CA1054294A - Millable, sulfur-vulcanizable elastomers - Google Patents
Millable, sulfur-vulcanizable elastomersInfo
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- CA1054294A CA1054294A CA240,631A CA240631A CA1054294A CA 1054294 A CA1054294 A CA 1054294A CA 240631 A CA240631 A CA 240631A CA 1054294 A CA1054294 A CA 1054294A
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- 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
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- 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
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- 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
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
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- 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
- C08G65/48—Polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/20—Cross-linking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polyethers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Epoxy Compounds (AREA)
Abstract
TITLE: MILLABLE, SULFUR-VULCANIZABLE
ELASTOMERS
ABSTRACT OF THE DISCLOSURE
Polythioether polyols based on a major proportion of thiodiethanol and chain-extended by reaction with a diepoxide provide millable, sulfur-vulcanizable elastomeric compositions that provide, when vulcanized, good low tem-perature flexibility and low oil swell.
ELASTOMERS
ABSTRACT OF THE DISCLOSURE
Polythioether polyols based on a major proportion of thiodiethanol and chain-extended by reaction with a diepoxide provide millable, sulfur-vulcanizable elastomeric compositions that provide, when vulcanized, good low tem-perature flexibility and low oil swell.
Description
This invention relates to millable, sulfur-vul-canizable elastomeric compositions comprising certain chain-extended polythioether polyols. More particularly, this invention relates to such elastomeric compositions wherein the polythioether polyol is based on a major proportion of thiodiethanol, a minor proportion of a diol furnishing external unsaturation, and, optionally, other diols, the polythioether polyol being chain-extended by reaction with a diepoxide to improve its processability on rubber mills.
Thiodiethanol exhibits unusual reactivity because - of the positioning of its hydroxyl groups at the betaposi-tions with respect to the sulfur atom in the aliphatic chain.
Thus, unlike conventional aliphatic diols, it will undergo autocondensation in the presence of certain acidic catalysts to provide polymeric materials. Within certain limits and under certain conditions, thiodiethanol will condense with one or more aliphatic diols to give rubbery polymers. Such polymers are described in commonly assigned, copending Canadian application, Serial No. 233,291, filed August 12, 1975.
Thiodiethanol will also undergo condensation with one or more aromatic dihydroxy compounds, or with a mixtùre of one or more aromatic dihydroxy compounds and one or more aliphatic diols, to provide sulfur-vulcanizable elastomeric compositions. Such compositions are described in commonly assigned, copending Canadian application Serial No. 233,431, filed August 14, 1975.
It is well-known that the Mooney value of an elas-tomeric composition is indicative of its processability on rubber mills. The Mooney value of a natural rubber, for ~054'~94 example, is high due to naturally occurring cross-links.
Natural rubber, with a Mooney value of about 60, must be broken down on the rubber mill before conventional compoun-ding ingredients can be incorporated. Most synthetic elas-tomers have Mooney values in the range of about 15 to 50,and most elastomers having Mooney values of about 5 to 15 cannot be handled easily on a rubber mill~ Depending in part on the chemical nature of the composition, is not always possible to provide an elastomer having a Mooney value above about 15~ In addition, even some of those elastomers that have Mooney values above 15 could be im-proved in processability by increases in their Mooney value.
A problem that arises with respect to some of the aforementioned condensation polymers is that they are gums having low Mooney values. Thus, even though they are curable by conventional sulfur vulcanization techniques, they are difficult to process on rubber mills. Thus, although such polymers have desirable properties for use in vulcanized rubber applicationsr the difficulties of pro-cessing such polymers tends to limit their use.
The provision of polymers of the type described,modified so as to have the necessary Mooney value to be acceptably processable, would constitute a notable advance in the art and promote utilization of such polymers in vulcanized rubber applications.
In accordance with the present invention, there is provided a millable, sulfur-vulcanizable elastomeric com-position comprising a copolymer represented by a polymer chain of the formula:
~ R* OG
~054294 wherein R represents a radical derived from a diepoxide, or mixture of diepoxides, by cleavage on one bond on each oxygenation of the diepoxide, the cleavage being the result of reaction of the diepoxide with the terminal hydroxyl groups of a polythioether polyol represented by the formula H ~ G3x OH, wherein ~ OG ~
comprises randomly alternating units of (I) ~ C2H4SC2H4~ , (II) ~ OR' ~ , (III) ~ OR" ~ , and (IV) ~OR"'~
wherein R' represents a radical remaining on-removal of both hydroxyl groups from an aliphatic diol or mixture of ali-phatic diols, R" is an aromatic radical remaining on removal of both hydroxyl groups from an aromatic dihydroxy compound or mixture of aromatic dihydroxy compounds, R"' is the radical remaining on removal of both hydroxy groups of an aliphatic diol that provides an allylic double hond external to said polymer chain, wherein the mole ratio of structural units (I) to the total of units ~II), (III), and (IV) is greater than 1:1 and the content of structural units (IV) is about 1 to 10 mole percent of the total mole content of ~ OG ~ ; and wherein units (II) and (III) are optional and wherein X is a number such that the Mooney value of said polythioether polyol is less than about 20 and n is an integer such that the Mooney value of said copolymer is substantially higher than the Mooney value of said polythio-ether polyol. In preferred instances the Mooney value ofthe copolymer will be in excess of about 30.
The elastomeric compositions of the present inven-tion are readily processed on conventional rubber mills and, when subsequently cured by conventional techniques, produce useful elastomers.
The copolymers of the present invention result from chain-extending a polythioether polyol with a diepoxide, such chain-extension providing an increase in Mooney value 1054;~94 so as to impart desirable porcessability on rubber mills to the resulting copolymer.
In preparing the polythioether polyol for use in the pres~nt invention, two essential ingredients are invol-ved, thiodiethanol and an aliphatic diol containing an allylic double bond external to the polymer chain. In addition to these essential ingredients, use can also be made of one or more aliphatic diols, one or more aromatic dihydroxy compounds, or a combination of one or more aro-matic dihydroxy compounds and aliphatic diols.
