒粒径大小呈现先下降后上升的趋势,当w(ODA)为0.5%左右时,乳液分子粒径较小。
流变研究表明在低剪切速率下,乳液黏度随着KH-570用量的增加而下降,但当KH-570用量高于1.5%时,乳液黏度又开始上升,颗粒间相互作用增强。而当剪切速率高于1s~(-1)时,乳液黏度基本与剪切速率无关,而是随着KH-570用量的增加呈现增大的趋势。流变亦表明乳液是一种假塑性流体,且随着硅溶胶用量的增加,乳液的假塑行为增强,黏度增大。
力学性能测试表明随着KH-570用量的增加,胶膜的拉伸强度逐渐增加,断裂伸长率下降,但当KH-570的用量超过2.5%后,拉伸强度有所下降。随着硅溶胶用量的增加,胶膜的拉伸强度增加,但当其用量超过6%之后,胶膜脆性增加,拉伸强度下降,断裂伸长率下降。
动态力学性能(DMA)测试表明随着KH-570和硅溶胶用量的增加,胶膜的储能模量增加,但当KH-570用量高于2.5%时,硅溶胶用量高于6%时,储能模量又有所下降,刚性减弱。
X-射线衍射(WXRD)显示当有机硅烷偶联剂KH-570用量由0.5%增加至2%时,结晶度由3.04%增加至5.12%;但继续增加KH-570用量至3%时,结晶度由5.12%降至4.52%。随着结晶度的提高,材料的耐热性和耐溶剂性有明显的提高。4%硅胶的加入使乳胶膜的结晶度由5.12%增加至10.98%,从而在一定程度上提高乳胶膜的力学性能和耐介质性。
热重-微分热重(TG-DTG)研究表明随着KH-570用量的增加,胶膜的热分解温度上升,热稳定性得到改善:但当KH-570用量超过1.5%时,体系的热降解温度又开始下降,热稳定性变差。随着硅溶胶用量的增加,乳胶膜的热降解温度有所提高,热稳定性得到改善。但当硅溶胶用量达10%时,由于相容性问题,热稳定性又有所下降。
(2)应用实验
当w(乳化剂)=2%,w(KH-570)=2%,w(硅溶胶)=6%,w(正十二硫醇)=2%时,纸张性能较佳。
扫描电镜表明,未进行表面施胶的纸张,其表面纤维之间未互相联结,施胶处理后的纸页细小纤维互相粘结成片后和较粗纤维贯串起来,使得纤维编织的更加紧密。
单独使用改性淀粉表面施胶时,纸张基本无施胶度,抗张强度为27N,耐折度为140次,环压强度为4.2KN.m/g。随着体系中聚合物乳液BS-1比例的增加,施胶度增加,表面强度有所下降,但下降幅度不大。单独使用BS-1施胶的纸张的抗张强度达35N,耐折度为241次,环压强度为6.8KN.m/g。当m(淀粉)/m(乳液)=2:1时,耐折度可达276次,纸张环压强度可达到7.6 KN.m/g。
当将BS-1与PVA复配使用,在相同聚合度下,PVA水解程度越高,纸张性能越佳,但由于PVA溶解后黏度较大,宜采用中等聚合度的PVA。且PVA使用效果强于改性淀粉,经PVA施胶的纸张施胶度达到5s左右,表面强度4.5m/s,而淀粉施胶的纸张施胶度几乎趋于0s。表面强度只有2.8m/s。当m(PVA):m(BS-1)=2:1时,纸张的耐折度可达326次,纸张环压强度可达到8.5 KN.m/g。
替代浆内施胶研究试验表明,当用2.0Kg/吨纸的BS-1表面施胶,浆内AKD中性施胶剂用量为0时,纸张的Cobb可达到24%,表面强度可达到3.9 m/s,纸张性能要优于浆内AKD中性施胶剂用量为18Kg/吨纸,表面施胶AKD用量3Kg/吨纸的纸张。
产品工厂大试应用实验亦表明BS-1完全可以在不添加浆内施胶剂的前提下,达到纸张的物理性能指标,当BS-1用量为1.5公斤/吨纸时,纸张性能与德国K-532用量为1.8公斤/吨纸,硫酸铝用量3公斤/吨淀粉液的纸张性能相当。
Internal sizing has been widely used since 1807,although the amount has been reduced to certain extent,it has not yet been completely replaced by the surface Sizing.The main reason is that there still exist some major technical problems in the application of polymer surface sizing agent.For example,individual surface sizing still can not guarantee equivalent sizing performance with internal sizing; furthermore,the shortcoming in water resistance and surface strength are still serious.
