CA1071347A - Vulcanizable elastomers derived from thiodiethanol - Google Patents
Vulcanizable elastomers derived from thiodiethanolInfo
- Publication number
- CA1071347A CA1071347A CA239,460A CA239460A CA1071347A CA 1071347 A CA1071347 A CA 1071347A CA 239460 A CA239460 A CA 239460A CA 1071347 A CA1071347 A CA 1071347A
- Authority
- CA
- Canada
- Prior art keywords
- mole percent
- thiodiethanol
- acid
- aliphatic
- diol
- 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.)
- Expired
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Classifications
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6888—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A B S T R A C T
Copolymers of thiodiethanol, one or more alyphatic or cycloalyphatic diols containing about 1-10 mole percent allylic unsaturation and 10-20 mole percent of an aromatic or cycloalyphatic dicarboxylic acid which may be vulcanized into useful elastomeric products.
Copolymers of thiodiethanol, one or more alyphatic or cycloalyphatic diols containing about 1-10 mole percent allylic unsaturation and 10-20 mole percent of an aromatic or cycloalyphatic dicarboxylic acid which may be vulcanized into useful elastomeric products.
Description
2~ 58~ 107~3~7 1 This inven-tion relates to novel copolymers of thio~
diethanol with aromatic dicarboxylic acids, to copolymers thereof with aliphatic diols, and to elastomeric compositions obtained thereErom. More particularly, it relates to vulcan izable elastomeric compositions obtained by copolymerization of a major proportion of thlodiethanol with an aromatic di-carboxylic acid and, optionally, with a minor proportion of one or more aliphatic diols.
Thiodiethanol exhibits unusual reactivity because of the positioning of its hydroxyl groups beta to a sulfur atom in an aLiphatic chain. ~hus, unlike conventional ali-phatic diols, it will undergo autocondensation in the presence of certain acidic catalysts to afford polymeric materials.
Within certain limits and under certain conditions, thiodi-ethanol will condense with aliphatic diols to give rubbery ; polymers.
Thiodie-thanol and, optionally, aliphatic diols, will react within certain limits and under certain conditions with a diphenolic compound to provide su].fur vulcanizable elastomers.
The present invention is based on the discovery that thiodiethanol will undergo polycondensation reactions with certain aromatic dicarboxylic acids to provide useful polymeric compositions under the conditions defined herein-below, and that high molecular weight, rubbery, vulcanizable elastomeric compositions are obtained ~herefrom which, when vulcanized by conventional techniques, produces elastomers exhibiting excellent low temperature flexibility and outstand~
ing resistance to hydrocarbon oils.
The present invention provides vulcanizable elast ~;
omers having significantly higher Mooney viscosities than previously known. Mooney viscosity is a measure of the "tough-ness" of an elastomer and is manifested by mill handling ~ .
~7~L3~7 l characteristics, i.e. -the higher Mooney elastomers are more readily processed on a rubber mill. This is an lmportant property in a "millable" or "vulcanizable" gum.
In accordance with the invention, a major propor-tion of thiodiethanol or a mixture of thiodiethanol and oneor more aliphatic diols, in which a major proportion of said mixture is thiodiethanol, is copolymerized within the lim-itations and under the conditions described hereinbelow with certain dicarboxylic acids to provide useful elastomeric com-positions havin~ improved Mooney viscosities.
Thus, in accordance with this invention, elasto-meric compositions are obtained from copolymers of 80 to 90 n~n,~er~,a ~?,~7qO~r,'~mole percent of1thiodiethanol or a mixture of1thiodiethanol and one or more aliphatic or cvcloaliphatic diols, and lO to 20 mole percent of an aromatic dicarboxylic acid; character-ized in that the proportion of thiodiethanol in said mixture with aliphatic or cycloaliphatic diols is at least 50 mole percent, and further characterized in that up to about lO
mole percent of said mixture comprises a diol having external unsaturation with an allylic hydrogen atom.