Thiodiethanol, HOCHzCH2-S-CH2CH2OH, is the major ingredient of the polyether polyol and will constitute at least 50 mole percent of the total molar content of the polythioether polyol. This diol furnishes the (I) -OCH2CH2SCH~CH~-, structural units of the polythioether polyol. When the aliphatic diol furnishing allylic unsatu-ration as defined is the only other ingredient of the poly-thioether polyol, thiodiethanol will furnish from 90 to 99 mole percent of the structural units of the polythioether polyol. It is generally preferred that another diol, or dihydroxy compound, also be present with thiodiethanol and the unsaturated diol within the range states, but this is optional.
As indicated, one or more aliphatic diols may also ~5 be employed in preparing the polythioether polyol, such content being from 0 to about 49 percent, based on the total mole percent of structural units of the polythioether polyol.
Suitable aliphatic diols include compounds in which the entire structure is aliphatic or cycloaliphatic as well as compounds in which mixed aromatic and aliphatic structures are involved so long as the hydroxyl groups are linked directly with the aliphatic structure. Suitable aliphatic structure. Suitable aliphatic diols, as defined immediately above, include but are not limited to ethylene glycol, propane -1,2-diol, propane -1,3-diol, butane -1,4-diol, pentane -1,5-diol, hexane -1,6-diol, diethylene glycol, cyclohexane -1,4-diol, cyclohexane -l,l-dimethanol, cyclo-hexane -1,3-dimethanol, cyclohexane -1,4-dimethanol, bis-ethers of dihydroxy aromatic compounds such as bis(hydroxy-ethoxy)hydroquinone or bis(hydroxyethoxy) resorcinol, and the like.
As also indicated, one or more aromatic dihydroxy compounds may be employed in place of or in conjunction with one or more aliphatic diols, such content being from O to about 49 mole percent, based on the total mole percent of structural units of the polythioether polyol. Sultable aromatic dihydroxy compounds include compounds containing two hydroxyl groups each of which is attached to an aromatic ring, not necessarily the same aromatic ring, and thus con-tain two phenol groups. Aromatic compounds that have the hydroxyl groups attached to side chains pendant from the aromatic ring or rings are, for the purpose of the present ~0 invention considered aliphatic diols, as defined above.
Useful aromatic dihydroxy compounds according to the above definition include 4,4'-dihydroxybenzophenone, 4,4'-iso-propylidenebisphenol, 4,4'-sulfonyldiphenol; hydroquinone, resorcinol, 1,4-naphthalene diol, 2,6-naphthalene diol, 1,
Thiodiethanol exhibits unusual reactivity because - of the positioning of its hydroxyl groups at the betaposi-tions with respect to the sulfur atom in the aliphatic chain.
Thus, unlike conventional aliphatic diols, it will undergo autocondensation in the presence of certain acidic catalysts to provide polymeric materials. Within certain limits and under certain conditions, thiodiethanol will condense with one or more aliphatic diols to give rubbery polymers. Such polymers are described in commonly assigned, copending Canadian application, Serial No. 233,291, filed August 12, 1975.
Thiodiethanol will also undergo condensation with one or more aromatic dihydroxy compounds, or with a mixtùre of one or more aromatic dihydroxy compounds and one or more aliphatic diols, to provide sulfur-vulcanizable elastomeric compositions. Such compositions are described in commonly assigned, copending Canadian application Serial No. 233,431, filed August 14, 1975.
It is well-known that the Mooney value of an elas-tomeric composition is indicative of its processability on rubber mills. The Mooney value of a natural rubber, for ~054'~94 example, is high due to naturally occurring cross-links.
Natural rubber, with a Mooney value of about 60, must be broken down on the rubber mill before conventional compoun-ding ingredients can be incorporated. Most synthetic elas-tomers have Mooney values in the range of about 15 to 50,and most elastomers having Mooney values of about 5 to 15 cannot be handled easily on a rubber mill~ Depending in part on the chemical nature of the composition, is not always possible to provide an elastomer having a Mooney value above about 15~ In addition, even some of those elastomers that have Mooney values above 15 could be im-proved in processability by increases in their Mooney value.
A problem that arises with respect to some of the aforementioned condensation polymers is that they are gums having low Mooney values. Thus, even though they are curable by conventional sulfur vulcanization techniques, they are difficult to process on rubber mills. Thus, although such polymers have desirable properties for use in vulcanized rubber applicationsr the difficulties of pro-cessing such polymers tends to limit their use.
The provision of polymers of the type described,modified so as to have the necessary Mooney value to be acceptably processable, would constitute a notable advance in the art and promote utilization of such polymers in vulcanized rubber applications.
In accordance with the present invention, there is provided a millable, sulfur-vulcanizable elastomeric com-position comprising a copolymer represented by a polymer chain of the formula:
~ R* OG
~054294 wherein R represents a radical derived from a diepoxide, or mixture of diepoxides, by cleavage on one bond on each oxygenation of the diepoxide, the cleavage being the result of reaction of the diepoxide with the terminal hydroxyl groups of a polythioether polyol represented by the formula H ~ G3x OH, wherein ~ OG ~
comprises randomly alternating units of (I) ~ C2H4SC2H4~ , (II) ~ OR' ~ , (III) ~ OR" ~ , and (IV) ~OR"'~
wherein R' represents a radical remaining on-removal of both hydroxyl groups from an aliphatic diol or mixture of ali-phatic diols, R" is an aromatic radical remaining on removal of both hydroxyl groups from an aromatic dihydroxy compound or mixture of aromatic dihydroxy compounds, R"' is the radical remaining on removal of both hydroxy groups of an aliphatic diol that provides an allylic double hond external to said polymer chain, wherein the mole ratio of structural units (I) to the total of units ~II), (III), and (IV) is greater than 1:1 and the content of structural units (IV) is about 1 to 10 mole percent of the total mole content of ~ OG ~ ; and wherein units (II) and (III) are optional and wherein X is a number such that the Mooney value of said polythioether polyol is less than about 20 and n is an integer such that the Mooney value of said copolymer is substantially higher than the Mooney value of said polythio-ether polyol. In preferred instances the Mooney value ofthe copolymer will be in excess of about 30.
The elastomeric compositions of the present inven-tion are readily processed on conventional rubber mills and, when subsequently cured by conventional techniques, produce useful elastomers.
