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2-白炭黑轮胎加工所面临的挑战


Challenges for Silica Tread Processing
白炭黑轮胎加工所面临的挑战

Dr.Lothar Steger /范汝良 Rhein Chemie Rheinau GmbH 莱茵化学(青岛)有限公司

Why 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 road
[ 13.09.2013 ] Steger - Silica Tread I [ Folie: 2 ]

Benefits of Silica Technology vs. Carbon Black白炭黑技术优势与炭黑比较
Rolling Efficiency 滚动阻力
100

Carbon Black 炭黑

80 60 40 20

Tread Life

胎面寿命

0

Wet Traction

抗湿滑性

Silica 白炭黑
Snow Traction 抗雪滑性
[ 13.09.2013 ] Steger - Silica Tread I [ Folie: 3 ]

Properties of Silica with respect to Carbon Black 白炭黑与炭黑的性能对比

130 120 110 100 90
wet skid Snow/ice rollling resistance abrasion

Carbon Black Silica

80

抗湿滑
[ 13.09.2013 ]

抗雪/冰滑

滚动阻力
Steger - Silica Tread I

耐磨性
[ Folie: 4 ]

History of silica technology 白炭黑技术发展简史 1974 Blue silica tire developped by Metzeler / Germany High loading of silica and BR, no S-SBR available, insufficient processing equipment and know how 1975 Metzler stopped production of blue tire 1980- several developments: silanes, rubbers, 1990 processing equipment and processing know how 1992 Patent on Green Tire of Michelin / France S-SBR, less silica and BR, improved processing equipment and procedures 2000 State of the art silica tire achieves up to 30 % improvement of physical properties but has remarkable processing deficiencies
[ 13.09.2013 ] Steger - Silica Tread I [ Folie: 5 ]

Green Tire Target for Economic Benefit 绿色轮胎的目标是获得经济效益

Up to 35 % reduced rolling resistance with silica
使用白炭黑可使滚动阻力最多可降低35%

Up to 5 % less fuel consumption per car
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

or approx. 2 billion litres of fuel savings per year in Germany alone

Green Tire Concept: Economic Benefit

绿色轮胎的概念:获得经济效益
[ 13.09.2013 ] Steger - Silica Tread I [ Folie: 6 ]

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 in 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)
[ 13.09.2013 ] Steger - Silica Tread I [ Folie: 7 ]

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 Silanization 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)

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[ Folie: 8 ]

?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 GT Aktiplast ST Aflux GE1837 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-75 Silane + 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
[ 13.09.2013 ] Steger - Silica Tread I [ Folie: 9 ]

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 additives, 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、压延和模压硫化性能并且不会对硫化胶性能带来负 面影响。

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[ Folie: 11 ]

Correlation – 生产过程与实验设备的相关性 Production and Laboratory Equipment
Viscosity 粘度 (Pa x s)
高压毛细管流变仪

10

4
门尼粘度
Mooney

High Pressure Capillary Rheometer (HKR)

流变硫化仪 挤出机
Extruder Rheovulcameter

10 10

2

模压硫化

混炼

挤出

注压硫化

0

Compression moulding

Mixing

Extrusion

Injection moulding

10 1
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10

2

10 3

10 4
[ Folie: 12 ]

Shear rate ( s -1) 剪切速率
Steger - Silica Tread I

Division of Processing Promoters according to Their Chemical Composition 根据化学组成对加工助剂的分类

Chemical description
Hydrocarbons碳氢化合物

Examples
Paraffinic waxes and oils链烷烃蜡

Metal soaps金属皂类
Carboxyl-organic compounds羧基化 合物 Resins树脂类 Crosslinked glycerides交联甘油酯

Zn-, Ca-, Mg-, K-soaps锌/钙/镁/钾皂
Fatty-acids, -alcohols, -esters 脂肪酸、 脂肪醇、 脂肪脂类 Petroleum-, Indene-Coumarone-, Phenolic-resins石油/古马隆-茚/酚醛 Vulcanized vegetable oils交联植物油

Polymers with low molecular weigth低 Poly-ethylene, -propylene, -butadiene 分子量聚合物 聚乙烯、 聚丙烯、 丁二烯 Other organic compounds with hetereoatoms其它杂原子有机物
[ 13.09.2013 ]