The innovation of this research lies in following four points:(1) Internal sizing procedure can be cancelled through the use of the product,which can reduce the variability of wet-end chemistry and the burden of papermaking whitewater to achieve nonpolluting production. (2) The products are endowed with the structure of organic/inorganic interpenetrating three-dimensional Network,not only possess the flexibility of polymeric material but also rigidity and wear resistance, which can greatly improve the comprehensive properties of paper.(3) strengthening crosslinking structure can be formed in paper surface by the introduction of silica sol.The bonding strength among fibers can be enhanced due to the interaction between active group and fiber, resulting in the improvement of solvent resistance,ink absorption and washing durability.(4) Organic solvent and small molecular emulsifier were not used in the preparation process,which is beneficial to environment protection.
In this research,with the action of maleic half-ester polymeri sable emulsifier(MT),series of core-shell emulsions with "soft co re and hard shell" were prepared with butyl acrylate(BA) as core monomer,and BA,styrene(St) andγ-methacryloxypropyltrimetho xysilane(KH-570) as shell monomers,at the same time,functional monomer methacrylic acid(MAA) was introduced.Factors influen cing the stability,micromorphology and rheological properties of t he emulsion were studied,as well as factors influencing mechanic al properties,medium resistance,crystallinity and dynamic mechan ical properties.Furthermore,the products were applied in paper su rface sizing,and its substitute effect for internal sizing was invest igated.The detailed conclusions were described as following:
(1) Structure and properties of core-shell emulsion with action of MT
FT-IR spectra indicated that a characteristic peak correspondin g to polymerisable group- double bond was found in the chain str ucture of MT,but this peak disappeared in the core-shell copolym er,indicating that most of polymerisable emulsifier has been bond ed to the molecular chain of copolymer.
Transmission electron microscope(TEM) indicated that core-shell emulsions displayed sphere morphology,and a remarkable core-shell structure was detected.Atomic force microscope(AFM) indicated that the surface of the membrane with 0.0%KH-570 was relative smoother, but it became coarse with the increase of KH-570 dosage.
It was also found that the stability of the emulsion was optimum under the following conditions:w(MT)＞1.5%,w(ODA)=0.5%,the pH value ranges from 7 to 9,the solid content lower than 40%,w(dodecyl mercaptan)＞1%,w(KH-570)＜2.5%,w(silica sol)＜8%.
Light scattering experiment indicates that the particle size of emulsion increases with the increase of KH-570 dosage.While with the increase of w(ODA),particle size decreases and then increases,and a smaller particle size was found when w(ODA) equals to 0.5%.
Rheological investigation was also performed on the system.The viscosity of the emulsion decreased with KH-570 addition,but increased when KH-570 dosage was greater than 1.5%,which can be ascribed to enhanced interaction among particles.However,when the shear rate was higher than 1s~(-1),viscosity almost kept invariable with shear rate,but increased with KH-570 and silica sol dosage.It was also found that the emulsion presented pseudoplastic behavior,and an enhanced pseudoplastic was detected with the increase of silica sol dosage.
Mechanical test indicates that tensile strength increased gradually with KH-570 and silica sol addition,while the breaking elongation was opposite.However,tensile strength decreased when KH-570 dosage was greater than 2.5%and silica sol dosage greater than 6%.
Dynamic mechanical Analysis(DMA) indicated storage modulus increased gradually with KH-570 and silica sol addition.However,it decreased when KH-570 dosage was greater than 2.5%and silica sol dosage greater than 6%.
Wide X-ray diffraction(WXRD) indicated that crystallinity increased from 3.04%to 5.12%when KH-570 dosage increased from 0.5%to 2%,however,it decreased from 5.12%to 4.52%when KH-570 dosage greater than 3%.The heat-resistance and solvent resistance can be improved with the increase of crystallinity.Furthermore,the crystallinity increased from 5.12%to 10.98%with 4%silica sol addition,resulting in the improvement of mechanical properties and medium resistance.
Thermal Gravimetry(TG-DTG) indicated that the initial decomposition temperature increased with KH-570 and silica sol addition,but thermal stability was weakened when KH-570 dosage higher than 1.5%and silica sol dosage reach 10%.
(2)Application experiment
The paper properties reached optimum under following conditions: w(MT)=2%,w(KH-570)=2%,w(silica)=6%,w(dodecyl mercaptan)=2%.
Scanning Electron microscope(SEM) indicated that compacted knitted fibers were found after surface sizing.
The sizing degree of paper sized with modified starch nearly close to zero,with 27 N tensile strength,140 times folding strength,4.2 KN.m/g ring crush strength.And the sizing degree increased with the increase of polymer emulsion(BS-1),while surface strength was opposite,with little decrease amplitude.The tensile strength of the paper sized with individual BS-1 reached 35N,folding strength reached 241 times,and ring crush strength reached 6.8KN.m/g.Furthermore,the folding strength reached 276 times and ring crush strength reached 7.6 KN.m/g when m(starch)/m(BS-1)=2:1.