The term thiodiethanol as used herein means thiodi-ethanol monomer. Polythiodiethanol, copolymers of thiodieth- ~`
anol with aliphatic diols, and polyesters of thiodiethanol with dibasic acids, which contain terminal thiodiethanol un-its, will not condense with aromatic dicarboxyllc acids to ; provide useful elas~omers within the definition of the inven-tion. The discovery that such polymers will not react with an aromatic dicarboxylic acid to provide elastomeric compo-sitions with a high Mooney viscosity is one of the unexpected features of the present invention.
Moreover, it has been found that when the elasto-meric composition comprises less than about lO mole percent of the aromatic dicarboxylic acid componentr high Mooney vis-cosity is not readily obtained, and ~hen it contains more thanabout 20 ~ole percent of the aromatic dicarboxylic acid, the glass transition temperature (Tg) is rai~ed to the level where the composition, although it may be elastomeric at room tem perature embrittles at temperatures which may be encountered in the use, e.g. in winter weather, and hence such compositions are relatively less desirable than those containing less than about 20 ~ole percent of the aromatic dicarboxylic acid.
~he term "high Mooney viscosity" as usea herein means a Mooney viscosity ~MI-~), as determined by ASTM #D1646, of about 20 to about 50. ~oon~yviscosity is a measure of mill handlin~ characteristics. Natural rubber, e.g., has a Mooney viscosity of about 60, which is high because of nat-urally occurring cross-linking. Matural rubber, there*ore, must be "broken down" on the rubber mill before compounding ingredients can be incorporated therein. Most synthetic elas-tomers have Mooney viscosities in the range of about 20 to 50. Although elastomers have lo~er Mooney viscosit~, iOe.
in the range 5 to 20, can be handled on a rubber mill with difPiculty, lt is far more desirable to compound elastomers with Mooney viscosities in the range 20 to 50, preferably 35 ~ to 50. In accordance with the objects of the present inven-; tion, therefore, polymers prepared in accordance with the procedures desc~ibed herein are elas-tomeric, posse~s excel-lent low -temperature properties a~d outstandine resistance to hydrocarbon oils ~hen compounded and cured according to con~entional procedures, and, ;n addition, have excellent gum streneth, as manifested by high Mooney viscosities.
Elastomers derived by the condensation of 80 to ; 30 90 mole percent o~ thiodiethanol ~ith 10 to 20 mole percent of an aromatic dicarboxylic acid are within the scope of the present inYention, but are not preferred species thereof.
diethanol with aromatic dicarboxylic acids, to copolymers thereof with aliphatic diols, and to elastomeric compositions obtained thereErom. More particularly, it relates to vulcan izable elastomeric compositions obtained by copolymerization of a major proportion of thlodiethanol with an aromatic di-carboxylic acid and, optionally, with a minor proportion of one or more aliphatic diols.
Thiodiethanol exhibits unusual reactivity because of the positioning of its hydroxyl groups beta to a sulfur atom in an aLiphatic chain. ~hus, unlike conventional ali-phatic diols, it will undergo autocondensation in the presence of certain acidic catalysts to afford polymeric materials.
Within certain limits and under certain conditions, thiodi-ethanol will condense with aliphatic diols to give rubbery ; polymers.
Thiodie-thanol and, optionally, aliphatic diols, will react within certain limits and under certain conditions with a diphenolic compound to provide su].fur vulcanizable elastomers.
The present invention is based on the discovery that thiodiethanol will undergo polycondensation reactions with certain aromatic dicarboxylic acids to provide useful polymeric compositions under the conditions defined herein-below, and that high molecular weight, rubbery, vulcanizable elastomeric compositions are obtained ~herefrom which, when vulcanized by conventional techniques, produces elastomers exhibiting excellent low temperature flexibility and outstand~
ing resistance to hydrocarbon oils.
The present invention provides vulcanizable elast ~;
omers having significantly higher Mooney viscosities than previously known. Mooney viscosity is a measure of the "tough-ness" of an elastomer and is manifested by mill handling ~ .
~7~L3~7 l characteristics, i.e. -the higher Mooney elastomers are more readily processed on a rubber mill. This is an lmportant property in a "millable" or "vulcanizable" gum.
