白炭黑轮胎加工所面临的挑战

1、Challenges for Silica Tread Processing 白炭黑轮胎加工所面临的挑战Dr.Lothar Steger /Rhein Chemie Rheinau GmbHWhy silica compounds ?为何要发展白炭黑胎面？By applying silica instead of carbon black in tire tread compounds the following results can be achieved : 用白炭黑代替炭黑具有如下优越性能：much lower rolling resistance of the tire 轮胎滚动损失

2、降低很多much better ice and snow performance 抗冰滑和抗雪滑行能优越很多much better wet skid behaviour 抗湿滑性能改善很多at similar tread wear patterns 具有相近的耐磨性ABS-brake works only with silica on the wet roadBenefits of Silica Technology vs. Carbon Black白炭黑技术优势与炭黑比较炭黑白炭黑滚动阻力胎面寿命抗湿滑性抗雪滑性Properties of Silica with respect to Car

3、bon Black 白炭黑与炭黑的性能对比抗湿滑抗雪/冰滑滚动阻力耐磨性History of silica technology白炭黑技术发展简史1974 Blue silica tire developped by Metzeler / GermanyHigh loading of silica and BR, no S-SBR available, insufficient processing equipment and know how1975Metzler stopped production of blue tire1980-several developments: silane

4、s, rubbers,1990processing equipment and processing know how 1992Patent on Green Tire of Michelin / FranceS-SBR, less silica and BR, improved processingequipment and procedures2000State of the art silica tire achieves up to 30 % improvement of physical properties but has remarkable processing deficie

5、nciesUp to 35 % reduced rolling resistance with silicaUp to 5 % less fuel consumption per caror approx. 2 billion litres of fuel savings per year in Germany aloneGreen Tire Concept: Economic Benefit绿色轮胎的概念：获得经济效益使用白炭黑可使滚动阻力最多可降低35% 每辆轿车的耗油量最多可节省5%仅在德国，每年可以节省20亿升的燃料 Green Tire Target for Economic Ben

6、efit 绿色轮胎的目标是获得经济效益 Disadvantages of current silica technology 目前白炭黑技术的缺陷1.Difficult to mix highly loaded silica compounds高填充白炭黑胶料门尼粘度较高难于加工2.Long mixing cycles increase mixing costs长时间返炼/混炼，增加混炼成本3.Temperature peaks during mixing lead to scorch problems; 混炼温度高，易导致焦烧;4.Parts of silane are absorbed i

7、n porous silica getting inefficient; 多孔的白炭黑吸收部分硅烷偶联剂，导致效率降低;5.Manufacturers need to buy more powerful equipment. i.e. intermeshing rotors.加工者必须购买功率更高的设备，如：互齿式转子 (GKE密炼机) Challenges for Silica Tread Processing 白炭黑轮胎加工所面临的挑战1.Good Dispersion of High Dosage Silica高填充白炭黑的良好分散2.Activation and Silanizatio

8、n of Silica白炭黑的活化和硅烷化反应3.Coupling Reaction between Diene Silica and Rubbers白炭黑与二烯烃橡胶之间的偶联反应4.New Curing Systems 新型硫化体系5.More Powerful Equipment. i.e. intermeshing rotors.功率更高的设备，如：互齿式转子 (GKE密炼机) OEM Products Development for Silica Tire白炭黑轮胎所需的配套产品开发用于白炭黑的高效分散剂提高白炭黑的分散性Aktiplast GTAktiplast STAflux G

9、E1837白炭黑的有效硅烷偶联体系提高白炭黑的硅烷化反应程度和提高白炭黑与二烯烃橡胶的偶联反应程度Si-69/Si-75Silane + SASD适合于高用量白炭黑的新型硫化体系二烷基二硫代磷酸锌Processing Promoters for Tire Compound Processing用于轮胎胶料的加工助剂Dr.Lothar Steger /范汝良Rhein Chemie Rheinau GmbH莱茵化学（青岛）有限公司Processing Promoters : Definition加工助剂的定义Processing Promoters are tailer made additiv

10、es, which enable a homogeneous mixing and the subsequent processing of the rubber compound“加工助剂是一种量身定做的添加剂，它们可以实现均相混炼并改善后续加工行为。 Processing Promoters improve the extrusion, calandering and molding performance but do not negatively influence the vulcanization properties of the mixture.“它们可以改善挤出、压延和模压硫