When BS-1/PVA blend was applied in paper surface sizing,better papers' properties were detected while hydrolysis degree of PVA with the same polymerization degree was higher.But PVA with moderate polymerization degree was usually adopted owing to higher viscosity of PVA solution.Besides,the application performance of PVA was better than modified starch.The sizing value of paper sized with PVA is about 5s,the surface strength was 4.5m/s,while the sizing degree of paper sized with starch close to 0s,and surface strength was only about 2.8m/s.Furthermore,the folding strength reached 326 times and ring crush strength reached 8.5 KN.m/g when m(starch)/m(BS-1)=2:1.
The test of surface sizing substituting for internal sizing showed that the Cobb value of paper sized with 2.0 kg/t BS-1 and 0g AKD reached 24%,surface strength reached 3.9 m/s,which was better than that of the paper sized with 18 Kg/t internal sizing AKD and 3Kg/t surface sizing AKD.
The test in factory also indicated the paper can reach physical performance index with individual BS-1 instead of internal sizing agents.The properties of paper sized with 1.5 Kg/t BS-1 was nearly equal to that of paper sized with 1.5 Kg/t Germany K-532 and 3Kg aluminum sulfate per ton of 5%starch suspensions.
引文
[1]顾民.造纸化学品[M].北京:中国石化出版社,2006:74.
[2]许夕峰,靳光秀,梁福根等.表面施胶剂的发展及其在现代造纸工业中的用.纸和造纸[J].2007,26(5):1-4.
[3]吴宗华,赖晓玲,陈少平.阳离子型苯乙烯-丙烯酸酯共聚物的表面施胶性[J].造纸化学品,2008,20(3):4-7.
[4]向冰莲,武书彬,杨卿.苯乙烯/丙烯酸醋乳液对表面施胶性能的影响[J].造纸化学品2008,27(3):58-59.
[5]王斌.D-1表面施胶剂的施胶效果[J].纸和造纸,2008,27(2):54-55.
[6]徐腾.黄原胶的表面施胶工艺[J].中华纸业,2006,28(2):39-40.
[7]张宏伟,唐爱民,陈港.淀粉氧化程度与其表面施胶作用的关系[J].造纸科学与技术,2006,25(6):61-64.
[8]张光华,李慧.含氟丙烯酸酯乳液水溶性聚合物复配用于纸张表面施胶的研究[J].化工新型材料,2006,34(11):71-73
[9]王卓妮,张光华.氰乙基淀粉制备及其纸张表面施胶性能[J].中国造纸,2006,25(4):9-11.
[10]成培芳,王秋利,王立军编译.接触角法测评纸张表面施胶聚合物的性能[J].国际造纸,2006,25(2):27-31.
[11]徐春,花芸.淀粉酶在表面施胶中的应用[J].黑龙江造纸,2006,1:44-45.
[12]胡惠仁,徐立新,董荣业.造纸化学品[M].北京:化学工业出版社,2002.
[13]沈一丁.造纸化学品的制备和作用机理[M].北京:中国轻工业出版社1999.
[14]张光华编著.造纸湿部化学原理及其应用[M].北京:中国石化出版社,1998.
[15]谢亮,表面施胶剂的发展动向和应用:造纸化学品,2000(2),17.
[16]林龙平,郑丽萍,应晓荣等.聚合物表面施胶剂DP2000的研制与应用造纸化学品,2001(3):14-17.
[17]张光华编著.精细化学品配方技术山[M].北京:中国石化出版社,1998.
[18]姚献平.造纸化学品的现况与发展趋势[A].2001.
[19]林龙平.合成聚合物表面施胶剂[J].造纸化学品.2000(2):13-16.
[20]梁超,吕建平,邵利斌.合成表面施胶剂PAS,PMS的制备和应用[J].造纸化学品.2001(2)33-35.
[21]Misra S C,Pichot C.El-Aasser MSand Vanderhoff JW[J].Polym Chem Ed,1983(21):2383.
[22]安郁琴,刘忠.制浆造纸助剂[M].北京:中国轻工业出版社,2003.
[23]邓宇.淀粉化学品及其应用[M].北京:化学工业出版社,2002.
[24]Reiner Exner.Sythesis and application of polymer sizing agents[J].Paper Technology,2002(7):45.
[25]王永斌,马政生.新型聚合物表面施胶剂WP-0367的制备与应用研究[J].兰州大学学报,2004(1).
[26]美国专利.US5240771[P].
[27]WShen,Y Filonanko,Y Truong.Contact angle measurement and surface energetics of sizedand unsized paper[J]Colloids and Surfaces A:Physicochemical and Engineering Aspects2000(173):117-126.
[28]George L,Batten Jr.The effects of SMA surface sizes on paper end-used properties[J].Tappi Journal1995,78(1):142-146.
