CA1094742A - Process for producing vulcanizable acrylic rubber - Google Patents
Process for producing vulcanizable acrylic rubberInfo
- Publication number
- CA1094742A CA1094742A CA277,275A CA277275A CA1094742A CA 1094742 A CA1094742 A CA 1094742A CA 277275 A CA277275 A CA 277275A CA 1094742 A CA1094742 A CA 1094742A
- Authority
- CA
- Canada
- Prior art keywords
- malonic acid
- acid derivative
- process according
- parts
- acrylic rubber
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
Abstract
Abstract of the Disclosure A process for producing acrylic rubber vulcanizable with curing agents in the thiuram series is provided. The process includes the copolymerization of an acrylic ester or esters with a malonic acid derivative having an active methylene group. The acrylic rubber thus produced shows better physical properties than the conventional one.
Description
10`'~ ~7~:~
1 The present invention relates to a process for pro-ducing vulcanizable acrylic rubber. , Conventional acrylic rubbers are stable to heat and oilproof because of high polarity of their ester structure, but are unvulcanizable with sulfur because they do not have any unsaturated groups or double bonds in their polymer backbone.
Therefore, the conventional process for producing acrylic rubbers is by copolymerizing acrylic esters with a suitable amount of a cross-linking monomer which reacts with a vulcanizing agent such as soaps, ethyltetramines and tetraethylpentamines, and curing the copolymer with such a vulcanizing agent. Such monomers include those which contain halogen such as ~-chloroethyl vinyl ether and vinyl chloroacetate, and those which contain an epoxy group such as allyl glycidyl ether, glycidyl acrylate and glycidyl methacrylate.
Such conventional acrylic rubbers are, however, liable to scorch during storage and have low resistance to cold and poor processibility. Particularly, the acrylic rubbers produced by use of liquid polyamine as a vulcanizing agent have undue adhesiveness to a mixing roll, poor bin stability, high corrosive-ness, and offensive odor and toxicity coming from the amine.
It is an object of this invention to provide a processof producing vulcanizable acrylic rubber which does nc~ have such disadvantages.
According to the present invention, an acrylic ester or esters are copolymerized with a malonic acid derivative having an acti~e methylene group to produce acrylic rubber which can be cured with vulcanizing agents in the thiuram series ~or cross-linking.
1 The present invention relates to a process for pro-ducing vulcanizable acrylic rubber. , Conventional acrylic rubbers are stable to heat and oilproof because of high polarity of their ester structure, but are unvulcanizable with sulfur because they do not have any unsaturated groups or double bonds in their polymer backbone.
Therefore, the conventional process for producing acrylic rubbers is by copolymerizing acrylic esters with a suitable amount of a cross-linking monomer which reacts with a vulcanizing agent such as soaps, ethyltetramines and tetraethylpentamines, and curing the copolymer with such a vulcanizing agent. Such monomers include those which contain halogen such as ~-chloroethyl vinyl ether and vinyl chloroacetate, and those which contain an epoxy group such as allyl glycidyl ether, glycidyl acrylate and glycidyl methacrylate.
Such conventional acrylic rubbers are, however, liable to scorch during storage and have low resistance to cold and poor processibility. Particularly, the acrylic rubbers produced by use of liquid polyamine as a vulcanizing agent have undue adhesiveness to a mixing roll, poor bin stability, high corrosive-ness, and offensive odor and toxicity coming from the amine.
It is an object of this invention to provide a processof producing vulcanizable acrylic rubber which does nc~ have such disadvantages.
According to the present invention, an acrylic ester or esters are copolymerized with a malonic acid derivative having an acti~e methylene group to produce acrylic rubber which can be cured with vulcanizing agents in the thiuram series ~or cross-linking.
- 2 109~7~2 1 FIG. 1 is a graph showing the vulcanization curves for ~n acrylic rubber produced according to this invention and for the conventional acrylic rubber.
FTG. 2 is a similar graph for the acrylic rubbers pre-pared in Example 9.
The malonic acid derivative having an active methylene group utilized in the present invention has the following general formula:
/ COORl C 2 \ (1) wherein Rl represents vinyl, allyl or methallyl group and X
represents COOR2 or cyano group.
First, if X represents COOR2 in the formula (1), the malonic acid derivative has the following general formula:
~ COORl 2Q CH2 (2 COOR
wherein R2 represents methyl, ethyl or propyl group. Thus, the derivatives are malonic acids with an active methylene group having one of two acid radicals esterified with an unsaturated alcohol such as allyl alcohol, and having the other acid radical esterified with a saturated alcohol. Such derivatives include allyl ethyl malonate and allyl methyl malonate, for example.
