Source: https://patents.justia.com/patent/5086123
Timestamp: 2019-09-17 08:20:00
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US Patent for Fluoroelastomer compositions containing fluoroaliphatic sulfonamides as curing agents Patent (Patent # 5,086,123 issued February 4, 1992) - Justia Patents Search
Justia Patents Ethylenic Reactant Contains A Fluorine AtomUS Patent for Fluoroelastomer compositions containing fluoroaliphatic sulfonamides as curing agents Patent (Patent # 5,086,123)
Nov 28, 1990 - Minnesota Mining and Manufacturing Company
R.sub.f (A).sub.z SO.sub.2 NR(M.sub.1/2) I
R.sub.f '[(A)SO.sub.2 NR(M.sub.1/x)].sub.2 II
A represents an organic linkage such as --CR.sup.1 R.sup.2 --, --CR.sup.1 R.sup.2 CR.sup.3 R.sup.4 --, and --CR.sup.1 .dbd.CR--, wherein R.sup.1,R.sup.2,R.sup.3, and R.sup.4 are selected from the group consisting of hydrogen atom, fluorine atom, chlorine atom, and lower alkyl group, having, for example, 1 to 2 carbon atoms,
R.sub.f SO.sub.2 F+RNH.sub.2 .fwdarw.R.sub.f SO.sub.2 NHR
R.sub.f C.sub.2 H.sub.4 SO.sub.2 Cl+RNH.sub.2 .fwdarw.R.sub.f C.sub.2 H.sub.4 SO.sub.2 NHR
R.sub.f SO.sub. NHR+NaOCH.sub.3 .fwdarw.R.sub.f SO.sub.2 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.degree. C to 200.degree. 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.degree. arc. Minimum torque (M.sub.L) and the torque attained at a stated time (M.sub.H) were determined. Also determined were time in minutes for torque to increase 0.1 N.multidot.m(1 lbf.multidot.in), t.sub.sl, or time for torque to reach 5.6 N.multidot.m (50 lbf.multidot.in), t.sub.5.6, respectively.
Elastomer sheets 150 mm.times.150 mm.times.1.8 mm were prepared for determination of physical properties by pressing uncured compounded gumstock at about 6.9.times.10.sup.3 kPa for the indicated time at 177.degree. C.
Post cured samples were placed in a circulating air oven for the indicated time at 275.degree. C. The samples were then removed for measurement of physical properties according to ASTM D-573-81.
No.  Designation Chemical identity
1    Bisphenol AF
4,4'-HOC.sub.6 H.sub.4 C(CF.sub.3).sub.2 C.sub.6 H.sub.4
2    Bisphenol S 4,4'-HOC.sub.6 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 OH
3    Biphenol C  4,4'-HOC.sub.6 H.sub.4 COC.sub.6 H.sub.4 OH
4    HQ          1,4-HOC.sub.6 H.sub.4 OH
5    Biphenol    4,4'-HOC.sub.6 H.sub.4 --C.sub.6 H.sub.4 OH
6    Bisphenol   a. HOC.sub.6 H.sub.4 C(CH.sub.3).sub.2 C.sub.6 H.sub.4
A-AE (mixture
b. HOC.sub.6 H.sub.4 C(CH.sub.3).sub.2 C.sub.6 H.sub.4
OCH.sub.2 CH=CH.sub.2
c. CH.sub.2 =CHCH.sub.2 OC.sub.6 H.sub.4 C(CH.sub.3).sub.
a:b:c in 1.1:1.6:1
.sup.  C.sub.6 H.sub.4 OCH.sub.2 CH=CH.sub.2
7    FC-diol     HOCH.sub.2 (CF.sub.2).sub.4 CH.sub.2 OH
No.    Designation   Chemical identity
1      TPBPC         (C.sub.6 H.sub.5).sub.3 P(CH.sub.2 C.sub.6 H.sub.5).s
up.+ Cl.sup.-
2      TBBAC         (C.sub.4 H.sub.9).sub.3 N(CH.sub.2 C.sub.6 H.sub.5).s
3      TTSC          [(CH.sub.3)C.sub.6 H.sub.4 ].sub.3 S.sup.+ Cl.sup.-
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 CF.sub.2 .dbd.CH.sub.2 and 20 mole percent CF.sub.3 CF.dbd.CF.sub.2. In one of the runs, a fluoroalkiphatic 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.
