EP0047736A1 - Vulcanization system for thiodiethanol-based elastomers - Google Patents
Vulcanization system for thiodiethanol-based elastomersInfo
- Publication number
- EP0047736A1 EP0047736A1 EP80902074A EP80902074A EP0047736A1 EP 0047736 A1 EP0047736 A1 EP 0047736A1 EP 80902074 A EP80902074 A EP 80902074A EP 80902074 A EP80902074 A EP 80902074A EP 0047736 A1 EP0047736 A1 EP 0047736A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- vulcanizable elastomer
- accordance
- elastomer composition
- acid
- structural units
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 41
- 239000000806 elastomer Substances 0.000 title claims abstract description 39
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004073 vulcanization Methods 0.000 title abstract description 13
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 33
- -1 cyclic diols Chemical class 0.000 claims description 11
- 229920000768 polyamine Polymers 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- 238000010494 dissociation reaction Methods 0.000 claims description 3
- 230000005593 dissociations Effects 0.000 claims description 3
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 8
- 150000007524 organic acids Chemical class 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229960002447 thiram Drugs 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 239000008116 calcium stearate Substances 0.000 description 4
- 235000013539 calcium stearate Nutrition 0.000 description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229920001198 elastomeric copolymer Polymers 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000010059 sulfur vulcanization Methods 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- MQXNNWDXHFBFEB-UHFFFAOYSA-N 2,2-bis(2-hydroxyphenyl)propane Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1O MQXNNWDXHFBFEB-UHFFFAOYSA-N 0.000 description 2
- ASGOOCMKHNKTQP-UHFFFAOYSA-N 2-n-(2,2-diaminoethyl)ethane-1,1,1,2-tetramine Chemical compound NC(N)CNCC(N)(N)N ASGOOCMKHNKTQP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ZUHRGSQCGNLZFH-UHFFFAOYSA-N 1,3-benzothiazole-5-thiol Chemical compound SC1=CC=C2SC=NC2=C1 ZUHRGSQCGNLZFH-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- QBZUBYHCCJDUPQ-UHFFFAOYSA-N NCCNCCNCCNCCNCCN.NCCNCCNCCNCCN.NCCNCCNCCN.NCCNCCN.C(CN)N Chemical compound NCCNCCNCCNCCNCCN.NCCNCCNCCNCCN.NCCNCCNCCN.NCCNCCN.C(CN)N QBZUBYHCCJDUPQ-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- YXEBFFWTZWGHEY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohex-3-en-1-yl]methanol Chemical compound OCC1(CO)CCC=CC1 YXEBFFWTZWGHEY-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- FQXGWIPOXCDJAD-UHFFFAOYSA-N n'-(2-aminoethyl)ethane-1,2-diamine;carbonic acid Chemical compound OC(O)=O.NCCNCCN FQXGWIPOXCDJAD-UHFFFAOYSA-N 0.000 description 1
- AHDOGNDVBRYQHI-UHFFFAOYSA-N n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine;octadecanoic acid Chemical compound NCCNCCNCCN.CCCCCCCCCCCCCCCCCC(O)=O AHDOGNDVBRYQHI-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- GPNLWUFFWOYKLP-UHFFFAOYSA-N s-(1,3-benzothiazol-2-yl)thiohydroxylamine Chemical class C1=CC=C2SC(SN)=NC2=C1 GPNLWUFFWOYKLP-UHFFFAOYSA-N 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
Definitions
- 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 et al., U.S. Patent 3,985,708; Chang, U.S. Patent 4,000,213; and Li et al., U.S. Patent 4,028,305, all of which are incorporated herein by reference.
- elastomer In order for an elastomer to achieve commercial success, it must be vulcanizable to useful products with an efficient, practical vulcanization system. It is an object of the invention to rovide useful vulcanized products from thiodiethanol-based elastomers, and to provide elastomers exhibiting significantly improved aged properties, such as compression set.
