孙幼红 李小华 冯连生
(南京晓庄学院化学系，南京210017)
摘要：在辅助处理剂的存在下，六甲基二硅氮烷(HMDZ)可以很好地对气相法白炭黑进行表面处理。
处理后的气相法白炭黑适合于制作双组分室温硫化(RTV-2)硅橡胶；讨论了气相法白炭黑与HMDZ的 配比、反应温度、反应时间等对RTV-2硅橡胶性能的影响。最佳反应条件为:100份气相法白炭黑用17
份HMDZ处理，反应温度120℃，反应时间60min以上，采用处理后的白炭黑填充的RTV硅橡胶具有优
施雪华
良的机械性能和操作性能。
关键词：气相法白炭黑，室温硫化，硅橡胶，表面处理，六甲基二硅氮烷
收稿日期:2003-02-10。
作者简介：孙幼红(1967-)，女，研究方向为有机硅与涂
料化学。E-mail:youhong
-sun@yahoo 1com1cn
六甲基二硅氮烷(HMDZ)已广泛用于气相法白炭黑的表面处理。但采用普通方法处理的白炭黑用于双组分室温硫化(R TV-2)硅橡胶体系时，存在不少问题，如胶料粘度过高、添加硫化剂后流平性差、排泡困难、贮存期短、易结构化等。我们在实验中发现：通过加入辅助处理剂，与HMDZ协同处理气相法白炭黑，可以很好地解决这些问题。
1 实验
111 主要原料及设备
端羟基聚二甲基硅氧烷(107胶):10000～50000mPa·s，江西蓝星化工厂；二甲基硅油:350mPa·s，江西蓝星化工厂；气相法白炭黑:M-5，美国Cabot公司；六甲基二硅氮烷(HMDZ)：纯度99%，浙江新安化工集团公司；硅微粉:5μm，产地比利时，台湾瑞商公司；正硅酸乙酯:28%，江西星火有机硅厂；二月桂酸二丁基锡:18%，东北师范大学科技开发中心。
捏合机:N H-5，如皋晨光捏合机厂；三辊研磨机:S60，江阴化工机械厂；强力高速电动搅拌釜:115L，自制；真空干燥箱:ZK-82A 型，上海市实验仪器总厂；真空泵:SK-013，南京真空泵厂；旋转粘度计:N
DJ-1型，上海天平仪器厂；拉力试验机:XL-100A，广州实验仪器厂。112 样品制作
首先，在辅助处理剂存在下，用HMDZ对气相法白炭黑进行表面处理；然后进行脱氨处理。加入剩余其它组分充分混合均匀，升温并抽真空脱去体系中水分；研磨过滤，得RTV胶料。
R TV胶料中加入硫化剂，手工快速搅拌均匀后，倾于170mm×120mm×2mm的有机玻璃板模具中，真空脱气后室温放置24h；然后测其力学性能。硫化胶配方:100份107胶、41份白炭黑、88份二甲基硅油、61份硅微粉、216份正硅酸乙酯、018份二月桂酸二丁基锡、适量硫化促进剂。
113 性能测试
R TV胶料粘度：使用旋转粘度计于25℃下测定；硫化胶片硬度：参照G B/T531-1999测定；硫化胶片撕裂强度：参照G B/T529-1999测定；硫化胶片扯断强度、扯断伸长率：参照G B/T528-1998测定。
2 结果与讨论
211 HMDZ用量的选择
气相法白炭黑的表面羟基密度约为3187个/ nm2(也有资料介绍为2～3个/nm2[1]),M-5的比表面积为200m2/g；据此可以大致推算出
工艺·装备有机硅材料,2003,17(2):11～13
SIL ICON E MA TERIAL
处理100g M -5的表面羟基需要1016g HMDZ 。这里的1016g 仅为设计配方参考之用；因为羟基密度、比表面积等都为估计值，而白炭黑表面羟基的处理也并非越彻底越好。白炭黑表面羟基的处理率以27%～61%为佳；过低或过高都将导致硅橡胶的机械性能下降[2]。
表1为HDMZ 用量对R TV -2硅橡胶性能
的影响。由表1可见，随着HMDZ 用量的增加,R TV -2硅橡胶胶料粘度呈下降趋势；当HMDZ 用量超过M -5用量的15%时,R TV -2硅橡胶胶料的粘度和力学性能趋于稳定。所以我们选择HMDZ 的用量为M -5质量的17%。212 反应温度对R TV -2硅橡胶性能的影响
hkj表1 HMDZ 用量对RTV -2硅橡胶性能的影响1)
HMDZ 质量分数/%粘度/mPa ·s
邵尔A 硬度/度扯断强度/MPa 扯断伸长率/%撕裂强度/kN ·m -1
8流动性极差，粘度超出量程，无法做出硫化胶试片
11900001831448022137700018313500
23155200019315520241753000203164902519
51000
19
315
500
24
注:1)反应温度120℃，反应时间120min 。
表2为反应温度对R TV -2硅橡胶性能的
影响。
HMDZ 的沸点约为125℃，所以，我们将
此温度作为反应温度的中间值并上下浮动；考虑到反应速度和工艺稳定性，将反应温度控制在120℃左右。
120℃左右应是HMDZ 与羟基反应的较佳
温度。若温度过低，则体系粘度高，搅拌效果与下步的脱氨处理效果大打折扣；若温度过高，则HMDZ 挥发损失大，体系压力也增大。最重要的是,120℃可以保证气相法白炭黑的处理效果能满足制备R TV -2硅橡胶的性能要求。
表2 反应温度对RTV -2硅橡胶性能的影响1)
温度/℃
粘度/mPa ·s
邵尔A 硬度/度
扯断强度/MPa
扯断伸长率/%
撕裂强度/kN ·m -1
100630001831550022110540001931452023120530002031649025130520002031548024140
53000
19
314
490
23
注:1)HMDZ 用量是M -5质量的17%，反应时间为120min 。
213 反应时间对R TV -2硅橡胶性能的影响表3为反应时间对R TV -2硅橡胶性能的影响。