In accordance with the invention, a major propor-tion of thiodiethanol or a mixture of thiodiethanol and oneor more aliphatic diols, in which a major proportion of said mixture is thiodiethanol, is copolymerized within the lim-itations and under the conditions described hereinbelow with certain dicarboxylic acids to provide useful elastomeric com-positions havin~ improved Mooney viscosities.
Thus, in accordance with this invention, elasto-meric compositions are obtained from copolymers of 80 to 90 n~n,~er~,a ~?,~7qO~r,'~mole percent of1thiodiethanol or a mixture of1thiodiethanol and one or more aliphatic or cvcloaliphatic diols, and lO to 20 mole percent of an aromatic dicarboxylic acid; character-ized in that the proportion of thiodiethanol in said mixture with aliphatic or cycloaliphatic diols is at least 50 mole percent, and further characterized in that up to about lO
mole percent of said mixture comprises a diol having external unsaturation with an allylic hydrogen atom.
The term thiodiethanol as used herein means thiodi-ethanol monomer. Polythiodiethanol, copolymers of thiodieth- ~`
anol with aliphatic diols, and polyesters of thiodiethanol with dibasic acids, which contain terminal thiodiethanol un-its, will not condense with aromatic dicarboxyllc acids to ; provide useful elas~omers within the definition of the inven-tion. The discovery that such polymers will not react with an aromatic dicarboxylic acid to provide elastomeric compo-sitions with a high Mooney viscosity is one of the unexpected features of the present invention.
Moreover, it has been found that when the elasto-meric composition comprises less than about lO mole percent of the aromatic dicarboxylic acid componentr high Mooney vis-cosity is not readily obtained, and ~hen it contains more thanabout 20 ~ole percent of the aromatic dicarboxylic acid, the glass transition temperature (Tg) is rai~ed to the level where the composition, although it may be elastomeric at room tem perature embrittles at temperatures which may be encountered in the use, e.g. in winter weather, and hence such compositions are relatively less desirable than those containing less than about 20 ~ole percent of the aromatic dicarboxylic acid.
~he term "high Mooney viscosity" as usea herein means a Mooney viscosity ~MI-~), as determined by ASTM #D1646, of about 20 to about 50. ~oon~yviscosity is a measure of mill handlin~ characteristics. Natural rubber, e.g., has a Mooney viscosity of about 60, which is high because of nat-urally occurring cross-linking. Matural rubber, there*ore, must be "broken down" on the rubber mill before compounding ingredients can be incorporated therein. Most synthetic elas-tomers have Mooney viscosities in the range of about 20 to 50. Although elastomers have lo~er Mooney viscosit~, iOe.
in the range 5 to 20, can be handled on a rubber mill with difPiculty, lt is far more desirable to compound elastomers with Mooney viscosities in the range 20 to 50, preferably 35 ~ to 50. In accordance with the objects of the present inven-; tion, therefore, polymers prepared in accordance with the procedures desc~ibed herein are elas-tomeric, posse~s excel-lent low -temperature properties a~d outstandine resistance to hydrocarbon oils ~hen compounded and cured according to con~entional procedures, and, ;n addition, have excellent gum streneth, as manifested by high Mooney viscosities.
Elastomers derived by the condensation of 80 to ; 30 90 mole percent o~ thiodiethanol ~ith 10 to 20 mole percent of an aromatic dicarboxylic acid are within the scope of the present inYention, but are not preferred species thereof.
- 3 -1~97:~39~7 1 Such elas-tomeric compositions may be cured or vulcanized by means known to those skilled in the art, such as by peroxides, e.~. benzoyl peroxide or dicumyl peroxide, or by use of cer-tain resins. It i5 preferred, for practical reasons, to in-corporate into such polymer compositions at least 1 mole per-cent of a copolymerizable aliphatic or cycloaliphatic diol containing external unsaturation. It is even more preferable elastomeric compositions which contain, in addition to at least 50 mole percent of thiodiethanol, up to about 40 mole percent of one or more aliphatic or cycloaliphatic diols, which may include ~rom 1 to 10 mole percent of a diol con-taining external unsaturation.