- the present invention provides a novel vulcanization 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. DESCRIPTION OF THE INVENTION
- 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:
- n is an integer from 1 to about 10, to complex reaction products of ethylene dichloride and ammonia, which boil above the boiling point of diethylenetriamine (206.7°C), 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 representative of the above formula (1) 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: H 2 N-CH 2 CH 2 -NH-CH 2 CH 2 -NH-CH 2 CH 2 -NH-CH 2 CH 2 -NH-CH 2 CH 2 -NH 2 CH 2 -NH 2 CH 2 -NH 2
- Aminoethyl diperazinoethane In addition to the linear, branched chain and cyclic polyethyleneamines, organic salts thereof, which dissociate under vulcanization conditions to liberate the free amine, may also be used.
- Useful organic salts are those which are formed from acids having a dissociation constant less than about 10 -3 , and including salts of aliphatic carboxylic acids, especially those of 2-18 carbon atoms, carbonic acid, carbamic acid and the like. Particularly useful salts are the fatty acid salts, e.g., the stearate. Useful salts also include the condensation products of polyethylene amines 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 disclosed in the aforementioned patent to Aloia and Chang et al. (708).
- the vulcanizable elastomers of thiodiethanol is a polymer represented by the formula: (II) H wherein comprises randomly alternating structural units selected from
- 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 unsatu ration having an allylic hydrogen atom, wherein R' is one 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 of at least 8000; (2) the molar ratio of (III) to (IV), when said polymer comprises structural units (E), or the molar ratio of (III) to the total of (IV) and (V) when said polymer comprises structural units (F), being not less than 1:1 and (3) they contain from about 1 to 10 mole percent of said diol (b) based on the total of all units (III), (IV)
- the vulcanization system of 3 the invention comprises sulfur in an amount of from about 0.3 to 3.0 parts by weight per hundred parts of elastomer, preferably 0.3 to 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 4 parts, same basis.
- 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 carbonate, calcium silicate, and the like; calcium oxide or calcium stearate (or other fatty acid salt) to neutralize acid catalyst residues in the elastomer; processing aids, such as sorbitan monostearate or stearic acid; sulfur-donating compounds; mercaptobenzothiazole; sulfenamides; thiuram sulfides, and the like, without departing from the scope of the invention.
- fillers and reinforcing agents e.g., carbon black, precipitated hydrous silica, titanium dioxide, calcium carbonate, calcium silicate, and the like
- calcium oxide or calcium stearate (or other fatty acid salt) to neutralize acid catalyst residues in the elastomer
- processing aids such as sorbitan monostearate or ste
- the vulcanizable compositions may be prepared by conventional rubber compounding techniques, using a tworoll rubber mill or a Banbury mixer, at temperatures of
- compositions are vulcanized at similar temperatures, preferably about 325-350°F for about 15 to 60 minutes and, optionally, post-cured for periods of time to develop full cures.
- the following examples are set forth for purposes of illustration only and are not to be construed as limitations on the present invention. All parts and percentages are by weight unless otherwise specified.
- EXAMPLE 1 An elastomeric copolymer of 80% thiodiethanol, 15% isopropylidenebisphenol and 5% trimethylolpropane, monoallyl ether was compounded as follows:
- compositions A thru C were cured for 60 minutes at 330°F and then post-cured for 16 hours at 120°C before testing.
- composition A which represents a conventional sulfur vulcanization system, provides 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 mechanical properties.
- Composition B demonstrates that a very poor cure is obtained without zinc oxide in a conventional vulcanization system.
