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Patent US5086123 - Fluoroelastomer compositions containing fluoroaliphatic sulfonamides as ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsVulcanizable fluorocarbon elastomer compositions containing a vinylidene fluoride copolymer and a fluoroaliphatic sulfonamide curing agent. A second curing agent selected from organic polyhydroxy compounds or derivatives thereof, and an organo-onium accelerator are also employed. The compositions of...http://www.google.com/patents/US5086123?utm_source=gb-gplus-sharePatent US5086123 - Fluoroelastomer compositions containing fluoroaliphatic sulfonamides as curing agentsAdvanced Patent SearchPublication numberUS5086123 APublication typeGrantApplication numberUS 07/619,669Publication dateFeb 4, 1992Filing dateNov 28, 1990Priority dateFeb 27, 1984Fee statusPaidPublication number07619669, 619669, US 5086123 A, US 5086123A, US-A-5086123, US5086123 A, US5086123AInventorsRichard A. Guenthner, Robert E. KolbOriginal AssigneeMinnesota Mining And Manufacturing CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (21), Referenced by (82), Classifications (5), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetFluoroelastomer compositions containing fluoroaliphatic sulfonamides as curing agents
US 5086123 AAbstract
1. A composition comprising at least one fluorocarbon elastomer gum, at least one polyhydroxy compound or derivative thereof as a curing agent therefor, at least one fluoroaliphatic sulfonamide as a curing agent for the fluorocarbon elastomer gum, and at least one organo-onium accelerator, the amount of said fluoroaliphatic sulfonamide curing agent being present in said composition in the range of about 0.002 to about 0.006 mole per hundred grams of said gum, the amounts of said curing agents being sufficient to bring about cross-linking of said fluorocarbon elastomer gum, said fluoroaliphatic sulfonamide curing agent being represented by the general formula: Rf (A)z SO2 NR(M1/x) or Rf '((A)z SO2 NR(M1/x))2 wherein Rf represents a monovalent fluoroaliphatic radical having from 1 to 20 carbon atoms, Rf ' represents a divalent fluoroaliphatic radical having from 1 to 20 carbon atoms; A represents an organic linkage selected from the group consisting of --CR1 R2, --CR1 R2 CR3 R4 --, and --CR1 ═CR2 --, wherein R1, R2, R3, and R4 are selected from the group consisting of hydrogen atom, fluorine atom, chlorine atom, and lower alkyl group, Z is zero or one, R represents hydrogen atom or alkyl radical having from 1 to 20 carbon atoms, and M represents hydrogen atom or salt forming cation with valence x, which is 1, 2, or 3. 2. The composition of claim 1, wherein Rf represents a monovalent fluoroaliphatic radical having from 4 to 10 carbon atoms.
8. A composition comprising:(a) at least one fluorocarbon elastomer gum, (b) at least one fluoroaliphatic sulfonamide as a curing agent therefor selected from the group consisting of C8 F17 SO2 NR(M1/x), C8 F17 C2 H4 SO2 N(R)(M1/x), C4 F9 SO2 NR(M1/x), where R represents hydrogen atom or alkyl radical having from 1 to 20 carbon atoms, M represents hydrogen atom or salt forming cation with valence x, which is 1, 2, or 3, said sulfonamide being present in the composition in the range of about 0.0002 to about 0.006 mole per hundred grams of said gum, (c) at least one organo-onium accelerator, and (d) at least one polyhydroxy compound or derivative thereof as a curing agent for the fluorocarbon elastomer gum, the amount of said curing agents being sufficient to bring about cross-linking of the fluorocarbon elastomer gum. 9. The composition of claim 8, wherein the fluorocarbon elastomer gum is a polymer of vinylidene fluoride and hexafluoropropene.