Any aliphatic diol which will condense with ali-phatic dicarboxylic acids, as for example in the preparation ; 15 of aliphatic polyesters, wil] be suitable for the preparation of copolymers in accordance with the present invention. The fo~lowing list is representative of useful diols, but the in-vention is not limited thereto. They include ethylene gly-col, propane-1,2-diol, propane 1,3-diol, diethylene glycol;
cyclohexane di(lower alkylene)diols, such as cyclohexane 1,2-and 1,4-dimethanol, either cls or trans or mixtures thereof, cyclobutane di(lower alkylene)diols, such as cyclobutane-1,2-dimethanol; aralkylene diols, such as the bis(hydroxyethyl)-ether of hydroquinone or of resorcinol; the monoallyl ether of trimethylol propane, the monoallyl ether of glycerol, 3--cyclohexene-l,l-dimethanol, and the like. Preferred satur~
ated diols include diethylene ylycol and butane-1,4-diol.
Preferred unsaturated diols include the monoallyl ether of trimethylol propane, the monoallyl ether of glycerol and cy-clohexene-1,1-dimethanol.
The expression "external unsaturation" as used nere-in refers to the position of the unsaturation in the diol molecule such that at least one continuous chain of atoms ~ 71347 remains in the diol, extending between the two diol oxygen ato~s, which chain does not include any carbon-to-carbon double bonds.
~'he unsaturated diols disclosed herein are exa~ples of those con-taining external unsaturation and having ~n allylic hydrogen atom.
The arom~tic dicarboxylic ~cid which is preferred is terephthalic acid. Others include phthalic acid or phthalicyanhydride, isophthalic acid~ naphthalene-1,4-dicar-boxylic acid and naphthalene-115-dicarboxylic acid.
~ he polymers o~ this invention are prepared under dehydrating conditions using an acidic catalyst. Acids hav-ing a pK of 5 or less are useful. Certain acid catalysts, although useful, tend to produce undesirable side reactions leading to the formation of odori~erous thioxane and/or di-thiane, and are therefore less desirably used. Suitable cat-alysts include hydrogen chloride and sulfuric acid, p-toluene sulfonic acid, sulfamdc acid, picric acid, fluoboric acid, phosphorous acid, trialkyl phosphitesl and the like. Phos-phorous acid is a preferred catalyst, fluoboric acid is also a preferred catalyst. Effective c~talysis is achieved using from 0.01 to 3 percent by weight, based`on the total weight of monomers, preferably 0.1 to 1 percent.
~he polymers are readily prepared ~y condensing the monomers, in the presence of the appropriate catalyst and under~an inert atmosphere, e~g. nitrogen, for about 4-6 hours at about 180-2Q0C. until the maJor proportion of water formed in the reaction h~s been removed, followed by a sim- ~
ilar reaction at reduced pressure, e.g. 5-10 mm. Hg3 at a tem- O
perature of 160-180 CO for a suitable period of time~ e.g.
10-24 hours to co~plete the condensation from a low molecular weight sy~up to a gum ha~ing a high Mooney viscosity. The latter reaction is con~eniently conducted usine a high shear mixer, such as an Atlantic*ZCV reactor, available from 5 ~
. .
. .
~:)'7gL3~7 Atlan~ic Research Co., Gainesville, Virginia. Other suiteble high shear mixers may be used to ef~ect molecular ~eight buildup.
~ he mill handling characteristics of the elastomers are evaluated by the so-called Mooney value (ML-4). The Mooney value is measured according to AS~M No. D1646.
~ he elastomers h&ve excellent lo~ temperature flex-ibility as measured by thermomechanical analysis, e.g. using a duPont*~hermomechanical Analyzer, ~odel 990~ Module 942.
The method basically measures the first transition -temperature of a specimen which is warmea from -120C. in contact with a weighted, needle-like probe~ The transition temperature is determined from the first de~lection point on a con-tinuously recorded chart. This first transition temperature is analogous to the glasæ transition temperature (Tg) and is referred to herein as brittle point. *=trademQrk Similarly, the elastomers have outstanding resist-ance to hydrocarbon oils, as evidenced by lo~ rolume swell in contact with the oil~. This is measured in accordance with ASTM ~o. D471.
The elastomers o~ this in~ention can be cured into useful elastomeric products by conventional compounding and vulcanization using standard rubber compounding techniques.