- Polyamine D See Example 1 2 3 4 The compositions were cured for 30 minutes at
- compositions were cured for 30 minutes at 330°F and post-cured for 4 hours at 120°C. Torque (inch-pounds) was measured at 330°F after
- the stress-strain properties were as follows: Tensile , psi 520 1550 1500 1540
- compositions were cured for 60 minutes at
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Elastomeres vulcanisables au soufre derives de thiodiethanol et, en particulier, nouveau systeme de vulcanisation comprenant du soufre et une chaine ramifiee lineaire aliphatique ou une polyethylene amine cyclique ou un sel organique dissociable.Sulfur vulcanizable elastomers derived from thiodiethanol and, in particular, new vulcanization system comprising sulfur and an aliphatic linear branched chain or a cyclic polyethylene amine or a dissociable organic salt.
Description
VULCANIZATION SYSTEM FOR THIODIETHANOL-BASED 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 et al., U.S. Patent 3,985,708; Chang, U.S. Patent 4,000,213; and Li et al., U.S. Patent 4,028,305, all of which are incorporated herein by reference. Heretofore, application of 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 vulcanized elastomers exhibit poor heat aging 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, it must be vulcanizable to useful products with an efficient, practical vulcanization system. It is an object of the invention to rovide useful vulcanized
products from thiodiethanol-based elastomers, and to provide elastomers exhibiting significantly improved aged properties, such as compression set.
SUMMARY OF THE INVENTION The present invention provides a novel vulcanization 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. DESCRIPTION OF THE INVENTION
INCLUDING PREFERRED 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:
(I)
wherein n is an integer from 1 to about 10, to complex reaction products of ethylene dichloride and ammonia, which boil above the boiling point of diethylenetriamine (206.7°C), 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 representative of the above formula (1) 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:
H2N-CH2CH2-NH-CH2CH2-NH-CH2CH2-NH-CH2CH2-NH-CH2CH2-NH2
Pentacthylenehexamine H2N-CH2CH2-NH-CH2CH2-N-CH2CH2-NH-CH2CH2-NH2
I
CH2
I
CH2
I
NH2 Symmetrical diaminoethyltriaminoethylamine H2N-CH2CH2-N-CH2CH2-NH-CH2CH2-NH-CH2CH2-NH2 I
CH2
I
CH2
I
NH2 Unsymmetrical diaminoethyltriaminoethylamine
H2N-CH2CH2 CH2CH2NH2 N-CH2CH2-N H2N-CH2CH2
CH2CH2-NH2
Symmetrical diaminoethy1triethylenetetramine CH2CH2 H2NOCH2CH2-NH-CH2CH2-N N-CH2CH2-NH-CH2CH2-NH2
CH2CH2
Symmetrical diaminoethyldiaminoethyl piperazine CH2CH2 H2N-CH2CH2-N N-CH2CH2-NH-CH2CH2-NH-CH2CH2-NH2
CH2CH2
Unsymmetrical diaminoethyldiaminoethyl piperazine CH2CH2 HN
N(-CH2CH2-NH2)3CH2CH2-NH2
CH2CH2
Pipeτazinoethyl triethylene tetramine H2N-CH2CH2-N-CH2-NH-CH2CH2-NH2
I
CH2
I
CH2
H 4-(N-pipeτazinoethyl)triethylene tetramine -CH2CH2-NH-CH2CH2
Bispiperazinoethylamine
H2N-CH2CH2 -CH2CH2
Aminoethyl diperazinoethane In addition to the linear, branched chain and cyclic polyethyleneamines, organic salts thereof, which dissociate under vulcanization conditions to liberate the free amine, may also be used.
Useful organic salts are those which are formed from acids having a dissociation constant less than about 10-3 , and including salts of aliphatic carboxylic acids, especially those of 2-18 carbon atoms, carbonic acid, carbamic acid and the like. Particularly useful salts are the fatty acid salts, e.g., the stearate. Useful salts also include the condensation products of polyethylene
amines 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 disclosed in the aforementioned patent to Aloia and Chang et al. (708).
