CA1138475A - HYDROQUINONE BIS[.omega.-(O-AMINOPHENYLTHIO) ALKL] ETHERS AND HARDENER FOR POLYURETHANE ELASTOMER THEREOF - Google Patents
HYDROQUINONE BIS[.omega.-(O-AMINOPHENYLTHIO) ALKL] ETHERS AND HARDENER FOR POLYURETHANE ELASTOMER THEREOFInfo
- Publication number
- CA1138475A CA1138475A CA000358566A CA358566A CA1138475A CA 1138475 A CA1138475 A CA 1138475A CA 000358566 A CA000358566 A CA 000358566A CA 358566 A CA358566 A CA 358566A CA 1138475 A CA1138475 A CA 1138475A
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- CA
- Canada
- Prior art keywords
- aminophenylthio
- ether
- hydroquinone bis
- hardener
- omega
- 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.)
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Abstract
ABSTRACT OF THE DISCLOSURE
Hydroquinone bis[.omega.-(o-aminophenylthio)alkyl)ethers having the formula
Hydroquinone bis[.omega.-(o-aminophenylthio)alkyl)ethers having the formula
Description
~l~ 3~9L7~
The present invention relcltes to hydroquinone bis [~-(o-aminophenylthio)alkyl] ethers and -their use as hardeners for polyurethane elastomer.
Heretofore, aromatic diamines have been used as hardeners in the preparation of polyurethane elastomers. Various aromatic diamine type hardeners have been proposed. The import-ant characteristics required for the hardeners are as follows:-Firstly, the ilardeners should be a low meltlng point solid or liquid from processability, labour hygiene and energy saving considerations;
Secondly, the pot life, i.e. the time from mixing the hardener with a mixture of polyisocyanate and polyol or a pre-polymer having the terminal isocyanate group to the mixture being non-flowable for casting, should be suitable;
Thirdly, the set time as the time from molding the mixture to demolding the cast product for processability, espec-ially efficiency, should be suitable;
~` Fourthly, the hardener should be easily produced and be stable; and Fifthly, the resulting polyurethane elastomer should have excellent physical properties.
However, these requirements are contradictory. For example, if the short set time is required, the pot life is shortened to cause trouble in processing. Accordingly, it is difficult to obtain a hardener having satisfactory and balanced characteristics. Thus for example, p-bis(o-aminophenylthio-methyl)benzene has a structure similar to that of the hardeners of the present invention, however, it has high melting point as 134 to 136~C to provide poor processability.
The present invention provides hardeners for poly-urethane elastomers which have the above-mentioned balanced characteristics.
~ 3~?47~
According to the presen-t invention there are provided hydroqulnone bis[~ (o-aminophenylthio)alkyl ethers having the formula ~ S -(CH2)n- ~ O -(C112)n-S ~ (I) wherein n is 2 or 3 which are useful as hardeners for polyurethane elastomers .
The hydroquinone bis[~-(o-aminophenylthio)alkyl ethers having the formula <~ S--(CH2)n-- ~0 (CH2)n S~
where n is 2 or 3 include the following compounds:
hydroquinone bis[2-(o-aminophenylthio)ethyl]ether, and hydroquinone bis[3-(o-aminophenylthio)propyl]ether.
The hydroquinone bis[~-(o-aminophenylthio)alkyl]ethers of the present invention may be produced by reacting a hydro-quinone with a dihalo compound having the formula : -X-(CH2)n-X (II) . ,~.
where X represents a halogen atom; and n is 2 or 3 in the .
presence of a dehydrohalogenating base to produce a hydroquinone ~ - :
bis(~-haloalkyl)ether having the formula X-(CH2)n~ ~ ~ O-(CH2)n-X (III) - 30 where n and X are defined above and then reacting benzothiazole with the product in the presence of a dehydrohalogenating base.
~ 3~
The reaction in the first step is usually carried out in a polar organic solvent such as dimetliylsulfoxide, hexamethyl-phosphoric triamide, dimethylformamide and dimethylacetamide.
The reaction in the second step is usually carried out in an aqueous solution.
The dihalo compounds having the formula (II) used in the process of the present invention include 1,2-dichloroethane, 1,3-dichloropro~ane, 1,2-dibromoethane and 1,3-dibromopropane.