Theg may be compounded ~i.th conventional compounding ingredi-ents, such as carbon black or other pigments and ~illers, vulca~izing agents such as accelerators and sulfur, promoters such as zinc oxide, lubricants and mold release agents, anti-oxid~nts, plasticizers and the like, and compression molded into use~ul elastomeric products.
~he in~ention is more completely illustrated by the following examples.
Thiodiethanol (300 grams~ 2~5 moles), terephthalic ' 13~7 1 acid (58 grams, 0.35 mole), monoallyl ether of -trlmethylol-propane (26 grams, 0.15 mole) and 1 gram phosphorous acid were reacted under nitrogen for 1.5 hours at 195C., for 5 hours at 185C. and finally distilled to remove the remain-ing water and unreacted diol.
To an Atlantic 2CV Reactor (1) was charged 265grams of the low molecular weight polymer obtained above and the reaction was continued at 175C./10 mm. Hg. for about 18 hours. The product was a -tough rubbery gum having a Mooney viscosity value o~ 51.
100 Parts of the gum was milled on a standard rub-ber mlll with the following:
Parts per 100 pts. gum Carbon black 40 Calcium oxide 4 Mercaptobenzothiazole 1.5 Tetramethylthiuram disulfide 1.5 Sulfur 0.8 Zinc oxide 5.0 The composition was cured by compression molding for 15 minutes at 300F. followed by post-conditioning for about 15 hours at 100C. in an oven. The elastomer had the following properties:
Tensile, psi 1030 25 Elongation, ~ 210 Hardness, Shore A 67 Tear Strength, pli (Die C)130 Tear Strength, pli (Split tear) 19 Brittle point, C. (2) ~49 (1) High shear mixer sold by Atlantic Research Co., Gainesville, Virginia.
(2) Thermomechanical Analysis method using duPont Ther-momechanical Analyzer.
_ 7 _ .' ' ' ' ' ' ', ~' ., ,, '.' ~ ' ; ' , . . . ~ .
~0~3~7 1 Example 2 Thiodiethanol (366 grams, 3.0 moles), 1,4-butane-diol tl80 grams, 2.0 moles), terephthalic acid (110 grams, 0.66 mole) and 1.5 grams phosphorous acid were reacted under nitrogen for 3 hours at 195C. Monoallylether of trimethylol-propane (59 grams, 0.34 mole) was added and the reaction con-tinued under nitrogen for 2.5 hours at 185C.
55 Grams of the above low molecular ~eight polymer was charged to an Atlantic 2CV reactor along with 0.1 gram p-toluene sulfonic acid and the reaction continued at 150-160C./5-10 mrn. Hg. under nitrogen for 48 hours. The prod-uct was a gum having a ~ooney value of 25.
; The gum was compounded using the following formu-lation (parts per 100 parts gum).
Parts by Weight Carbon black 40 Calcium oxide 2 Mercaptobenzothiazole 1.5 Tetramethylthiuram disulfide 1.5 :~i :~ 20 Sulfur 0.8 ` Zinc oxide 5.0 and cured by compression molding for 15 minutes at 300F.
and post-cured for about 18 hours at 100C. The elastomer exhibited the following properties:
Hardne5s, Shore A 67 : Modulus, psi @ 100~ elongation 480 @ 200~ elongation 1110 .
@ 300% elongation 1710 Tensile, p5i 1770 Elongation, ~ 330 Cornpression set, % 10 Volume Swell, ~, in ~7~3~'7 1 ASTM No. 3 oil; 7 days at 150C. Method s 10.4, 18.5 Brittle Point, C. -51 Example 3 Following a procedurè similar to Example 2, thio-diethanol (150 grams, 1.25 moles), 1,4-cyclohexanedimethanol (118 grams, 0.85 mole), and terephthalic acid (~5 grams, 0.3 mole) were condensed in the presence of Q.6 gram phosphorous acid for 4.5 hours at 190-195C. Trimethylolpropane monoallyl ether (16.5 grams, 0.1 mole) and 0.6 gram p-toluene sulfonic acid were then added and the reaction continued at 170C.
for 2 hours.