The copolymers of the present invention result from chain-extending a polythioether polyol with a diepoxide, such chain-extension providing an increase in Mooney value 1054;~94 so as to impart desirable porcessability on rubber mills to the resulting copolymer.
In preparing the polythioether polyol for use in the pres~nt invention, two essential ingredients are invol-ved, thiodiethanol and an aliphatic diol containing an allylic double bond external to the polymer chain. In addition to these essential ingredients, use can also be made of one or more aliphatic diols, one or more aromatic dihydroxy compounds, or a combination of one or more aro-matic dihydroxy compounds and aliphatic diols.
Thiodiethanol, HOCHzCH2-S-CH2CH2OH, is the major ingredient of the polyether polyol and will constitute at least 50 mole percent of the total molar content of the polythioether polyol. This diol furnishes the (I) -OCH2CH2SCH~CH~-, structural units of the polythioether polyol. When the aliphatic diol furnishing allylic unsatu-ration as defined is the only other ingredient of the poly-thioether polyol, thiodiethanol will furnish from 90 to 99 mole percent of the structural units of the polythioether polyol. It is generally preferred that another diol, or dihydroxy compound, also be present with thiodiethanol and the unsaturated diol within the range states, but this is optional.
As indicated, one or more aliphatic diols may also ~5 be employed in preparing the polythioether polyol, such content being from 0 to about 49 percent, based on the total mole percent of structural units of the polythioether polyol.
Suitable aliphatic diols include compounds in which the entire structure is aliphatic or cycloaliphatic as well as compounds in which mixed aromatic and aliphatic structures are involved so long as the hydroxyl groups are linked directly with the aliphatic structure. Suitable aliphatic structure. Suitable aliphatic diols, as defined immediately above, include but are not limited to ethylene glycol, propane -1,2-diol, propane -1,3-diol, butane -1,4-diol, pentane -1,5-diol, hexane -1,6-diol, diethylene glycol, cyclohexane -1,4-diol, cyclohexane -l,l-dimethanol, cyclo-hexane -1,3-dimethanol, cyclohexane -1,4-dimethanol, bis-ethers of dihydroxy aromatic compounds such as bis(hydroxy-ethoxy)hydroquinone or bis(hydroxyethoxy) resorcinol, and the like.
As also indicated, one or more aromatic dihydroxy compounds may be employed in place of or in conjunction with one or more aliphatic diols, such content being from O to about 49 mole percent, based on the total mole percent of structural units of the polythioether polyol. Sultable aromatic dihydroxy compounds include compounds containing two hydroxyl groups each of which is attached to an aromatic ring, not necessarily the same aromatic ring, and thus con-tain two phenol groups. Aromatic compounds that have the hydroxyl groups attached to side chains pendant from the aromatic ring or rings are, for the purpose of the present ~0 invention considered aliphatic diols, as defined above.
Useful aromatic dihydroxy compounds according to the above definition include 4,4'-dihydroxybenzophenone, 4,4'-iso-propylidenebisphenol, 4,4'-sulfonyldiphenol; hydroquinone, resorcinol, 1,4-naphthalene diol, 2,6-naphthalene diol, 1,
2~ 6-naphthalene diol, 1,8-naphthalene diol, p,p'-biphenol, o,o'-biphenol, and the like.
The expression "allylic unsaturation external to the polymer chain" d~notes the chemical structure -CH-CII=CH- incorporated into the polymer in a manner such that it is possible to pass from one end of the main polymer chain to the other without traversing the allylic structure.
The structure may thus be pendant to the main chain or may be included in an alicyclic ring. Aliphatic diols that lOS4294 contain allylic unsaturation that wi1l be external to the polymer chain upon condensation of said diol include 3-cyclo-hexene-l,l-dimethanol, monoallyl ether of trimethylol pro-pane, monoallyl ether of glycerol, and the like.
The various ingredients, essential and optional, to be used in preparing the polythioether polyol in the pro-portions specified, are reacted together in the presence of an acidic catalyst having a pK of 5 or less, usually at an elevated temperature, in accordance with conventional procedures. The preferred catalyst is phosphorous acid.
Other useful acids include hydrochloric acid, sulfuric acid, sulfamic acid, picric acid, trialkyl phosphites, ~-toluene-sulfonic acid, phosphoric acid-, and the like. It is to be noted that certain of the catalytic acids can give rise to undesirable side reactions such as formation of odoriferous thioxane or dithiane, and where this is objectionable such catalytic acids should be avoided. Effective catalysis is usually achieved using from about 0.0l to 3 weight percent of acid based on the weight of the reactants, preferably 0.l to l.0 weight percent, same basis. Although higher amounts of acid may be used, no advantage has been found to arise from such use.
The chain-extending reaction is carried out by mixing sufficient of a diepoxide therewith and effecting reaction at a moderately elevated temperature, preferably at about 120 to 180C. The reaction is carried out so as to produce a chain-extended polythioether polyol of substan-tially increased MoGney value which either imparts proces-sability on rubber mills to an otherwise unprocessable polyether polyol or provides an improvement with respect to processability.
As employed herein, the term "diepoxide" means any compound containing two epoxy groups. Useful diepoxides include: diglycidyl ether: 1,2,3j4-diepoxybutaine: 1,2,7,8-diepoxyoctane; 1,2,5,6-diepoxycyclooctane; dicylopentadiene diepoxide; the diglycidyl ethers of such compounds as 1,3-propanediol, 1,4-butanediol, 1,6-hexandiol, cyclohexane-l, 4-diol, cyclohexane~ dimethanol, cyclohexane-1,2-dimeth-anol, cyclohexane-1,3-dimethanol, cyclohexane-1,4-dimethanol, diethylene glycol, hydroquinone, resorcinol, 4,4-isopropyli-- denebisphenol, naphthalene diols, and the like.
The amount of diepoxide that is to be used in any given instance to provide the necessary chain extension cannot be precisely stated. This is because such usage varies depending upon the polythioether polyol to be chain extended and the diepoxide selected for use. In any case, the amount of diepoxide to be used will be that amount that provides the desired increase in processability on rubber - mills as reflected by Mooney values. Generally an effective amount of diepoxide is found in the range of about 0~05 to 5.0 weight percent based on the weight of the polyester polyol to be chain extended.
