CA1136339A - Vulcanization system for thiodiethanol elastomers - Google Patents

Abstract

27,738 TITLE
Vulcanization System for Thiodiethanol Elastomers ABSTRACT
The present invention relates in general to sul-fur-vulcanizable elastomers derived from thiodiethanol and, in particular to the provision of a novel vulcanization sys-tem therefor comprising sulfur and an aliphatic linear, branched chain or cyclic polyethyleneamine or a dissociable organic salt thereof.

Description

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27,738 VULCANIZABLE SYSTEM FOR THIODIETHANOL ELASTOMERS
Background of the Invention Elastomers, based on the condensation of a major proportion of thiodiethanol with one or more aliphatic diols containing a sulfur-vulcanizable double bond, are described by Aloia, U.S. Patent 3,951,927; Chang etal., U.S. Patent 3,985,708; Chang, U.S. Patent 4,000,213; and Li etal., U.S. Patent 4,028,305. Heretofore, application oE conventional sulfur vulcanization systems, e.g., sulfur, zinc oxide, benzothiazole sulfenamides, thiuram sulfides, mercaptobenzothiazole, and the like, to the vulcanization of these elastomers has been less than satisfactory. Zinc oxide has heretofore been considered to be essential to the vulcanization of unsaturated elastomers with sulfur.
In the vulcanization of thiodiethanol-based elastomers of the invention, conventional sulfur-vulcanization systems containing zinc oxide result in a fast cure, but the vulcan-ized elastomers exhibit poor heat ageing as manifested by high compression set and poor continuous stress-relaxation.
However, when zinc oxide is omitted from the cure system, the cure rate is impractically slow. All of these factors indicate that there is a need for a vulcanization system to vulcanize thiodiethanol-based elastomers.
In order for an elastomer to achieve commercial ~ : . .
-~ success, lt must be vulcanlzable to useful products with an efficient, practical vulcanization system. It is an object of the invention to provide useful vulcanized products from thiodiethanol-based elastomers, and to pro-: A ~

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vide elastomers exhibiting significantly impro~ed aged properties, such as compression set.
Summary of the Invention The present inventio:n provides a novel vulcaniza-tion system for thiodiethanol-based elastomers, comprising sulfur and an aliphatic linear, branched chain or cyclic polyethyleneamine, or mixture thereof, or a dissociable organic salt thereof.
Descrip~ion of the Invention Including Preerred Embodiments The aliphatic linear, branched chain or cyclic polyethyleneamines which are useful in the vulcanization system of the present invention range from relatively simple polyethyleneamines, which are represented by the formula:

H ~ IIN-(C~l2)2 ~ NH2 (I) n wherein n is an integer from 1 to about 10, to complex re-action products of ethylene dichloride and ammonia, which 20 boil above the boiling point of diethylenetriamine (206.7C), to dissociable organic salts of polyethyleneamines produced by reaction thereof with acids having a dissociation constant less than about 10 3, or mixtures of any of the above materials.
Polyethyleneamines repxesentative of the above formula (I) include:
ethylenediamine diethylenetriamine triethylenetetramine tetraethylenepentamine pentaethylenehexamine, and the like.
The complex polyethyleneamine reaction mixtures contain linear, branched chain and cyclic structures which include, for example, the following:

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2 2 2 C~2C~2 NH-C5~2C~2-NH-c~l2c~2-NH-c~2c5~2-NH

~ t~lethylcllel~examine 2 ~ ~2 Nll C~l2c~2-lN-cll2cl~2-Nll~cH2cH2-NH2 C~
icl~2 ~ diaminoethyltriaminoethylamine 2N-cll2cll2-N-c~l2c5l2-NH-c~l2cH2-NH CH2CH2-NH2 C~2 Nli2 Unsy~metr_c ]. diaminoethyltriaminoethylamine H2N-C~2C~12~ ~ CH2CH2-N~12 N CH2cH2-N
H2~l-cll2cEl -- CE12CH2- NH2 Symmetrical diaminoethyltriethylenetetramine H2N CH2CE12 Nll-C1~2C~32-N ~ N-CH2CH2-NH-cH2cH2-NH2 Symmetrical diaminoethyldiaminoethyl piperazine ~ C112C~I2 ~ - --- -_- .,. ~.~,.
2N-cll2cll2-N N-C112C512-NII-C112CE12-NII-CH2CE12-N112 C112CI~2 :: :

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Unsymmetric~l ~liaminoethylc1iaminoethyl piperazine ~ Cll?C112 HN N(~ 2C1-12-N11t-3 C~12CH2-NH2 ~ C112C~12--Pip~raz.inocthyl triethylene tetramine _C~12C112~N-C112C112 N11 C12 2 2 C~12 cil2 I

N
Cl-12 Cl~l2 1112 C}12 ~ N
: 11 (N-p~erdzinoethyl)triethylene tetramine . 20 '' ~ Cl'2C112~ CH2C~2\
HN N-CH2CH2-~11-Cll2c~l2-N\ N-~

ispiperazinoethylamlne ~, .
2C1~2 \ / 2 2 \
H2N-C112C112-N j N CH?.C~12 j NH
. C112c}12 C~12C112 ~minoethyl diperazinoethane ,~ ", , j In addition tG the linear, branched chain and cyclic polyethyleneamines, or~anic salts thereof, which ~: - dissociate under vulcani2ation conditions to liberate the free amine, may also be used.