11、化性能并且不会对硫化胶性能带来负面影响。Correlation 生产过程与实验设备的相关性Production and Laboratory Equipment高压毛细管流变仪门尼粘度挤出机流变硫化仪模压硫化混炼挤出注压硫化剪切速率粘度Division of Processing Promoters according to Their Chemical Composition 根据化学组成对加工助剂的分类Chemical descriptionExamplesHydrocarbons碳氢化合物Paraffinic waxes and oils链烷烃蜡 Metal soaps金属皂类Zn-,

12、Ca-, Mg-, K-soaps锌/钙/镁/钾皂Carboxyl-organic compounds羧基化合物Fatty-acids, -alcohols, -esters 脂肪酸、 脂肪醇、 脂肪脂类Resins树脂类Petroleum-, Indene-Coumarone-, Phenolic-resins石油/古马隆-茚/酚醛Crosslinked glycerides交联甘油酯Vulcanized vegetable oils交联植物油Polymers with low molecular weigth低分子量聚合物Poly-ethylene, -propylene, -butadi

13、ene聚乙烯、 聚丙烯、 丁二烯Other organic compounds with hetereoatoms其它杂原子有机物Aryldisulphide, Fatty-acid-amide芳基二硫化物、脂肪酸酰胺Division of Processing Promoters according to their effects in the tire compound根据对轮胎胶料的影响的分类Effect in tire 轮胎胶compound 料影响Chemical Composition化学组成Trade Names 商品名Mastication Agent塑解剂2,2-diben

14、zamido-diphenyldisulfideFe-complex with organic additivesRenacit 11Aktiplast 8Dispersant分散剂Fatty-acid,-alcohol,-ester脂肪酸醇酯Mixture of Zn-soap,fatty-ester, fillerAflux 42Aktiplast STLubricant润滑剂Zn-soaps锌皂Ca-soaps钙皂Aktiplast PPAflux 16Homogenizer 均匀剂Special fraction hydrocarbon resins特殊碳氢树脂Rhenosin TP

15、100Tackifier增粘剂Indene-Coumarone-Resin /low m.w. Alkylated phenolic resin古马隆-茚/烷基化酚醛树脂Rhenosin C-30Rhenosin PT 100Processing Promoters with Mastication Effect具有塑炼效果的加工助剂Description组成Effects效果Product产品Fatty-acid,-ester, Fe-hemi脂肪酸/脂/铁的络合物Mastication of NR塑炼Aktiplast 8Zn-soaps (mainly saturated), Fe-he

16、mi饱和脂肪酸锌和铁的络合物Mastication of NR, Improvement of flow 塑炼和改善流动性Aktiplast MZn-soaps (mainly unsaturated) Fe-hemi不饱和脂肪酸锌和铁的络合物Mastication of NR, Filler Dispersion塑炼和填料分散Aktiplast FAlkylated-Poly-Sulfides, Fatty-acids, Fe-hemi烷基多硫化物/脂肪酸/铁的络合物Mastication of NR,塑炼Filler Dispersion,填料分散Improvement of flow 改

17、善流动Aflux 61Mastication Effect塑炼效果Mooney Viscosity ML1+4/100CFatty AcidFe-hemiNoneNoneZn-soapsaturatedFe-hemiZn-soapUnsaturatedFe-hemiAlk.-Poly-sulfideFatty-acidsFe-hemiNR, Internal Mixer, 3, dumped at 140，天然橡胶在密炼机中密炼3分钟排胶温度140 Aktiplast 8Aktiplast MAktiplast FAflux 61ML1+4/100C无塑解剂脂肪酸与铁络合物饱和锌皂与铁络合物不

18、饱和锌皂与铁络合物烷基多硫化物、脂肪酸与铁络合物Mode of Action of Processing Promoters加工助剂的作用原理内润滑作用溶解于橡胶中外润滑作用不溶解于橡胶中分散润滑Processing Promoter Effects as a function of their polymer solubility溶解度不同加工助剂作用效果不同Polymersoluble additive与橡胶相容intramolecularLubricant分子内润滑surface coating of fillers; leads to polymer swelling填料表面涂层导致橡