The polythioether polyols that are to be chain extended are, in general, those whose processability on rubber mills would benefit by such chain extension. Generally, any polythioether polyol that has a Mooney value below about 20 can benefit to some extent by chain extension to increase - its Mooney value substantially above its initial value. In preferred instances, polythioether polyols having Mooney values of about 20 and below are advantageously chain-extended to Mooney values of about 30 and above.
The term "Mooney value", sometimes called "Mooney viscosity", is a standard expression in the rubber com-pounding art. It is defined by the procedure described in ASTM Method D 1646-72, with measurement at 212F. using the large rotor described in the procedureO The rubber sample is inserted between the rotor and the die, heated for one minute, the rotor turned on for four minutes, and the viscosity (in Mooney units) is then read.
In general, increasing the molecular weight of a polymer will also increase its Mooney value. In the co-polymer . ~ OR3-~OG ~
increasing either x or n will increase the total molecular weight and hence the Mooney valueO All that is necessary for an understanding of the present invention is that the Mooney value of the copolymer is substantially higher than the Mooney value of the polythioether polyol, the increase arising due to the combination of subscripts x and n as opposed to the subscript x alone.
It is to be noted that the Mooney value of the - polymer compositions of the present invention may addition-ally be increased by the incorporation of small amounts of cross-linking, without departing from the scope of the invention. Such cross-linking is optional, and may be ob-tained by incorporating minor amounts of polyfunctional component in the polymer composition, for example, a triol, such as trimethylolpropane.
Particularly preferred embodiments of this invention are sulfur vulcanizable polythioether polyols derived from thiodiethanol and an unsaturated aliphatic diol, with or without 4,4'-isopropylidenebisphenol, chain-extended with about 0.1 percent to about 2 percent of the diglycidyl ether of 4,4'-isopropylidenebisphenol on the weight of the poly-thioether polyol.
The millable gums of this invention may be compoundedon standard rubber processing e~uipment with conventional compounding ingredients, such as carbon black or other pigments and fillers, w lcanizing agents such as accelera-tors and sulfur, promotors such as zinc oxide, lubricants and mold release agents, antioxidants, plasticizers and the like, and compression molded into useful elastomeric products.
Preparation of and the effectiveness of the compo-sitions employed in the present invention are further demon-strated in the examples below which are not to be taken as being limitative of the present invention~ Unless otherwise indicated, all parts and percentages employed herein are by weight.
A. Preparation of Polythioether Polyol In a suitable glass vessel, a mixture of 59.85 grams, 0.49 mole, of thiodiethanol, 7~0 grams, 0.03 mole, or 4,4'-isopropylidenebisphenol, 3.15 grams, 00022 mole, of 3-cyclo-hexane-l,l-dimethanol, and 0.56 gram of phosphorus acid, is heated ~or 1 hour in a 215C. oil bath under a nitrogen ; atmosphere. Vacuum is then applied reducing the internal pressure gradually from 760 mm to about 380 mm, then more slowly to about 7.5 mm and the temperature of the oil bath is reduced to 190-200C. After 2 hours the vessel is vented, an additional 0.14 gram of phosphorous acid is added to the reaction mixture and the reaction mixture is heated for 40 minutes at 190C./7.5 mm. The total amount of phosphorous acid is added represents 1.0 percent on the weight of the reactants used.
The vessel is vented, and the resulting polythio-ether polyol is recovered. The product is a gum so soft that it cannot be processed on a rubber mill.
B. Chain Extension of Polythioether Poly~
To the product of Part A is added 1.4 grams, 0.004 mole, of the diglycidyl ether of 4,4'-isopropylidenebisphenolr 2 percent on the weight of the reactants used, and the ~054294 reaction mixture is heated under vacuum at 190C. at 7O5 mm of mercury to chain-extend the copolymer. The chain-exten-ded polythioether polyol is a millable gum having a Mooney value of 23 at 100C.
A. Preparation of Polythioether Polyol In a conical mixer reactor a mixture of 85.0 grams, 0.690 mole, of thiodiethanol, 5.0 grams, 0.029 mole, of the monoallyl ether of 2-ethyl-2-(hydroxymethyl)-1,3-propane-10 diol, 10.0 grams, 0.044 mole, of 4,4'-isopropylidenebis-phenol, and 0.8 gram of phosphorous acid is heated for 1 hour in a 215C. oil bath under a nitrogen atmosphere.
Vacuum is then applied reducing the internal pressure step-wise from 760 mm to about 380 mm, then more slowly to about 15 7.5 mm and the temperature of the oil bath is reduced to 200C. and maintained at 200C. for 2 hours and 40 minutes.
The reactor is then coded and vented.
B. Chain Extension of Polythioether Polyol To the polythioether polyol of Part A is added 20 0.35 gram, 0.001 mole, of the diglycidyl ether of 4,4'-isopropylidenebisphenol, 0.35 percent on the weight of the reactants used, and the reaction mixture is heated for 2 hours at 190C./7.5 mm to chain-extend the polythioether polyol. The chain-extended polythioether polyol is a 25 millable gum having a Mooney value of 25 at 100C.
A. Preparation of Polythioether Polyol The procedure of Example 2, Part A, is followed except that the amounts used are 90.0 grams, 0.737 mole, of 30 thiodiethanol, 5.0 grams, 0.029 mole of the monoallyl ether of 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, 5.0 grams, 0.022 mole of 4,4'-isopropylidenebisphenol, and Q.8 gram of phosphorous acid.
B~ Chain Extension of Polythioether Polyol The reactor is vented and to the resulting poly-thioether polyol is added 0.50 gram, 0.0025 mole, of the diglycidyl ether of 1,4-butanediol, 0.5 percent on the weight of the original reactants, and the reaction mixture is heated for 2 hours at 190C./7~5 mm. The chain-extended polythioether polyol has a Mooney value of 22 at 100C.
. EXAMPLE 4 100 grams of the gum of Example 2, Part B, is com-pounded on a standard 2-roll rubber mill as follows:
Parts Gum 100 Carbon black 60 Calcium carbonate . 4 Calcium hydroxide 3 - Zinc oxide 5 Sulfur 2-mercaptobenzothiazole 1.5 Tetramethylthiuram disulfide 1.5 .