Rf (A)z SO2 NR(M1/2)                   I
Rf '[(A)SO2 NR(M1/x)]2                 II
Rf SO.sub. NHR+NaOCH3 &#8594;Rf SO2 N(R)Na
C8 F17 SO2 N(CH3)Mg1/2 C8 F17 SO2 N(CH3)NH4 C8 F17 SO2 N(CH3)N(C2 H5)3 H
Assignee's U.S. Pat. No. 3,632,788 discloses a composition comprising a copolymer of perfluoropropene and vinylidene fluoride or a terpolymer of perfluoropropene, vinylidene fluoride and tetrafluoroethylene and containing highly fluorinated fluid plasticizer in excess of the ordinary compatibility limit therein but in amounts less than about 280 parts by weight for each 100 parts of the elastomer, at least one compatibility extender comprising a low molecular weight, polar, fluoroaliphatic compound containing at least one polar group and containing at least 45% by weight of fluorine in the form of at least one fluoroaliphatic radical, said fluoroaliphatic compound having a melting point in the range of 50� C to 200� C, said compatibility extender content being from about 0.5 to about 2 parts by weight per each part by weight of said plasticizer excess.
ASTM D-2048-82 was run on uncured compounded gumstock using the Oscillating Disc Rheometer (ODR) Model 100S (Monsanto Company), an oscillating frequency of 100 cpm and a 3� arc. Minimum torque (ML) and the torque attained at a stated time (MH) were determined. Also determined were time in minutes for torque to increase 0.1 N�m(1 lbf�in), tsl, or time for torque to reach 5.6 N�m (50 lbf�in), t5.6, respectively.
Elastomer sheets 150 mm�150 mm�1.8 mm were prepared for determination of physical properties by pressing uncured compounded gumstock at about 6.9�103 kPa for the indicated time at 177� C.
Post cured samples were placed in a circulating air oven for the indicated time at 275� C. The samples were then removed for measurement of physical properties according to ASTM D-573-81.
TABLE I______________________________________Curing agentsNo.  Designation Chemical identity______________________________________1    Bisphenol AF            4,4'-HOC6 H4 C(CF3)2 C6 H4            OH2    Bisphenol S 4,4'-HOC6 H4 SO2 C6 H4 OH3    Biphenol C  4,4'-HOC6 H4 COC6 H4 OH4    HQ          1,4-HOC6 H4 OH5    Biphenol    4,4'-HOC6 H4 --C6 H4 OH6    Bisphenol   a. HOC6 H4 C(CH3)2 C6 H4            OHA-AE (mixture            b. HOC6 H4 C(CH3)2 C6 H4            OCH2 CH=CH2of components            c. CH2 =CHCH2 OC6 H4 C(CH3).sub.            2 --a:b:c in 1.1:1.6:1            .sup.  C6 H4 OCH2 CH=CH2weight ratio)7    FC-diol     HOCH2 (CF2)4 CH2 OH______________________________________
TABLE II______________________________________Cure acceleratorsNo.    Designation   Chemical identity______________________________________1      TPBPC         (C6 H5)3 P(CH2 C6 H5).s                up.+ Cl-2      TBBAC         (C4 H9)3 N(CH2 C6 H5).s                up.+ Cl-3      TTSC          [(CH3)C6 H4 ]3 S+ Cl-______________________________________
TABLE III______________________________________                 Run no.                1       2______________________________________Curable gumstock ingredientsFKM C, high viscosity gum, part                  100       100Carbon black (N-110), phr                  25        25Ca(OH)2, phr      6         6TPBPC, mhr � 103                  1.4       0.77Bisphenol AF, mhr � 103                  0.625     0.625C8 F17 SO2 N(CH3)Na, mhr � 103                  0         2.81Curing characteristicsODR, 177� C.:ML, N.m           4.86      5.20MH, N.m, 12 minutes                  5.54      5.99tsl, minutes      3         2.1t5.6, minutes     8         5.0Properties of cured gumstockPress cure properties (2.5 hrs/177� C.)Tensile strength, MPa  7.51      20.04Elongation at break, % 718       550Modulus, 300%, MPa     4.79      9.51Post cure properties (20 hrs/177� C.)Tensile strength, MPa  10.42     21.63Elongation at break, % 550       411Modulus, 300%, MPa     7.31      15.24Hardness, Shore A      78        76Tear resistance, kN/m  26        28(ASTM D 624-81, Die C, 25� C.)______________________________________
TABLE IV______________________________________Curable gumstock ingredients______________________________________FKM C, parts         100Carbon black (N-990), phr                30MgO, phr             3Ca(OH)2, phr    6TPBPC, mhr � 103                1.22Bisphenol AF, mhr � 103                2.23Fluoroaliphatic sulfonamide                1.22curing agent, mhr � 103______________________________________