Curable gumstock ingredients
FKM C, high viscosity gum, part
Carbon black (N-110), phr
Ca(OH).sub.2, phr      6         6
TPBPC, mhr .times. 10.sup.3
1.4       0.77
Bisphenol AF, mhr .times. 10.sup.3
0.625     0.625
C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)Na, mhr .times. 10.sup.3
0         2.81
ODR, 177.degree. C.:
M.sub.L, N.m           4.86      5.20
M.sub.H, N.m, 12 minutes
5.54      5.99
t.sub.sl, minutes      3         2.1
t.sub.5.6, minutes     8         5.0
Press cure properties (2.5 hrs/177.degree. C.)
Tensile strength, MPa  7.51      20.04
Elongation at break, % 718       550
Modulus, 300%, MPa     4.79      9.51
Post cure properties (20 hrs/177.degree. C.)
Tensile strength, MPa  10.42     21.63
Elongation at break, % 550       411
Modulus, 300%, MPa     7.31      15.24
Hardness, Shore A      78        76
Tear resistance, kN/m  26        28
(ASTM D 624-81, Die C, 25.degree. C.)
FKM C, parts         100
Carbon black (N-990), phr
MgO, phr             3
Ca(OH).sub.2, phr    6
curing agent, mhr .times. 10.sup.3
Run no.      Curing agent
3            Control
4            C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)Na
5            C.sub.4 F.sub.9 SO.sub.2 N(CH.sub.3)Na
6            C.sub.8 F.sub.17 SO.sub.2 N(C.sub.4 H.sub.9)Na
7            H(CH.sub.3)NSO.sub.2 (CF.sub.2).sub.8 SO.sub.2 N(CH.sub.3)Na
8            C.sub.8 F.sub.17 C.sub.2 H.sub.4 SO.sub.2 N(CH.sub.3)Na
9            C.sub.8 F.sub.17 SO.sub.2 N(H)Na
10           C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)(Mg).sub.1/2
11           C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)NH.sub.4
12           C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)N(C.sub.2 H.sub.5).sub.3
3   4    5   6    7   8    9   10   11  12
M.sub.L, N.m       1.92
M.sub.H, N.m (12 minutes)
6.33 6.21
5.65 7.91
6.33 6.55
t.sub.sl, minutes  2.0 1.3  1.3 1.5  2.0 1.8  3.1 1.8  1.7 1.7
t.sub.5.6, minutes --  2.6  2.6 7.0  3.4 --   --  3.6  3.2 3.4
Press cure properties (10 min./177.degree. C.):
9.29 9.60
9.53 9.86
9.02 8.71
9.79 9.12
730 427  409 456  374 536  646 464  376 446
Modulus, 100%, MPa 1.91
Hardness, Shore A  66  67   67  67   68  67   66  67   66  66
Postcure properties (20 hrs./260.degree. C.):
517 283  297 270  242 386  337 312  247 274
Modulus, 100%, MPa 2.02
2.93 3.57
2.60 2.43
2.79 2.03
Hardness, Shore A  68  68   67  67   69  67   67  68   67  67
Aging Properties (70 hrs/275.degree. C.):
6.03 6.90
7.31 7.18
640 326  327 287  248 500  393 311  285 265
Modulus, 100%, MPa 1.60
2.23 2.36
2.68 3.05
2.78 3.03
Hardness, Shore A  70  70   68  71   72  69   71  71   70  70
Compression set (70 hrs/200.degree. C.), %
35.5 30.6
Run no.         Curing agent
13              Control
14              C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)H
15              C.sub.4 F.sub.9 SO.sub.2 N(CH.sub.3)H
16              C.sub.8 F.sub.17 SO.sub.2 N(C.sub.12 H.sub.25)H
17              C.sub.8 F.sub.17 C.sub.2 H.sub.4 SO.sub.2 N(CH.sub.3)H
6.33 5.76
t.sub.sl, minutes  2.0 1.5 1.6  1.8 1.5
t.sub.5.6, minutes --  2.9 3.1  6.0 --
Press cure properties (10 min/177.degree. C.):
730 373 424  459 649
Hardness, Shore A  66  67  67   67  66
517 267 281  291 445
2.89 2.73
Hardness, Shore A  68  67  67   67  68
640 331 326  268 --
Hardness, Shore A  70  68  70   71  --
Compression set    52.8
(70 hrs/200.degree. C.)