The compounded gum is compression moulded for 30 minutes at 150C~ and post-cured in an oven for 16 hours at ; 120C. The cured elastomer has the following stress-strain - properties:
Hardness, Shore A 70 Modulus at 100~, psi610 Tensile strength, psi1600 Elongation, % 240 The cured sample has an oil swell of ~ percent after 70 hours in No. 3 oil at 100C., and a low temperature flexibility of -52C.
A~ Preparation of Polythioether Polyol To a suitable glass vessel are added 465~0 grams, ~054Z94
The expression "allylic unsaturation external to the polymer chain" d~notes the chemical structure -CH-CII=CH- incorporated into the polymer in a manner such that it is possible to pass from one end of the main polymer chain to the other without traversing the allylic structure.
The structure may thus be pendant to the main chain or may be included in an alicyclic ring. Aliphatic diols that lOS4294 contain allylic unsaturation that wi1l be external to the polymer chain upon condensation of said diol include 3-cyclo-hexene-l,l-dimethanol, monoallyl ether of trimethylol pro-pane, monoallyl ether of glycerol, and the like.
The various ingredients, essential and optional, to be used in preparing the polythioether polyol in the pro-portions specified, are reacted together in the presence of an acidic catalyst having a pK of 5 or less, usually at an elevated temperature, in accordance with conventional procedures. The preferred catalyst is phosphorous acid.
Other useful acids include hydrochloric acid, sulfuric acid, sulfamic acid, picric acid, trialkyl phosphites, ~-toluene-sulfonic acid, phosphoric acid-, and the like. It is to be noted that certain of the catalytic acids can give rise to undesirable side reactions such as formation of odoriferous thioxane or dithiane, and where this is objectionable such catalytic acids should be avoided. Effective catalysis is usually achieved using from about 0.0l to 3 weight percent of acid based on the weight of the reactants, preferably 0.l to l.0 weight percent, same basis. Although higher amounts of acid may be used, no advantage has been found to arise from such use.
The chain-extending reaction is carried out by mixing sufficient of a diepoxide therewith and effecting reaction at a moderately elevated temperature, preferably at about 120 to 180C. The reaction is carried out so as to produce a chain-extended polythioether polyol of substan-tially increased MoGney value which either imparts proces-sability on rubber mills to an otherwise unprocessable polyether polyol or provides an improvement with respect to processability.
As employed herein, the term "diepoxide" means any compound containing two epoxy groups. Useful diepoxides include: diglycidyl ether: 1,2,3j4-diepoxybutaine: 1,2,7,8-diepoxyoctane; 1,2,5,6-diepoxycyclooctane; dicylopentadiene diepoxide; the diglycidyl ethers of such compounds as 1,3-propanediol, 1,4-butanediol, 1,6-hexandiol, cyclohexane-l, 4-diol, cyclohexane~ dimethanol, cyclohexane-1,2-dimeth-anol, cyclohexane-1,3-dimethanol, cyclohexane-1,4-dimethanol, diethylene glycol, hydroquinone, resorcinol, 4,4-isopropyli-- denebisphenol, naphthalene diols, and the like.
The amount of diepoxide that is to be used in any given instance to provide the necessary chain extension cannot be precisely stated. This is because such usage varies depending upon the polythioether polyol to be chain extended and the diepoxide selected for use. In any case, the amount of diepoxide to be used will be that amount that provides the desired increase in processability on rubber - mills as reflected by Mooney values. Generally an effective amount of diepoxide is found in the range of about 0~05 to 5.0 weight percent based on the weight of the polyester polyol to be chain extended.
The polythioether polyols that are to be chain extended are, in general, those whose processability on rubber mills would benefit by such chain extension. Generally, any polythioether polyol that has a Mooney value below about 20 can benefit to some extent by chain extension to increase - its Mooney value substantially above its initial value. In preferred instances, polythioether polyols having Mooney values of about 20 and below are advantageously chain-extended to Mooney values of about 30 and above.
The term "Mooney value", sometimes called "Mooney viscosity", is a standard expression in the rubber com-pounding art. It is defined by the procedure described in ASTM Method D 1646-72, with measurement at 212F. using the large rotor described in the procedureO The rubber sample is inserted between the rotor and the die, heated for one minute, the rotor turned on for four minutes, and the viscosity (in Mooney units) is then read.
In general, increasing the molecular weight of a polymer will also increase its Mooney value. In the co-polymer . ~ OR3-~OG ~
increasing either x or n will increase the total molecular weight and hence the Mooney valueO All that is necessary for an understanding of the present invention is that the Mooney value of the copolymer is substantially higher than the Mooney value of the polythioether polyol, the increase arising due to the combination of subscripts x and n as opposed to the subscript x alone.
It is to be noted that the Mooney value of the - polymer compositions of the present invention may addition-ally be increased by the incorporation of small amounts of cross-linking, without departing from the scope of the invention. Such cross-linking is optional, and may be ob-tained by incorporating minor amounts of polyfunctional component in the polymer composition, for example, a triol, such as trimethylolpropane.
Particularly preferred embodiments of this invention are sulfur vulcanizable polythioether polyols derived from thiodiethanol and an unsaturated aliphatic diol, with or without 4,4'-isopropylidenebisphenol, chain-extended with about 0.1 percent to about 2 percent of the diglycidyl ether of 4,4'-isopropylidenebisphenol on the weight of the poly-thioether polyol.
The millable gums of this invention may be compoundedon standard rubber processing e~uipment with conventional compounding ingredients, such as carbon black or other pigments and fillers, w lcanizing agents such as accelera-tors and sulfur, promotors such as zinc oxide, lubricants and mold release agents, antioxidants, plasticizers and the like, and compression molded into useful elastomeric products.
Preparation of and the effectiveness of the compo-sitions employed in the present invention are further demon-strated in the examples below which are not to be taken as being limitative of the present invention~ Unless otherwise indicated, all parts and percentages employed herein are by weight.