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Useful organic salts are those which are formed from acids having a dissociation conskant less than about 10 3, and including salts of aliphatic carboxylic a~ids, especially those of 2-18 carbon atoms, carbonic acid, carba-mic acid and the like. Particularly useful salts are thefatty acid salts, e~g., the stearate. Useful salts also include the condensation products of polyethyleneamines and the aforementioned fatty acids, for example stearic acid, such as diethylenetriamine-stearic acid condensate.
The vulcanizable thiodiethanol-based elastomers useful in the present invention are preferably those dis-closed in the aforementioned patent to Aloia and Chang et al ('708).
Specifically, the vulcanizable elastomers of thio-15 diethanol is a polymer represented by the formula (II) H ~ OG ~m OHwherein fOG~ comprises randomly alternating structural units selected from (E) structural units (III) and (IV) (III) fC2H4SC2H4 (IV) ~OR~
or ~F) structural units (III), (IV) and (V) (V) ~OR'~
25 wherein R is one or more radicals remaining on removal of two hydroxyl groups from:
(a) saturated aliphatic, linear, branched chain or cyclic diols, or (b) aliphatic linear, branched chain or cyclic diols containing external unsaturation having an allylic hydrogen atom, wherein R' is one x or more radicals which remain on removal of two hydroxyl groups from a diphenolic compound, said polymers comprising structural units (E) and (F) being characterized in that:
(1) m is an integer sufficient to provide in said polymer an average molecular weight ~ .

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(2) the molar ratio of (III) to (I~), when said polymer comprises structural units (E), or the molar ratio of (III) to the total of (IV) and (~) when said polymer comprises structural units (F), being not less than 1:1 and

(3) they contain from about 1 to 10 mole per-cent of said diol (b) based on the total of all units (III), (IV) and (V) present in said polymer.
The vulcanization system of the invention compri-ses sulfur in an amount of from about 0.3 to 3,0 parts by weight per hundred parts of elastomer, preferably 0.3 to 15 2.0 parts, same basis. The polyethylene amine may be used in an amount of from about 1 to 6 parts thereof per 100 parts of elastomer, preferably from about 2 to ~ parts, same basis In addition to sulfur and the polyamine compound, 20 the vulcanizable elastomer composition may contain other conventional rubber compounding ingredients, such as fillers and reinforcing agents, e.g., carbon black, precipitated ,~ hydrous silica, titanium dioxide, calcium carbanate, calcium j~ silicate, and the like; calcium oxide or calcium stearate 25 (or other fatty acid salt) to neutralize acid catalyst resi-dues in the elastomer; processing aids, such as sorbitan monostearate or stearic acid; sulfur-donating compounds;
mercaptobenzothiaæole; sulfenamides; thiuram sulfides, and the like, without departing from the scope of the invention.
~` 30 The ~ulcanizable compositions may be prepared by conventional rubber compounding techniques, using a two-roll rubber mill or a Banbury mixer, at temperatures of 300F
The compositions are vulcanized at similar temperatures, preferably about 3~5-350F for about 15 to 60 minutes and, ~ 35 optionally, post-cured for periods of time to de~elop ;~ full cures.