在辅助处理剂存在下，气相法白炭黑与
HMDZ 在120℃下反应时间超过60min ，处理
后的白炭黑可以满足制备R TV -2硅橡胶的性能要求。214 操作性能
表3 反应时间对RTV -2硅橡胶性能的影响1)
时间/min
粘度/mPa ·s
邵尔A 硬度/度
扯断强度/MPa
扯断伸长率/%
撕裂强度/kN ·m -1
3059000193154802360540001831450023120530002031649025180
53000
20
313
490
24
注:1)HMDZ 用量为M -5质量的17%，反应温度120℃。
·12 ·有机硅材料第17卷
除机械性能外,R TV -2硅橡胶一般还需要
具有良好的操作性能以满足应用需要。采用本法处理的气相法白炭黑填充的R TV -2硅橡胶，操作性能良好，具体表现为：与硫化剂混合时，手工搅拌无明显“加重感”；混合胶料真空脱气后，能自动流平和消泡；硫化胶片平整光滑，机械性能测试时数据的重复性良好。
王立军自白3 结论第三方环境检测机构管理
在辅助处理剂的存在下，用17份HMDZ 于
120℃下处理100份气相法白炭黑(M -5)60min 以上，处理后的白炭黑填充的R TV -2硅橡
胶不仅具有良好的机械性能，还具有良好的操作性能，粘度低、流动性好，加入硫化剂后流平性与排泡性也很好。
参 考 文 献
1 李光亮1有机硅高分子化学1北京：科学出版社,
19981150
2 幸松民，王一璐1有机硅合成工艺及产品应用1北
京：化学工业出版社,20001555颜氏家训pdf
2003年“热硫化硅橡胶信息交流会”通知
2003年中国氟硅有机材料工业协会有机硅专业委员会与全国合成树脂及塑料工业信息总站有机硅信息分站联合
在2003年4月16～20日在南京召开“热硫化硅橡胶信息交流会”。本次会议的宗旨是：为国内外厂商提供展示产品和技术、交流信息、扩大合作、开拓市场和洽谈贸易的机会和场所。这是一次同行、朋友聚会的好机会，欢迎您来参加，并请您将此好消息转告您的朋友。
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全国合成树脂及塑料工业信息总站有机硅信息站
承办单位:《有机硅材料》编辑部 赞助单位：江苏海外集团物资技术有限公司 会议主题：热硫化硅橡胶 会议地点：南京国际会议大酒店 会议时间:2003年4月16～20日报告主要内容
热硫化硅橡胶生胶生产工艺的改进
王伟良关于高温硫化硅橡胶生产技术的几点讨论陈光琦
浅耐热硅橡胶的研究
苏正涛 米志安 李跟华等
沉淀法白炭黑主要性能参数对混炼硅橡胶性能的影响黄文润白炭黑在硅橡胶中的补强作用
陈光琦
硅橡胶用补强填料白炭黑的研究进展罗穗莲 潘慧铭 王跃林
热硫化硅橡胶按键的弹性
张飞 黄薇
冷收缩电缆附件与其它电力产品用硅橡胶的研究柯德刚硅橡胶在医学领域的应用
刘爱堂硅橡胶补强剂—SiO 2纳米粒子链庄清平硅橡胶与按键
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第2期孙幼红等.气相法白炭黑表面处理的新方法·13 ·
Synthesis&structure characterization of N0N-diethylaminopropylmethyldimethoxysilane.L I J un -ying
1,FEN G Sheng-yu1,ZHOU Jian-hua2, L I Tian-duo2,ZHAN G Qing-si2(1.Chem2 istry and Chemical Engineering College,Shandong Univ.,Jinan,Shandong250100; 2.Chem En2 gineering Department,Shandong Institute of Light Industry,Jinan,Shandong,250100,Chi2 na),Y oujigui Cailiao,2003,17(2):1～4
N0N-diethylaminopropylmethyldimethoxysilane was synthesized by takingγ-chloropropy2 lmethyldimethoxysilane and diethylamine as raw materials in the process of amination.The domi2 nant element of the reaction was temperature ac2 cording to orthogonality experiment.The most op2 timal conditions were that molar ratio of diethy2 lamine andγ-chloropropylmethyldime-thoxysi2 lane was4to1,reaction time was20hours at11℃,and the production yield would be over80%. The structure was characterized by IR and 1HNMR spectra and its molecular structure was calculated by ab initio molecular orbital method with HF/6-31G3level.
K eyw ords:γ-chloropropylmethyldimethoxy silane,amination,N,N-diethylaminopropyl-methyldimethoxysilane,diethylamine