______________________________________Run no.      Curing agent______________________________________3            Control4            C8 F17 SO2 N(CH3)Na5            C4 F9 SO2 N(CH3)Na6            C8 F17 SO2 N(C4 H9)Na7            H(CH3)NSO2 (CF2)8 SO2 N(CH3)Na8            C8 F17 C2 H4 SO2 N(CH3)Na9            C8 F17 SO2 N(H)Na10           C8 F17 SO2 N(CH3)(Mg)1/211           C8 F17 SO2 N(CH3)NH412           C8 F17 SO2 N(CH3)N(C2 H5)3         H______________________________________
TABLE V__________________________________________________________________________              Run no.              3   4    5   6    7   8    9   10   11  12__________________________________________________________________________Curing CharacteristicsODR, 177� C.:ML, N.m       1.92                  1.92 2.03                           2.03 1.69                                    1.92 1.36                                             1.92 1.81                                                      1.69MH, N.m (12 minutes)              3.62                  6.33 6.21                           5.65 7.91                                    4.75 3.95                                             6.33 6.55                                                      5.88tsl, minutes  2.0 1.3  1.3 1.5  2.0 1.8  3.1 1.8  1.7 1.7t5.6, minutes --  2.6  2.6 7.0  3.4 --   --  3.6  3.2 3.4Properties of cured gumstockPress cure properties (10 min./177� C.):Tensile strength, MPa              7.37                  9.29 9.60                           9.53 9.86                                    9.02 8.71                                             9.79 9.12                                                      9.94Elongation at break, %              730 427  409 456  374 536  646 464  376 446Modulus, 100%, MPa 1.91                  2.46 2.45                           2.34 3.23                                    2.16 1.92                                             2.36 2.52                                                      2.26Hardness, Shore A  66  67   67  67   68  67   66  67   66  66Postcure properties (20 hrs./260� C.):Tensile strength, MPa              8.15                  12.66                       13.29                           12.07                                12.51                                    10.92                                         11.80                                             13.47                                                  10.62                                                      12.18Elongation at break, %              517 283  297 270  242 386  337 312  247 274Modulus, 100%, MPa 2.02                  2.96 2.88                           2.93 3.57                                    2.60 2.43                                             2.79 2.03                                                      2.69Hardness, Shore A  68  68   67  67   69  67   67  68   67  67Aging Properties (70 hrs/275� C.):Tensile strength, MPa              3.81                  6.03 6.90                           7.31 7.18                                    4.97 6.79                                             7.61 7.69                                                      8.42Elongation at break, %              640 326  327 287  248 500  393 311  285 265Modulus, 100%, MPa 1.60                  2.23 2.36                           2.68 3.05                                    1.99 2.05                                             2.78 3.03                                                      3.16Hardness, Shore A  70  70   68  71   72  69   71  71   70  70Compression set (70 hrs/200� C.), %              52.8                  28.2 27.5                           35.5 30.6                                    42.6 33.0                                             --   --  --__________________________________________________________________________
TABLE VI______________________________________Curable gumstock ingredients                Parts______________________________________FKM C, parts         100Carbon black (N-990), phr                30MgO, phr             3Ca(OH)2, phr    6TPBPC, mhr � 103                1.22Bisphenol AF, mhr � 103                2.23Fluoroaliphatic sulfonamide                1.22curing agent, mhr � 103______________________________________