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The following examples are set forth for purposes of illustration only and are not to be construed as limi-tations on the present invention. All parts and percentages are by weight unless otherwise specified.
S Example 1 An elastomeric copolymer of 80% thiodiethanol, 15% isopropylidenebisphenol and 5% trimethylolpropane, mono-allyl ether was compounded as follows:
Part~y Weight 10 Elastomer 100 Carbon Black 60 Calcium oxide 3 Sorbitan monostearate 2 Sulfur 1.5 15 Tetramethyl thiuram disulfide 1.5 16~.0 To separate portions (168 parts) of the above formulation was added:
A - B - C
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~, 20 Zinc oxide 5,0 - -Mercaptobenzothiazole 1.5 2.0 2.0 Polyamine D* - - 4.0 *Mixture of aliphatic and cyclic polyethyleneamines boiling above 340~C
~, 25Each of the compositions A thru C was cured for ~,~ 60 minutes at 330F and then post-cured for 16 hours at 120C before testing.
Rheology of the compositions was studied using a Monsanto Oscillating Disc Rheometer operating at 330F.
30Rheometer ~ A B C
; Max. cure rate 6.5 0.1 1.45 (inch - lbs./min.) Max. torque (inch - lbs.) 40.5 - 87 35 Tor~ue after 15 minutes40.5 g 35 (inch - lbs.) - Stress-strain properties of the cured compositions :
-, ~; . - :
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Tensile, psi 1100 750 1660 Elongation, % 220 375 300 Hardness~ Shore "A" 71 60 78 Continuous stress~relaxation studies were made to measure the thermal stability of the compositions. The elastomer samples were tested on an autographic stress--relaxometer consisting of load-sensing elements, a means for extending and maintaining the specimens at a constant 10 elongation, and a circulating air oven, The oven tempera-ture was maintained at a temperature of 150C i 0.1C and the samples extended to 5 + .05%. The decrease in modulus with time is recorded automatically. Data relating to the relative thermal stability are obtained from plots of f(t)/
15 f(0) versus log time, or log f(t)/f(0) versus time, where f(t) and f(0) are the forces at time t and t - 0, respec-tively, required to maintain the sample at a given extension.
The data are reported as ~50, which represents the time at 150C that is required for a sample to degrade to a value 20 equal to 50~ of the initial stress, which is a measure of the amount of degradation experienced by the specimen.
Continuous Stress-~elaxation A B C
~ 50, minutes 350 - 2450 The data illustrate that Composition A, which re-- presents a conventional sulfur vulcanization system, pro-vides a fast cure rate, but exhibits poor thermal stability compared to Composition C which is many times more stable and which exhibits a good cure rate and develops good mech-30 anical properties. Composition B demonstrates that a very poor cure is obtained without zinc oxide in a conventional vulcanization system.

Followin~ the procedure of Example 1 an elastomeric 35 copolymer of 90% thiodiethanol -5% diethyleneglycol -5% tri-methylolpropane, monoallyl ether was compounded as follows:

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g Parts by W~ t Elastomer 100 Carbon black 50 Antioxidant* 2 5 Tetramethyl thiuram disulfide 1.5 Mercaptobenzothiazole 2.0 Sulfur 1.5 Calcium stearate 3.0 160.0 10 *Di-~-naphthyl-p-phenylenediamine To separate portions (160 parts) of the above formulation was added:
D E F
Polyamine D (See Example 1) 2 3 4 15 The compositions were cured for 30 minutes at 330F and post-cured for 16 hours at 120C. Properties were as follows:
Monsanto Rheometer @ 330F
D E F
20 Max. cure rate 1.4 2l1 2.4 Max. torque 80+ 95+ 95 Torque after 15 minutes 39 S1 51 Instron Stress-Strain ProPerties - - --D E F
25 Tensile, psi 1645 1715 1490 Elongation, % 370 300 270 Compression Set, % 89 62 41 (Method B- 22 hrs. at 120C) Continuous Stress-Relaxati n 30 rS0, minutes 125 425 1200 The data illustrate that good cures are obtained using 2 to 4 parts per hundred of Polyamine D and that the higher concentrations tend to provide increased thermal stability, as mani~ested by improved compression set and stress-relaxation.
Example;3 An elastomeric copolymer of 90% thiodiethanol - 5%

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diethyleneglycol - 5~ trimethylolpropane, monoallyl ether was compounded as follows:
Parts b Elastomer 100 s Carbon black 50 Clacium stearate 5 Sulfur 1.5 Mercaptoben~othiazole 1.5 ; Tetramethyl thiuram disulfide 1.5 159.5 Separate portions (159.5 parts) were compounded with the following (all at 4 parts per hundred of rubber of active material).
G H J K
15 Triethylenetetramine 4 _ _ _ Tetraethylenepentàmine - 4 ~ -Polyamine D** (50% on silica) - - 8 Polyamine H* - - - 4 *Complex polyethyleneamine reaction product boiling a~ove 20 340C and containing 24-28-~ by weight of diethylenetriamine ** See Example 1 The compositions were cured for 30 minutes at 330F and post-cured for 4 hours at 120C.
Torque (inch~pounds) was measured at 330F after ; 25 30 minutes using a Monsanto Oscillating Disc Rheometer.
This is an indication of the extent of cure of the compo-sition.
G H J K
Torque after 30 min~ 61 60 66 66 The stress-strain properties, obtained on an In-stron tester, were as follows:
Tensile, psi 1520 1550 1500 1540 Elongation, ~ 490 455 470 435 Hardness, Shore "A" 74 76 75 77 35 Compression Set, % 34 33 37 27 (Method B: 22 hrs~
- at 120C) .