Aryldisulphide, Fatty-acid-amide芳基 二硫化物、脂肪酸酰胺
Steger - Silica Tread I [ Folie: 13 ]

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 Mastication Agent 塑解剂 Dispersant分散剂 Lubricant润滑剂 Homogenizer 均匀剂 Tackifier增粘剂 Chemical Composition化学组成 2,2‘-dibenzamido-diphenyldisulfide Fe-complex with organic additives Fatty-acid,-alcohol,-ester脂肪酸醇酯 Trade Names 商 品名 Renacit 11 Aktiplast 8 Aflux 42

Mixture of Zn-soap,fatty-ester, filler
Zn-soaps锌皂 Ca-soaps钙皂 Special fraction hydrocarbon resins 特殊碳氢树脂

Aktiplast ST
Aktiplast PP Aflux 16 Rhenosin TP 100

Indene-Coumarone-Resin /low m.w. Rhenosin C-30 Alkylated phenolic resin古马隆-茚/烷 Rhenosin PT 100 基化酚醛树脂
Steger - Silica Tread I [ Folie: 14 ]

[ 13.09.2013 ]

Processing Promoters with Mastication Effect具有塑炼效果的加工助剂 Description组成
Fatty-acid,-ester, Fe-hemi脂肪 酸/脂/铁的络合物 Zn-soaps (mainly saturated), Fe-hemi饱和脂肪酸锌和铁的络 合物 Zn-soaps (mainly unsaturated) Fe-hemi不饱和脂肪酸锌和铁的 络合物 Alkylated-Poly-Sulfides, Fattyacids, Fe-hemi烷基多硫化物/脂 肪酸/铁的络合物

Effects效果
Mastication of NR塑炼 Mastication of NR, Improvement of flow 塑炼和改善流动性 Mastication of NR, Filler Dispersion塑炼和填料分 散 Mastication of NR,塑炼 Filler Dispersion,填料分散 Improvement of flow
改善流动

Product产品
Aktiplast 8 Aktiplast M

Aktiplast F

Aflux 61

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Mastication Effect 塑炼效果Mooney Viscosity ML1+4/100°C
ML1+4/100°C NR, 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 80


70
Aktiplast 8 Aktiplast M Aktiplast F Aflux 61

60 50 40 30 20 10o
n 0e N

1 day 6 days 11 days

None
无塑解剂

Fatty Acid Fe-hemi
脂肪酸与 铁络合物

Zn-soap saturated Fe-hemi
饱和锌皂与 铁络合物

Zn-soap Alk.-Poly-sulfide Unsaturated Fatty-acids Fe-hemi Fe-hemi
不饱和锌皂 与铁络合物 烷基多硫化物、脂 肪酸与铁络合物
[ Folie: 16 ]

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Mode of Action of Processing Promoters
加工助剂的作用原理
内润滑作用 外润滑作用

Inrt nL ta i eu r b l c a n
Sio on e le l r uP b y l m
溶解于橡胶中

ELt x u tar e b r ni l c a n
不溶解于橡胶中

IuP ne le sl o on r l i y b m

Dt i r 分散 s p e s a n
[ 13.09.2013 ] Steger - Silica Tread I

Ln ut b 润滑 r i c a
[ Folie: 17 ]

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

Polymer
soluble additive 与橡胶相容 intramolecular Lubricant 分子内润滑 surface coating of fillers; leads to polymer swelling 填料表面涂层导致 橡胶溶胀

Dispersant
分散

Polymer
insoluble additive
与橡胶不相容 extramolecular Lubricant 分子外润滑 migration to the polymer surface under stress 应力作用下迁移到 橡胶表面
Steger - Silica Tread I

Lubricant 润滑

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[ Folie: 18 ]

Processing Promoter Lubricant Effects 加工助剂的润滑作用

Effects at critical shear stress without processing promoter 不含加工助剂时临界剪切应力影响

Effects at critical shear stress with active processing promoters 含加工助剂时临界剪切应力影响

Mixture
Vg

p > pcrit
Vg

Mixture
Vg
high processing prom. Concentration加工助剂浓度高

Filmslippage膜滑动 wall wall wall

Wall-Slip
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Wall-Stick
Steger - Silica Tread I