A. Preparation of Polythioether Polyol In a suitable glass vessel, a mixture of 59.85 grams, 0.49 mole, of thiodiethanol, 7~0 grams, 0.03 mole, or 4,4'-isopropylidenebisphenol, 3.15 grams, 00022 mole, of 3-cyclo-hexane-l,l-dimethanol, and 0.56 gram of phosphorus acid, is heated ~or 1 hour in a 215C. oil bath under a nitrogen ; atmosphere. Vacuum is then applied reducing the internal pressure gradually from 760 mm to about 380 mm, then more slowly to about 7.5 mm and the temperature of the oil bath is reduced to 190-200C. After 2 hours the vessel is vented, an additional 0.14 gram of phosphorous acid is added to the reaction mixture and the reaction mixture is heated for 40 minutes at 190C./7.5 mm. The total amount of phosphorous acid is added represents 1.0 percent on the weight of the reactants used.
The vessel is vented, and the resulting polythio-ether polyol is recovered. The product is a gum so soft that it cannot be processed on a rubber mill.
B. Chain Extension of Polythioether Poly~
To the product of Part A is added 1.4 grams, 0.004 mole, of the diglycidyl ether of 4,4'-isopropylidenebisphenolr 2 percent on the weight of the reactants used, and the ~054294 reaction mixture is heated under vacuum at 190C. at 7O5 mm of mercury to chain-extend the copolymer. The chain-exten-ded polythioether polyol is a millable gum having a Mooney value of 23 at 100C.
A. Preparation of Polythioether Polyol In a conical mixer reactor a mixture of 85.0 grams, 0.690 mole, of thiodiethanol, 5.0 grams, 0.029 mole, of the monoallyl ether of 2-ethyl-2-(hydroxymethyl)-1,3-propane-10 diol, 10.0 grams, 0.044 mole, of 4,4'-isopropylidenebis-phenol, and 0.8 gram of phosphorous acid is heated for 1 hour in a 215C. oil bath under a nitrogen atmosphere.
Vacuum is then applied reducing the internal pressure step-wise from 760 mm to about 380 mm, then more slowly to about 15 7.5 mm and the temperature of the oil bath is reduced to 200C. and maintained at 200C. for 2 hours and 40 minutes.
The reactor is then coded and vented.
B. Chain Extension of Polythioether Polyol To the polythioether polyol of Part A is added 20 0.35 gram, 0.001 mole, of the diglycidyl ether of 4,4'-isopropylidenebisphenol, 0.35 percent on the weight of the reactants used, and the reaction mixture is heated for 2 hours at 190C./7.5 mm to chain-extend the polythioether polyol. The chain-extended polythioether polyol is a 25 millable gum having a Mooney value of 25 at 100C.
A. Preparation of Polythioether Polyol The procedure of Example 2, Part A, is followed except that the amounts used are 90.0 grams, 0.737 mole, of 30 thiodiethanol, 5.0 grams, 0.029 mole of the monoallyl ether of 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, 5.0 grams, 0.022 mole of 4,4'-isopropylidenebisphenol, and Q.8 gram of phosphorous acid.
B~ Chain Extension of Polythioether Polyol The reactor is vented and to the resulting poly-thioether polyol is added 0.50 gram, 0.0025 mole, of the diglycidyl ether of 1,4-butanediol, 0.5 percent on the weight of the original reactants, and the reaction mixture is heated for 2 hours at 190C./7~5 mm. The chain-extended polythioether polyol has a Mooney value of 22 at 100C.
. EXAMPLE 4 100 grams of the gum of Example 2, Part B, is com-pounded on a standard 2-roll rubber mill as follows:
Parts Gum 100 Carbon black 60 Calcium carbonate . 4 Calcium hydroxide 3 - Zinc oxide 5 Sulfur 2-mercaptobenzothiazole 1.5 Tetramethylthiuram disulfide 1.5 .
The compounded gum is compression moulded for 30 minutes at 150C~ and post-cured in an oven for 16 hours at ; 120C. The cured elastomer has the following stress-strain - properties:
Hardness, Shore A 70 Modulus at 100~, psi610 Tensile strength, psi1600 Elongation, % 240 The cured sample has an oil swell of ~ percent after 70 hours in No. 3 oil at 100C., and a low temperature flexibility of -52C.
A~ Preparation of Polythioether Polyol To a suitable glass vessel are added 465~0 grams, ~054Z94
3.81 moles, of thiodiethanol, and 35.0 grams, 0.20 mole, of the monoallyl ether of 2-ethyl-2-~hydroxymethyl)-1,3-propane-diol. The mixture is purged with nitrogen for 15 minutes while stirring and then heated. When the temperature reaches 80C., 5.0 grams of phosphorous acid is added and the reac-tion mixture is heated to 192C. The vessel is then placed under vacuum while-bleeding nitrogen through the system and heating is continued to collect about 110 ml~ of distillate.
The vacuum is then broken with nitrogen and the syrupy product is stored under nitrogen. The product was unsuitable for processing on a rubber mill.
; B. Chain Extension of Polythioether Polyol An aliquot of 214.0 grams of the product of Part A
is placed in a suitable reaction vessel and purged with nitrogen while stirring for about 10 minutes. The material is then heated under a vacuum of 6-7 mm if mercury at 190-195C. for a period of about 2 1/2 hours while stirring slowly. To the reaction mixture is added 2.1 grams of the diglycidyl ether of 4,4'-isopropylidenebisphenol, 1 percent on the weight of the polythioether polyol, and stirring is continued under a vacuum of 6-7 mm of mercury at 190-192C.
for 2 hours to chain-extend the polythioether polyol. The reaction mixture is then cooled to room temperature and the vacuum is broken. The product has a Mooney value of 49 at 100C.
E~AMPLE 6 A. Preparation of Polythioether Polyol The procedure of Example 5, Part A, is followed except that 1425.0 grams, 11.67 moles, of thiodiethanol is reacted with 75.0 grams, 0.52 mole, of 3-cyclohexene-1,1-dimethanol, in the presence of 15~0 gram~ of phosphorous acid until 355 mil. of distillate is collected~ The reaction mixture is then cooled to room temperature and the vàcuum is broken. The product is too soft to process on a rubber mill.