______________________________________Run no.         Curing agent______________________________________13              Control14              C8 F17 SO2 N(CH3)H15              C4 F9 SO2 N(CH3)H16              C8 F17 SO2 N(C12 H25)H17              C8 F17 C2 H4 SO2 N(CH3)H______________________________________
TABLE VII__________________________________________________________________________              Run no.              13  14  15   16  17__________________________________________________________________________Curing CharacteristicsODR, 177� C.:ML, N.m       1.92                  2.05                      1.86 1.82                               1.81MH, N.m, 12 minutes              3.62                  6.44                      6.33 5.76                               3.84tsl, minutes  2.0 1.5 1.6  1.8 1.5t5.6, minutes --  2.9 3.1  6.0 --Properties of cured gumstockPress cure properties (10 min/177� C.):Tensile strength, MPa              7.37                  9.47                      9.68 9.35                               7.97Elongation at break, %              730 373 424  459 649Modulus, 100%, MPa 1.91                  2.49                      2.46 2.27                               2.02Hardness, Shore A  66  67  67   67  66Postcure properties (20 hrs./260� C.):Tensile strength, MPa              8.15                  11.55                      12.97                           12.35                               8.78Elongation at break, %              517 267 281  291 445Modulus, 100%, MPa 2.02                  2.88                      2.89 2.73                               2.50Hardness, Shore A  68  67  67   67  68Aging Properties (70 hrs/275� C.):Tensile strength, MPa              3.81                  7.37                      7.18 7.13                               --Elongation at break, %              640 331 326  268 --Modulus, 100%, MPa 1.60                  2.43                      2.25 2.63                               --Hardness, Shore A  70  68  70   71  --Compression set    52.8                  30.2                      26.3 38.6                               --(70 hrs/200� C.)__________________________________________________________________________
TABLE VIII__________________________________________________________________________             Run no.Curable gumstock ingredients             18 19 20  21 22 23  24 25 26  27 28 29 30 31__________________________________________________________________________FRM C, parts      100                100                   100 100                          100                             100 100                                    100                                       100 100                                              100                                                 100                                                    100                                                       100Carbon black (N-990), phr             30 30 30  30 30 30  30 30 30  30 30 30 30 30MgO, phr          3  3  3   3  3  3   3  3  3   3  3  3  3  3Ca(OH)2, phr 6  6  6   6  6  6   6  6  6   6  6  6  6  6TPBPC, mhr � 103             1.22                1.22                   1.22                       1.22                          1.22                             1.22                                 1.22                                    1.22                                       1.22                                           1.22                                              1.22                                                 1.22                                                    1.22                                                       1.22Fluoraliphatic sulfonamide             -- 1.22                   --  1.22                          -- 1.22                                 -- 1.22                                       --  1.22                                              -- 1.22                                                    -- 1.22curing agentC8 F17 SO2 N(CH3)H, mhr � 103Dihydroxy curing agents aBisphenol AF, mhr � 103             6.50                6.50                   --  -- -- --  -- -- --  -- -- -- -- --Bisphenol S, mhr � 103             -- -- 6.50                       6.50                          -- --  -- -- --  -- -- -- -- --Bisphenol C, mhr � 103             -- -- --  -- 6.50                             6.50                                 -- -- --  -- -- -- -- --Bisphenol, mhr � 103             -- -- --  -- -- --  6.50                                    6.50                                       --  -- -- -- -- --HQ, mhr � 103             -- -- --  -- -- --  -- -- 6.50                                           6.50                                              -- -- -- --Bisphenol A-AE mixture, mhr � 103             -- -- --  -- -- --  -- -- --  -- 3.80                                                 3.80                                                    -- --FC-diol, mhr � 103             -- -- --  -- -- --  -- -- --  -- -- -- 6.50                                                       6.50__________________________________________________________________________ a Structures of cocuring agents are shown in Table I.