The dehydrohalogenating bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
The compounds of the present invention may be used as hardeners for producing polyurethane elastomers. The polyurethane elastomer is produced by reacting a polyhydroxy compound with a diisocyanate and a hardener for a main chain extending reaction and a crosslinking reaction to harden the product.
In the manufacture of polyurethane elastomer using the compound of the present invention as hardener, the hardener in a molten condition is added to a heated reaction mixture of a poly-isocyanate with a polyol or a polyurethane prepolymer having terminal isocyanate groups or a polyisocyanate is added to a mixture of a polyol and the hardener and then, the mixture is thoroughly mixed and poured into a casting mold and hardened.
Suitable polyisocyanates include hexamethylene diiso-cyanate (HMDI), cyclohexane diisocyanate, 2,4-tolylene diiso-cyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), and a - mixture of 2,4-TDI and 2,6-TDI, dimer and trimer of 2,4-tolylene diisocyanate, xylylene diisocyanate (XDI), meta-xylylene diiso-cyanate (MXDI), m-phenylene diisocyanate, 4,4'-biphenyl diiso-cyanate, diphenyl ether-4,4'-diisocyanate, 3,3'-ditoluene-4,4'-diisocyanate (TODI), dianisidine diisocyanate (DADI), 4,4'-di-phenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4'-diphenyl-metilane diisocyanate, 1,5-naphthalene diisocyanate, (NDI) and g7~
triphenylmethane triisocyanate (TTI ~ .
Suitable polyols include polyols having a molecular weight of 500 to 8,000 and two or more hydroxyl groups such as aliphatic polyester glycols e.g. polyethylene adipate, poly-butylene adipate and polypropylene adipate which are obtained by a condensation polymerization of an aliphatic glycol and a dicarboxylic acid; polyalkylene ether glycols e.g. polypropylene ether glycol and tetramethylene ether glycol which are obtained by a ring-opening polymerization of ethyleneoxide, propylene-oxide and tetrahydrofuran; a polyester glycol obtained by a ring-opening polymerization of -caprolactone; a diol obtained by hydroxylation of terminal groups of polybutadiene; copolymers of two types of alkyleneoxides; copolymers of two kinds of glycols and a dicarboxylic acid; polyester polyols obtained by the co-condensation polymerization of dicarboxylic acid with a polyol such as an aromatic glycol, a long chain diol, glycerine or trimethylol propanei and polyetherpolyols obtained by a ring-.
opening polymerization epoxide and ether compound, such as ethyleneoxide, propyleneoxide and tetrahydrofuran with a polyol initiator such as glycerin, trimethylolpropane.
The polyurethane prepolymers having terminal isocyanate group are produced by reacting said polyol with excess of said .
polyisocyanate and may be prepolymers having terminal isocyanate groups based on a polyether or a polyester glycol. Typical pre-polymers include a prepolymer obtained by reacting polytetra-methylene glycol with excess of tolylenediisocyanate, a prepoly-mer obtained by reacting polyethylene adipate with excess of tolylenediisocyanate and a prepolymer obtained by reacting poly-caprolactonediol with excess of tolylenediisocyanate.
The hardeners used in the present invention is added at an amount of about 0.8 to 1.2, preferably 0.80 to 1.0, equivalents of the total of amino groups of the hardener and 1~.3~7~
hydroxy groups of the polyols depending upon the polyols per equivalent of isocyanate yroups. A ra-tio of hydroxy groups of the polyol to amino ~roups of the hardener can be varied in wide range and is preferably 0.~ to 5 equivalents of hydroxy groups of the polyol per equivalent of the amino groups.
The hardeners used in the present invention are novel.
The processability can be remarkably improved by using the com-pound (I) as hardener in comparison with the use of the conven-tional hardeners.
~oreover, polyurethane elastomers having the balanced hardeners characteristics and excellent mechanical properties can be obtained by incorporating the compound (I) as hardener of the present invention.
