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Tetraisobutylthiuram monosulfide (TiBTM) - a unique retarder/kicker in one molecule.


Recently, we reported (ref. (1)) the use of N,N,N',N'-tetraisobutylthiuram disulfide di·sul·fide
n.
A chemical compound containing two sulfur atoms combined with other elements or radicals. Also called bisulfide.
 (TiBTD) as a low nitrosamine ni·tros·a·mine
n.
Any of a class of organic compounds present in various foods and other products and found to be carcinogenic and mutagenic in laboratory animals.
 generating kicker Kicker

A right, warrant, or some other feature added to a debt instrument to make it more desirable to potential investors.

Notes:
The ability to trade a bond or other debt instrument in for stock may entice investors, if they feel the stock will appreciate.
 for sulfenamides. When used as a kicker for benzothiazole Benzothiazole is a colorless, slightly viscous liquid with a melting point of 2 °C, and a boiling point of 227-228 °C. The density of benzothiazole is 1.238 g/ml (25 °C). It is a heterocyclic organic compound. Benzothiazole has no household use. It is used in industry and research.  sulfenamides, this thiuram had better scorch safety than, but cured at the same rate as, TMTD TMTD

tetramethylthiuram disulfide.
 in similar recipes Recipes by category
Albanian cuisine
Albanian vegetable pie: article,
Baked lamb and yogurt:
Baked leeks:
Bean Jahni soup:
Elli's veal or chicken with walnuts
. In that publication we also briefly described a new material, N,N,N',N'-tetraisobutylthiuram monosulfide (TiBTM), which acted as a retarder retarder,
n a chemical added to a substance to slow a chemical reaction, prolong the set of the material, and provide more working time.
 as well as a kicker for 2-benzothiazole sulfenamides in SBR/BR.

Generally, a kicker or secondary accelerator accelerator: see particle accelerator.


(1) A key combination such as Alt-G or Ctrl-Shift H that is used to activate a task.

(2) An incubator that expects to develop the company considerably faster than normal. See incubator.
 increases the cure rate of a primary accelerator but at the same time shortens the scorch time (ref. (2)), sometimes an undesired side effect. Conversely con·verse 1  
intr.v. con·versed, con·vers·ing, con·vers·es
1. To engage in a spoken exchange of thoughts, ideas, or feelings; talk. See Synonyms at speak.

2.
, a cure retarder will increase the scorch delay but can slow the cure rate of the primary accelerator (ref. (3)). A single molecule molecule (mŏl`əkyl) [New Lat.,=little mass], smallest particle of a compound that has all the chemical properties of that compound.  possessing the characteristics of increasing scorch safety while increasing the cure rate when used with a specific primary accelerator is certainly unique and deserves further attention for potential exploitation Exploitation
See also Opportunism.

Barnum, P. T.

(1810–1891) circus impressario famous for his saying, “Never give a sucker an even break.” [Am. Hist.
.

In our first report (ref. (1)), we provided data demonstrating the above effect of TiBTM with TBBS TBBS The Bread Board System
TBBS The Big Blue Sky (website) 
, a primary accelerator, in SBR/BR, at varying levels of the two accelerators. It was not established, however, that the effect could be extended to other primary accelerators and rubbers, at what loadings the effect is most pronounced, and how effective these retarding/kicking characteristics are relative to commercial retarders and kickers kickers

See bells and whistles.
. Thus, in this article, we explore these various ramifications ramifications nplAuswirkungen pl  with TiBTM.

[ILLUSTRATION OMITTED]

[Part 1 of 3]

Table 1 - comparison of TiBTM vs. CTP used with TBBS in an SBR/BR
stock

                               1        2        3        4

SBR/BR masterbatch        214.00   214.00   214.00   214.00
TBBS                        1.35     1.35     1.35     1.35
CTP                                   .10      .20      .30
TiBTM
Sulfur                       2.0      2.0      2.0      2.0