TABLE IX__________________________________________________________________________              Run no.              18  19  20  21  22  23  24__________________________________________________________________________Curing CharacteristicsODR, 177� C.:ML, N.m       1.02                  0.68                      1.24                          0.68                              1.47                                  0.79                                      1.47MH, N.m; 12 minutes              10.96                  10.39                      2.37                          5.65                              5.76                                  7.34                                      6.78tsl, minutes  6.0 5.0 7.2 6.0 4.8 4.8 3.0t5.6, minutes 8.7 7.0 --  11.9                              11.6                                  7.6 13Properties of cured gumstockPress cure properties (10 min/177� C.):Tensile strength, MPa              9.45                  10.91                      8.93                          10.70                              8.94                                  11.02                                      7.96Elongation at break, %              235 229 401 320 318 274 259Modulus, 100%, MPa 4.32                  4.58                      2.72                          3.16                              2.96                                  3.44                                      3.36Hardness, Shore A  74  72  70  --  70  72  68Postcure properties (20 hrs./260� C.):Tensile strength, MPa              14.84                  15.18                      12.07                          15.28                              12.31                                  13.17                                      9.31Elongation at break, %              172 158 288 218 248 191 177Modulus, 100%, MPa 6.83                  6.89                      3.31                          4.46                              3.67                                  4.58                                      4.41Hardness, Shore A  76  74  72  73  71  72  69Aging Properties (70 hrs/275� C.):Tensile strength, MPa              9.47                  9.89                      8.38                          10.40                              7.79                                  9.45                                      5.39Elongation at break, %              206 157 382 265 346 224 266Modulus, 100%, MPa 4.27                  5.49                      2.47                          3.21                              2.49                                  3.43                                      2.61Hardness, Shore A  76  --  72  74  72  73  73Compression set (70 hrs/200� C.), %              14.7                  19.3                      23.3                          18.8                              21.1                                  20.1                                      25.4__________________________________________________________________________              Run no.              25  26  27  28  29  30  31__________________________________________________________________________Curing CharacteristicsODR, 177� C.:ML, N.m       0.68                  1.47                      1.24                          1.81                              1.69                                  2.37                                      1.92MH, N.m; 12 minutes              9.72                  7.00                      8.81                          2.26                              3.73                                  4.29                                      9.38tsl, minutes  5.0 2.7 2.3 2.3 1.8 1.4 1.4t5.6, minutes 8   4.5 3.6 --  --  --  9.38Properties of cured gumstockPress cure properties (10 min/177� C.):Tensile strength, MPa              10.42                  8.96                      10.51                          .sup. -- a                              10.34                                  5.56                                      10.30Elongation at break, %              214 299 258 --  594 526 269Modulus, 100%, MPa 4.23                  3.06                      3.58                          --  1.92                                  2.16                                      3.50Hardness, Shore A  69  67  67  --  64  66  69Postcure properties (20 hrs./260� C.):Tensile strength, MPa              15.18                  13.24                      14.22                          --  12.53                                  9.71                                      15.26Elongation at break, %              171 242 187 --  236 396 188Modulus, 100%, MPa 5.81                  3.67                      4.51                          --  3.41                                  2.72                                      5.34Hardness, Shore A  70  67  67  --  68  68  70Aging Properties (70 hrs/275� C.):Tensile strength, MPa              8.63                  6.55                      9.13                          --  7.67                                  --  10.96Elongation at break, %              159 348 216 --  207 --  198Modulus, 100%, MPa 4.85                  2.19                      3.54                          --  3.45                                  --  3.67Hardness, Shore A  68  67  69  --  66  --  --Compression set (70 hrs/200� C.), %              24.0                  22.4                      25.5                          --  35.9                                  --  18.3__________________________________________________________________________ a poor cured properties
TABLE X__________________________________________________________________________           Run no.Curable gumstock ingredients           32  33  34  35  36  37__________________________________________________________________________FKM C, parts    100 100 100 100 100 100Carbon black (N-990), phr           30  30  30  30  30  30MgO, phr        3   3   3   3   3   3Ca(OH)2, phr           6   6   6   6   6   6Bisphenol AF, mhr � 103           2.23               2.23                   2.23                       2.23                           2.23                               2.23C8 F17 SO2 N(CH3)Na, mhr � 103           --  1.22                   --  1.22                           --  1.22Cure acceleratorsaTPBPC, mhr � 103           1.22               1.22                   --  --  --  --TBBAC, mhr � 103           --  --  1.22                       1.22                           --  --TTSC, mhr � 103           --  --  --  --  1.22                               1.22__________________________________________________________________________ a See Table II for structures of cure accelerators.