Study on crosslinking of polycarbosilane/polysi2 lazane precursor system.J IAN K e,ZHEN Wen -wei,MA Qing-song,CHEN Zhao-hui,HU Hai-feng(CFC K ey Lab,College of Aerospace and Materials
Engineering,National Univ.of De2 fense Technology,Changsha,Hunan410073, China),Y oujigui Cailiao,2003,17(2):5～7 The effects of the crosslinking condition of Si-C-N ceramic precursor system containing polycarbosi2 lane(PCS)and polysilazane(PSZ),including cure time,temperature,kinds and dosage of ini2 tiator and catalyst,on the appearance of cured product and ceramic yield were investigated.The process of crosslinking and cracking of PCS/PSZ were studied by thermogravimetry.The result shows when the weight ratio of PCS∶PSZ∶Xylene∶DCP was2∶2∶1∶0105,the temperature,pressure and time of crosslinking reaction were respectively 120℃,2MPa and6hours,cured product is good appearance and higher ceramic yield,7718%.
K eyw ords:polycarbosilane,polysilazane, crosslinking,precursor,ceramic Synthesis of polymethylsesquisiloxane.HUAN G Chao1,CHEN Yue-ping1,HU Ping2(Institute of Applied Chemistry,Jiangxi Academy of Sci., Nanchang,Jiangxi330029; 2.Jiangxi computa2 tion center,Nanchang,Jiangxi330006,China), Y oujigui Cailiao,2003,17(2):8～10 Methylsesquisiloxane was synthesized by taking methyltrichlorosilane as raw material and organic amine as trapezium control agent.The effects of trapezium control agent,hydrolyze medium,cata2 lyst,monomer consistency,temperature on molar mass and structure regularity of polymer were dis2 cussed.Agreeable trapezium control agent and polymerization condition were filtered out.When the
molar ratio of methyltrichlorosilane and ethylenediamine equals to1∶111,product yield was higher,about90%.When the molar ratio of methyltrichlorosilane and H2O equals to1∶15, product had a larger molar mass and good regulari2 ty.After the hydrolization,when taking tetram2 ethyl ammonium hydroxide as catalyst,condensa2 tion reaction was carried out at35℃,if reaction time was short,the product had low molar mass and narrow distribution of molar mass.On the oth2 er hand,if reaction time was long,the product had high molar mass and wide distribution of molar mass.When taking acid as catalyst the condensa2 tion reaction was carried out at higher tempera2 ture,by lower molar mass of polymer and narrow distribution of molar mass.