60 Grams of the syrup resulting from the above reaction was then reacted in the presence of 0.3 mol. of a 48~ solution of fluoboric acid at 150-160C./5-10 mm. Hg un-der a nitrogen atmosphere, using an Atlantic 2CV reactor, to give an elastomeric gum having a Mooney value of 25.
When the gum is compounded as described in Example 2 except for the use of 2 grams of calcium carbonate instead of calcium oxide, similar properties are obtained.
Similar results are obtained when terephthalic acid is replaced by isophthalic acid.
' ' ~: .
.
., '' .
.
~ ' ".'
Any aliphatic diol which will condense with ali-phatic dicarboxylic acids, as for example in the preparation ; 15 of aliphatic polyesters, wil] be suitable for the preparation of copolymers in accordance with the present invention. The fo~lowing list is representative of useful diols, but the in-vention is not limited thereto. They include ethylene gly-col, propane-1,2-diol, propane 1,3-diol, diethylene glycol;
cyclohexane di(lower alkylene)diols, such as cyclohexane 1,2-and 1,4-dimethanol, either cls or trans or mixtures thereof, cyclobutane di(lower alkylene)diols, such as cyclobutane-1,2-dimethanol; aralkylene diols, such as the bis(hydroxyethyl)-ether of hydroquinone or of resorcinol; the monoallyl ether of trimethylol propane, the monoallyl ether of glycerol, 3--cyclohexene-l,l-dimethanol, and the like. Preferred satur~
ated diols include diethylene ylycol and butane-1,4-diol.
Preferred unsaturated diols include the monoallyl ether of trimethylol propane, the monoallyl ether of glycerol and cy-clohexene-1,1-dimethanol.
The expression "external unsaturation" as used nere-in refers to the position of the unsaturation in the diol molecule such that at least one continuous chain of atoms ~ 71347 remains in the diol, extending between the two diol oxygen ato~s, which chain does not include any carbon-to-carbon double bonds.
~'he unsaturated diols disclosed herein are exa~ples of those con-taining external unsaturation and having ~n allylic hydrogen atom.
The arom~tic dicarboxylic ~cid which is preferred is terephthalic acid. Others include phthalic acid or phthalicyanhydride, isophthalic acid~ naphthalene-1,4-dicar-boxylic acid and naphthalene-115-dicarboxylic acid.
~ he polymers o~ this invention are prepared under dehydrating conditions using an acidic catalyst. Acids hav-ing a pK of 5 or less are useful. Certain acid catalysts, although useful, tend to produce undesirable side reactions leading to the formation of odori~erous thioxane and/or di-thiane, and are therefore less desirably used. Suitable cat-alysts include hydrogen chloride and sulfuric acid, p-toluene sulfonic acid, sulfamdc acid, picric acid, fluoboric acid, phosphorous acid, trialkyl phosphitesl and the like. Phos-phorous acid is a preferred catalyst, fluoboric acid is also a preferred catalyst. Effective c~talysis is achieved using from 0.01 to 3 percent by weight, based`on the total weight of monomers, preferably 0.1 to 1 percent.
~he polymers are readily prepared ~y condensing the monomers, in the presence of the appropriate catalyst and under~an inert atmosphere, e~g. nitrogen, for about 4-6 hours at about 180-2Q0C. until the maJor proportion of water formed in the reaction h~s been removed, followed by a sim- ~
ilar reaction at reduced pressure, e.g. 5-10 mm. Hg3 at a tem- O
perature of 160-180 CO for a suitable period of time~ e.g.
10-24 hours to co~plete the condensation from a low molecular weight sy~up to a gum ha~ing a high Mooney viscosity. The latter reaction is con~eniently conducted usine a high shear mixer, such as an Atlantic*ZCV reactor, available from 5 ~
. .
. .
~:)'7gL3~7 Atlan~ic Research Co., Gainesville, Virginia. Other suiteble high shear mixers may be used to ef~ect molecular ~eight buildup.
~ he mill handling characteristics of the elastomers are evaluated by the so-called Mooney value (ML-4). The Mooney value is measured according to AS~M No. D1646.
~ he elastomers h&ve excellent lo~ temperature flex-ibility as measured by thermomechanical analysis, e.g. using a duPont*~hermomechanical Analyzer, ~odel 990~ Module 942.