TABLE XI__________________________________________________________________________              Run no.              32  33  34  35  36  37__________________________________________________________________________Curing CharacteristicsODR, 177� C.:ML, N.m       1.92                  1.92                      1.58                          1.64                              1.41                                  1.58MH, N.m; 12 minutes              3.62                  6.33                      2.82                          5.65                              2.60                                  --tsl, minutes  2.0 1.3 2.1 1.9 3.3 2.9t5.6, minutes --  2.6 --  5.0 --  --Properties of cured gumstockPress cure properties (10 min/177� C.):Tensile strength, MPa              7.37                  6.33                      7.65                          9.84                              4.20                                  9.23Elongation at break, %              730 427 673 415 765 529Modulus, 100%, MPa 1.91                  2.46                      2.03                          2.65                              1.63                                  2.16Hardness, Shore A  66  67  67  68  65  66Postcure properties (20 hrs./260� C.):Tensile strength, MPa              8.15                  12.66                      8.80                          12.45                              4.95                                  11.87Elongation at break, %              517 283 500 268 680 403Modulus, 100%, MPa 2.02                  2.96                      2.26                          3.11                              1.81                                  2.34Hardness, Shore A  68  68  67  67  67  67Aging Properties (70 hrs/275� C.):Tensile strength, MPa              3.81                  6.93                      4.02                          6.92                              --  --Elongation at break, %              640 326 521 280 --  --Modulus, 100%, MPa 1.60                  2.23                      1.64                          2.69                              --  --Hardness, Shore A  70  70  68  71  --  --Compression set (70 hrs/200� C.), %              52.8                  28.2                      66.8                          36.1                              --  --__________________________________________________________________________
TABLE XII______________________________________Curable gumstock           Run no.ingredients     38      39       40    41______________________________________FKM C, parts    100     100      100   100Carbon black (N-990), phr           30      30       30    30MgOa, phr  15      15       15    15DIAK No. 1b, mhr � 103           8.70    8.70     --    --DIAK No. 3c, mhr � 103           --      --       8.70  8.70C8 F17 SO2 N(CH3)H,           --      1.86     --    1.86mhr � 103______________________________________ a MAGLITE Y, commercially available from Merck b Hexamethylenediamine carbamate, + H3 N(CH2)6 NHCOO.sup. c N,N',dicinnamylidine-l,6-hexanediamine, (CH2)6 (N=CHCH=CHC6 H5)2 Curing characteristics and properties of cured gumstock are shown in Table XIII.
TABLE XIII______________________________________         Run no.         38    39       40      41______________________________________Curing CharacteristicsODR, 177� C.:ML, N.m    1.92    1.81     0.90  1.13MH, N.m; 12 minutes           6.89    7.34     2.60  8.02tsl, minutes           2.5     2.4      5.0   4.0t5.6, minutes           7.0     6.4      --    7.8Properties of cured gumstockPress cure properties(10 min/177� C.):Tensile strength, MPa           13.82   12.62    10.40 9.38Elongation at break, %           268     242      520   300Modulus, 100%, MPa           3.58    3.58     2.01  3.10Hardness, Shore A           68      68       65    69Postcure properties(20 hrs./260� C.):Tensile strength, MPa           13.20   11.34    9.98  10.31Elongation at break, %           232     187      247   145Modulus, 100%, MPa           4.06    4.54     3.18  6.40Hardness, Shore A           71      73       74    83______________________________________ a Run 40 was press cured for 20 min. at 177� C.