18 19 20  21 22 23  24 25 26  27 28 29 30 31
FRM C, parts      100
30 30 30  30 30 30  30 30 30  30 30 30 30 30
MgO, phr          3  3  3   3  3  3   3  3  3   3  3  3  3  3
Ca(OH).sub.2, phr 6  6  6   6  6  6   6  6  6   6  6  6  6  6
Fluoraliphatic sulfonamide
--  1.22
C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)H, mhr .times. 10.sup.3
Dihydroxy curing agents .sup.a
--  -- -- --  -- -- --  -- -- -- -- --
Bisphenol S, mhr .times. 10.sup.3
-- -- 6.50
-- --  -- -- --  -- -- -- -- --
Bisphenol C, mhr .times. 10.sup.3
-- -- --  -- 6.50
-- -- --  -- -- -- -- --
Bisphenol, mhr .times. 10.sup.3
-- -- --  -- -- --  6.50
--  -- -- -- -- --
HQ, mhr .times. 10.sup.3
-- -- --  -- -- --  -- -- 6.50
Bisphenol A-AE mixture, mhr .times. 10.sup.3
-- -- --  -- -- --  -- -- --  -- 3.80
FC-diol, mhr .times. 10.sup.3
-- -- --  -- -- --  -- -- --  -- -- -- 6.50
.sup.a Structures of cocuring agents are shown in Table I.
M.sub.L, N.m       1.02
M.sub.H, N.m; 12 minutes
t.sub.sl, minutes  6.0 5.0 7.2 6.0 4.8 4.8 3.0
t.sub.5.6, minutes 8.7 7.0 --  11.9
235 229 401 320 318 274 259
Modulus, 100%, MPa 4.32
Hardness, Shore A  74  72  70  --  70  72  68
172 158 288 218 248 191 177
Modulus, 100%, MPa 6.83
Hardness, Shore A  76  74  72  73  71  72  69
206 157 382 265 346 224 266
Modulus, 100%, MPa 4.27
Hardness, Shore A  76  --  72  74  72  73  73
M.sub.L, N.m       0.68
t.sub.sl, minutes  5.0 2.7 2.3 2.3 1.8 1.4 1.4
t.sub.5.6, minutes 8   4.5 3.6 --  --  --  9.38
.sup. -- .sup.a
214 299 258 --  594 526 269
Modulus, 100%, MPa 4.23
--  1.92
Hardness, Shore A  69  67  67  --  64  66  69
--  12.53
171 242 187 --  236 396 188
Modulus, 100%, MPa 5.81
--  3.41
Hardness, Shore A  70  67  67  --  68  68  70
--  7.67
--  10.96
159 348 216 --  207 --  198
Modulus, 100%, MPa 4.85
--  3.45
--  3.67
Hardness, Shore A  68  67  69  --  66  --  --
--  35.9
--  18.3
.sup.a poor cured properties
FKM C, parts    100 100 100 100 100 100
MgO, phr        3   3   3   3   3   3
Ca(OH).sub.2, phr
Cure accelerators.sup.a
TBBAC, mhr .times. 10.sup.3
--  --  1.22
TTSC, mhr .times. 10.sup.3
--  --  --  --  1.22
.sup.a See Table II for structures of cure accelerators.