The method basically measures the first transition -temperature of a specimen which is warmea from -120C. in contact with a weighted, needle-like probe~ The transition temperature is determined from the first de~lection point on a con-tinuously recorded chart. This first transition temperature is analogous to the glasæ transition temperature (Tg) and is referred to herein as brittle point. *=trademQrk Similarly, the elastomers have outstanding resist-ance to hydrocarbon oils, as evidenced by lo~ rolume swell in contact with the oil~. This is measured in accordance with ASTM ~o. D471.
The elastomers o~ this in~ention can be cured into useful elastomeric products by conventional compounding and vulcanization using standard rubber compounding techniques.
Theg may be compounded ~i.th conventional compounding ingredi-ents, such as carbon black or other pigments and ~illers, vulca~izing agents such as accelerators and sulfur, promoters such as zinc oxide, lubricants and mold release agents, anti-oxid~nts, plasticizers and the like, and compression molded into use~ul elastomeric products.
~he in~ention is more completely illustrated by the following examples.
Thiodiethanol (300 grams~ 2~5 moles), terephthalic ' 13~7 1 acid (58 grams, 0.35 mole), monoallyl ether of -trlmethylol-propane (26 grams, 0.15 mole) and 1 gram phosphorous acid were reacted under nitrogen for 1.5 hours at 195C., for 5 hours at 185C. and finally distilled to remove the remain-ing water and unreacted diol.
To an Atlantic 2CV Reactor (1) was charged 265grams of the low molecular weight polymer obtained above and the reaction was continued at 175C./10 mm. Hg. for about 18 hours. The product was a -tough rubbery gum having a Mooney viscosity value o~ 51.
100 Parts of the gum was milled on a standard rub-ber mlll with the following:
Parts per 100 pts. gum Carbon black 40 Calcium oxide 4 Mercaptobenzothiazole 1.5 Tetramethylthiuram disulfide 1.5 Sulfur 0.8 Zinc oxide 5.0 The composition was cured by compression molding for 15 minutes at 300F. followed by post-conditioning for about 15 hours at 100C. in an oven. The elastomer had the following properties:
Tensile, psi 1030 25 Elongation, ~ 210 Hardness, Shore A 67 Tear Strength, pli (Die C)130 Tear Strength, pli (Split tear) 19 Brittle point, C. (2) ~49 (1) High shear mixer sold by Atlantic Research Co., Gainesville, Virginia.
(2) Thermomechanical Analysis method using duPont Ther-momechanical Analyzer.
_ 7 _ .' ' ' ' ' ' ', ~' ., ,, '.' ~ ' ; ' , . . . ~ .
~0~3~7 1 Example 2 Thiodiethanol (366 grams, 3.0 moles), 1,4-butane-diol tl80 grams, 2.0 moles), terephthalic acid (110 grams, 0.66 mole) and 1.5 grams phosphorous acid were reacted under nitrogen for 3 hours at 195C. Monoallylether of trimethylol-propane (59 grams, 0.34 mole) was added and the reaction con-tinued under nitrogen for 2.5 hours at 185C.
55 Grams of the above low molecular ~eight polymer was charged to an Atlantic 2CV reactor along with 0.1 gram p-toluene sulfonic acid and the reaction continued at 150-160C./5-10 mrn. Hg. under nitrogen for 48 hours. The prod-uct was a gum having a ~ooney value of 25.
; The gum was compounded using the following formu-lation (parts per 100 parts gum).
Parts by Weight Carbon black 40 Calcium oxide 2 Mercaptobenzothiazole 1.5 Tetramethylthiuram disulfide 1.5 :~i :~ 20 Sulfur 0.8 ` Zinc oxide 5.0 and cured by compression molding for 15 minutes at 300F.
and post-cured for about 18 hours at 100C. The elastomer exhibited the following properties:
Hardne5s, Shore A 67 : Modulus, psi @ 100~ elongation 480 @ 200~ elongation 1110 .
