THE AUTOXIDATION OF POLY(PROPYLENE OXIDE)S

被引:23
作者
GRIFFITHS, PJF [1 ]
HUGHES, JG [1 ]
PARK, GS [1 ]
机构
[1] UNIV WALES COLL CARDIFF,COLL CARDIFF,SCH CHEM & APPL CHEM,POB 912,CARDIFF CF1 3TB,WALES
关键词
Degradation - Oxidation - Reaction kinetics - Thermodynamic properties;
D O I
10.1016/0014-3057(93)90116-W
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
The autoxidation of poly(propylene oxide)s of molecular weights 398, 1020 and 2030 at 95, 110, 125 and 140-degrees follows the same kinetic path independent of the molecular weight of the polymer indicating random hydroperoxidation along the polymer chain. When the -OH end-groups are replaced by -O-CO-NH-C2H5 groups the kinetic path is unchanged confirming random hydroperoxidation and showing similarity of polymer breakdown in simple polyether and in the derived urethane elastomers. The volatile oxidation products produced account for only approximately 2 % of the absorbed oxygen, the major part of the rest leads to water (45%) and to carbonyl groups in the structures at the ends of newly formed chains produced by scission of the polymer molecules. Vapour phase osmometry indicates at least 0.48 chain scissions for each oxygen molecule absorbed. A reaction scheme based on three routes for hydroperoxide decay is presented to rationalize the findings.
引用
收藏
页码:437 / 442
页数:6
相关论文
共 6 条
  • [1] Boehmer JW, 1936, RECL TRAV CHIM PAY-B, V55, P379
  • [2] GRASSIE N, 1956, CHEM HIGH POLYM DEGR, P226
  • [3] OXYGEN INHIBITION IN POLYPROPYLENE GLYCOL AUTOXIDATION
    GRIFFITHS, PJ
    HUGHES, JG
    PARK, GS
    [J]. JOURNAL OF POLYMER SCIENCE PART C-POLYMER LETTERS, 1973, 11 (03) : 157 - 160
  • [4] GRIFFITHS PJF, 1977, MAKROMOL CHEM, V178, P465
  • [5] GROSBORNE P, 1968, REV INST FR PET ANN, V23, P508
  • [6] RYSZARD J, 1988, WIADOMOS CHEM, V42, P687