New Development of Polymer Additives

Transcription

1 New Development of Polymer Additives Sumitomo Chemical Co., Ltd. Fine Chemicals Research Laboratory Toshiya TAKAHASHI Ryoji SMA Kenji KIMURA Naoki INUI In response to specific customer needs, we have developed SUMILIZER, SUMILIZER, SUMILIZER GM, SUMILIZER GA-8 polymer additives (stabilizing agents) as unique products which have properties hitherto unseen. We have utilized these new properties to apply these unique products in a wide range of applications. This paper describes the mechanism of polyolefin stabilizing agents, and also trends in customer needs as a result of changes in the market environment, and presents the responses our company has made in the field of additives due to these factors. We will also introduce some of the steps we have been taking toward development of our new G series. Table 1 ur original development product Product Chemical Structure Main Application SUMILIZER SUMILIZER SUMILIZER GM SUMILIZER GA-8 GM GA-8 G SUMILIZER P H LLDPE, HDPE, LDPE, PP Table 1 SUMILIZER H SBS, ABS, PS, PP, HDPE SUMILIZER H SBS, SBR, GM ABS, BR G SUMILIZER GA-8 H C HDPE, PP, PU Ar-H Scheme 1 RH R 9-

2 RH RH (phenol) Ar-H R R RH R + H RH RH RH (R )3P (phosphite) Scheme 1 Auto-oxidation mechanism of polyolefins R R R RH R RH RH R RHH R RH 1) Ar-H R H RH Ar- R RHRH RH G Scheme GA-8Ar-HScheme a) R H RH R Scheme b) RHRH RH GM/Ar-H R 1 a) GA-8 H C R + RH C b) P H RH P H + RH Scheme Basic stabilizing mechanism of GA-8, 9-

3 VC 3 G G LLDPE Fig. 1 LLDPE RH 3 Fig. Fig. 1 P P-1 P 3 C4H614P 661 CAS No H Chemical structure of SUMILIZER P- P P Fig. Chemical structure of phosphite R RH RH ) LLDPE PP A-1 P-1 Fig MFRFig. 4, 5 PP 9-

4 A-1 P-1 Fig. 3 P H H C 4 P 3 Stabilizers used in this study A-1/P- 1 8 A-1/P-1MFR A-1/P-1 MFRYI PP Nx Fig. 6 MFR (g/1min.) Fig. 4 1st pass 3rd pass 5th pass (.1) Resin :Homo PP Temp. :5 C A-1/P-1 (.5/.5) A-1 (.1) P-1 (.1) (phr) Processing stabilization of when used alone YI Resin : Homo PP 5 Loading level Extrusion : 7 C, 5 times MFR : 3 C 4.5 Nx : 65ppm, 3 weeks Fig. 6 A-1/P-1 Loading level MFR (after 5th pass) Trade-off problem between MFR and YI MFR (g/1min.) Fig. 5 1st pass 3rd pass 5th pass Resin :Homo PP Temp. :8 C (.75) (.1) A-1/P-1 A-1/P-1 A-1/P-1 (.5/.1) (.75/.75) (.1/.5) (phr) Processing stabilization of in a low loading level A-1 P-18 MFR5MFR Fig. 6A-1/ P-1YI BHT BHT Nx 3) YI Nx Nx Scheme 3 9-

5 P H [] P (1) Colorless Product H P (1) N H N N H HN P P () H Colorless Product P N H N P N N H P N N (3) H Colorless Product Scheme 3 Estimated reaction mechanism of with Nx 4 P-1 Fig. 7 P-1 P-1 P-1 5) IT A-1, P-1, PP ITFig. 8 mw ( C) 4 Blank PP 15 Mol Ratio P Fig. 7 H + (R)3P xylene, rt xidized Reaction Time (h) H + (R)3P= HPLC analysis xidized P-1 Decomposition aspect of hydroperoxide with phosphite A-1 (.3 phr) 1 P-1 (.3 phr) (.3 phr) Time (min.) Fig. 8 xidation induction time (IT) by DSC P-1 A-1 9-

6 A-1 A-1 3 Fig. 9 P-1 Gelation time (min.) Detected (mmol) Fig Fig. 1 xidized xidized P-1 /P-1 (.757/.773) (1.513) (mmol/kg) Resin :Homo PP P-1 (1.546) Detected amount of oxidized antioxidants after extruded 3 times at 5 C (.1) A/B (.5/.5) (phr) P H Gelation time of phenolic and phosphonic moiety A B H Kneader Resin : LLDPE 4 C, 1 rpm Under N P Me H Fig. 1 R H RH RH RH R R HRH RH R PE Fig. 6 Fig min PE 9-

7 3 C, 4min, under Air Fig. 11 Blank (.3) A-1/P-1 (.1/.) Heat stabilization effect of LLDPE (1) Zn-St (.1) RH R R R GM Scheme 4 Scheme 1 R R R RH R G 3 Fig. 1 R RH R R R (Step 1) H R R H R (Step ) H Scheme 4 Basic stabilizing mechanism of, GM 9-

8 Stabilizer toluene Acid or Alkali water g 15g 1g dissolving stirring 6deg.C for 3min. Retention (%) of purity after treatment Stabilizer A-1 Fig. 1 CH3CH concentrating Treated Stabilizer CH3CLi Hydrolytic Stability of To 8deg.C at 7Pa for 1hr analysis (6deg.C for 3min.) LiH PS Fig. 13 PS 3 3 A-.phr A- Styrene Monomer (%) H (.1phr) A- C18H37 A- (.phr) (.phr) A- (.3phr) SBS GM/R PET Scheme 4 SBS Table SBS Table X 3 Table Build-up time of X Stabilizer (mmol/kg) Fig. 13 Effect to reduce Styrene Monomer SBS (1phr) additive (.5phr) X 5 C Build-up time (min.)

9 LLDPEPP HDPE G 1) J. Pospisil and P. P. Klemchuk, xidation Inhibition in rganic Materials Vol.1, CRC Press Inc., (199), P1-9. ),, (1). 3) K. C. Smeltz, Textile Chem. Color., 15 (4), 5 (1983). 4) R. Soma, and K. Kimura, International Polyolefins Conference (9). 5),,, (6). PRFILE Toshiya TAKAHASHI Kenji KIMURA Ryoji SMA Naoki INUI 9-