Development of the Solution SBRs for High-performance Tires. Sumitomo Chemical Co., Ltd. Petrochemicals Research Laboratory Katsunari INAGAKI Mayumi H

Size: px

Start display at page:

Download "Development of the Solution SBRs for High-performance Tires. Sumitomo Chemical Co., Ltd. Petrochemicals Research Laboratory Katsunari INAGAKI Mayumi H"

まれあさかいざわ
4 years ago
Views:

1 Development of the Solution SBRs for High-performance Tires. Sumitomo hemical o., Ltd. Petrochemicals Research Laboratory Katsunari IAGAKI Mayumi HAYASHI Advanced Polymers Division Akio IMAI In the latest decade, synthetic rubbers and fillers for automotive tires have been changed drastically. The tendency to make much of energy saving (fuel economy) has come to be more remarkable year by year. In order to satisfy this demand, new silica compound systems have been developed in stead of the conventional B (carbon black) systems for tire tread. In addition, for the purpose of improving the performances of this silica compound systems, precise polymer designs such as the functionalization are needed. ving anionic polymerization procedure is a very useful method to meet this aim. or example, precise chain-end functionalization and multi-functionalization can be achieved. In this article, the trend in the field of the silica compound system and the polymer design of solution SBRs are surveyed, including the authors study on the new multi-functionalization method

2 requency ig. 2 (Brake) WG Wet Grip Tread Hz Road (Energy Saving) Rolling Resistance Whole Tire Hz Wet Grip and Rolling Resistance. E-SBR Polymer design Degree of freedom: large ( cat.) Process conversion S-SBR Micro structure ving polymer modification omposition or general use or all season tire or energy saving tire or high performance tire (or race) Low temperature properties Resilience Skid resistance omposition distribution: narrow Random copolymer Molecular weight distribution composition change Modification Block composition ontinuous method ondition change Operation change Modification process Operation change Molecular weight distribution or HIPS Gross Molecular weight Micro structure ondition change Operation change or damping parts Damping properties Block composition Modification Operation change Modification process ig. 1 Expansion of the degree of freedom about the S-SBR designs

3 Max µ ig RRI Silica compounded arbon Black compounded 130 Max µ (maximum friction coefficient) and RRI (Rolling Resistance Index) on wet asphalt surface

4 SiOH O SiOH Mixing (high temp.) ig. 4 Table 1 2H5O 2H5OSi-3H6-SX-3H6-Si O2H5 2H5O 2H5OH React with modified chain-end? O2H5 O2H5 H5O Si O Si-3H6-Sx- O H5O Si OH SBR double bond SBR hemical reactions between silica and silane-coupling agent. Example unctionalized chain-end omparative Example omposition (A) Kind* 1 A1 A1 A1 A1 Amount (wt) Silica Amount (wt) Silane coupling agent Amount (wt) (D) Kind* 2 D1 - D1 - Amount (wt) Maximum Temperature During Kneading ( ) Evaluation Tear Strength kgf/cm % Modulus kgf/cm Loss on Wearing mg/1000 cycle Tan (60 ) Index Vulcanization Velocity t90 min Table 2 Example omposition (A) Kind* 1 A2 A2 A2 A2 Amount (wt) Silica Amount (wt) Silane coupling agent Amount (wt) (D) Kind* 2 D1 D1 D1 D1 Amount (wt) Maximum Temperature During Kneading ( ) Evaluation Tear Strength kgf/cm % Modulus kgf/cm Loss on Wearing mg/1000 cycle Tan (60 ) Index Vulcanization Velocity t90 min X 1 X 5 A-H2jj SiO SiO SiO kh2k-b ( I ) X 2 X 3 X 4 X 6 l m *1 (A1): a solution polymerized SBR (styrene unit/vinyl unit: 15/45 (wt %/%) ML = 87) manufactured by adding Sil4 as a coupling agent A2: a solution polymerized SBR (styrene unit/vinyl unit: 29/49 (wt %/%) ML = 91) manufactured by adding Sil4 as a coupling agent *2: D1: A compound (molecular weight: 611) of formula ( I ) as defined above, wherein A and B are hydroxyl groups, j, k and m are 0, 1 is 7 and x1, x2, x5 and x6 are methyl groups