[29]Otto S de Pierne,David L Dauplaise,Robert J et al.Styrene/acrylic-type polymers for use as surface sizing agents[P].US:5138004.1992.
[30]Dieter Urban.Polymer dispersions and their industrial applications [M].Wiley-VCH:2002:79-81.
[31]Kimpimdki Tomi,Rennes Sami.New surface sizing concept significantly reduce prosity liquid penetration and surface roughness[J].Paper Technology,2001,42(6):23-28.
[32]Scott WE.Fines management and control in wet eng chenmlstry[J].Tappi J.1986,69(11):31-34.
[33]Gu Sheng Jiu,Wang Yun Pu,Zhang Fa Ai.Study on acrylic enmlsion with core-shell structure containing high hydroxyl content[J].Journal of Macromolecular Science Pure and Applied Chemistry,2005,42(6):771-781.
[34]Sindt Olivier,Gauthier Catherine,Hamaide Thierry,et al.Reactive surfactants in heterophase polymerization.ⅩⅥ.Emulsion copolymerization of styrene-butyl acrylate-acrylic acid in the presence of simple maleate reactive surfactants[J].Journal of Applied Polymer Science,2000,77(12):2768-2776.
[35]Slawinski M,Meuldijk J,Van Herk A M,et al.Seeded emulsion polymerization of styrene:Incorporation of acrylic acid in latex products[J].Journal of Applied Polymer Science,2000,78(4):875-885.
[36]涂伟萍.水性涂料[M].北京:化学化工出版社,2006:212.
[37]Tang C,Chu F.Senficontlnuous enmlsion polymerization of styrene butyl acrylate methacrylic acid with high solid content[J].Journal of Applied Polymer Science,2001,82(10):2352-2356.
[38]Mahdavian AliReza,Abdollahi Mahdi.Investigation into the effect of carboxylic acid monomer on particle nucleation and growth in emulsifier free emulsion copolymerization of styrene-butadiene-acrylic acid source[J].Polymer,2004,45(10):3233-3239.
[39]王志杰,张亚娟.表面施胶提高铝箔衬纸平滑度的研究[J].中国造纸,2006,25(7):69-70.[40]Reynhout Xaviera E E,Beekers Mark,Meuldijk Jan,et al.Electrosteric stability of styrene/acrylic acid copolymer latices under emulsion polymerization reaction conditions[J].Journal of Polymer Science,Part A:Polymer Chemistry,2005,43(4):726-732.
[41]Shao Qian,Wang Cheng Guo,Zhu Yun Feng,et al.Surface modification and characterization of nanometer TiO2 for nanometer styrene-acrylate emulsion polymerization[J].Gongneng Cailiao/Journal of Functional Materials,2006,37(4):642-645.
[42]潘春来.苯乙烯-丙烯酸酯聚合物胶乳在无碳复写原纸表面施胶中的应用[J].中华纸业,2006,S1.
[43]徐腾.超低甲醛树脂用于表面施胶[J].中华纸业,2006,27(7):73-74.
[44]Wang Shou Ting,Poehlein W.Characterization of watersoluble oligomer in acrylic acid styrene emulsion copolymerization[J].Journal of Applied Polymer Science,1993,50(12):2173-2183.
[45]Han Shuzhen,Chen Daimin,Qi Yincheng,et al.Study on emulsion copolymerization of acrylic ester and styrene with core/shell structure[J].Journal of Beijing Institute of Technology,1991,18(4):22-28.
[46]曹丰,管自生,李东旭.类荷叶表面疏水结构的材料表面制备[J].材料科学与工程学报,2007,4:4-9
[47]YoonJee-Young.Studies on the application of starch for paper surface sizing (Ⅲ)[J].Journal of Korea Technical Association of the Pulp and Paper Industry,2002,34(2):1-12.
[48]TsaiYi-Guan.Surface sizing of cellulose based products[P].US:6087457,2000-6-11.
[49]Brungardt,Clement L,Riehle.Alkaline paper surface sizing agents[P].US:6048392,2000-4-11.
[50]Blanchard P,Trouve P.Use of styrene and maleic anhydride copolymers as dispersing agents and/or for treatment of mineral fillers and thermoplastic compounds containingsame[P].US:6114454,2000-9-5.
[51]Claytor R C P.Method of producing paperboard packaging with an improved sizing layer including a styrene maleic anhydride binder for reduced edgewicking[P].US:916637,1999-6-29.
[52]李小瑞,沈一丁.SMA共聚合反应及改性的研究[J].高分子材料科学与工程,2000,16(3):56-60.
[53]Pierne O S.Styrene/acrylic-type polymers for use as surface sizing agents.[P].US:5138004,1992-8-11.
[54]Exner,Reiner.Synthesis and application of polymer sizing agents[J].Paper Technology,2002,43(6):45-51.