19、胶溶胀Dispersant分散Polymerinsoluble additive与橡胶不相容extramolecularLubricant分子外润滑migration to the polymer surface under stress应力作用下迁移到橡胶表面Lubricant润滑Processing Promoter Lubricant Effects加工助剂的润滑作用p pcritVgVgwallMixturewallVgFilmslippage膜滑动high processing prom. Concentration加工助剂浓度高wallMixtureEffects at criti

20、cal shear stress with active processing promotersEffects at critical shear stresswithout processing promoter Wall-Slip Wall-StickFilm-Slippage不含加工助剂时临界剪切应力影响含加工助剂时临界剪切应力影响Change of polymer conformation with shear stress随剪切橡胶聚集体结构的变化statistical polymer coil in the core of the flow as area of low shea

21、r低剪切速率区域橡胶分子链的卷曲polymer chain orientation at high shear stress高剪切应力下的橡胶分子链取向Capillary Wall毛细管壁Analytical determination of surface concentration表面浓度的检测分析Surface analysis via FTIR-Spectroscopy:SampleCalibration of the EPDM-Zinc-Soap mixture :2468100,40,60,811,2Concentration Zn-soap phrExtinctionRefere

22、nce peak: 1376/cmRegression coeff. = 0,99927Characteristical pattern of the zinc soap : 1532 1/cmProcessingPromoterProcessing Promoters Lubricant Effect加工助剂的润滑效果Processing Promoters perform a certain function determined by their solubility in the rubber. 加工助剂润滑效果取决于它们在橡胶中的溶解度They reduce shear stress

23、 due to high surface concentrations at location of high shear gradient. They resolve in the mix after leaving the shear zone (die). 加工助剂降低剪切应力，这是因为在高剪切区域其浓度很高Each polymer or blend needs its unique processing promoter taking into accaount the processing technique. 任何橡胶或其共混物都有与其相适应的加工助剂Processing Prom

24、oetrs increase quality and quantity of extrusion and injection molding significantly. 加工助剂有效增加挤出、注射产品的质量和产量Processing Promoter for Silica Tread Compounds 用于白炭黑胎面胶的加工助剂Aktiplast STAktiplast GTAflux GE1837Tread: Aktiplast GT in Carbon Black / E-SBR 莱茵塑分GT用于E-SBR/炭黑胎面SBR 1712110BR-Buna CB 10 20N-220 80

25、Aromatic Oil 10Aktiplast GT 3Stearic acid 16PPD 1TMQ 1Wax/Antilux 654 2Zn0 3Sulfur 2,2TBBS/Vukacit NZ0,9Processing Promoter : Aktiplast GT (Zn-soap / mainly saturated)Control without Processing Promoter100Mixing (Mooney, HPCR)ML 1+4/100C 85 HPCR 100C/11s-1 85Extrusion (Torsiograph)Extrusion rate g/m

26、in 104 Extrusion volume cm/min 117Curing (Rheovulcameter)Injection volume mm3 160Injection speed mm3/sec 115LiteratureITEC 1998 Akron/OHRhein Chemie Technical Report 63Tread: Aktiplast ST in Silica / S-SBR 莱茵塑分ST用于S-SBR/白炭黑胎面S-SBR-Buna VSL 1955-S2596Nd-BR-Buna CB 2430Silica-Ultrasil 700070Carbon Bla

27、ck N-11010X-50 S (50% Si-69)12,5Aktiplast ST 5ZnO 3Stearic acid 1Aromatic Oil20TMQ 16PPD 1,5Antilux 654 1,5CBS 1,5DPG 2Sulphur 1,5Processing Promoter : Aktiplast ST (mixture of Zn-soap, fatty-ester, filler)Control without Processing Promoter 100Mixing (Mooney, HPCR)ML 1+4/100C 83HPCR 100C/11s-1 85Ex

28、trusion (Torsiograph)Extrusion rate g/min 116Extrusion volume cm/min 117Curing (Rheovulcameter)Injection volume mm3 200Injection speed mm3/sec 155LiteratureITEC 1996 Akron/OHRhein Chemie Technical Report 60Influence of Aktiplast ST Flow properties莱茵塑分ST对流动性的影响01020304050600 phr1 phr2 phr3 phr4 phr5