5 omparative example 1-3 (carbon black is formulated) ----omparative example 4-6 (silica is formulated) ----Example 1-3 (silica surface- carbon black 1+silane coupling agent) ----Example 4-6 (silica surface- carbon black 2+silane coupling agent) ----Example 7-8 (silica surface- carbon black 1) ----Example 7-8 (silica surface- carbon black 2) ig. 5 Temperature Dependency of Tan Table 3 Type of carbon used itrogen specific surface area of carbon used (m 2 /g) DBP oil adsorption of carbon used (ml/100 g) Silica content (wt %) B1 B2 B3 B4 B5 B6 B7 339(HA) 110(SA) 550(E) Table 4 Kinds of Aluminum Hydroxide Loosed bulk density; g/cm 3 Physical properties DOP oil absorption; cm 3 /100 g BET specific surface area; m 2 g rystal structure rystal size of boehmite (020) plane; nm Example Aaluminum hydroxide A boehmite 12.9 Example Baluminum hydroxide B boehmite 7.3 omparativealuminum hydroxide example boehmite 2.4 omparativealuminum hydroxide D example Dbayerite boehmite 3.0 omparativealuminum hydroxide E example E gibbsite

6 Table 5 Examples omparative examples (Parts by weight) Ingredients SBR. 9520(pure polymer) 1) BR 150B 2) arbon black 220 3) Aluminum hydroxide A Aluminum hydroxide B 40 Aluminum hydroxide 40 Aluminum hydroxide D 40 Aluminum hydroxide E 40 Silica V3 4) 40 TESPT 5) Aromatic oil (incl. oil extended polymer) Antioxidant WAX Stearic acid Zinc oxide Sulfur Vulcanization accelerator Evaluation Mooney viscosity Abrasion resistance Rolling resistance Wet grip performance (ABS brakeage) ) SBR : styrene content : 35% by weight, 37.5 PHR oil extended rubber, glass transition temperature (Tg): ) BR : polybutadiene rubber BR150B 3) carbon black : Diablack I (220), BET specific surface area by nitrogen adsorption : 115m 2 /g 4) silica : V3 5) silane coupling agent TESPT : Si

7 Table 6 SBR 1500 : styrene-butadiene rubber with 23.5% of styrene content ; acrylonitrile-butadiene rubber with 35% acrylonitrile content; Z175 : silica; Si69: silane coupling agent, bis-(3-(triethoxisilyl)propyl)tetrasulfide (TESPT); 330 : carbon black ; HDDP : - phenyl-'-(1,3-dimethylbutyl)-p-phenylenediamine ; DPG : diphenylguanidine ; TBBS : -tert-butyl-2-benzothiazolesulfenamide. Table 7 ompound o. Ingredients S1 S2 S3 S R 5 R 1 R 2 H H-R 3 O H H-R 4 O n ig. 6 Polymer modification agent

8 sec- Bu + ig. 7 Various Multi-unctional Polymers : unctional Group sec- Bu-H2 sec- Bu-H2 + o Reaction + sec- Bu + sec- Bu-H2 + sec- Bu-H2 Scheme 1 Reactions of Anionic Species with DPE Derivatives Scheme 2 Synthesis of End-Modified Polymers by Using DPE Derivatives 2004-

9 polymerization sec- Bu + sec- Bu-H2 sec- Bu-H2 2 2 (1) (1) 2 2 sec- Bu-H2 sec- Bu-H polymerization (1) sec- Bu-H2 2 sec- Bu-H2 H : unctional Group Scheme 3 Synthesis of Multi-unctionalized Polymers sec- Bu sec- Bu-H St / Bd sec- Bu-H (1) St / Bd sec- Bu-H h 0.5h (1) (1) sec- Bu-H OH sec- Bu-H2 H (1) Scheme 4 One-Step thod for Synthesis of Multi-unctional Polymers 2004-

10 (A) Standard SBR (B) ew unctionalized SBR ig. 8 Silica Dispersion by TEM (X 200,000) 2004-

11 PROILE 2004-

第117号(A4、E)4C/3 湯浅ほか

第117号(A4、E)4C/3 湯浅ほか Improved Silica Dispersibility with Functionalized S-SBR for Lower Rolling Resistance Takeshi Yuasa Takuo Sone Tetsuo Tominaga Munetaka Iwano Generally, rolling resistance of tire is closely related to