The present invention will be further illustrated by the following Examples EXAMPLE 1:
Synthesis of Compound (1):
In a 1 Q four necked flask equipped with a thermometer, a condenser, a dropping funnel and a stirrer, 27.5 g (0.25 mol) of hydroquinone, 28.1 g (0.5 mol) of potassium hydroxide and 300 mQ of dimethylsulfoxide were charged and stirred and 247.5 g (2.5 mol) of 1,2-dichloroethane was added dropwise. After the addition, the mixture was refluxed for 3 hours. After the reac-tion, benzene was added to extract the oily product and the benzene phase was washed with water and benzene was distilled off to obtain 54.1 g of hydroquinone bis(2-chloroethyl)ether as a brown liquid (yield of 92%).
In a 500 mQ four necked flask equipped with a thermo-meter, a condenser, and a stirrer, 45 g (0.33 mol) of benzo-thiazole, 27.3 g (0.68 mol) of sodium hydroxide and 150 mQ of water were charged.
The mixture was refluxed with stirring for 3 hours to ~L~ 3~ 5 form a solution. Into the solution, 40.4 g (0.172 mol) of hydroquinone bis(2-chloroethyl)ether was added and the mixture was refluxed for 3 hours. After the reaction, toluene was ; added to the reaction mixture to extract with toluene. The toluene phase was washed with water and toluene was distilled off and the resulting residue was recrystalli~ed from toluene to obtain 58.1 g bis[2-(o-aminophenylthio)ethyl]ether (yield of 82% based on hydroquinone bis(2-chloroethyl)ether).
Appearance: yellow crystal Melting point: 105 to 108.5C
IR spectrum:
-NH2 structure: 3320 cm 1; 3450cm EXAMPLE 2:
Synthesis of Compound (2): ~ -In accordance with the process of Example 1 except using 282.5 g (2.5 mol) of 1,3-dichloropropane instead of 1,2-dichloro-ethane and using 45.3 g (0.172 mol) of hydroquinone bis(3-chloro-propyl)ether instead of hydroquinone bis(2-chloroethyl)ether, the reactions were carried out to obtain 59.9 g of hydroquinone bis - 20 [3-(o-aminophenylthio)propyl]ether (yield of 79.0% based on hydroquinone bis(3-chloropropyl)ether).
Appearance: brown oily product IR spectrum:
-NH2 structure: 3320cm 1; 334 EXAMPLE 3:
Production of polyurethane elastomer:
After melting 19.2 g of hydroquinone bis[2-(o-amino-phenylthio)ethyl]ether obtained in Example 1, it was added to 100 g of a prepolymer having isocyanate groups of 4.34 wt. %
obtained by reacting polytetramethyleneglycol (OH value of 114) with tolylenediisocyanate (95% of 2,4-TDI and 5% of TDI) (ratio of -NCO: -NH2 of 1:09) which was heated at 80C.
1~ 3~
The reaction mixt~re was stirred for about 60 seconas so as to be h~rrlocJeneous ana was poured in-to a mold (lOOmm x 250 mm x 2 mm) ileated to 100C. After setting the product, it was taken out of the mold and it was heated at 100C for 15 hours as an after curing to obtain a polyurethane elastomer. Various physical properties of the polyurethane elastomer were measured by Japanese Industrial Standard K-6301. The rèsul-ts are shown in Table l.
EX~PLE 4:
In accordance wi-th the process of Example 3 except using hydroquinone bis[3-(o-aminophenylthio)propyl]ether obtained in Example 2, as a hardener, a polyurethane elastomer was pro-duced and tested.
Reference l:
In accordance with the process of Example 3 except using p-bis(o-aminophenylthiomethyl)benzene as a hardener, a polyurethane elastomer was produced and tested.
The results are shown in Table l.
Table 1: -Reference Potlife (min.) 8 10 6 Set time (min.) 30 45 30 Physical properties:
Hardness (Shore A) 95 85 75 Tensile strength (kg/cm2) 348 243 71 Tear strength (kg/cm) 100 57 39 Rebound elasticity (%) 48 46 38 Modulus 100% (kg/cm2) 91 42 29 Modulus 300% (kg/cm2) 123 98 41 Elongation (%) 520 450 450 Permanent strain (%)38 41 45 EX~PLE 5:
~ _ _ After melting 13. 2 g of hydroquinone bis [2- (o-amino-phenylthio)ethyl]e-ther, it was added to 100 g of a prepolymer naving isocyanate groups of 3.0 wt. % obtained by reacting poly-ethyleneadipate (OH value of 56.5) with tolylenediisocyanate (80% of 2,4-TDI and 20% of 2,6-TDI) (ratio of -NCO; -Nh of 1:0.9) which was heated at 80C.