29、phr05001.0001.5002.0002.5000 phr1 phr2 phr3 phr4 phr5 phr05.00010.00015.00020.00025.0000 phr1 phr2 phr3 phr4 phr5 phr010203040506070800 phr1 phr2 phr3 phr4 phr5 phrHKR (90C,11/s)Viscosity (Pas)ML1+4100Rheovulc. volumeFormulation GEL 30437配方试验GEL 30437MDR 160C硫化仪特性Viscosity ; Mooney-Scorch门尼焦烧GEL 304

30、37ControlAflux GE 1837Aktiplast GTAktiplast STMooneyML1+4/100C99566375Rheovulcameter;IM-volume (mm3)493170513701005Rheovulcameter; IM-speed (g/mm3)16494230Mooney-scorch;t-5 (min)8:3717:9221:6816:53Mooney-scorch;t-35 (min) 13:7524:3730:4524:30Physicals物性 GEL 30437ControlAflux GE 1837Aktiplast GTAktip

31、last STModulus 100(MPa)3.723.763.143.33Modulus 300(MPa)12.012.110.210.9Tensile Strength(MPa)16.717.117.116.4Elongation at break (%)395422479426Hardness(Shore A)80797980Tear Strength(N/mm)69.266.447.053.0Rebound (%)33333535RPA2000 GEL 30437 RPA2000研究Payne效应ControlAktiplast STAktiplast GTAflux GE 1837

32、Aflux GE 1837 Anti-sticky effectAdvantages of Aflux GE 1837 in S-SBR/silica白炭黑分散助剂Aflux GE 1837的优点Reduced compound viscosities降低混炼胶粘度Improved flow properties in extrusion 改善挤出流动性Improved flow properties in molding 改善模压流动性Anti-sticky effect 具有防粘效果Improved filler dispersion.改善填料分散Lower energy use in e

33、xtrusion and calandering降低挤出压延能耗Optimized compound processingwithout negative effect onproduct performanceReaction Mechanism for Silica/SilaneTechnology 白炭黑/硅烷技术的反应机理Dr.Lothar Steger /范汝良Rhein Chemie Rheinau GmbH莱茵化学（青岛）有限公司6.1 What is Silane?硅烷偶联剂的概念SiSilicaRubberInorganicFiberglassFillersMetalsOrg

34、anicRubberPolymersPlasticsSi6.2 Silane/Silica Coupling Reaction Dependent on Temperature and TimeC2H5OC2H5OC2H5OOC2H5OC2H5OC2H5Si-(CH2)3-S-S-S-S-(CH2)3-Si-O-Si-O-Si-O-OHOH-O-Si-O-Si-O-OHOHSILICA硅烷偶联剂/白炭黑偶联反应依赖于温度和时间TESPT: Si-696.3 Silanization Reaction Mechanism 硅烷化反应机理SilicaSilica6.5 Silane/Silica

35、Diene Rubber Matrix Reaction Caused by Temperature 155 硅烷偶联剂/白炭黑、橡胶相反应温度1556.6 Sulfidosilane Reaction in Vulcanization 硫化过程中的偶联机理SilicaRubberSilicasssssssThe silane can react in theSulfur vulcanization6.7 Interpenetrating Network Theory 形成的互穿网络结构Si-O-Si-Si-O-Si-Si-O-Si-Si-O-Si- RubberChemically Bond

36、ed InterfaceSilicaCoupling agentDiffuse Interphase6.8 SEM Photograph of Silica-filled Rubber 白炭黑填充二烯烃橡胶的扫描电镜照片 Without silane With silane 6.9 Considerations When Using Silica/Silane Technology白炭黑/硅烷技术应用原理1. More mixing is needed in non-productive steps compared to all carbon black compounds需要更多的混炼段数

37、2. Temperature control is importantDont be too high or too low混炼温度既不能太高也不能太低3. TESPT (Si-69) have a limit of 160 of processing Si-69混炼温度不得超过160 4. TESPD (Si-75) enable better processing quality and speedSi-75混炼温度不得超过170 Slightly more coverage for the same weight of silane Higher processing temperatu

38、res are possible, typically up to 170 , so silanization reaction reaches more completion sooner It is possible to improve mixing times by 25 to 50%Working Mechanism of New Silane新型硅烷的反应机理Working Mechanism of New Silane新型硅烷的反应机理3. Silane + SASD improve blend & filler dispersion双组分新型硅烷改善混炼和填料分散Silane +SASDrubber matrix dispersed rubber phase dispersed silica