K eyw ords:methylsesquisiloxane,trapezium con2 trol agent,methyltrichlorosilane,ethylenediamine T reatment method of f umed silica surface.SUN Y ou-hong,L I Xiao-hua,FEN G Lian-sheng (Nanjing Xiaozhuang College,Nanjing,Jiangsu 210017,China),Y oujigui Cailiao,2003,17 (2):11～13
The surface of fumed silica can be well treated by henamethyldisilazane(HMDZ)with auxilliary surface treatment agent.The treated fumed silica is suitable for the preparation of two-part R TV sili2 cone rubber.The effects of the ratio of fumed silica and HMDZ,reaction temperature and reaction time on the performance of two-part R TV silicone rubber were discussed.The optimum reaction con2 ditions would be that100portion fumed silica was treated by17portion HMDZ at120℃,above60
min.R TV silicone rubber,which was treated by
ABSTRACT有机硅材料,2003,17(2):43～44
SIL ICON E MA TERIAL
fumed silica has good mechanical and operating per2 formance.
K eyw ords:fumed silica,R TV,silicone rubber, surface preparation,henamethyldisilazane
Q uality evaluation of VMC.WAN G Wei-liang (Chenguang Research Institute of Chemical Indus2 try,Chengdu,Sichuan610041,China).Y ou2 jigui Cailiao.2003,17(2):14～16
The factors affecting the quality of VMC specially used in synthesis of VMQ gum were discussed. Pointed out that the contents of trifunctional group chain,vinylmethylcyclictrisiloxane and vinyl groups were the dominant factors affecting quality of VMC.The reasonable technical requirements for VMC and a simple method for testing quality of VMC were put forward.Meanwhile,the technical requirements for VMC of shin-etsu Chemical Co. and Rhodia Corp.were introduced.
K eyw ords:VMC,VMQ,silicone rubber,mix2 ture of VMQ
R esearch progress in silicone microparticles. ZHAN G Dun-ming,J IAN G Xi-qun,YAN G Chang-zheng(College of Chemistry and Chemical Engineering,Nanjing Univ.,Nanjing,Jiangsu 210093,China),Y oujigui Cailiao,2003,17 (2):(2):17～21
The preparation and application of silicone mi2 croparticles,including silicone resin microspheres and silicone microencapsulates whose particle size is around nanon in recent years are reviewed.
K eyw ords:silicone,nanometer,microparticle, microsphere,microencapsulate
Source analysis of import primary polysiloxane in China in recent years.ZHOU Qin(Chenguang Research Institute of Chemical Industry,Cheng2 du,Sichuan610041,China).Y oujigui Cailiao. 2003,17(2):22～24
According to the custom’s statistics data,the im2 port and export situations of primary polysiloxane in China during1996～2002were analyzed.The source of the imported primary polysiloxane in Chi2 na was emphatically analyzed.It showed that the primary polysiloxane in China mostly came from Japan,Chinese Taiwan,America,G ermany, England and K orea.
K eyw ords:primary silicone,import,export, Japan,Taiwan Present situation of silicone-modif ied coati
ngs. L IU Guo-jie(China Paints and Coatings Techni2 cal Information&Training Center,Beijing 100083,China),Y oujigui Cailiao,2003,17 (2):25～28
The present situations of high performance building coatings in China were summarized.Silicone-modified acrylate coatings of solvent type,silicone -modified acrylate emulsion coatings of water-based,silicon-containing elasticity coatings of ce2 ramics composite and siloxane-containing polyester coil coatings were introduced.
K eyw ords:silicone,acrylate,polyester,archi2 tecture,coil,tetraethylorthosilicate
R esearch progress in chemically bonded silica sta2 tionary phases of HPLC.CHEN Guo-wen, FEN G Sheng-yu(New Materials Research Insti2 tute,Shandong Univ.,Jinan,Shangdong 250100,China),Y oujigui Cailiao,2003,17 (2):29～33
Progress in chemically bonded silica phases used in high performance of liquid chromatography (HPLC)was reviewed in three aspects:firstly, new phases designed for new analyses,fullerenes and chiral stationary phases;secondly,further re2 searches and improvements of conventional phases. Works dealing with base-endurable properties of reversed phases;thirdly,theories on retention properties.
K eyw ords:high performance liquid chromato2 graphy,chemically bonded silica stationary phas2 es,progress
Dispensing of one-part RTV silicone rubber (V).HUAN G Wen-run(Chenguang Research Institute of Chemical Industry,Chengdu, Sichuan610041,China).Y oujigui Cailiao.2003, 17(2):34～41
The preparation methods of deketoxime type one-part R TV silicone rubber sealant on spreadability and for formed inplace gasket were introduced re2 spectively.The dispensing process of deketoxime type one-part R TV silicone rubber sealant of formed inplace gasket like type of fast cured,resis2 tance to engine oil and transmission oil,adhesivity to oily surface were particularly discussed.
K eyw ords:R TV,silicone rubber,deketoxime type,sealant,formed inplace,gasket
·44
·有机硅材料第17卷
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