Specifically, the vulcanizable elastomers of thiodiethanol is a polymer represented by the formula: (II) H
wherein
comprises randomly alternating structural units selected from
(E) structural units (III) and (IV) (III)
(IV) [OR] or (F) structural units (III), (IV) and (V)
(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 unsatu ration having an allylic hydrogen atom, wherein R' is one 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 of at least 8000; (2) the molar ratio of (III) to (IV), when said polymer comprises structural units (E), or the molar ratio of (III) to the total of (IV) and (V) when said
polymer comprises structural units (F), being not less than 1:1 and (3) they contain 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 polymer.
The vulcanization system of3the invention comprises sulfur in an amount of from about 0.3 to 3.0 parts by weight per hundred parts of elastomer, preferably 0.3 to 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 4 parts, same basis.
In addition to sulfur and the polyamine compound, 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 carbonate, calcium silicate, and the like; calcium oxide or calcium stearate (or other fatty acid salt) to neutralize acid catalyst residues in the elastomer; processing aids, such as sorbitan monostearate or stearic acid; sulfur-donating compounds; mercaptobenzothiazole; sulfenamides; thiuram sulfides, and the like, without departing from the scope of the invention.
The vulcanizable compositions may be prepared by conventional rubber compounding techniques, using a tworoll rubber mill or a Banbury mixer, at temperatures of
300°F. The compositions are vulcanized at similar temperatures, preferably about 325-350°F for about 15 to 60 minutes and, optionally, post-cured for periods of time to develop full cures. The following examples are set forth for purposes of illustration only and are not to be construed as limitations on the present invention. All parts and percentages are by weight unless otherwise specified.
EXAMPLE 1 An elastomeric copolymer of 80% thiodiethanol, 15% isopropylidenebisphenol and 5% trimethylolpropane, monoallyl ether was compounded as follows:
Parts by Weight Elastomer 100 Carbon Black 60
Calcium oxide 3
Soirbitan monostearate 2
Sulfur 1.5
Tetramethyl thiuram disulfide 1.5 168.0
To separate portions (168 parts) of the above formulation was added:
A B C
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.
Each of the compositions A thru C was cured for 60 minutes at 330°F and then post-cured for 16 hours at 120°C before testing.
Rheology of the compositions was studied using a Monsanto Oscillating Disc Rheometer operating at 330°F.
Rheometer
A B C
Max. cure rate 6.5 0. 1 1.45
(inch-lbs./min.) Max. torque (inch-lbs.) 40.5 _ 87 Torque after 15 minutes 40.5 9 35 (inch - lbs.)
Stress-strain properties of the cured compositions using an Instron tester were as follows: 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 stressrelaxometer consisting of load-sensing elements, a means for extending and maintaining the specimens at a constant elongation, and a circulating air oven. The oven temperature was maintained at a temperature of 150°C + 0.1°C 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)/f(O) 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-O, respectively, required to maintain the sample at a given extension. The data are reported as
5 0 which represents the time at 150°C that is required for a sample to degrade to a value equal to 50% of the initial stress, which is a measure of the amount of degradation experienced by the specimen. Continuous Stress-Relaxation A B C 50'minutes 350 - 2450
The data illustrate that Composition A, which represents a conventional sulfur vulcanization system, provides 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 mechanical properties. Composition B demonstrates that a very poor cure is obtained without zinc oxide in a conventional vulcanization system.
EXAMPLE 2 Following the procedure of Example 1 an elastomeric copolymer of 90% thiodiethanol - 5% diethyleneglycol - 5% trimethylolpropane, monoallyl ether was compounded as follows:
Parts by Weight
Elastomer 100
Carbon black 50
Antioxidant* 2
Tetramethyl thiuram disulfide 1.5
Mercaptobenzothiazole 2.0
Sulfur 1.5
Calcium stearate 3.0
160.0 *Di-B-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 The compositions were cured for 30 minutes at
330°F and post-cured for 16 hours at 120°C. Properties were as follows.