t.sub.sl, minutes  2.0 1.3 2.1 1.9 3.3 2.9
t.sub.5.6, minutes --  2.6 --  5.0 --  --
730 427 673 415 765 529
Hardness, Shore A  66  67  67  68  65  66
517 283 500 268 680 403
Hardness, Shore A  68  68  67  67  67  67
640 326 521 280 --  --
Hardness, Shore A  70  70  68  71  --  --
ingredients     38      39       40    41
FKM C, parts    100     100      100   100
30      30       30    30
MgO.sup.a, phr  15      15       15    15
DIAK No. 1.sup.b, mhr .times. 10.sup.3
8.70    8.70     --    --
DIAK No. 3.sup.c, mhr .times. 10.sup.3
--      --       8.70  8.70
C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)H,
--      1.86     --    1.86
mhr .times. 10.sup.3
.sup.a MAGLITE Y, commercially available from Merck
.sup.b Hexamethylenediamine carbamate, .sup.+ H.sub.3 N(CH.sub.2).sub.6
NHCOO.sup.
.sup.c N,N',dicinnamylidine-l,6-hexanediamine, (CH.sub.2).sub.6
(N=CHCH=CHC.sub.6 H.sub.5).sub.2
38    39       40      41
M.sub.L, N.m    1.92    1.81     0.90  1.13
6.89    7.34     2.60  8.02
t.sub.sl, minutes
2.5     2.4      5.0   4.0
t.sub.5.6, minutes
7.0     6.4      --    7.8
Press cure properties
(10 min/177.degree. C.):
13.82   12.62    10.40 9.38
268     242      520   300
3.58    3.58     2.01  3.10
68      68       65    69
Postcure properties
(20 hrs./260.degree. C.):
13.20   11.34    9.98  10.31
232     187      247   145
4.06    4.54     3.18  6.40
71      73       74    83
.sup.a Run 40 was press cured for 20 min. at 177.degree. C.
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 CF.sub.2 .dbd.CH.sub.2 and 20 mole percent CF.sub.3 CF.dbd.CF,. FKM T contains 60 mole percent CF.sub.2 .dbd.CH.sub.2, 20 mole percent CF.sub.3 CF.dbd.CF.sub.2, and 20 mole percent CF.sub.2 .dbd.CF.sub.2. 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.
ingredients    42      43       44    45
FKM C, parts   100     100      0     0
FKM T, parts   --      --       100   100
MgO.sup.a, phr 3       3        3     3
TPBPC.sup.b, mhr .times. 10.sup.3
1.22    1.22     1.22  1.22
Bisphenol AF.sup.c, mhr .times. 10.sup.3
6.49    6.49     6.49  6.49
C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)Na,
0       1.27     0     1.27
.sup.a MAGLITE D, commercially available from Merck
.sup.b Cure accelerator No. 1 in Table II
.sup.c Curing agent No. 1 in Table I
42   43     44     45
M.sub.L, N.m         1.02   0.96   2.26 1.92
11.1   11.5   10.8 12.2
t.sub.sl, minutes    5.3    4.0    4.1  5.1
t.sub.5.6, minutes   7.3    5.9    6.7  7.6
8.62   9.39   9.78 8.45
255    232    306  265
Modulus, 100%, MPa   4.12   4.29   4.42 4.06
Hardness, Shore A    74     75     76   79
14.70  13.48  15.42
184    169    222  179
Modulus, 100%, MPa   6.45   6.37   5.90 6.89
Hardness, Shore A    76     77     80   82
9.71   10.01  8.06 8.01
193    183    338  254
Modulus, 100%, MPa   4.84   4.83   3.14 3.96
Hardness, Shore A    77     77     80   82
Compression set      20     18     24   21.7
(70 hrs/200.degree. C.), %
Curable gumstock    Run no.
ingredients         46      47       48
FKM C, parts        100     100      100
15      15       15
PbO, phr            20      20       20
DIAK No. 1.sup.a, mhr .times. 10.sup.3
6.25    6.25     0
0       1.28     1.28
Fluoroether A, phr  27      27       27
C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)C.sub.2 H.sub.4 OPO(OH).sub.2,
30.72   30.72    30.72
.sup.a Hexamethylenediamine carbamate, .sup.+ H.sub.3 N(CH.sub.2).sub.6
46    47      48
M.sub.L, N.m         0.22    0.22    0.22
M.sub.H, N.m, 12 min.