Monsanto rheometer,
160[degrees]C
[[M.sub.H]-M.sub.L]
  N[??]m                     2.7      2.7      2.7      2.7
Scorch time
  [(t.sub.2]), min           7.0      7.6      8.1      8.7
Cure time
  [(t.sub.9.sub.0]),
  min                       13.4     14.6     15.6     16.6
Cure time
  [(t.sub.9.sub.0]),
  min                       15.2     16.4     17.3     18.4
Cure rate index             13.2     12.0     11.0     10.2

Mooney scorch,
138[degrees]C
Scorch time
  [(t.sub.5]),
  min                       17.8     19.9     22.5     24.5
Cure time
  [(t.sub.3.sub.5]),
  min                       21.2     23.9     26.6     29.0
Cure index                   3.4      4.0      4.1      4.5

Stress-strain, opt cure
[(t.sub.9.sub.5]) at
160[degrees]C
Tensile strength, MPa       17.5     18.1     16.1     17.9
Elongation, %                494      526      462      506
300% modulus, MPa            8.9      8.2      8.8      8.8

[Part 2 of 3]

Table 1 - comparison of TiBTM vs. CTP used with TBBS in an SBR/BR
stock

                               5        6        7        8        9

SBR/BR masterbatch        214.00   214.00   214.00   214.00   214.00
TBBS                        1.35     1.35     1.35     1.22     1.08
CTP
TiBTM                        .10      .20      .50      .10      .20
Sulfur                       2.0      2.0      2.0     2.01     2.02

Monsanto rheometer,
160[degrees]C
[[M.sub.H]-M.sub.L]
  N[??]m                     2.8      2.8      3.0      2.7      2.7
Scorch time
  [(t.sub.2]), min           7.4      7.0      6.9      7.5      7.4
Cure time
  [(t.sub.9.sub.0]),
  min                       12.9     12.3     10.7     13.4     12.7
Cure time
  [(t.sub.9.sub.0]),
  min                       14.4     13.8     11.9     15.1     14.3
Cure rate index             15.1     16.4     21.9     14.4     16.0

Mooney scorch,
138[degrees]C
Scorch time
  [(t.sub.5]),
  min                       19.8     20.1     19.5     19.9     21.1
Cure time
  [(t.sub.3.sub.5]),
  min                       22.7     23.0     22.1     23.0     23.9
Cure index                   2.9      2.9      2.6      3.1      2.8

Stress-strain, opt cure
[(t.sub.9.sub.5]) at
160[degrees]C
Tensile strength, MPa       12.9     12.3     14.4     16.4     16.8
Elongation, %                377      358      361      482      489
300% modulus, MPa            9.3      8.4     11.4      8.6      8.5

[Part 3 of 3]

Table 1 - comparison of TiBTM vs. CTP used with TBBS in an SBR/BR
stock

                              10       11       12

SBR/BR masterbatch        214.00   214.00   214.00
TBBS                         .95      .81      .54
CTP
TiBTM                        .30      .40      .60
Sulfur                      2.03     2.04     2.06

Monsanto rheometer,
160[degrees]C
[[M.sub.H]-M.sub.L]
  N[??]m                     2.7      2.7      2.7
Scorch time
  [(t.sub.2]), min           7.5      7.3      7.0
Cure time
  [(t.sub.9.sub.0]),
  min                       12.8     12.4     12.1
Cure time
  [(t.sub.9.sub.0]),
  min                       14.4     14.0     13.8
Cure rate index             15.6     16.6     17.1

Mooney scorch,
138[degrees]C
Scorch time
  [(t.sub.5]),
  min                       20.0     19.9     21.1
Cure time
  [(t.sub.3.sub.5]),
  min                       22.6     22.5     24.1
Cure index                   2.6      2.6      3.0

Stress-strain, opt cure
[(t.sub.9.sub.5]) at
160[degrees]C
Tensile strength, MPa       16.2     15.9     15.0
Elongation, %                472      468      446
300% modulus, MPa            8.7      8.4      8.6