Monsanto Rheometer @ 330°F
D E F Max. cure rate 1.4 2.1 2.4 Max. torque 80+ 95+ 95+
Torque after 15 minutes 39 51 51 Instron Stress-Strain Properties
D E F Tensile, psi 1645 1715 1490 Elongation, % 370 300 270 Compression Set, % 89 62 41
(Method B: 22 hrs. at 120°C) Continuous Stress-Relaxation 50'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 manifested by improved compression set and stress-relaxation.
EXAMPLE 3 An elastomeric copolymer of 90% thiodiethanol - 5% diethyleneglycol - 5% trimethylolpropane, monoallyl ether was compounded as follows:
Parts by Weight Elastomer 100
Carbon black 50
Calcium stearate 5
Sulfur 1.5
Mercaptobenzothiazole 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
Triethylenetetramine 4 - - - Tetraethylenepentamine : - 4
Polyamine D** (50% on silica) - - 8 - Polyamine H * - - - 4 *Complex polyethyleneamine reaction product boiling above
340°C and containing 24-28% by weight of diethylenetriamine **See Example 1.
The compositions were cured for 30 minutes at 330°F and post-cured for 4 hours at 120°C. Torque (inch-pounds) was measured at 330°F after
30 minutes using a Monsanto Oscillating Disc Rheometer. This is an indication of the extent of cure of the composition.
G H J K Torque after 30 min. 61 60 66 66
The stress-strain properties, obtained on an Instron tester, were as follows:
Tensile , psi 520 1550 1500 1540
Elongation, % 490 455 470 435
Hardness, Shore "A" 74 76 75 77
Compression Set, % 34 33 37 27 (Method B: 22 hrs. at 120°C)
The data illustrate that good cures are obtained using various polyethyleneamines with sulfur and that the cured compositions exhibit good ageing resistance, as manifested by low compression set. EXAMPLE 4
An elastomer of 90 percent thiodiethanol - 5% diethyleneglycol - 5% trimethylolpropane, monoallyl ether, was compounded as follows:
Parts by Weight
Control K
Elastomer 100 100
Carbon black 50 50
Calcium stearate 5 5
Sulfur 1.5 1.5 Mercaptobenzothiazole 1.5 1.5
Tetramethyl thiuram disulfide 1.5 1.5
Triethylenetetramine stearate - 4
The compositions were cured for 60 minutes at
330°F. Stress-strain properties are as follows: 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-cyclohexene-1, 1-dimethanol. Similar results were achieved.
EXAMPLE 7 When the procedure of Example 4 was again followed except that the diethylene glycol was replaced by isopropylidene bisphenol, similar results were achieved.
EXAMPLE 8 The procedure of Example 1 was again followed except that Polyamine D was replaced by diethylenetriamine carbonate. Excellent results were observed.
EXAMPLE 9 Following the procedure of Example 8 except that the carbonate was replaced by the corresponding carbamate, the results were comparable.
Claims
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 polyethyleneamines with organic acids having a dissociation constant less than about 10-3; and (D) mixtures thereof; said vulcanizable elastomer of thiodiethanol being a copolymer represented by the formula (II): (II) wherein [OG] comprises randomly alternating structural units selected from:
(E) structural units (III) and (IV) OR 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 having an allylic hydrogen atom; wherein R' is one or more radicals which remain on removal of two hydroxyl groups from a diphenolic compound; said copolymers 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 structural 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 accordance with Claim 1 wherein said copolymer of thiodiethanol comprises randomly alternating structural units (E).
3. A vulcanizable elastomer composition in accordance with Claim 1 wherein said copolymer of thiodiethanol comprises randomly alternating structural units (F).
4. A vulcanizable elastomer composition in accordance with Claim 1 wherein said polyamine comprises a polyethyleneamine represented by (A).
5. A vulcanizable elastomer composition in accordance with Claim 4 wherein n is an integer from 3 to 6.
6. A vulcanizable elastomer composition in accordance with Claim 1 wherein said polyamine comprises (B).
7. A vulcanizable elastomer composition in accordance with Claim 1 wherein said polyamine comprises (C).
8. A vulcanizable elastomer composition in accordance with Claim 7 wherein said acid is an aliphatic carboxy lic acid, carbonic acid, or carbamic acid.