[55]Schmid,Markus,Chowdhry.Process for the production of aqueous polymer dispersions[P].US:6800699,2004-10-5.
[56]Hagiopol,Cornel.Styrene-acrylate copolymer composition suitable for surface size[P].US:6734232,2004-5-11.
[57]Bechara,Ibrahim.Sizing composition[P].US:6465559,2002-10-15.
[58]Andersson C,Jarnstrom L,Mesic B.Distribution of starch and hydrophobic sizing agents[J].International Paper and Coating Chemistry Symposium Proceedings,2003:73-78.
[59]李刚辉,沈一丁,任庆海.阳离子含氟PUA表面施胶剂的制备及应用[J].中国造纸,2005,24(11):17-20.
[60]Watanabe S,Ibuki I.Polyisocyanate composition having high emulsifiability and stability and aqueous coating composition comprising the composition [P].US:5852111,1998-12-22.
[61]Wandelmaier K,Wiggershaus S.Aqueous binder dispersion for physically drying coating agents and their use[P].US:5854337,1998-12-29.
[62]Duan Youlu,Stammler,et al.Aqueous polyurethane dispersion adhesive compositions with improved heat resistance[P].US:5608000,1997-4-4.
[63]Xiaorui,LiGuiqiang,FeiHaihua Wang,et al.Mechanical and surface properties of membranes prepared from waterborne cationic hydroxyl-terminated polydimethylsiloxane/polyurethane surfactant-free micro-emulsion[J].J Appl.Polym.Sci,2006,100(1):28-35.
[64]Guiqiang Fei,Xiaorui Li,Haihua Wang.Effects of Poly(dimethylsiloxane)Concentration on Properties of Polyurethane/Polydimethylsiloxane Hybrid Dispersions[J].Journal of applied polymer science,2006:11-19.
[65]谭安琪.无甲醛抗水剂[J].造纸化学品,19935,(2):18-22.
[66]Floyd W C,Dragner L R.Non-formaldehyde self-crosslinking latex[P].US:5116890,1992-5-26.
[67]Nagashima,Yumiko.Polyacrylamide-based surface strength agents characterization of polyacrylamide-based surface strength agents[J].Japan Tappi Journal,2002,56(8):46-52.
[68]Yang C Q,Xu G.Polymer-aldehyde additives to improve paper properties [P].US:6379499,2002-4-30.
[69]李春利,萨莎.戊二醛交联聚乙烯醇膜在醇/水介质中溶胀性能的研究[J].河北工业大学学报,2005,34(6):35-38.
[70]沈一丁,赖小娟,葛小娟.三聚氰胺乙二醛树脂涂布抗水剂的制备及应用[J].中国造纸学报,2007,(3):14-19.
[71]Kawamura Akira,Tanikawa Akira,Hasegawa Toshiyuki et al.Water soluble resins and application thereof to paper coating[P].US:5849856,1998-12-15.
[72]Floyd W C,Hui S H.Coating binder additive[P].US:4695606,1987-9-22.
[73]费贵强,沈一丁,王海花.无皂苯丙乳液/水溶性环氧树脂复合制备表面施胶剂及其应用[J].中国造纸,2006:5-9.
[74]费贵强,沈一丁,王海花.阳离子热反应性聚丙烯酸酯/环氧硅氧烷无皂乳液对纸张的表面性能[J].现代化工,2006:13-19.
[75]Norio Y,Munetoshi M.Surfactants having polyfluoroalkyl chains[J].Journal of Fluorine Chemistry,1995,(70):187-191.
[76]吴中杰,谢孔良.纸张用含氟防油剂的合成和应用研究[J].造纸化学品,2005,(2):39-42.
[77]Ameduri B.Use of original fluoroacrylates as surface modifier[C].Fluorine in Coating Conference Papers.Brussels International Center for Coatings Technology,2001.
[78]Bongiovanni R,Surface properties of acrylic coatings containing perfluoropolyether chains[C].Fluorine in Coating Conference Papers.Brussels International Center for Coatings Technology,2001.
[79]Anton D R.Coating compositions of an acrylic fluorocarbon polymer and a fluorinated polyisocyanate[P].US:5705276,1998-1-6.
[80]Douglas R.Auton.Coating compositions acrylic fluorocarbon polymer and a fluorinated polyisocyanate[P].US:5597874,1997-1-28.
[81]辛华.含氟丙烯酸酯共聚物乳液纸张表面处理剂的制备及其应用[D].咸阳:陕西科技大学,2005.
[82]张光华,李慧.含氟丙烯酸酯乳液水溶性聚合物复配用于纸张表面施胶的研究[J].化工新型材料,2006,34(11):71-73.
[83]郭小丽,易昌凤,徐祖顺.含氟丙烯酸酯共聚物细乳液的制备及表征[J].粘结,2008,29(6):11-13.