The reaction mixture was stirred for about 60 seconds so as to be homogeneous and it was poured into a mold and treated in accordance with the process of Example 3 so as to obtain a polyurethane elastomer. Various physical properties of the poly-urethane elastomer were measured. The results are shown in Table 2.
EXAMPLE 6:
In accordance with the process of Example 5 except using hydroquinone bis[3-(o-aminophenylthio)propyl]ether as a hardener, each polyurethane elastomer was produced and properties were measured. The results are shown in Table 2.
Reference 2:
In accordance with the process of Example 5 except using p-bis(o-aminophenylthiomethyl) benzene as a hardener, a polyurethane elastomer was produced and properties were measured.
The results are shown in Table 2.
S
Table 2 ______ _ ________ __ j 5 _ ¦ 6 2 Pot life (min.) 13 20 10 Set time (min . )120 180 120 ____ _ Physical propertics:
.
Hardness (Shore A)86 77 70 Tensile strength (kg/cm2) 400 415 365 Tear strength (kg/cm) 78 61 46 Rebound e]asticity ( %) 41 40 35 Modulus 100% (kg/cm2) 44 36 33 Modulus 300% (kg/cm2) 70 71 63 Elongation ( %) 720 650 730 Permanent strain ( %) 60 54 60 As shown in Tables l and 2, the hardeners of the pre-sent invention have remarkably lower melting point in comparison with that of p-bis (o-aminophenylthiomethyl) benzene and have balanced superior characteristics as hardeners.
, ,
The present invention relcltes to hydroquinone bis [~-(o-aminophenylthio)alkyl] ethers and -their use as hardeners for polyurethane elastomer.
Heretofore, aromatic diamines have been used as hardeners in the preparation of polyurethane elastomers. Various aromatic diamine type hardeners have been proposed. The import-ant characteristics required for the hardeners are as follows:-Firstly, the ilardeners should be a low meltlng point solid or liquid from processability, labour hygiene and energy saving considerations;
Secondly, the pot life, i.e. the time from mixing the hardener with a mixture of polyisocyanate and polyol or a pre-polymer having the terminal isocyanate group to the mixture being non-flowable for casting, should be suitable;
Thirdly, the set time as the time from molding the mixture to demolding the cast product for processability, espec-ially efficiency, should be suitable;
~` Fourthly, the hardener should be easily produced and be stable; and Fifthly, the resulting polyurethane elastomer should have excellent physical properties.
However, these requirements are contradictory. For example, if the short set time is required, the pot life is shortened to cause trouble in processing. Accordingly, it is difficult to obtain a hardener having satisfactory and balanced characteristics. Thus for example, p-bis(o-aminophenylthio-methyl)benzene has a structure similar to that of the hardeners of the present invention, however, it has high melting point as 134 to 136~C to provide poor processability.
The present invention provides hardeners for poly-urethane elastomers which have the above-mentioned balanced characteristics.
~ 3~?47~
According to the presen-t invention there are provided hydroqulnone bis[~ (o-aminophenylthio)alkyl ethers having the formula ~ S -(CH2)n- ~ O -(C112)n-S ~ (I) wherein n is 2 or 3 which are useful as hardeners for polyurethane elastomers .
The hydroquinone bis[~-(o-aminophenylthio)alkyl ethers having the formula <~ S--(CH2)n-- ~0 (CH2)n S~
where n is 2 or 3 include the following compounds:
hydroquinone bis[2-(o-aminophenylthio)ethyl]ether, and hydroquinone bis[3-(o-aminophenylthio)propyl]ether.
The hydroquinone bis[~-(o-aminophenylthio)alkyl]ethers of the present invention may be produced by reacting a hydro-quinone with a dihalo compound having the formula : -X-(CH2)n-X (II) . ,~.
where X represents a halogen atom; and n is 2 or 3 in the .
presence of a dehydrohalogenating base to produce a hydroquinone ~ - :
bis(~-haloalkyl)ether having the formula X-(CH2)n~ ~ ~ O-(CH2)n-X (III) - 30 where n and X are defined above and then reacting benzothiazole with the product in the presence of a dehydrohalogenating base.