Film-Slippage
[ Folie: 19 ]

Change of polymer conformation with shear stress 随剪切橡胶聚集体结构的变化

Capillary Wall毛细管壁

statistical polymer coil in the core of the flow as area of low shear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

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[ Folie: 20 ]

Analytical determination of surface concentration
表面浓度的检测分析

Surface analysis via FTIR-Spectroscopy:
Sample

Calibration of the EPDM-ZincSoap mixture :
Extinction 1,2

1

Reference peak: 1376/cm

Characteristical pattern of the zinc soap : 1532 [1/cm]

0,8

Processing Promoter

0,6

0,4

Regression coeff. = 0,99927

2

6 8 4 Concentration Zn-soap [phr]

10

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[ Folie: 21 ]

Processing 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 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 Promoetrs 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
[ 13.09.2013 ] Steger - Silica Tread I [ Folie: 22 ]

Processing Promoter for Silica Tread Compounds 用于白炭黑胎面胶的加工助剂

Aktiplast GT Aktiplast? ST Aflux GE1837

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[ Folie: 23 ]

Tread: Aktiplast GT in Carbon Black / E-SBR 莱茵塑分GT用于E-SBR/炭黑胎面
SBR 1712 BR-Buna CB 10 N-220 Aromatic Oil Aktiplast GT Stearic acid 6PPD TMQ 110 20 80 10 3 1 1 1 Processing Promoter : Aktiplast GT (Zn-soap / mainly saturated)
Control without Processing Promoter 100

Mixing (Mooney, HPCR)
ML 1+4/100°C HPCR 100°C/11s-1 85 85

Extrusion (Torsiograph)
Extrusion rate g/min Extrusion volume cm/min 104 117

Curing (Rheovulcameter)
Injection volume mm3 Injection speed mm3/sec 160 115

Wax/Antilux 654
Zn0 Sulfur TBBS/Vukacit NZ

2
3 2,2 0,9

Literature ITEC 1998 Akron/OH

Rhein Chemie Technical Report 63
[ 13.09.2013 ] Steger - Silica Tread I [ Folie: 24 ]

Tread: 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-S25 96

Processing Promoter : Aktiplast ST (mixture of Zn-soap, fatty-ester, filler) Control without Processing Promoter 100 Mixing (Mooney, HPCR)
ML 1+4/100°C 83

Nd-BR-Buna CB 24
Silica-Ultrasil 7000 Carbon Black N-110 X-50 S (50% Si-69)

30
70 10 12,5 5 3 1 20 1

Aktiplast ST
ZnO Stearic acid Aromatic Oil TMQ

HPCR 100°C/11s-1

85

Extrusion (Torsiograph)
Extrusion rate g/min Extrusion volume cm/min 116 117

6PPD
Antilux 654 CBS DPG Sulphur

1,5
1,5 1,5 2 1,5

Curing (Rheovulcameter)
Injection volume mm3 Injection speed mm3/sec 200 155

Literature ITEC 1996 Akron/OH Rhein Chemie Technical Report 60

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Influence of Aktiplast ST Flow properties莱茵塑分ST对流动性的影响

60
50 40

80

ML1+4100℃

0 phr 1 phr 2 phr 3 phr 4 phr 5 phr

70 60 50 40 30

Extrusion: Torque (Nm)

0 phr 1 phr 2 phr 3 phr 4 phr 5 phr

30
20

20 10 10 0 25.000

0
2.500

Rheovulc. volume
2.000 1.500

0 phr 1 phr 2 phr 3 phr 4 phr 5 phr

20.000

HKR (90°C,11/s) Viscosity (Pas)

0 phr 1 phr 2 phr 3 phr 4 phr 5 phr

15.000

1.000

10.000

500

5.000

0

0

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Formulation GEL 30437配方试验

NR; SMR-10 S-SBR, Buna VSL 5025-0 BR; Buna CB 25 HD-silica, Ultrasil 7000 Silane; Si-69 TDAE-Oil Carbon black; N 339 ZnO 6PPD Wax; Antilux 654