Experimental

The SBR/BR masterbatch, weight 214.0, used in this study contains OE-SBR, Ameripol 1712, 55; SBR SBR - Spectral Band Replication , Ameripol 1500, 25; Taktene 1203, 35; zinc oxide zinc oxide, chemical compound, ZnO, that is nearly insoluble in water but soluble in acids or alkalies. It occurs as white hexagonal crystals or a white powder commonly known as zinc white. , 3; stearic acid stearic acid /ste·a·ric ac·id/ (ste-ar´ik) a saturated 18-carbon fatty acid occurring in most fats and oils, particularly of tropical plants and land animals; used pharmaceutically as a tablet and capsule lubricant and as an emulsifying , 2; N234 carbon black, 70; Sundex 8125, 20; antioxidant antioxidant, substance that prevents or slows the breakdown of another substance by oxygen. Synthetic and natural antioxidants are used to slow the deterioration of gasoline and rubber, and such antioxidants as vitamin C (ascorbic acid), butylated hydroxytoluene , Agerite Resin D, 2; antiozonant, Antozite 67F, 2. These ingredients were combined in a BR internal mixer mixer, either of two electronic devices in which two or more signals are combined. In the type of mixer used in radio receivers, radar receivers, and similar systems, a signal is translated upward or downward in frequency. , and a masterbatch was obtained by combining a number of batches on a mill. The curatives were added on the mill. The NR masterbatch, weight 159.0, contains NR, 100.0; N234 carbon black, 45.0; Sundex Oil 790, 6.0; zinc oxide, 5.0; stearic acid, 2; and antioxidant, Agerite Resin D, 1.0.

The Monsanto The Monsanto Company (NYSE: MON) is a multinational agricultural biotechnology corporation. It is the world's leading producer of the herbicide glyphosate, marketed as "Roundup".  oscillating-disc rheometer rhe·om·e·ter
n.
An instrument for measuring the flow of viscous liquids, such as blood.
, Model R100, was run using a 1[degrees] arc. The commercial accelerators and retarders were used without further purification purification, in religion, the ceremonial removal of what the religion deems unclean. The usual agents of purification are water (as in baptism), bodily alteration (as in circumcision), and fire. .

[Part 1 of 2]

Table 2 - comparison of TiBTM vs. CTP used with CBS in an SBR/BR
stock

                               1        2        3        4        5

SBR/BR masterbatch        214.00   214.00   214.00   214.00   214.00
CBS                         1.50     1.50     1.50     1.50     1.50
CTP                                   .10      .20
TiBTM                                                   .10      .20
Sulfur                       2.0      2.0      2.0      2.0      2.0

Monsanto rheometer,
160[degrees]C
[[M.sub.H]-M.sub.L],
  N[??]m                     2.7      2.8      2.8      2.8      3.0
Scorch time
  [(t.sub.2]),
  min                        6.2      6.3      7.1      6.5      6.9
Cure time
  [(t.sub.9.sub.0]),
  min                       12.5     13.4     13.9     11.4     11.4
Cure time
  [(t.sub.9.sub.5]),
  min                       14.2     15.3     15.5     12.9     12.9
Cure rate index             13.8     14.1     12.3     17.6     18.7

Mooney scorch,
138[degrees]C
Scorch time
  [(t.sub.5]),
  min                       18.5     19.4     21.7     17.9     18.2
Cure time
  [(t.sub.3.sub.5]),
  min                       21.1     22.3     24.7     20.0     20.4
Cure index                   2.6      2.9      3.0      2.1      2.2

Stress-strain, opt cure
[(t.sub.9.sub.5]) at
160[degrees]C
Tensile strength, MPa       13.0     17.0     17.4     17.0     15.9
Elongation, %                386      470      497      468      424
300% modulus, MPa          1,308    1,317    1,277    1,331    1,434

[Part 2 of 2]

Table 2 - comparison of TiBTM vs. CTP used with CBS in an SBR/BR
stock

                               6        7        8        9

SBR/BR masterbatch        214.00   214.00   214.00   214.00
CBS                         1.35     1.20     1.05     0.90
CTP
TiBTM                        .10      .20      .30      .40
Sulfur                      2.01     2.02     2.03     2.04