~ 3~
The reaction in the first step is usually carried out in a polar organic solvent such as dimetliylsulfoxide, hexamethyl-phosphoric triamide, dimethylformamide and dimethylacetamide.
The reaction in the second step is usually carried out in an aqueous solution.
The dihalo compounds having the formula (II) used in the process of the present invention include 1,2-dichloroethane, 1,3-dichloropro~ane, 1,2-dibromoethane and 1,3-dibromopropane.
The dehydrohalogenating bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
The compounds of the present invention may be used as hardeners for producing polyurethane elastomers. The polyurethane elastomer is produced by reacting a polyhydroxy compound with a diisocyanate and a hardener for a main chain extending reaction and a crosslinking reaction to harden the product.
In the manufacture of polyurethane elastomer using the compound of the present invention as hardener, the hardener in a molten condition is added to a heated reaction mixture of a poly-isocyanate with a polyol or a polyurethane prepolymer having terminal isocyanate groups or a polyisocyanate is added to a mixture of a polyol and the hardener and then, the mixture is thoroughly mixed and poured into a casting mold and hardened.
Suitable polyisocyanates include hexamethylene diiso-cyanate (HMDI), cyclohexane diisocyanate, 2,4-tolylene diiso-cyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), and a - mixture of 2,4-TDI and 2,6-TDI, dimer and trimer of 2,4-tolylene diisocyanate, xylylene diisocyanate (XDI), meta-xylylene diiso-cyanate (MXDI), m-phenylene diisocyanate, 4,4'-biphenyl diiso-cyanate, diphenyl ether-4,4'-diisocyanate, 3,3'-ditoluene-4,4'-diisocyanate (TODI), dianisidine diisocyanate (DADI), 4,4'-di-phenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4'-diphenyl-metilane diisocyanate, 1,5-naphthalene diisocyanate, (NDI) and g7~
triphenylmethane triisocyanate (TTI ~ .
Suitable polyols include polyols having a molecular weight of 500 to 8,000 and two or more hydroxyl groups such as aliphatic polyester glycols e.g. polyethylene adipate, poly-butylene adipate and polypropylene adipate which are obtained by a condensation polymerization of an aliphatic glycol and a dicarboxylic acid; polyalkylene ether glycols e.g. polypropylene ether glycol and tetramethylene ether glycol which are obtained by a ring-opening polymerization of ethyleneoxide, propylene-oxide and tetrahydrofuran; a polyester glycol obtained by a ring-opening polymerization of -caprolactone; a diol obtained by hydroxylation of terminal groups of polybutadiene; copolymers of two types of alkyleneoxides; copolymers of two kinds of glycols and a dicarboxylic acid; polyester polyols obtained by the co-condensation polymerization of dicarboxylic acid with a polyol such as an aromatic glycol, a long chain diol, glycerine or trimethylol propanei and polyetherpolyols obtained by a ring-.
opening polymerization epoxide and ether compound, such as ethyleneoxide, propyleneoxide and tetrahydrofuran with a polyol initiator such as glycerin, trimethylolpropane.
The polyurethane prepolymers having terminal isocyanate group are produced by reacting said polyol with excess of said .
polyisocyanate and may be prepolymers having terminal isocyanate groups based on a polyether or a polyester glycol. Typical pre-polymers include a prepolymer obtained by reacting polytetra-methylene glycol with excess of tolylenediisocyanate, a prepoly-mer obtained by reacting polyethylene adipate with excess of tolylenediisocyanate and a prepolymer obtained by reacting poly-caprolactonediol with excess of tolylenediisocyanate.
The hardeners used in the present invention is added at an amount of about 0.8 to 1.2, preferably 0.80 to 1.0, equivalents of the total of amino groups of the hardener and 1~.3~7~
hydroxy groups of the polyols depending upon the polyols per equivalent of isocyanate yroups. A ra-tio of hydroxy groups of the polyol to amino ~roups of the hardener can be varied in wide range and is preferably 0.~ to 5 equivalents of hydroxy groups of the polyol per equivalent of the amino groups.
The hardeners used in the present invention are novel.
The processability can be remarkably improved by using the com-pound (I) as hardener in comparison with the use of the conven-tional hardeners.
~oreover, polyurethane elastomers having the balanced hardeners characteristics and excellent mechanical properties can be obtained by incorporating the compound (I) as hardener of the present invention.