[84]景宜,李忠正.原纸表面施胶对涂布涂层覆盖率和印刷墨斑的影响[J].中国造纸,2006,25(1):1-4.
[85]王志杰.淀粉表面施胶提高铝箔衬纸的平滑度[J].西南造纸,2005,34(6):30-31.
[86]冯明仕,刘延春,郭义.原纸表面施胶液对铜版纸表面强度的影响[J].造纸化学品,2007,19(1):39-41.
[87]郭义.淀粉糊液的变化对表面施胶纸张颜色的影响[J].西南造纸,2006,35(5):41-42.
[88]徐腾.轻型印刷纸表面施胶工艺探讨[J].中华纸业,2006,10:70-72.
[89]李楠,张光华.低黏度阳离子淀粉的制备及其表面施胶性能研究[J].造纸化学品,2007,19(6):19-22.
[90]Okubo M,Yamada A,Matsumosoto T.Estimation of morphology of composite polymer emulsion particles by soap tination method,Polym Sci,1980,(16):3219.
[91]朱永骅,诸秋萍.我国聚合物乳液和建筑乳胶漆的综述[C].全国化学建材协调组建筑涂料专家组汇编.中国建筑涂料发展战略与技术研讨会论文集.北京:2001:8-12.
[92]Ugelstad J.Monodisperse polymer particles and their dispersions[J].Po lm,Sci,Polym Symo,1985,(72):225.
[93]Market M P,Dimonie V L,El-Aasser M S,et al.Morphplogy and grafting reactions in core-shell latexes[J].Polym Sci.Part A,Polym Chem Ed,1987,(25):1219-1233.
[94]Min T I.Morphology and grafting in poly(butylacrylate) polystyrene core-shell emulsion polymerization[J].Polym Sci,Polym Chem Ed,1983,21(10):2845.
[95]潘祖仁著,高分子化学[M].北京,化学工业出版社,2003.
[96]Williams D J.Morphology of the monomer-polymer particle in styrene emulsion polymerization[J].Polym.Sci(A-1),1970,(8):2617.
[97]Dimonie V.core-shell emulsion copolymeriztion of styrene and acrylonitrile on seed particles[J].Polym Sci,Polym Chem Ed,1984,(22):2197.
[98]施良和,胡汉杰.高分子科学的今天与明天[M].北京:化学工业出版社,2000.
[99]张留成,互穿网络聚合物[M].北京:轻工业出版社,2001.
[100]曹同玉,刘庆普,胡金生著,聚合物乳液全成原理性能及应用[M].北京:化学工业出版社,1997.
[101]L Rois,M Hidalgo,J Y Gavailleetal.Polystyrene(1)/poly(butylacrylate methacrylic acid)(2)core-shell emulsion polymer themodynamic considerations[J].Coll Polym Sci,1991,(269):812.
[102]黄鹤,程时远,李建宗.合成聚合物乳液的研究与开发[J].湖北化工,1997,(1):13-16.
[103]宋吉照,顾利霞,核壳乳液聚合综述,上海化工,2000,(6):29-32.
[104]段明,胡星琪,核/壳乳液聚合及其在涂料中的应用,西南石油学院学报,2002,24(2):59-62.
[105]徐祖顺,易昌凤,李晓琴等,PS/P(BA-BOA)核壳乳液的研究[J].高分子材料科学与工程,1996,(6):35.
[106]Greene B W,Sheetz D P.J.Colloid Interface.Sci,1970,32(1):96-100.
[107]Digioia F A,Nelson R E.[J].Ind..Eng.Chem,1953,45(4):745-748.
[108]Hulden M,Sjoblom E.[J].Prog.Colloid Polym.Sci,1990,(82):28-37.
[109]Guyot A.[J].Adv.Colloid Interface Sci.,2004,108-109:3-22.
[110]彭顺金,张贵军,等反应性乳化剂及其乳液聚合[J].涂料工业,1999,(5):36-39.
[111]张洪涛,任天斌.可聚合乳化剂的类型及乳液聚合[J].粘结,1999,20(2):26-28
[112]Krister surfactant in organic coatings.[J].1992,(20):325-337.
[113]周家华,崔英德,等表面活性剂HLB值的分析测定与计算[J].精细石油化工,2001,(4):38-41.
[114]Broniarz J,Wisniewsk M.New approach for the calculation of HLB values of surfactants[J].Tenside,1974,11(2):27-32.
[115]龙复,王玮,许涌深等.硅溶胶.有机高分子复合乳液的研究[J].化工学报,1992,24(5):577-582.
[116]龙复,王玮.无机/有机复合高分子乳液研究的进展[J].化工进展,1991,2:1-5.
[117]E.Bourgeat-Lami,Ph.Espiard and A.Guyot,Poly(ethyl acrylate)latexes encapsulating nanoparticles of silica:Functionaliztion and dis persion of silica[J].Polymer,1995,36(23):4385-4389.