Monsanto rheometer,
160[degrees]C
[[M.sub.H]-M.sub.L],
  N[??]m                     2.8      2.8      2.8      2.8
Scorch time
  [(t.sub.2]),
  min                        6.9      7.0     7.45      7.0
Cure time
  [(t.sub.9.sub.0]),
  min                       12.4     12.3     13.0     12.5
Cure time
  [(t.sub.9.sub.5]),
  min                       14.2     13.9     14.9     14.5
Cure rate index             15.6     16.7     15.7     15.6

Mooney scorch,
138[degrees]C
Scorch time
  [(t.sub.5]),
  min                       18.6     19.5     21.2     19.9
Cure time
  [(t.sub.3.sub.5]),
  min                       20.8     21.8     23.8     22.4
Cure index                   2.2      2.3      2.6      2.5

Stress-strain, opt cure
[(t.sub.9.sub.5]) at
160[degrees]C
Tensile strength, MPa       14.6     15.2     16.5     14.2
Elongation, %                421      435      458      407
300% modulus, MPa          1,317    1,316    1,324    1,336


[Part 1 of 2]

Table 3 - comparison of TiBTM vs. CTP/TMTM used with TBBS in an
SBR/BR stock

                           1       2       3       4       5       6

SBR/BR masterbatch     214.0   214.0   214.0   214.0   214.0   214.0
TBBS                    1.30    1.30    1.00    1.00    1.00    1.00
CTP                             0.10            0.10            0.10
TMTD                                    0.15    0.15
TMTM                                                    0.13    0.13
TiBTM
Sulfur                  1.80    1.80    1.80    1.80    1.82    1.82

Monsanto rheometer,
160[degrees]C
[[M.sub.H]-M.sub.L],
  N[??]m                 2.7     2.7     2.6     2.6     2.6     2.5
Scorch time
  [(t.sub.2]),
   min                   7.5     7.8     6.2     6.7     7.4     7.8
Cure time
  [(t.sub.9.sub.0]),
  min                   14.9    15.4    11.8    13.1    13.0    14.5
Cure time
  [(t.sub.9.sub.5]),
  min                   17.0    17.2    13.8    15.0    14.9    16.5
Cure rate index         11.3    10.9    15.8    13.9    15.4    12.6

Mooney scorch,
138[degrees]C
Scorch time
  [(t.sub.5]),
  min                   20.0    21.4    17.3    19.8    21.1    23.2
Cure time
  [(t.sub.3.sub.5]),
  min                   23.8    25.9    19.8    22.5    23.8    26.4
Cure index               3.8     4.5     2.5     2.7     2.7     3.2

Stress-strain, opt
cure
[(t.sub.9.sub.5]) at
160[degrees]C
Tensile strength,
MPa                     16.8    13.9    12.3    14.5    15.4    15.9
Elongation, %            503     423     413     477     483     545
300% modulus, MPa        8.2     8.5     7.6     7.3     7.8     6.6

[Part 2 of 2]

Table 3 - comparison of TiBTM vs. CTP/TMTM used with TBBS in an
SBR/BR stock

                           7       8

SBR/BR masterbatch     214.0   214.0
TBBS                    1.00    1.17
CTP
TMTD
TMTM
TiBTM                   0.23    0.11
Sulfur                  1.82    1.81

Monsanto rheometer,
160[degrees]C
[[M.sub.H]-M.sub.L],
  N[??]m                 2.7     2.7
Scorch time
  [(t.sub.2]),
   min                   8.0     7.8
Cure time
  [(t.sub.9.sub.0]),
  min                   14.4    14.5
Cure time
  [(t.sub.9.sub.5]),
  min                   16.4    16.4
Cure rate index         13.1    12.4

Mooney scorch,
138[degrees]C
Scorch time
  [(t.sub.5]),
  min                   23.3    22.5
Cure time
  [(t.sub.3.sub.5]),
  min                   26.7    25.8
Cure index               3.3     3.3

Stress-strain, opt
cure
[(t.sub.9.sub.5]) at
160[degrees]C
Tensile strength,
MPa                     11.8    16.3
Elongation, %            371     500
300% modulus, MPa        8.7     8.0





Results and discussion

TiBTM was evaluated as a retarder/kicker for both N-t-butyl-2-benzothiazole sulfenamide (TBBS) and N-cyclo-hexyl-2-benzothiazole sulfenamide (CBS (Cell Broadcast Service) See cell broadcast. ) in SBR/BR and natural rubbers. Additionally, TiBTM was compared to the retarder, N-cyclohexythio-phthalimide (CTP CTP (cytidine triphosphate): see cytosine.