The present invention will be further illustrated by the following Examples EXAMPLE 1:
Synthesis of Compound (1):
In a 1 Q four necked flask equipped with a thermometer, a condenser, a dropping funnel and a stirrer, 27.5 g (0.25 mol) of hydroquinone, 28.1 g (0.5 mol) of potassium hydroxide and 300 mQ of dimethylsulfoxide were charged and stirred and 247.5 g (2.5 mol) of 1,2-dichloroethane was added dropwise. After the addition, the mixture was refluxed for 3 hours. After the reac-tion, benzene was added to extract the oily product and the benzene phase was washed with water and benzene was distilled off to obtain 54.1 g of hydroquinone bis(2-chloroethyl)ether as a brown liquid (yield of 92%).
In a 500 mQ four necked flask equipped with a thermo-meter, a condenser, and a stirrer, 45 g (0.33 mol) of benzo-thiazole, 27.3 g (0.68 mol) of sodium hydroxide and 150 mQ of water were charged.
The mixture was refluxed with stirring for 3 hours to ~L~ 3~ 5 form a solution. Into the solution, 40.4 g (0.172 mol) of hydroquinone bis(2-chloroethyl)ether was added and the mixture was refluxed for 3 hours. After the reaction, toluene was ; added to the reaction mixture to extract with toluene. The toluene phase was washed with water and toluene was distilled off and the resulting residue was recrystalli~ed from toluene to obtain 58.1 g bis[2-(o-aminophenylthio)ethyl]ether (yield of 82% based on hydroquinone bis(2-chloroethyl)ether).
Appearance: yellow crystal Melting point: 105 to 108.5C
IR spectrum:
-NH2 structure: 3320 cm 1; 3450cm EXAMPLE 2:
Synthesis of Compound (2): ~ -In accordance with the process of Example 1 except using 282.5 g (2.5 mol) of 1,3-dichloropropane instead of 1,2-dichloro-ethane and using 45.3 g (0.172 mol) of hydroquinone bis(3-chloro-propyl)ether instead of hydroquinone bis(2-chloroethyl)ether, the reactions were carried out to obtain 59.9 g of hydroquinone bis - 20 [3-(o-aminophenylthio)propyl]ether (yield of 79.0% based on hydroquinone bis(3-chloropropyl)ether).
Appearance: brown oily product IR spectrum:
-NH2 structure: 3320cm 1; 334 EXAMPLE 3:
Production of polyurethane elastomer:
After melting 19.2 g of hydroquinone bis[2-(o-amino-phenylthio)ethyl]ether obtained in Example 1, it was added to 100 g of a prepolymer having isocyanate groups of 4.34 wt. %
obtained by reacting polytetramethyleneglycol (OH value of 114) with tolylenediisocyanate (95% of 2,4-TDI and 5% of TDI) (ratio of -NCO: -NH2 of 1:09) which was heated at 80C.
1~ 3~
The reaction mixt~re was stirred for about 60 seconas so as to be h~rrlocJeneous ana was poured in-to a mold (lOOmm x 250 mm x 2 mm) ileated to 100C. After setting the product, it was taken out of the mold and it was heated at 100C for 15 hours as an after curing to obtain a polyurethane elastomer. Various physical properties of the polyurethane elastomer were measured by Japanese Industrial Standard K-6301. The rèsul-ts are shown in Table l.
EX~PLE 4:
In accordance wi-th the process of Example 3 except using hydroquinone bis[3-(o-aminophenylthio)propyl]ether obtained in Example 2, as a hardener, a polyurethane elastomer was pro-duced and tested.
Reference l:
In accordance with the process of Example 3 except using p-bis(o-aminophenylthiomethyl)benzene as a hardener, a polyurethane elastomer was produced and tested.
The results are shown in Table l.