@ 300% elongation 1710 Tensile, p5i 1770 Elongation, ~ 330 Cornpression set, % 10 Volume Swell, ~, in ~7~3~'7 1 ASTM No. 3 oil; 7 days at 150C. Method s 10.4, 18.5 Brittle Point, C. -51 Example 3 Following a procedurè similar to Example 2, thio-diethanol (150 grams, 1.25 moles), 1,4-cyclohexanedimethanol (118 grams, 0.85 mole), and terephthalic acid (~5 grams, 0.3 mole) were condensed in the presence of Q.6 gram phosphorous acid for 4.5 hours at 190-195C. Trimethylolpropane monoallyl ether (16.5 grams, 0.1 mole) and 0.6 gram p-toluene sulfonic acid were then added and the reaction continued at 170C.
for 2 hours.
60 Grams of the syrup resulting from the above reaction was then reacted in the presence of 0.3 mol. of a 48~ solution of fluoboric acid at 150-160C./5-10 mm. Hg un-der a nitrogen atmosphere, using an Atlantic 2CV reactor, to give an elastomeric gum having a Mooney value of 25.
When the gum is compounded as described in Example 2 except for the use of 2 grams of calcium carbonate instead of calcium oxide, similar properties are obtained.
Similar results are obtained when terephthalic acid is replaced by isophthalic acid.
' ' ~: .
.
., '' .
.
~ ' ".'
Claims (4)
1. A vulcanizable elastomeric composition compris-ing 80 to 90 mole percent of a mixture of monomeric thio-diethanol and one or more aliphatic or cycloaliphatic diols, and 10 to 20 mole percent of an aromatic or cycloaliphatic dicarboxylic acid, characterized in that the proportion of monomeric thiodiethanol in said mixture of aliphatic and cycloaliphatic diols is at least 50 mole percent, and further characterized in that from about 1-10 mole percent of said mixture comprises a diol having an external double bond with an allylic hydrogen atom.
2. A composition according to Claim 1 wherein said elastomeric composition comprises up to about 40 mole percent of one or more aliphatic or cycloaliphatic diols, which include 1 to 10 mole percent of a diol containing external unsaturation containing an allylic double bond.
3. A composition according to Claim 1 wherein said aromatic dicarboxylic acid is terephthalic acid.
4. A composition according to Claim 1 wherein said diol containing external unsaturation is the monoallyl ether of trimethylol propane.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US53454574A | 1974-12-19 | 1974-12-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1071347A true CA1071347A (en) | 1980-02-05 |
Family
ID=24130530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA239,460A Expired CA1071347A (en) | 1974-12-19 | 1975-11-12 | Vulcanizable elastomers derived from thiodiethanol |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5936654B2 (en) |
| BR (1) | BR7507975A (en) |
| CA (1) | CA1071347A (en) |
| DE (1) | DE2557168A1 (en) |
| FR (1) | FR2295077A1 (en) |
| GB (1) | GB1502906A (en) |
| NL (1) | NL7514327A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018111750A1 (en) * | 2016-12-15 | 2018-06-21 | Dow Global Technologies Llc | Polyurethane product with sulfur-containing polyester polyol |
-
1975
- 1975-11-12 CA CA239,460A patent/CA1071347A/en not_active Expired
- 1975-11-14 GB GB4709275A patent/GB1502906A/en not_active Expired
- 1975-12-02 BR BR7507975A patent/BR7507975A/en unknown
- 1975-12-09 NL NL7514327A patent/NL7514327A/en not_active Application Discontinuation
- 1975-12-16 FR FR7538508A patent/FR2295077A1/en active Granted
- 1975-12-16 JP JP14920975A patent/JPS5936654B2/en not_active Expired
- 1975-12-18 DE DE19752557168 patent/DE2557168A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| NL7514327A (en) | 1976-06-22 |
| DE2557168A1 (en) | 1976-06-24 |
| GB1502906A (en) | 1978-03-08 |
| JPS5936654B2 (en) | 1984-09-05 |
| BR7507975A (en) | 1976-08-24 |
| FR2295077A1 (en) | 1976-07-16 |
| JPS5186590A (en) | 1976-07-29 |
| FR2295077B1 (en) | 1981-09-25 |
| AU8659775A (en) | 1977-05-19 |
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