30 30 40 100 7,5 40 10 2,5 2 2

Stearic acid

1
0 0 0 2
Steger - Silica Tread I 2 [ Folie: 27 ]

Aflux GE 1837
Aktiplast GT Aktiplast ST S
[ 13.09.2013 ]

5 0 0

0 5 0

0 0 5

CBS

GEL 30437 MDR 160°C硫化仪特性
MDR 160° C

30

25

20

S' (dNm)

Control 15 Aflux GE 1837 Aktiplast GT Aktiplast ST 10

5

0 0.00

5.00

10.00

15.00

20.00

25.00

30.00

35.00

Zeit (m in)

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Viscosity ; Mooney-Scorch门尼焦烧

GEL 30437 Mooney ML1+4/100°C

Control 99

Aflux GE 1837
56

Aktiplast GT Aktiplast ST 63 75

Rheovulcameter; IM-volume (mm3)
Rheovulcameter; IM-speed (g/mm3) Mooney-scorch; t-5 (min) Mooney-scorch; t-35 (min)
[ 13.09.2013 ]

493
16 8:37 13:75

1705
49 17:92 24:37

1370
42 21:68 30:45

1005
30 16:53 24:30

Steger - Silica Tread I

[ Folie: 29 ]

Physicals物性

GEL 30437 Modulus 100 (MPa) Modulus 300 (MPa) Tensile Strength (MPa)

Control 3.72 12.0 16.7

Aktiplast Aflux GE 1837 GT 3.76 12.1 17.1 3.14 10.2 17.1

Aktiplast ST 3.33 10.9 16.4

Elongation at break (%)
Hardness (Shore A) Tear Strength (N/mm) Rebound (%)
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395
80 69.2 33

422
79 66.4 33
Steger - Silica Tread I

479
79 47.0 35

426
80 53.0 35
[ Folie: 30 ]

RPA2000– GEL 30437 RPA2000研究Payne效应
RPA Strain Sw eep @ 100° 0,5Hz C

4000

3500

3000

Aktiplast ST
G' (kPa)

2500

2000

Control
1500

Aktiplast GT

Aflux GE 1837

1000

Aflux GE 1837 Anti-sticky effect

500

0 0.1
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1

10 strain (%) Steger - Silica Tread I

100

1000
[ Folie: 31 ]

Advantages 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 extrusion and calandering降低挤出压延能耗

Optimized compound processing without negative effect on product performance
[ 13.09.2013 ] Steger - Silica Tread I [ Folie: 32 ]

Reaction Mechanism for Silica/Silane Technology 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

Inorganic
Fiberglass Fillers Metals Silica

Organic

Si

Rubber Polymers Plastics

Rubber

Si

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6.2 Silane/Silica Coupling Reaction – Dependent on Temperature and Time

C2H5O C2H5O C2H5O Si-(CH )3-S-S-S-S-(CH )3-Si
2 2

OC2H5
OC2H5 OC2H5

TESPT: Si-69
OH OH -O-Si-O-Si-OOH OH

SILICA

-O-Si-O-Si-O-

硅烷偶联剂/白炭黑偶联反应-依赖于温度和时间
[ 13.09.2013 ] Steger - Silica Tread I [ Folie: 35 ]

6.3 Silanization Reaction Mechanism 硅烷化反应机理
EtO Si OEt OEt

Si O Si O Si O Si O Si O Si

OH

Sx

OH EtO Si OH OH OH OH
OEt

OEt

Silica

EtO Si

OEt OEt

Silica

Sx

Si O Si O Si O Si O Si O Si

O OH

OEt Si OEt OEt

Sx

OEt Si OEt OEt

O O

Si O Si

Sx OEt Si OEt OEt

O O Si OEt O

Sx

EtO

Si OEt OEt

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6.5 Silane/Silica Diene Rubber Matrix Reaction – Caused by Temperature > 155 ℃
硅烷偶联剂/白炭黑、橡胶相反应-温度155℃