0.22    0.33    0.22
t.sub.sl, minutes    *       12      *
t.sub.5.6, minutes   *       *       *
5.05    3.91    **
301     279     **
Modulus, 100% MPa    0.96    0.92    **
Hardness, Shore A    50      50      **
Postcure properties (20 hrs/260.degree. C.):
7.42    5.99    **
360     252     **
Modulus, 100%, MPa   1.54    1.77    **
Hardness, Shore A    58      58      **
95      88.5    **
* The value of torque could not be measured because there was no change
between maximum and minimum values.
** The gumstock did not cure.
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 C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)H was used in place of the fluoroaliphatic sulfonamide C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)C.sub.2 H.sub.4 OPO(OH).sub.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.
Curable gumstock Run no.
ingredients      49        50      51
FKM C, parts     100       100     100
PbO, phr         20        20      20
6.25      6.25    0
0         1.28    1.28
C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)H,
30.72     30.72   30.72
Fluoroether A, phr
27        27      27
NHCOO.sup.-
49    50      51
M.sub.L, N.m         0.34    0.45    0.23
1.02    2.15    0.23
t.sub.sl, minutes    3.4     1.6     *
5.58    5.61    **
310     261     **
Modulus, 100% MPa    1.03    1.23    **
Hardness, Shore A    47      49      **
7.68    6.71    **
245     186     **
Modulus, 100%, MPa   1.95    2.14    **
Hardness, Shore A    55      49      **
87      82      **
* The value of torque could not be measured because the difference betwee
the maximum and minimum torque was too low.
Curable gumstock      Run no.
ingredients           52  53  54  55  56  57
FKM C, parts          100 100 100 100 100 100
MgO.sup.a, phr        3   3   3   3   3   3
Ca(OH).sub.2, phr     6   6   6   6   6   6
C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)H, mhr .times. 10.sup.3
--  --  --  1.21
C.sub.8 F.sub.17 SO.sub.2 (C.sub.2 H.sub.5)C.sub.2 H.sub.4 OPO(OH).sub.2,
mhr .times. 10.sup.3  --  1.21
52  53  54  55 56 57
M.sub.L, N.m       1.69
M.sub.H, N.m; 12 min.
t.sub.sl, minutes  1.1 1.0 1.5 *  *  1.8
t.sub.5.6, minutes 3.8 *   *   *  *  *
434 545 544 ** ** ***
Modulus, 100%, MPa 2.5 2.06
Hardness, Shore A  65  66  65  ** ** ***
286 375 467 ** ** ***
Modulus, 100%, MPa 2.77
Hardness, Shore A  66  68  68  ** ** ***
35  42  70  ** ** ***
*** The gumstock did not cure sufficiently to form a molded product.
R.sub.f represents a monovalent fluoroaliphatic radical having from 1 to 20 carbon atoms,
R.sub.f ' represents a divalent fluoroaliphatic radical having from 1 to 20 carbon atoms;
A represents an organic linkage selected from the group consisting of --CR.sup.1 R.sup.2, --CR.sup.1 R.sup.2 CR.sup.3 R.sup.4 --, and --CR.sup.1.dbd.CR.sup.2 --, wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are selected from the group consisting of hydrogen atom, fluorine atom, chlorine atom, and lower alkyl group,
(b) at least one fluoroaliphatic sulfonamide as a curing agent therefor selected from the group consisting of C.sub.8 F.sub.17 SO.sub.2 NR(M.sub.1/x), C.sub.8 F.sub.17 C.sub.2 H.sub.4 SO.sub.2 N(R)(M.sub.1/x), C.sub.4 F.sub.9 SO.sub.2 NR(M.sub.1/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,
2803656 August 1957 Albrecht et al.
3352798 November 1967 Breslow et al.
3632788 January 1972 Stivers et al.
3915907 October 1975 Hopper
4250278 February 10, 1981 Suzuki et al.
Inventors: Richard A. Guenthner (Birchwood, MN), Robert E. Kolb (St. Paul, MN)
Application Number: 7/619,669
Current U.S. Class: Ethylenic Reactant Contains A Fluorine Atom (525/276); 525/3264