(1) (Computer-To-Plate) The production of printing plates directly from the computer without requiring film as an intermediate step.
), and the kicker, N,N,N',N',-tetramethylthiuram monosulfide (TMTM TMTM The Muppets Take Manhattan (movie)
TMTM The More, the Merrier
) in these systems for any advantages/disadvantages.

Performance in SBR/BR rubber compounds

It was demonstrated earlier (ref. (1)) that increasing the loading of TiBTM above 0.2 phr did not increase the scorch delay or cure rate beyond that which was observed ob·serve  
v. ob·served, ob·serv·ing, ob·serves

v.tr.
1. To be or become aware of, especially through careful and directed attention; notice.

2.
 at 0.2 phr. The data in table 1 show that increasing the loading of TiBTM beyond 0.1 phr while keeping the loading of TBBS constant (recipes 5-7) did not improve the scorch time any further beyond the 2 min. increase compared to the control of TBBS alone (recipe 1). The cure rate, however, continued to increase because of the increasing total amount of accelerators present. Unfortunately, the stress-strain properties dropped off relative to those for the TBBS control. By replacing equivalent amounts of TBBS by TiBTM, e.g., removal of 10% of TBBS and replacing it by .10 parts of TiBTM, an improvement in the physical properties of the vulcanizates resulted (recipes 8-12). While all recipes showed an increase in the scorch time of about two minutes, the cure indexes increased by three units compared to the TBBS control. This approach results in some cost savings in that less primary accelerator is used.
Table 4 - comparison of TiBTM vs. CTP/TMTM used with CBS in an
SBR/BR stock

                                   1       2       3       4       5

SBR/BR masterbatch             214.0   214.0   214.0   214.0   214.0
CBS                             1.44    1.44    1.15    1.15    1.30
CTP                                     0.10            0.10
TMTM                                            0.13    0.13
TiBTM                                                           0.11
Sulfur                          1.80    1.80    1.82    1.82    1.81

Monsanto rheometer,
160[degrees]C
[[M.sub.H]-M.sub.L], N[??]m      2.7     2.6     2.6     2.6     2.6
Scorch time [(t.sub.2]),
   min                           6.2     7.1     6.7     7.0     7.0
Cure time [(t.sub.9.sub.0]),
   min                          11.7    13.6    11.6    11.7    12.7
Cure time [(t.sub.9.sub.5]),
   min                          13.4    15.2    13.2    13.2    14.3
Cure rate index                 15.6    13.0    18.0    18.9    15.5

Mooney scorch, 138[degrees]C
Scorch time [(t.sub.5]), min    16.2    20.8    16.7    19.5    21.3
Cure time [(t.sub.3.sub.5]),
min                             18.9    23.4    20.2    21.4    23.7
Cure index                       2.7     2.6     3.5     1.9     2.4

Stress-strain, opt cure
[(t.sub.9.sub.5]) at
160[degrees]C
Tensile strength, MPa           15.1    16.4    13.0    13.7    15.4
Elongation, %                    488     504     435     443     483
300% modulus, MPa                7.6     7.9     7.5     7.8     7.8


[Part 1 of 2]

Table 5 - comparison of TiBTM vs. CTP used with TBBS in a natural
rubber stock

                           1       2       3       4       5       6

NR masterbatch         159.0   159.0   159.0   159.0   159.0   159.0
TBBS                    1.00    1.00    1.00    1.00    1.00    0.90
CTP                              0.1    0.20
TiBTM                                           0.10    0.20    0.10
Sulfur                  2.00    2.00    2.00    2.00    2.00    2.01