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33~3 The data illustrate that good cures are obtained using various polyethyleneamirles with sulfur and that the cured compositions exhibit good ageing resistance, as mani-fested by low compression set.
Example 4 An elastomer of 90 percent thiodiethanol - 5~
diethyleneglycol - 5% trimethylolpropane, monoallyl ether, was compounded as follows:

Control K
Elastomer 100 100 Carbon black 50 50 Calcium stearate 5 5 Sulfur 1.5 1.5 15 Mercaptobenzothiazole 1~5 1.5 Tetramethyl thiuram disulfide 1.5 1.5 Triethylenetetramine stearate - 4 The compositions were cured for 60 minutes at 330F. Stress-strain properties are as follows:
20 Tensile, psi under 1530 Elongation, ~ cured 510 Hardness, Shore "A" ~ 67 Example 5 The procedure of Example 1 was again followed except that the elastomer was prepared from thiodiethanol (95 parts) and the monoallyl ether of trimethylolpropane (5 parts). Similar results were achieved.
Example 6 The procedure of Example 4 was again followed except that the monoallyl ether was replaced by 3-cyclo-hexene-l,l-dimethanol. Similar results were achieved.
Example 7 When the procedure of Example 4 was again followed except that the diethylene glycol was replaced by isopropyl-idene bisphenol, similar results were achieved.

The procedure of Example 1 was again followed . - ~

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~ 12 -except that Polyamine D was replaced by diethylenetriamine carbonate. Excellent results were observed.
ExampLe Following the procedure of Example 8 except that the carbonate was replaced by the corresponding carbamate, the results were comparable.

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Claims (11)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A vulcanizable elastomer composition comprising a mixture of (1) a vulcanizable elastomer of thiodiethanol, (2) sulfur, and (3) an aliphatic linear, branched chain, or cyclic polyamine selected from the group consisting of (A) polyethyleneamines represented by the formula (I):

(I) wherein n is an integer from 1 to about 10; (B) complex reaction mixtures of polyethyleneamines, boiling above the boiling point of diethylenetriamine, (C) salts of poly-ethyleneamines with organic acids having a dissociation constant less than about 10-3; and (D) mixtures thereof;
said vulcanizable elastomer of thiodiethanol being a copoly-mer represented by the formula (II):
(II) wherein ?OG? comprises randomly alternating structural units selected from:
(E) structural units (III) and (IV) [ OR ] (IV) [OC2H4SC2H4] (III) or (F) structural units (III), (IV), and (V) [ OR' ] (V) wherein R is one or more radicals remaining on removal of two hydroxyl groups from:
(a) saturated aliphatic linear, branched chain or cyclic diols, or (b) aliphatic linear, branched chain or cyclic diols containing external unsaturation hav-ing an allylic hydrogen atom;
wherein R' is one or more radicals which remain on removal of two hydroxyl groups from a diphenolic compound; said co-polymers comprising structural units (E) and (F) being characterized in that:

(1) m is an integer sufficient to provide in said copolymer an average molecular weight of at least 8000;
(2) the molar ratio of (III) to (IV), when said copolymer comprises structural units (E), or the molar ratio of (III) to the total of (IV) and (V) when said copolymer comprises struc-tural units (F), being not less than 1:1;
and (3) containing from about 1 to 10 mole percent of said diol (b), based on the total of all units (III), (IV), and (V) present in said copolymer.

2. A vulcanizable elastomer composition in accor-dance with Claim 1 wherein said copolymer of thiodiethanol comprises rendomly alternating structural units (E).

3, A vulcanizable elastomer composition in accor-dance with Claim 1 wherein said copolymer of thiodiethanol comprises randomly alternating structural units (F).

4. A vulcanizable elastomer composition in accor-dance with Claim 1 wherein said polyamine comprises a poly-ethyleneamine represented by (A).

5. A vulcanizable elastomer composition in accor-dance with Claim 4 wherein n is an integer from 3 to 6.

6. A vulcanizable elastomer composition in accor-dance with Claim 1 wherein said polyamine comprises (B).

7. A vulcanizable elastomer composition in accor-dance with Claim 1 wherein said polyamine comprises (C).

8. A vulcanizable elastomer composition in accor-dance with Claim 7 wherein said acid is an aliphatic carboxy-lic acid, carbonic acid, or carbamic acid.

9. A vulcanizable elastomer composition in accor-dance with Claim 8 wherein said acid is an aliphatic mono-carboxylic acid containing from 2 to 18 carbon atoms.

10. A vulcanizable elastomer composition in accor-dance with Claim 8 wherein said acid is carbonic acid.

11. A vulcanizable elastomer composition in accor-dance with Claim 8 wherein said acid is carbamic acid.