9. A vulcanizable elastomer composition in accordance with Claim 8 wherein said acid is an aliphatic monocarboxylic acid containing from 2 to 18 carbon atoms.
10. A vulcanizable elastomer composition in accordance with Claim 8 wherein said acid is carbonic acid.
11. A vulcanizable elastomer composition in accordance with Claim 8 wherein said acid is carbamic acid.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1980/000277 WO1981002740A1 (en) | 1980-03-17 | 1980-03-17 | Vulcanization system for thiodiethanol-based elastomers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0047736A1 true EP0047736A1 (en) | 1982-03-24 |
| EP0047736A4 EP0047736A4 (en) | 1982-07-19 |
Family
ID=22154242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19800902074 Withdrawn EP0047736A4 (en) | 1980-03-17 | 1980-03-17 | Vulcanization system for thiodiethanol-based elastomers. |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0047736A4 (en) |
| JP (1) | JPS6361965B2 (en) |
| BR (1) | BR8009040A (en) |
| WO (1) | WO1981002740A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4637253B2 (en) * | 2009-06-30 | 2011-02-23 | キヤノン株式会社 | Novel organic compound, organic light emitting device and image display device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3499864A (en) * | 1968-08-19 | 1970-03-10 | Edward Millen | Heat stable storable,one part polythiol compositions with amine-loaded molecular sieves |
| DE2324628A1 (en) * | 1972-05-22 | 1973-12-13 | Thiokol Chemical Corp | PROCESS FOR CURING BLOCKED LIQUID POLYSULFIDE POLYMERS |
| WO1981002741A1 (en) * | 1980-03-14 | 1981-10-01 | American Cyanamid Co | Elastomers derived from thiodiethanol having reduced odor and increased thermal stability |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3985708A (en) * | 1974-09-18 | 1976-10-12 | American Cyanamid Company | Polymeric reaction products of thiodiethanol and diphenols |
| US3951927A (en) * | 1974-09-18 | 1976-04-20 | American Cyanamid Company | Vulcanizable elastomers from polythiodiethanol |
| US4000213A (en) * | 1974-12-19 | 1976-12-28 | American Cyanamid Company | Use of diepoxides in polythiodiethanol millable gums |
| US4028305A (en) * | 1974-12-19 | 1977-06-07 | American Cyanamid Company | Vulcanizable elastomers derived from thiodiethanol |
-
1980
- 1980-03-17 WO PCT/US1980/000277 patent/WO1981002740A1/en not_active Application Discontinuation
- 1980-03-17 JP JP55502550A patent/JPS6361965B2/ja not_active Expired
- 1980-03-17 EP EP19800902074 patent/EP0047736A4/en not_active Withdrawn
- 1980-03-17 BR BR8009040A patent/BR8009040A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3499864A (en) * | 1968-08-19 | 1970-03-10 | Edward Millen | Heat stable storable,one part polythiol compositions with amine-loaded molecular sieves |
| DE2324628A1 (en) * | 1972-05-22 | 1973-12-13 | Thiokol Chemical Corp | PROCESS FOR CURING BLOCKED LIQUID POLYSULFIDE POLYMERS |
| WO1981002741A1 (en) * | 1980-03-14 | 1981-10-01 | American Cyanamid Co | Elastomers derived from thiodiethanol having reduced odor and increased thermal stability |
Non-Patent Citations (1)
| Title |
|---|
| See also references of WO8102740A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6361965B2 (en) | 1988-11-30 |
| WO1981002740A1 (en) | 1981-10-01 |
| JPS57500472A (en) | 1982-03-18 |
| EP0047736A4 (en) | 1982-07-19 |
| BR8009040A (en) | 1982-03-09 |
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