Monsanto rheometer,
150[degrees]C
[[M.sub.H]-M.sub.L],
 N[??]m                  3.6     3.5     3.5     3.6     3.6     3.5
Scorch time
  [(t.sub.2]),
  min                    7.5     8.9     9.4     8.1     8.3     7.9
Cure time
  [(t.sub.9.sub.0]),
  min                   14.3    16.0    16.6    12.6    12.2    12.3
Cure time
  [(t.sub.9.sub.5]),
  min                   15.8    17.4    18.0    13.6    12.9    13.3
Cure rate index         13.3    11.9    11.8    19.3    21.7    19.6

Mooney scorch,
130[degrees]C
Scorch time
  [(t.sub.5]),
  min                   19.5    23.7    27.8    20.6    22.8    21.7
Cure time
  [(t.sub.3.sub.5]),
  min                   22.2    27.1    32.3    22.4    24.7    23.3
Cure index               2.7     3.4     4.5     1.8     1.8     1.6

Stress-strain, opt
cure
[(t.sub.9.sub.5]) at
150[degrees]C
Tensile strength,
MPa                     29.7    29.1    29.9    30.1    27.9    29.8
Elongation, %            560     551     569     559     511     561
300% modulus, MPa       13.1    13.0    13.0    13.5    13.7    13.0

[Part 2 of 2]

Table 5 - comparison of TiBTM vs. CTP used with TBBS in a natural
rubber stock

                           7       8       9

NR masterbatch         159.0   159.0   159.0
TBBS                    0.80    0.70    0.60
CTP
TiBTM                   0.20    0.30    0.40
Sulfur                  2.02    2.03    2.04

Monsanto rheometer,
150[degrees]C
[[M.sub.H]-M.sub.L],
 N[??]m                  3.5     3.5     3.5
Scorch time
  [(t.sub.2]),
  min                    7.8     7.8     8.1
Cure time
  [(t.sub.9.sub.0]),
  min                   11.5    10.9    11.7
Cure time
  [(t.sub.9.sub.5]),
  min                   12.2    11.5    12.3
Cure rate index         22.7    26.3    23.3

Mooney scorch,
130[degrees]C
Scorch time
  [(t.sub.5]),
  min                   21.1    20.3    21.6
Cure time
  [(t.sub.3.sub.5]),
  min                   22.7    21.7    23.1
Cure index               1.6     1.3     1.5

Stress-strain, opt
cure
[(t.sub.9.sub.5]) at
150[degrees]C
Tensile strength,
MPa                     29.0    28.4    27.7
Elongation, %            535     530     514
300% modulus, MPa       13.6    13.4    13.5





The effective retarder CTP was also evaluated against TiBTM for comparison. One can see (recipes 2-4) that increasing the loadings of CTP continue concomitantly con·com·i·tant  
adj.
Occurring or existing concurrently; attendant. See Synonyms at contemporary.

n.
One that occurs or exists concurrently with another.
 to increase the scorch time while decreasing the cure rate index. However, when CTP and TiBTM are used at low levels (recipes 2, 8), both provide similar scorch improvements while TiBTM increases the cure rate and CTP decreases it compared to that of TBBS alone. Thus, one can replace CTP when used at low levels by TiBTM to achieve the same scorch safety with a resulting improvement in cure rate, and lower the amount of primary accelerator at the same time.

It is generally recognized that CBS itself exhibits a shorter scorch time and a faster cure rate relative to TBBS (ref. (4)). Thus, we evaluated TiBTM as a retarder/kicker for CBS in experiments similar to those discussed above. These data are shown in table 2. One can see that a higher loading of TiBTM is needed to improve the scorch time relative to the control (recipes 6-9 vs. 1) while the cure rate index increases immediately. However, there is still a leveling out effect at 0.2 phr. CTP, on the other hand, shows an immediate effect on scorch time but to a lesser extent than with TBBS (recipes 2 and 3 vs. 1). Again, the cure rate tends to slow down when CTP is added. Thus, similarities exist in the interactions of TBBS and CBS with TiBTM and CTP but the magnitude magnitude, in astronomy, measure of the brightness of a star or other celestial object. The stars cataloged by Ptolemy (2d cent. A.D.), all visible with the unaided eye, were ranked on a brightness scale such that the brightest stars were of 1st magnitude and the  of the changes are less pronounced with CBS.