Si-(CH2)3-S-S- (S)n-

( CC

C C C C

C C C C POLYMER C

C C C C

C

)n

C2H5O

C2H5O

Si-(CH2)3-S-S- (S)nO

OH

O

C2H5O

-O-Si-O-Si-O[ 13.09.2013 ]

SILICA
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-O-Si-O-Si-O[ Folie: 37 ]

C2H5O
OH

6.6 Sulfidosilane Reaction in Vulcanization 硫化过程中的偶联机理
EtO OEt Si OEt OEt Si OEt OH OEt O O Si O Si Sx Sx
Si O Si O Si O Si O Si O Si O OH OEt O O Si O Si S Sx OEt Si OEt S

s s s s

Silica

Si O Si O Si O Si O Si O Si

O

Sx

Silica

Rubber
s s s

O O Si OEt O EtO Si EtO OEt

O O Si OEt O

The silane can react in the Sulfur vulcanization
Steger - Silica Tread I [ Folie: 38 ]

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6.7 Interpenetrating Network Theory 形成的互穿网络结构

Diffuse Chemically Bonded Interface Interphase

Si--O--Si--

Si--O--Si-Silica

Si--O--Si-Si--O--Si-Coupling agent
[ 13.09.2013 ] Steger - Silica Tread I

Rubber
[ Folie: 39 ]

6.8 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

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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 2. Temperature control is important—Don’t 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 speed Si-75混炼温度不得超过170 ℃

★ Slightly more coverage for the same weight of silane ★ Higher processing temperatures are possible, typically up to 170
℃, so silanization reaction reaches more completion sooner ★ It is possible to improve mixing times by 25 to 50%
[ 13.09.2013 ] Steger - Silica Tread I [ Folie: 41 ]

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

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Steger - Silica Tread I

[ Folie: 42 ]

3. Silane + SASD improve blend & filler dispersion双组分新型硅烷改善混炼和填料分散
rubber matrix dispersed rubber phase dispersed silica phase

Silane + SASD

No diffusion control of curing chemicals causes bad physical properties 不分散的硫化体系中的化学品, 引起物性较差
[ 13.09.2013 ] Steger - Silica Tread I

Diffusion control of SASD achieves good physicals. Solubility is key factor SASD 控制分散,获得较好物性,可溶性 是关键因素

[ Folie: 43 ]

Test of silanisation grade 硅烷化反应程度的测定
Mooney viscosity 门尼粘度

Dynamics动态性能
G? little amplitude小振幅弹性模量 G? big amplitude 大振幅弹性模量

“Payne”-effect Payne 效应
Silica-dispersion 白炭黑分散

Silanisation grade high =
硅烷化反应程度越高 =

Mooney and G? low.
门尼粘度和弹性模量越低

[ 13.09.2013 ]

Steger - Silica Tread I

[ Folie: 44 ]

Mixing of silica compounds
白炭黑胶料的混炼 Description of the dispersion process during mixing 混炼期间的白炭黑分散 Description of the silanisation process 硅烷化反应过程 Establishment of any interaction between dispersion and silanisation 白炭黑分散和硅烷化反应之间的相互作用 Determining the most important process parameters 测定最重要的加工参数

[ 13.09.2013 ]

Steger - Silica Tread I

[ Folie: 45 ]

Mixing of silica compounds
白炭黑胶料的混炼

degree of dispersion is achieved in an early mixing stage 在前段混炼中已经获得优良的分散度
degree of dispersion determinates final degree of silanisation 分散度确定了最终的硅烷化反应程度 Longer mixing times yield higher degree of silanisation 较长的混炼时间可获得较高的硅烷化反应程度 Higher mixing temperatures yield higher degree of silanisation 较高的混炼温度可获得较高的硅烷化反应程度 However at T > 150℃ scorch is visible 但是,温度高于150℃时容易焦烧 Silane just slightly acts as a dispergator 硅烷偶联剂起到轻微的分散作用
[ 13.09.2013 ] Steger - Silica Tread I [ Folie: 46 ]

Dithiophosphates Applications in Silica Tire
二硫代磷酸盐应用于白炭黑轮胎

Dr.Lothar Steger /范汝良

Rhein Chemie Rheinau GmbH
莱茵化学(青岛)有限公司


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