TABLE XIV______________________________________Curable gumstock          Run no.ingredients    42      43       44    45______________________________________FKM C, parts   100     100      0     0FKM T, parts   --      --       100   100Carbon black (N-990), phr          30      30       30    30MgOa, phr 3       3        3     3Ca(OH)2, phr          6       6        6     6TPBPCb, mhr � 103          1.22    1.22     1.22  1.22Bisphenol AFc, mhr � 103          6.49    6.49     6.49  6.49C8 F17 SO2 N(CH3)Na,          0       1.27     0     1.27mhr � 103______________________________________ a MAGLITE D, commercially available from Merck b Cure accelerator No. 1 in Table II c Curing agent No. 1 in Table I
TABLE XV______________________________________              Run no.              42   43     44     45______________________________________Curing CharacteristicsODR, 177� C.:ML, N.m         1.02   0.96   2.26 1.92MH, N.m; 12 minutes                11.1   11.5   10.8 12.2tsl, minutes    5.3    4.0    4.1  5.1t5.6, minutes   7.3    5.9    6.7  7.6Properties of cured gumstockPress cure properties (10 min/177� C.):Tensile strength, MPa                8.62   9.39   9.78 8.45Elongation at break, %                255    232    306  265Modulus, 100%, MPa   4.12   4.29   4.42 4.06Hardness, Shore A    74     75     76   79Postcure properties (20 hrs./260� C.):Tensile strength, MPa                14.70  13.48  15.42                                   14.91Elongation at break, %                184    169    222  179Modulus, 100%, MPa   6.45   6.37   5.90 6.89Hardness, Shore A    76     77     80   82Aging Properties (70 hrs/275� C.):Tensile strength, MPa                9.71   10.01  8.06 8.01Elongation at break, %                193    183    338  254Modulus, 100%, MPa   4.84   4.83   3.14 3.96Hardness, Shore A    77     77     80   82Compression set      20     18     24   21.7(70 hrs/200� C.), %______________________________________
TABLE XVI______________________________________Curable gumstock    Run no.ingredients         46      47       48______________________________________FKM C, parts        100     100      100Carbon black (N-990), phr               15      15       15PbO, phr            20      20       20DIAK No. 1a, mhr � 103               6.25    6.25     0TPBPCb, mhr � 103               0       1.28     1.28Fluoroether A, phr  27      27       27C8 F17 SO2 N(C2 H5)C2 H4 OPO(OH)2,               30.72   30.72    30.72mhr � 103______________________________________ a Hexamethylenediamine carbamate, + H3 N(CH2)6 NHCOO.sup. b Cure accelerator No. 1 in Table II
TABLE XVII______________________________________              Run no.              46    47      48______________________________________Curing characteristicsODR, 177� C.:ML, N.m         0.22    0.22    0.22MH, N.m, 12 min.                0.22    0.33    0.22tsl, minutes    *       12      *t5.6, minutes   *       *       *Properties of cured gumstockPress cure properties (10 min/177� C.):Tensile strength, MPa                5.05    3.91    **Elongation at break, %                301     279     **Modulus, 100% MPa    0.96    0.92    **Hardness, Shore A    50      50      **Postcure properties (20 hrs/260� C.):Tensile strength, MPa                7.42    5.99    **Elongation at break, %                360     252     **Modulus, 100%, MPa   1.54    1.77    **Hardness, Shore A    58      58      **Aging properties (70 hrs/275� C.):                95      88.5    **Compression set(70 hrs/200� C.), %______________________________________ * The value of torque could not be measured because there was no change between maximum and minimum values. ** The gumstock did not cure.