Since TiBTM behaves as both a retarder and a kicker, it would be interesting to compare its processing properties to those of a CTP/TMTM recipe, since CTP is a retarder and TMTM is a kicker. The data from this study with TBBS as the primary accelerator are shown in table 3. For a true comparison, equivalent mole levels of TMTM and TiBTM should be used. Since the molecular weight is higher for TiBTM, 0.23 parts of TiBTM are equivalent to 0.13 parts of TMTM. One can see that TiBTM at .23 parts and even at half that level (recipes 7 and 8, respectively), provide a scorch delay and cure increase equivalent to that of a CTP/TMTM combination (recipe 6) over that of the control (recipe 1). As a comparison, a CTP/TMTD combination provides a cure rate increase but no scorch delay. The kicking effect of the TMTD overwhelms the scorch delay of the CTP.

[Part 1 of 3]

Table 6 - comparison of TiBTM vs. CTP used with CBS in a natural
rubber stock

                                         1       2       3       4

NR masterbatch                         159.0   159.0   159.0   159.0
CBS                                     1.11    1.11    1.11    1.11
CTP                                              .10     .20
TiBTM                                                            .10
Sulfur                                   2.0     2.0     2.0     2.0

Monsanto rheometer, 150[degrees]C
[[M.sub.H]-M.sub.L], N[??]m              3.5     3.4     3.4     3.5
Scorch time [(t.sub.2]), min             7.7     9.0     9.9     7.9
Cure time [(t.sub.9.sub.0]), min        13.2    14.9    16.2    11.5
Cure time [(t.sub.9.sub.5]), min        14.7    16.4    17.5    12.4
Cure rate index                         15.9    14.3    13.0    23.3

Mooney scorch, 130[degrees]C
Scorch time [(t.sub.5]), min            22.2    26.1    31.2    22.4
Cure time [(t.sub.3.sub.5]), min        24.4    28.8    34.2    23.8
Cure index                               2.2     2.7     3.0     1.4

Stress-strain, opt cure
[(t.sub.9.sub.5]) at 150[degrees]C
Tensile strength, MPa                   29.0    30.6    30.1    29.5
Elongation, %                            528     576     569     555
300% modulus, MPa                       13.7    13.2    13.0    13.3

[Part 2 of 3]

Table 6 - comparison of TiBTM vs. CTP used with CBS in a natural
rubber stock

                                         5       6       7       8

NR masterbatch                         159.0   159.0   159.0   159.0
CBS                                     1.11    1.00    0.89    0.78
CTP
TiBTM                                    .20     .10     .20     .30
Sulfur                                   2.0    2.01    2.02    2.03

Monsanto rheometer, 150[degrees]C
[[M.sub.H]-M.sub.L], N[??]m              3.6     3.5     3.5     3.5
Scorch time [(t.sub.2]), min             8.0     7.9     8.0     8.1
Cure time [(t.sub.9.sub.0]), min        11.2    11.7    11.4    11.2
Cure time [(t.sub.9.sub.5]), min        12.0    12.6    12.0    11.9
Cure rate index                         26.3    22.7    25.0    26.3

Mooney scorch, 130[degrees]C
Scorch time [(t.sub.5]), min            23.4    23.2    23.2    24.8
Cure time [(t.sub.3.sub.5]), min        24.8    24.6    24.8    27.8
Cure index                               1.4     1.4     1.6     3.0

Stress-strain, opt cure
[(t.sub.9.sub.5]) at 150[degrees]C
Tensile strength, MPa                   28.0    29.0    28.2    27.5
Elongation, %                            535     570     550     543
300% modulus, MPa                       12.8    13.0    12.3    12.4

[Part 3 of 3]

Table 6 - comparison of TiBTM vs. CTP used with CBS in a natural
rubber stock

                                         9

NR masterbatch                         159.0
CBS                                     0.67
CTP
TiBTM                                    .40
Sulfur                                  2.04