B. Chain Extension of Polythioether Polyol An aliquot of 50.0 grams of the product of Part A
is heated under nitrogen at 190-195C. under vacuum for 15 minutes. To the mixture is then added 1.0 gram of the diglycidyl ether of 4,4'-isopropylidenebisphenol, 2 percent on the weight of the polythioether polyol, and heating is continued for 7 hours. The reaction mixture is cooled to 10 room temperature to obtain a millable product.
The procedure of Example 1, Part Bl is used except that 1.4 grams, 0.011 mole, of diglycidyl ether, 2 percent on the weight of the original reactants, is used to chain-extend the polythioether polyol. The chain-extended poly-thioether polyol is a millable gum.
EXA~PLE 8 The procedure of Example 1, Part B, is used except that 1.4 grams, 0.016 mole, of butanediepoxide, 2 percent 2~ on the weight of the original reactants, is used to chain-extend the polythioether polyol. The resulting product is a millable gum.
The procedure of Example 1, Part B, is used except that 1.4 grams, 0.9985 mole, of dicyclopentadiene diepoxide, 2 percent on the weight of the original reactants is used for chain-extension. The product is a millable gum.
The procedure of Example 5, Part B, is used except that 2.1 grams, 0.016 mole, of diglycidyl ether, 2 percent on the weight of the polythioether polyol is used to chain-extend the polythioether polyol~ The chain-extended poly-thioether polyol is a millable gum.
~054294 The procedure of Example 5, Part B, is used except that 2.1 grams, 0.024 mole, of butane diepoxide, 2 percent on the weight of the polythioether polyol, is used to chain-extend the polythioether polyol. The chain-extended poly-thioether polyol is a millable gum.
EX~MPLE 12 The procedure of Example 5, Part B, is used except that 2.1 grams, 0.013 mole, of dicyclopentadiene diepoxide, 2 percent on the weight of the polythioether polyol, is used to chain-extend the polythioether polyol~ The chain-extended polythioether polyol is a millable gum.
The procedure of Example 6, Part B, is used except 15 that 1.0 gram, 0.011 mole, of butane diepoxide, 2 percent on the weight of the polythioether polyol, is used to chain-extend the polythioether polyol. The chain-extended poly-.thioether polyol is a millable gum~
The procedure of Example 6/ Part B, is used except that 1.0 gram, 0.006 mole, of dicyclopentadiene diepoxide, 2 percent on the weight of the polythioether polyol, is used to chain-extend the polythioether polyol. The chain-extended polythioether polyol is a millable gum.
The vacuum is then broken with nitrogen and the syrupy product is stored under nitrogen. The product was unsuitable for processing on a rubber mill.
; B. Chain Extension of Polythioether Polyol An aliquot of 214.0 grams of the product of Part A
is placed in a suitable reaction vessel and purged with nitrogen while stirring for about 10 minutes. The material is then heated under a vacuum of 6-7 mm if mercury at 190-195C. for a period of about 2 1/2 hours while stirring slowly. To the reaction mixture is added 2.1 grams of the diglycidyl ether of 4,4'-isopropylidenebisphenol, 1 percent on the weight of the polythioether polyol, and stirring is continued under a vacuum of 6-7 mm of mercury at 190-192C.
for 2 hours to chain-extend the polythioether polyol. The reaction mixture is then cooled to room temperature and the vacuum is broken. The product has a Mooney value of 49 at 100C.
E~AMPLE 6 A. Preparation of Polythioether Polyol The procedure of Example 5, Part A, is followed except that 1425.0 grams, 11.67 moles, of thiodiethanol is reacted with 75.0 grams, 0.52 mole, of 3-cyclohexene-1,1-dimethanol, in the presence of 15~0 gram~ of phosphorous acid until 355 mil. of distillate is collected~ The reaction mixture is then cooled to room temperature and the vàcuum is broken. The product is too soft to process on a rubber mill.
B. Chain Extension of Polythioether Polyol An aliquot of 50.0 grams of the product of Part A
is heated under nitrogen at 190-195C. under vacuum for 15 minutes. To the mixture is then added 1.0 gram of the diglycidyl ether of 4,4'-isopropylidenebisphenol, 2 percent on the weight of the polythioether polyol, and heating is continued for 7 hours. The reaction mixture is cooled to 10 room temperature to obtain a millable product.
The procedure of Example 1, Part Bl is used except that 1.4 grams, 0.011 mole, of diglycidyl ether, 2 percent on the weight of the original reactants, is used to chain-extend the polythioether polyol. The chain-extended poly-thioether polyol is a millable gum.
EXA~PLE 8 The procedure of Example 1, Part B, is used except that 1.4 grams, 0.016 mole, of butanediepoxide, 2 percent 2~ on the weight of the original reactants, is used to chain-extend the polythioether polyol. The resulting product is a millable gum.
The procedure of Example 1, Part B, is used except that 1.4 grams, 0.9985 mole, of dicyclopentadiene diepoxide, 2 percent on the weight of the original reactants is used for chain-extension. The product is a millable gum.
The procedure of Example 5, Part B, is used except that 2.1 grams, 0.016 mole, of diglycidyl ether, 2 percent on the weight of the polythioether polyol is used to chain-extend the polythioether polyol~ The chain-extended poly-thioether polyol is a millable gum.
~054294 The procedure of Example 5, Part B, is used except that 2.1 grams, 0.024 mole, of butane diepoxide, 2 percent on the weight of the polythioether polyol, is used to chain-extend the polythioether polyol. The chain-extended poly-thioether polyol is a millable gum.
EX~MPLE 12 The procedure of Example 5, Part B, is used except that 2.1 grams, 0.013 mole, of dicyclopentadiene diepoxide, 2 percent on the weight of the polythioether polyol, is used to chain-extend the polythioether polyol~ The chain-extended polythioether polyol is a millable gum.
The procedure of Example 6, Part B, is used except 15 that 1.0 gram, 0.011 mole, of butane diepoxide, 2 percent on the weight of the polythioether polyol, is used to chain-extend the polythioether polyol. The chain-extended poly-.thioether polyol is a millable gum~
The procedure of Example 6/ Part B, is used except that 1.0 gram, 0.006 mole, of dicyclopentadiene diepoxide, 2 percent on the weight of the polythioether polyol, is used to chain-extend the polythioether polyol. The chain-extended polythioether polyol is a millable gum.
