Source: http://www.google.com/patents/US5216085?dq=5,490,216
Timestamp: 2014-09-19 08:44:46
Document Index: 134399479

Matched Legal Cases: ['art                  100', 'arts       100', 'arts     100', 'arts     100', 'arts     100', 'arts         100', 'arts          100']

Patent US5216085 - Molding compositions comprising a vinylidene fluoride copolymer gum, another ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign in<nobr>Advanced Patent Search</nobr>PatentsVulcanizable 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/US5216085?utm_source=gb-gplus-sharePatent US5216085 - Molding compositions comprising a vinylidene fluoride copolymer gum, another curing agent of a polyhydroxy compound, an organo-onium accelerator and a acid acceptor; tensile strength; elongation; resilienceAdvanced Patent SearchPublication numberUS5216085 APublication typeGrantApplication numberUS 07/818,548Publication dateJun 1, 1993Filing dateJan 9, 1992Priority dateFeb 27, 1984Fee statusPaidPublication number07818548, 818548, US 5216085 A, US 5216085A, US-A-5216085, US5216085 A, US5216085AInventorsRichard A. Guenthner, Robert E. KolbOriginal AssigneeMinnesota Mining And Manufacturing CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (21), Referenced by (6), Classifications (4), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetMolding compositions comprising a vinylidene fluoride copolymer gum, another curing agent of a polyhydroxy compound, an organo-onium accelerator and a acid acceptor; tensile strength; elongation; resilienceUS 5216085 AAbstract Vulcanizable 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 this invention can be used to prepare shaped articles that exhibit high tensile strength accompanied by high elongation and a low value of compression set.
What is claimed is: 1. Method of preparing a shaped article comprising the steps of:(a) providing a curable 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, an acid acceptor, 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 0.0002 to about 0.006 mole per hundred grams of said 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 whereinRf 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, Z represents 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, the amounts of said curing agents being sufficient to bring about cross-linking of said fluorocarbon elastomer gum, (b) heating said composition to a temperature sufficient to cure said composition, and (c) recovering said shaped article. 2. The method of claim 1, wherein A is 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.
8. Method of preparing a shaped article comprising the steps of:(a) providing a curable composition comprising:(1) at least one fluorocarbon elastomer gum, (2) 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, (3) at least one organo-onium accelerator, and (4) 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; (b) heating said composition to a temperature sufficient to cure said composition; and (c) recovering said shaped article. 9. The method of claim 8, wherein the fluorocarbon elastomer gum is a polymer of vinylidene fluoride and hexafluoropropene.
Rf (A)z SO2 NR(M1/x)                   I
Rf '[(A)z SO2 NR(M1/x)]2          II
Rf SO2 NHR+NaOCH3 &#8594;Rf SO2 N(R)Na
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.
Curing Characteristics 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 0.1N�m(1 lbf�in), ts1, or time for torque to reach 5.6 N�m (50 lbf�in), t5.6, respectively.
Press Cure 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 Cure Samples were removed from the press and placed in a circulating air oven. The oven was maintained at the indicated temperature for the indicated time. The samples were then removed, cooled to room temperature, and physical properties determined.
Accelerated Aging 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.
Tensile Strength at Break, Elongation at Break, Modulus at 100% Elongation Samples cut from a 1.8 mm thick cured elastomer sheet were tested according to ASTM D-412-80 using the TENSOMETER, Model 500 (Monsanto Company) with a die having the following dimensions: A=3.5 mm, L=19 mm, C=51 mm.
Hardness, Shore A Hardness was measured at room temperature on cured samples according to ASTM D-2240-81 using Shore Instrument and Mfg. Co.'s "A-2" device.
Compression Set Tests according to ASTM D-395-78, Method B, were run on O-rings after the indicated press and post cures and the indicated temperature and time under compression. Results are reported as percent (%) change in dimension from original.
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&#9552;CH2of components            c. CH2 &#9552;CHCH2 OC6 H4 C(CH3).            sub.2 --a:b:c in 1.1:1.6:1            C6 H4 OCH2 CH&#9552;CH2weight ratio)7    FC-diol     HOCH2 (CF2)4 CH2 OH______________________________________
EXAMPLE 1 A vinylidene fluoride copolymer gum (FKM C) was compounded on a two-roll rubber mill with a low level of a conventional vulcanizing agent and a normal level of adjuvants. FKM C contains 80 mole percent CF2 =CH2 and 20 mole percent CF3 CF═CF2. In one of the runs, a fluoroaliphatic sulfonamide curing agent of this invention was incorporated into the formulation. A control run, i.e., a formulation without a fluoroaliphatic sulfonamide curing agent, was also run for the purpose of comparison. The milled, compounded gumstocks were evaluated for curing characteristics, and properties of the cured gumstocks were measured after press cure, post cure, and aging.