Table 1: -Reference Potlife (min.) 8 10 6 Set time (min.) 30 45 30 Physical properties:
Hardness (Shore A) 95 85 75 Tensile strength (kg/cm2) 348 243 71 Tear strength (kg/cm) 100 57 39 Rebound elasticity (%) 48 46 38 Modulus 100% (kg/cm2) 91 42 29 Modulus 300% (kg/cm2) 123 98 41 Elongation (%) 520 450 450 Permanent strain (%)38 41 45 EX~PLE 5:
~ _ _ After melting 13. 2 g of hydroquinone bis [2- (o-amino-phenylthio)ethyl]e-ther, it was added to 100 g of a prepolymer naving isocyanate groups of 3.0 wt. % obtained by reacting poly-ethyleneadipate (OH value of 56.5) with tolylenediisocyanate (80% of 2,4-TDI and 20% of 2,6-TDI) (ratio of -NCO; -Nh of 1:0.9) which was heated at 80C.
The reaction mixture was stirred for about 60 seconds so as to be homogeneous and it was poured into a mold and treated in accordance with the process of Example 3 so as to obtain a polyurethane elastomer. Various physical properties of the poly-urethane elastomer were measured. The results are shown in Table 2.
EXAMPLE 6:
In accordance with the process of Example 5 except using hydroquinone bis[3-(o-aminophenylthio)propyl]ether as a hardener, each polyurethane elastomer was produced and properties were measured. The results are shown in Table 2.
Reference 2:
In accordance with the process of Example 5 except using p-bis(o-aminophenylthiomethyl) benzene as a hardener, a polyurethane elastomer was produced and properties were measured.
The results are shown in Table 2.
S
Table 2 ______ _ ________ __ j 5 _ ¦ 6 2 Pot life (min.) 13 20 10 Set time (min . )120 180 120 ____ _ Physical propertics:
.
Hardness (Shore A)86 77 70 Tensile strength (kg/cm2) 400 415 365 Tear strength (kg/cm) 78 61 46 Rebound e]asticity ( %) 41 40 35 Modulus 100% (kg/cm2) 44 36 33 Modulus 300% (kg/cm2) 70 71 63 Elongation ( %) 720 650 730 Permanent strain ( %) 60 54 60 As shown in Tables l and 2, the hardeners of the pre-sent invention have remarkably lower melting point in comparison with that of p-bis (o-aminophenylthiomethyl) benzene and have balanced superior characteristics as hardeners.
, ,
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Hydroquinone bis[.omega.-(o-aminophenylthio)alkyl] ethers having the formula wherein n is 2 or 3.
2. Hydroquinone bis[2-(o-aminophenylthio)ethyl]ether.
3. Hydroquinone bis[3-(o-aminophenylthio)propyl]ether.
4. A process for producing a hydroquinone bis[.omega.-(o-aminophenylthio)alkyl]ether having the formula wherein n is 2 or 3 which comprises reacting hydroquinone with a dihalo compound having the formula X-(CH2)n-X in the presence of a dehydrohalogenating base to produce hydroquinone bis(.omega.-halo-alkyl)ether having the formula wherein n is 2 or 3 and X represents a halogen atom, and reacting benzothiazole with the product in the presence of a dehydro-halogenating base.
5. A polyurethane elastomer hardened by a hydroquinone bis[.omega.-(o-aminophenylthio)alkyl ether having the formula wherein n is 2 or 3 as hardener.
6. An elastomer as claimed in claim 5 in which the hardener is hydroquinone bis[2-(o-aminophenylthio)ethyl]ether.
7. An elastomer as claimed in claim 5 in which the hardener is hydroquinone bis[3-(o-aminophenylthio)propyl]ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000358566A CA1138475A (en) | 1980-08-19 | 1980-08-19 | HYDROQUINONE BIS[.omega.-(O-AMINOPHENYLTHIO) ALKL] ETHERS AND HARDENER FOR POLYURETHANE ELASTOMER THEREOF |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000358566A CA1138475A (en) | 1980-08-19 | 1980-08-19 | HYDROQUINONE BIS[.omega.-(O-AMINOPHENYLTHIO) ALKL] ETHERS AND HARDENER FOR POLYURETHANE ELASTOMER THEREOF |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1138475A true CA1138475A (en) | 1982-12-28 |
Family
ID=4117689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000358566A Expired CA1138475A (en) | 1980-08-19 | 1980-08-19 | HYDROQUINONE BIS[.omega.-(O-AMINOPHENYLTHIO) ALKL] ETHERS AND HARDENER FOR POLYURETHANE ELASTOMER THEREOF |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1138475A (en) |
-
1980
- 1980-08-19 CA CA000358566A patent/CA1138475A/en not_active Expired
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