TABLE XVIII______________________________________Curable gumstock Run no.ingredients      49        50      51______________________________________FKM C, parts     100       100     100Carbon black (N-990), phr            15        15      15PbO, phr         20        20      20DIAK No. 1a, mhr � 103            6.25      6.25    0TPBPCb, mhr � 103            0         1.28    1.28C8 F17 SO2 N(C2 H5)H,            30.72     30.72   30.72mhr � 103Fluoroether A, phr            27        27      27______________________________________ a Hexamethylenediamine carbamate, + H3 N(CH2)6 NHCOO- b Cure accelerator No. 1 in Table II
TABLE XIX______________________________________              Run no.              49    50      51______________________________________Curing characteristicsODR, 177� C.:ML, N.m         0.34    0.45    0.23MH, N.m, 12 min.                1.02    2.15    0.23tsl, minutes    3.4     1.6     *t5.6, minutes   *       *       *Properties of cured gumstockPress cure properties (10 min/177� C.):Tensile strength, MPa                5.58    5.61    **Elongation at break, %                310     261     **Modulus, 100% MPa    1.03    1.23    **Hardness, Shore A    47      49      **Postcure properties (20 hrs/260� C.):Tensile strength, MPa                7.68    6.71    **Elongation at break, %                245     186     **Modulus, 100%, MPa   1.95    2.14    **Hardness, Shore A    55      49      **Aging properties (70 hrs/275� C.):                87      82      **Compression set(70 hrs/200� C.), %______________________________________ * The value of torque could not be measured because the difference betwee the maximum and minimum torque was too low. ** The gumstock did not cure.
TABLE XX__________________________________________________________________________Curable gumstock      Run no.ingredients           52  53  54  55  56  57__________________________________________________________________________FKM C, parts          100 100 100 100 100 100Carbon black (N-990), phr                 30  30  30  30  30  30MgOa, phr        3   3   3   3   3   3Ca(OH)2, phr     6   6   6   6   6   6TPBPCb, mhr � 103                 1.21                     1.21                         1.21                             --  --  1.21Bisphenol AFc, mhr � 103                 2.23                     2.23                         2.23                             2.23                                 2.23                                     --C8 F17 SO2 N(C2 H5)H, mhr � 103                 1.21                     --  --  --  1.21                                     1.21C8 F17 SO2 (C2 H5)C2 H4 OPO(OH)2,mhr � 103  --  1.21                         --  --  --  --__________________________________________________________________________ a MAGLITE D, commercially available from Merck b Cure accelerator No. 1 in Table II c Curing agent No. 1 in Table I
TABLE XXI__________________________________________________________________________              Run no.              52  53  54  55 56 57__________________________________________________________________________Curing CharacteristicsODR, 177� C.:ML, N.m       1.69                  1.69                      1.69                          1.24                             1.24                                1.81MH, N.m; 12 min.              5.98                  5.08                      3.5 1.24                             1.24                                2.71tsl, minutes  1.1 1.0 1.5 *  *  1.8t5.6, minutes 3.8 *   *   *  *  *Properties of cured gumstockPress cure properties (10 min/177� C.):Tensile strength, MPa              10.30                  10.07                      5.52                          ** ** ***Elongation at break, %              434 545 544 ** ** ***Modulus, 100%, MPa 2.5 2.06                      2.03                          ** ** ***Hardness, Shore A  65  66  65  ** ** ***Postcure properties (20 hrs./260� C.):Tensile strength, MPa              12.40                  10.93                      6.75                          ** ** ***Elongation at break, %              286 375 467 ** ** ***Modulus, 100%, MPa 2.77                  2.38                      2.26                          ** ** ***Hardness, Shore A  66  68  68  ** ** ***Aging Properties (70 hrs/275� C.):              35  42  70  ** ** ***Compression set(70 hrs/200� C.), %__________________________________________________________________________ * The value of torque could not be measured because the difference betwee the maximum and minimum torque was too low. ** The gumstock did not cure. *** The gumstock did not cure sufficiently to form a molded product.
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