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 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 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,        3.62    6.44    6.33  5.76  3.8412 minutestsl, minutes        2.0     1.5     1.6   1.8   1.5t5.6, minutes        --      2.9     3.1   6.0   --Propertiesof cured gumstockPress cure properties(10 min/177� C.):Tensile strength, MPa        7.37    9.47    9.68  9.35  7.97Elongation at        730     373     424   459   649break, %Modulus, 100%, MPa        1.91    2.49    2.46  2.27  2.02Hardness, Shore A        66      67      67    67    66Post cure properties(20 hrs/260� C.):Tensile strength, MPa        8.15    11.55   12.97 12.35 8.78Elongation at        517     267     281   291   445break, %Modulus, 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        640     331     326   268   --break, %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.              18 19 20 21 22 23 24 25 26 27 28 29  30 31__________________________________________________________________________Curable gumstock ingredientsFRM 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                                                      1.22Fluoroaliphatic sulfonamidecuring agentC8 F17 SO2 N(CH3)H, mhr � 103              -- 1.22                    -- 1.22                          -- 1.22                                -- 1.22                                      -- 1.22                                            -- 1.22                                                   -- 1.22Dihydroxy curing agentsaBisphenol 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  69 Aging 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.            32  33  34  35  36  37__________________________________________________________________________Curable gumstock ingredientsFKM 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______________________________________          Run no.Curable gumstock 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- c N,Ndicinnamylidine-1,6-hexanediamine, (CH2)6 (N&#9552;CHCH&#9552;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.):aTensile 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(16 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.
EXAMPLE 7 A vinylidene fluoride copolymer gum (FKM C) and a vinylidene fluoride terpolymer gum (FKM T) were compounded in several different runs on a two-roll rubber mill with various conventional vulcanizing agents and adjuvants. FKM C contains 80 mole percent CF2 ═CH2 and 20 mole percent CF3 CF═CF2. FKM T contains 60 mole percent CF2 ═CH2, 20 mole percent CF3 CF═CF2, and 20 mole percent CF2 ═CF2. In two of the runs, a fluoroaliphatic sulfonamide curing agent suitable for use in this invention was incorporated into the formulation. The milled, compounded gumstocks were evaluated for curing characteristics, and properties of the cured gumstocks were measured after press cure, post cure, and aging. Compression set was also determined. The runs and results obtained are shown in Table XIV. Control runs, i.e., formulations without fluoroaliphatic sulfonamide curing agent, were also run for the purpose of comparison.
TABLE XIV______________________________________          Run no.Curable gumstock 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 min.            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______________________________________              Run no.Curable gumstock 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- 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.):Compression set       95      88.5    **(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.
COMPARATIVE EXAMPLE B The purpose of this comparative example is to show the properties of a cured composition similar to, but not identical to, that described in U.S. Pat. No. 3,632,788. In this example, the fluoroaliphatic sulfonamide C8 F17 SO2 N(C2 H5)H was used in place of the fluoroaliphatic sulfonamide C8 F17 SO2 N(C2 H5)C2 H4 OPO(OH)2. The composition of Run 49 was analogous to the composition used in Formulation D of the example of U.S. Pat. No. 3,632,788. The composition of Run 50 was identical to that of Run 49 with the exception that an organo-onium accelerator was employed. The composition of Run 51 was identical to that of Run 50 with the exception that the amine curing agent was omitted. The identities and amounts of the various ingredients are shown in Table XVIII.
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.):Compression set       87      82      **(70 hrs/200� C.), %______________________________________ *The value of torque could not be measured because the difference between the maximum and minimum torque was too low. **The gumstock did not cure.