Claims (10)
1. A millable, sulfur-vulcanizable elastomer composition comprising a copolymer represented by a polymer chain of the formula:
wherein R represents a radical derived from a diepoxide; or a mixture of diepoxides, by cleavage of one bond on each oxygen atom of the diepoxide, said cleavage resulting from reaction of the diepoxide with the terminal hydroxyl groups of a polythioether polyol represented by the formula , wherein ?OG? comprises randomly alternating units of (I) ?OC2H4SC2H4?, (II) ?OR'?, (III) ?ORI''?, and (IV) ?OR'''?, wherein R' represents a radical remaining on removal of both hydroxyl groups from an aliphatic diol or mixture of aliphatic diols, R'' is an aromatic radical remaining on re-moval of both hydroxyl groups from an aromatic dihydroxy com-pound, or mixture of aromatic dihydroxy compounds, R''' is the radical remaining on removal of both hydroxyl groups of an aliphatic diol that provides allylic unsaturation that is external to said polymer chain, wherein the mole ratio of structural units (I) to the total of units (II), (III), and (IV) is greater than 1:1, said structures (II) and (III) being optional, and the content of structural units (IV) is about 1 to 10 mole percent of the total mole content of [OG]; and wherein x is an integer such that the Mooney value of said polythioether polyol is less than about 20 and n is an integer such that the Mooney value of said copolymer is substantially higher than the Mooney value of said polythioether polyol.
wherein R represents a radical derived from a diepoxide; or a mixture of diepoxides, by cleavage of one bond on each oxygen atom of the diepoxide, said cleavage resulting from reaction of the diepoxide with the terminal hydroxyl groups of a polythioether polyol represented by the formula , wherein ?OG? comprises randomly alternating units of (I) ?OC2H4SC2H4?, (II) ?OR'?, (III) ?ORI''?, and (IV) ?OR'''?, wherein R' represents a radical remaining on removal of both hydroxyl groups from an aliphatic diol or mixture of aliphatic diols, R'' is an aromatic radical remaining on re-moval of both hydroxyl groups from an aromatic dihydroxy com-pound, or mixture of aromatic dihydroxy compounds, R''' is the radical remaining on removal of both hydroxyl groups of an aliphatic diol that provides allylic unsaturation that is external to said polymer chain, wherein the mole ratio of structural units (I) to the total of units (II), (III), and (IV) is greater than 1:1, said structures (II) and (III) being optional, and the content of structural units (IV) is about 1 to 10 mole percent of the total mole content of [OG]; and wherein x is an integer such that the Mooney value of said polythioether polyol is less than about 20 and n is an integer such that the Mooney value of said copolymer is substantially higher than the Mooney value of said polythioether polyol.
2. The composition of Claim 1 wherein x is an integer such that the Mooney value of said polyether polyol is less than about 20 and n is an integer such that the Mooney value of said copolymer is above about 30.
3. The composition of Claim 1 wherein R is the radical derived from a diepoxide selected from the group con-sisting of diglycidyl ether, butane diepoxide, the diglycidyl ether of 4,4'-isopropylidenebisphenol, and dicyclopentadiene diepoxide with an aliphatic or aromatic hydroxyl group.
4. The composition of Claim l wherein said poly-thioether polyol contains structural units of (I) and (IV).
5. The composition of Claim 1 wherein said poly-thioether polyol contains structural units of (I) (III) and, (IV).
6. The composition of Claim 3 wherein said poly-thioether polyol contains structural units of (I) and (IV).
7. The composition of Claim 3 wherein said poly-thioether polyol contains structural units of (I), (III), and (IV).
. 8. The composition of Claim 7 wherein R" is the radical remaining after the removal of both hydroxyl groups from 4,4'-isopropylidenebisphenol.
9. The composition of Claim 3 wherein R is the radical derived from the diglycidyl ether of 4,4'-isopropyli-denebisphenol.
10. The composition of Claim 9 wherein R'' is the radical remaining after the removal of both hydroxyl groups from 4,4'-isopropylidenebisphenol.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US53454474A | 1974-12-19 | 1974-12-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1054294A true CA1054294A (en) | 1979-05-08 |
Family
ID=24130522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA240,631A Expired CA1054294A (en) | 1974-12-19 | 1975-11-27 | Millable, sulfur-vulcanizable elastomers |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS6039692B2 (en) |
| BR (1) | BR7508288A (en) |
| CA (1) | CA1054294A (en) |
| DE (1) | DE2557167C2 (en) |
| FR (1) | FR2295078A1 (en) |
| GB (1) | GB1513010A (en) |
| NL (1) | NL7514645A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6320020B1 (en) | 1998-09-08 | 2001-11-20 | Mitsui Chemicals, Inc. | Sulfur-containing (thio)ether (co)polymer and a use thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1056824B (en) * | 1956-05-19 | 1959-05-06 | Bayer Ag | Process for the production of high molecular weight plastics from polythioethers and polyisocyanates |
-
1975
- 1975-11-27 CA CA240,631A patent/CA1054294A/en not_active Expired
- 1975-12-03 GB GB49650/75A patent/GB1513010A/en not_active Expired
- 1975-12-15 BR BR7508288*A patent/BR7508288A/en unknown
- 1975-12-16 FR FR7538507A patent/FR2295078A1/en active Granted
- 1975-12-16 NL NL7514645A patent/NL7514645A/en not_active Application Discontinuation
- 1975-12-18 DE DE2557167A patent/DE2557167C2/en not_active Expired
- 1975-12-19 JP JP50150717A patent/JPS6039692B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6039692B2 (en) | 1985-09-07 |
| DE2557167C2 (en) | 1985-12-19 |
| FR2295078A1 (en) | 1976-07-16 |
| AU8730275A (en) | 1977-06-09 |
| NL7514645A (en) | 1976-06-22 |
| DE2557167A1 (en) | 1976-06-24 |
| BR7508288A (en) | 1976-08-24 |
| FR2295078B1 (en) | 1979-03-16 |
| JPS5186557A (en) | 1976-07-29 |
| GB1513010A (en) | 1978-06-01 |
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