Monsanto rheometer, 150[degrees]C
[[M.sub.H]-M.sub.L], N[??]m              3.4
Scorch time [(t.sub.2]), min             8.0
Cure time [(t.sub.9.sub.0]), min        11.0
Cure time [(t.sub.9.sub.5]), min        11.5
Cure rate index                         27.8

Mooney scorch, 130[degrees]C
Scorch time [(t.sub.5]), min            24.7
Cure time [(t.sub.3.sub.5]), min        25.9
Cure index                               1.2

Stress-strain, opt cure
[(t.sub.9.sub.5]) at 150[degrees]C
Tensile strength, MPa                   26.7
Elongation, %                            527
300% modulus, MPa                       12.1





A similar study was done with CBS as the primary accelerator and the results are shown in table 4. In this case, the TiBTM was used at half the molar molar /mo·lar/ (mo´lar)
1. pertaining to a mole of a substance.

2. a measure of the concentration of a solute, expressed as the number of moles of solute per liter of solution. Symbol M, , or mol/L.
 loading compared to TMTM. The observed increase in scorch delay is larger for the TiBTM but with a smaller increase in cure rate relative to the CTP/TMTM system (recipe 5 vs. 4).
Table 7 - summary of changes in cure rates and scorch times for
TiBTM vs. CTP with TBBS and CBS in SBR/BR and NR stock(1)

                 Mooney scorch      Cure rate index
              time ([delta] min.)     (% change)
Sulfenamide    TiBTM       CTP      TiBTM     CTP

                SBR/BR     SBR/BR   SBR/BR   SBR/BR
TBBS               2.1        2.1       +9       -9
CBS                1.0        0.9      +13       +2

                    NR         NR       NR       NR
TBBS               2.2        4.2      +47      -10
CBS                1.0        3.9      +30      -10

(1) Loadings of TiBTM = CTP = 0.1 parts





Performance in natural rubber compounds

A similar series of experiments to those run in SBR/BR were run with natural rubber. With TBBS (table 5) or CBS (table 6) as the primary accelerator, TiBTM exhibits a smaller increase in the scorch delay but a substantial increase in cure rate compared to CTP recipes. In other words Adv. 1. in other words - otherwise stated; "in other words, we are broke"
put differently
, TiBTM is much better as an accelerator than as a retarder in natural rubber although both effects exist. Again, increasing the loadings of TiBTM does not significantly improve the scorch delay relative to the lower loadings.

When a TiBTM recipe is compared to a CTP/TMTM recipe with TBBS or CBS as the primary accelerator, similar increases in scorch times and cure rates are observed, even when less than molar equivalent A molar equivalent of a substance is an amount of matter quantity, multiplied by a stoichiometric factor, which depends on the exact reaction. The normality is defined as molar equivalent per litre. The gram equivalent is the same.  levels of TiBTM are used.

Conclusions

Table 7 shows a summary of the scorch time differences and percent changes in the cure rate indexes for TiBTM and CTP with the two primary accelerators in the two rubbers. In SBR/BR rubber, one can see that the changes in scorch time are of the same magnitude for TiBTM and CTP when used with the same primary accelerator. A similar comparison of cure rates shows, contrarily, a significant increase with TiBTM and typically no improvement or generally a loss with CTP. In natural rubber, CTP shows at least double the improvement in scorch time over that of TiBTM. The cure rate index change shows a 10% loss for CTP and a very large increase for TiBTM, in all examples, even when TiBTM is used at less than molar equivalent levels.

An explanation for the above behavior is not yet clear. Model reactions with monitoring of formed species may provide some insight into the observations. This work is in progress.

References

(1) . R.W. Layer and D.W. Chasar, Rubber Chem Technol., 67, 299 (1994).

(2) . M.A. Fath fath or fath.
abbr.
fathom
, Rubber World, 209 (1), 22 (1993).

(3) . M.A. Fath, Rubber World, 209 (3), 17 (1993).

(4) . M.A. Fath, Rubber World, 208 (5), 15 (1993).
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Author:Chasar, Dwight W.
Publication:Rubber World
Date:Aug 1, 1996
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