[118]董松.硅溶胶-丙烯酸乳液外墙涂料的配制[J].现代涂料与涂装,2001,5:15-18.
[119]汤新建,陈洪.新型复合水性建筑外墙涂料的研制[J].精细化工中间体,2001,31(3):40-42.
[120]周柞万,卢昌颖.水基复合高分子涂料[J].化学建材,1997,(1):18-19.
[121]K Yoshinage,F Nakashima,T Nishi.Polymer modification of colloidal particles by polymerization of surface active[J].Colloid Polymer Science,1999,(277):136-144.
[122]刘文芳,郭朝霞,于建.PS/SiO_2复合型纳米粒子的制备研究[J].化工进展,2004,23(9):993-997.
[123]于建,喻洁,高彦芳,郭朝霞.乙烯基高分子/无机粉体复合型纳米微球的合成制备[J].塑料,2001,30(6):14-18.
[124]高敬民,方冉.纳米二氧化硅胶体改性核壳型苯丙乳液的合成及性能研究,中国材料,2004,(4):18-21.
[125]徐峰.关于有机/无机复合型建筑涂料稳定性的问题[f].房材与应用,1999,(2):34-35.
[126]陈师,吉静.高SiO_2含量硅溶胶/聚丙烯酸酩复合乳液的制备[J].北京化工大学学报,2005,32(3):57-60.
[127]张小燕,孙争光,黄世强.乳液法制备聚合物纳米复合材料研究进展[J].胶体与聚合物,2004,22(2):27-30.
[128]夏华林.我国造纸工业现状与浆内施胶剂发展趋势[J].上海造纸,2005,3(6):3-9.
[129]张心亚,涂伟萍,陈焕钦.丙烯酸酯类共聚物乳液的研究进展[J].化学工业与工程,2003,20(2):84-88.
[130]易争明,周梅村,曹铭.丙烯酸酯乳液聚合研究进展[J].辽宁化工,2005,34(4):165-167.
[131]王小兵,王永法.丙烯酸酯微乳液研究进展[J].化学与黏合,2006,28(5):333-337.
[132]李株.丙烯酸酯的性能及其应用进展[J].辽宁化工,2001,30(6):245-247.
[133]郑承旺.2002年以来的丙烯酸行业[J].丙烯酸化工与应用,2003,16(4):1-14.
[134]Wen-Chang Chen,Chao-Ching Chang.Synthesis and characterization of large diameter acrylic polymer light conduits[J].J Mater Chem,1999,(9):2307-2312.
[135]孙志娟,张心亚,黄洪等.丙烯酸酯乳液改性的研究进展[J].中国胶黏剂,2005,14(1):40-43.
[136]陈华林,刘白玲,罗荣.丙烯酸酯乳液聚合的最新进展及改性[J].西部皮革,2007,29(4):18-22-26.
[137]周海鸥.丙烯酸酯类涂料改性研究进展[J].弹性体,2005,15(4):58-60.
[138]张玉坤,高晓丽,王沛喜.(甲基)丙烯酸酯在特殊化工技术及产品开发中的应用[J].丙烯酸化工与应用,2003,16(2):27-33.
[139]T Aslamazova,K Tauer,On the colloidal stability of polystyrene particles prepared with surface-active initiators[J].Advances in Colloid and Interface Science,2003,(104):273-283.
[140]Guanglt,Songmd,Haogh,et al.Studies on the preparation of stable and high solid content emulsifier-free latexes and characterization of the obtained copolymers for MMA/BA system with the addition ofAHPS[J].Appl polym Sci,2001,79(1):21-28.
[141]万涛,申红,李祥.氧化还原引发丙烯酸酯乳液共聚物的合成研究[J].弹性体,2002,12(2):9-13.
[142]黄宏志,沈玲,熊聘婷等.可聚合乳化剂对丙烯酸乳液性能的影响[J].涂 料工业,2003,36(12):28-30.
[143]Olivier S,Catherine G,Thierry H.Reactive surfactants in heterophase polymerization,ⅩⅥ Emulsion copolymerization of styrene-butyl acrylate-acrylic acid in the presence of simple maleate reactive surfactants[J].ApplpolymSci,2000,76(12):2768-2776.
[144]代杰,刘希刚,朱明辉.苯乙烯改性丙烯酸乳液性能的研究[J].皮革化工,2005,22(4):1-3.
[145]Iviorita M,Ogisu H,et al.Surface properties of perfluoroalkylethyl acrylate/n-alkyl acrylate copolymers[J].J Appl poly sci,1999,(73):1741.
[146]刘敬芹,张力,朱志博等.有机硅改性丙烯酸脂乳液的合成[J].应用化学,2002,19(6):569-573.