TABLE XX__________________________________________________________________________                 Run no.Curable gumstock 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.):Compression set (70 hrs/200�  C.), %               35  42  70  **  **  ***__________________________________________________________________________ *The value of torque could not be measured because the difference between the maximum and minimum torque was too low. **The gumstock did not cure. ***The gumstock did not cure sufficiently to form a molded product.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS2732398 *Aug 9, 1954Jan 24, 1956 cafiicfzsojkUS2803656 *Jan 23, 1956Aug 20, 1957Minnesota Mining & MfgFluorocarbonsulfonamidoalkanols and sulfates thereofUS2968649 *Dec 4, 1958Jan 17, 1961Du PontElastomeric terpolymersUS3051677 *Apr 29, 1957Aug 28, 1962Du PontCopolymer elastomer of vinylidenefluoride and hexafluoropropeneUS3318854 *Feb 5, 1960May 9, 1967Minnesota Mining & MfgFluorinated elastomeric copolymersUS3352798 *Jun 17, 1964Nov 14, 1967Hercules IncCross-linking coating polymers with polysulfonazidesUS3632788 *Nov 25, 1968Jan 4, 1972Minnesota Mining & MfgPerfluoro olefin vinylidene fluoride elastomer product and processUS3655727 *Jan 16, 1970Apr 11, 1972Minnesota Mining & MfgCuring systems for vinylidine fluoride elastomersUS3686143 *Mar 22, 1971Aug 22, 1972Du PontGuanidine and amidine accelerators for vulcanization of fluoroelastomersUS3712877 *Jul 6, 1971Jan 23, 1973Minnesota Mining & MfgCurable vinylidene fluoride elastomers containing phosphonium curing agentsUS3857807 *Nov 6, 1972Dec 31, 1974Daikin Ind LtdFluoroelastomer compositionUS3876654 *Feb 28, 1972Apr 8, 1975Du PontFluoroelastomer compositionUS3895062 *Apr 13, 1970Jul 15, 1975Minnesota Mining & MfgBiphenyl derivativesUS3915907 *Dec 16, 1974Oct 28, 1975Goodyear Tire & RubberChlorothio-sulfonamide-modified rubbery terpolymers and their blendsUS3933732 *May 14, 1974Jan 20, 1976E. I. Du Pont De Nemours And CompanyVinylidene fluoride copolymer, carboxylic acid ester of 4,4'-sulfonyldiphenolUS4233421 *Feb 26, 1979Nov 11, 1980Minnesota Mining And Manufacturing CompanyFluoroelastomer composition containing sulfonium curing agentsUS4250278 *May 1, 1979Feb 10, 1981Daikin Kogyo Co., Ltd.Fluorinated rubber compositionUS4259463 *Dec 8, 1978Mar 31, 1981Montedison S.P.A.Vulcanizable compositions based on copolymers of vinylidene fluoride and containing vulcanization accelerators which are aminophosphinic compoundsUS4287320 *Feb 19, 1980Sep 1, 1981Minnesota Mining And Manufacturing CompanyComposition of fluoroelastomer and diorganosulfuroxideUS4296034 *May 24, 1979Oct 20, 1981Produits Chimiques Ugine KuhlmannPolyfluorinated sulfonamidesUS4358559 *Nov 19, 1981Nov 9, 1982Minnesota Mining And Manufacturing CompanyTacky fluoroelastomer compositions* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS5654375 *May 24, 1996Aug 5, 1997Minnesota Mining And Manufacturing CompanyFluoroelastomer compositions containing organo-onium compoundsUS5882466 *Aug 8, 1996Mar 16, 1999Minnesota Mining And Manufacturing CompanyAqueous bonding compositionUS6838512Jun 5, 2003Jan 4, 20053M Innovative Properties CompanyCold shrink fluoroelastomeric articleUS7052567 *Jun 6, 2000May 30, 2006Verline Inc.Inflatable heating device for in-situ repair of conduit and method for repairing conduitUS7523764Dec 20, 2005Apr 28, 2009Energy Maintenance Services Group I, LlcMethod and apparatus for spot repair of pipeUS8084187 *Mar 25, 2009Dec 27, 2011Fujifilm CorporationResist composition and pattern forming method using the same* Cited by examinerClassifications U.S. Classification525/351International ClassificationC08K5/43Cooperative ClassificationC08K5/43European ClassificationC08K5/43Legal EventsDateCodeEventDescriptionDec 1, 2004FPAYFee paymentYear of fee payment: 12Sep 28, 2000FPAYFee paymentYear of fee payment: 8Jul 7, 1997ASAssignmentOwner name: DYNEON LLC, MINNESOTAFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MINNESOTA MINING AND MANUFACTURING COMPANY;REEL/FRAME:008579/0558Effective date: 19970519Sep 23, 1996FPAYFee paymentYear of fee payment: 4RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google