[147]王倩,张心亚,涂伟萍等.有机硅改性丙烯酸乳液性能的研究[J].中国胶黏剂,2002,12(2):5-7.
[148]张伟.高性能有机硅改性丙烯酸乳液的应用基础研究[D].浙江:浙江大学,2004.
[149]张心亚,蓝仁华,陈焕钦.单组分水性有机硅改性丙烯酸乳液胶黏剂的合成与性能[J].2003,(3):36-38.
[150]罗运军,桂红星.有机硅树脂及其应用[M].北京:化学工业出社,2001:90-91.
[151]Yang jun,Zhou Shuxue,You Bo,et al.The preparation and surface properties of silicone-grafted acrylic copolymer coatings[J].High Performance Polymers,2005,17(1):85-102.
[152]房俊卓,高继红,徐崇福.有机氟改性丙烯酸乳液的合成及其膜表面性能的研究[J].宁夏大学学报(自然科学版),2006,27(3)252-254.
[153]程时远,陈艳军,王康丽.含氟丙烯酸酯三元共聚物乳液的研究[J].高分子学报,2002,5(5)560-564.
[154]赵兴顺,丁小斌,张军华等.含氟丙烯酸酯共聚乳液及其膜表面性能的研究[J].高分子学报,2004,7(2):196-199.
[155]杨婷婷,王世敏,徐祖顺等.全氟丙烯酸酯聚合物乳液研究进展[J].高分子学报,2003,6(6):13-17.
[156]Ha J W,Park I J,Lee S B,et al.Preparation and characterization of core-shell particles containing perfluoroalkyl acrylate in the shell[J].Macronmlecules,2002,35(2):6811-6824.
[157]王玉香,孙东成.阳离子型丙烯酸酯聚氨酯塑料涂料的研究[J].热固性树脂,2007,22(3):13-16.
[158]Parmar Randhir,Patel Kalpesh,Parmar Jayant.High-performance waterborne coatings based on epoxy-acrylic-graft-copolymer-modified polyurethane dispersions[J].Polymlnt,2005,54(2):488-494.
[159]Dong-an Wang,Bao-lin Chen,Jian Ji,et cl.Selective Adsorption of Serum Albumin on Biomedical Polyurethanes Modified by a Poly(ethylene oxide)Coupling-Polymer with Cibacron Blue(F3G-A) Endgroups[J].Bioconjugate Chem,2002,(13):792-803.
[160]郭平胜,卢秀萍.阴离子型水性聚氨酯-丙烯酸酯复合乳液的合成与性能研究[J].中国皮革,2007,36(3):53-56.
[161]周琨,李业琛,杨元龙等.无皂聚合丙烯酸乳液与无机粉料复合体的性能研究[J].化学建材,2004(14):13-15.
[162]陈健.丙烯酸乳液复合防水涂料的性能特点及施工应用[J].山西化工,2005,25(3):49-51.
[163]刘仁,熊万斌,刘晓亚等.阳离子型丙烯酸树脂的合成及其水溶性研究[J].涂料工业,2005,35(8):8-11.
[164]Alince.Cationic latex as a multifunctional papermaking wet-end additive[J].J Tappi J,1999,82(3):175-188.
[165]Per Johan Rasmark,Martin Andersson,Jan Lindgren,et al.Differences in Binding of a Cationic Surfactant to Cross-Linked Sodium Poly(Acrylate)and Sodium Poly(Styrene Sulfonate) Studied by Raman Spectroscopy [J].Langmuir,2005,21(7):2761-2765.
[166]Chen,Yahn-Haur Yang,Chin-Ping.Coemulsion and electrodeposition properties of mixtures of cationic epoxy resin and cationic acrylic resin containing blocked-isocyanate groups[J].Journal of Applied Polymer Science,1994,51(9):1539-1547.
[167]沈一丁,陆楚,王春霞.阳离子聚丙烯酸酯乳液增干强剂[J].国际造纸,2002,20(6):38-42.
[168]沈一丁,卫静,任庆海.乳液型丙烯酸树脂改性阳离子使得淀粉增干强剂的制备及性能[J].精细化工,2001,18(4):228-231.
[169]沈一丁,李刚辉.阳离子丙烯酸酯共聚物乳液制备及对纸张增强性能的影响[J].高分子材料科学与工程,2004,20(5):203-207.
[170]林向阳.箱板纸增强剂的开发和应用[J].造纸化学品,1998,10(3):12-15.
[171]张国运,沈一丁.阳离子乳液型纸张增强剂的制备及应用[J].造纸化学品,2002,14(3):34-36.
[172]秋增昌,王海毅编译.采用新型表面施胶剂减少浆内施胶量[J].国际造纸,2005,24(2):57-59.
[173]L.T.Zhuravlev.The surface chemistry of amorphous silica[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2000,173:1-38.