10~7~2 1 A process for producing the former will be described by way of example. A mixture of 1 mole of ethyl cyanoacetate, 1 mole of sulfuric acid and 1 mole of water is kept at 80C or lower for about four hours under stirring. 1.5 mole of allyl alcohol is added, the mixture being allowed to react with slow stirring at room temperature for a~out 72 hours. The mixture is then rinsed dehydrated and distilled under reduced pressure.
During distillation, ethyl cyanoacetate distills off first and allyl ethyl malona~e distills off last. In this process, if allyl cyanoacetate and ethyl alcohol are used as the starting materials the reaction product contains only allyl cyano-acetate and allyl ethyl malonate, containing no ethyl cyano-acetate which has a bad effect on cross-linking.
Next, if X represents cyano group in the formula (1), the malonic acid derivative has the following general formula:
~ COORl 2 (3) CN
wherein Rl represents vinyl, allyl or methallyl group. The malonic acid derivatives include esters of cyanoacetic acid (that is, malonic acid mononitrile) having an active methylene group with an unsaturated alcohol, such as allyl cyanoacetate or methallyl cyanoacetate, and esters thereof with hydroxy-ethyl acrylate or hydroxyethyl methacrylate.
Such malonic acid derivative having the general formula ~3) may be produced by the conventional processes, one of which will be described by way of example. One part by weight of p-toluene sulfonic acid as a catalyzer is added to a mixture
FTG. 2 is a similar graph for the acrylic rubbers pre-pared in Example 9.
The malonic acid derivative having an active methylene group utilized in the present invention has the following general formula:
/ COORl C 2 \ (1) wherein Rl represents vinyl, allyl or methallyl group and X
represents COOR2 or cyano group.
First, if X represents COOR2 in the formula (1), the malonic acid derivative has the following general formula:
~ COORl 2Q CH2 (2 COOR
wherein R2 represents methyl, ethyl or propyl group. Thus, the derivatives are malonic acids with an active methylene group having one of two acid radicals esterified with an unsaturated alcohol such as allyl alcohol, and having the other acid radical esterified with a saturated alcohol. Such derivatives include allyl ethyl malonate and allyl methyl malonate, for example.
10~7~2 1 A process for producing the former will be described by way of example. A mixture of 1 mole of ethyl cyanoacetate, 1 mole of sulfuric acid and 1 mole of water is kept at 80C or lower for about four hours under stirring. 1.5 mole of allyl alcohol is added, the mixture being allowed to react with slow stirring at room temperature for a~out 72 hours. The mixture is then rinsed dehydrated and distilled under reduced pressure.
During distillation, ethyl cyanoacetate distills off first and allyl ethyl malona~e distills off last. In this process, if allyl cyanoacetate and ethyl alcohol are used as the starting materials the reaction product contains only allyl cyano-acetate and allyl ethyl malonate, containing no ethyl cyano-acetate which has a bad effect on cross-linking.
Next, if X represents cyano group in the formula (1), the malonic acid derivative has the following general formula:
~ COORl 2 (3) CN
wherein Rl represents vinyl, allyl or methallyl group. The malonic acid derivatives include esters of cyanoacetic acid (that is, malonic acid mononitrile) having an active methylene group with an unsaturated alcohol, such as allyl cyanoacetate or methallyl cyanoacetate, and esters thereof with hydroxy-ethyl acrylate or hydroxyethyl methacrylate.
Such malonic acid derivative having the general formula ~3) may be produced by the conventional processes, one of which will be described by way of example. One part by weight of p-toluene sulfonic acid as a catalyzer is added to a mixture
3-~
~0~7~Z "
1 of 100 parts of cyanoacetic acid, 100 parts of allyl alcohol, 50 parts of benzene and 50 parts of cyclohexane. The mixture undergoes esterification at 70 - 80C for about 24 hours while refluxing by means of a phase separator to remove water. After reaction, it is cooled, rinsed, dehydrated and distilled to remove the solvents. Thereafter it is further distilled under reduced pressure of 10 mmHg. The derivative aimed at is obtained by collecting the fraction at 110~ - 112C.
The acrylic esters used in this invention are methylacrylate, ethylacrylate and butylacrylate.
In the copolymerization according to this invention, the amount of the malonic acid derivative having the general formula (2) or (3) is preferably 2 - 10% by weight, and more preferably 2 - 6%, relative to the acrylic ester. If it were less than 2~, the addition of malonic acid derivative would not have a sufficient effect, whereas for more than 10~ the curing rate would be much higher and the tensile strength would increase owing to o~er-cure, but the hardness would increase, thus resulting in lower elongation and elasticity.
The reaction temperature for copolymerization is 50 - 70C, and the reaction time is preferably 30 to 40 minutes.
As vulcanizing agents used for the acrylic rubber produced according to the present invention, tetramethylthiuram disulfide and tetraethylthiuram disulfide are preferable. Also, tetramethylthiuram monosulfide or thiazole is preferably used as a vulcanizing accelerator.
The acrylic rubbers produced according to the present invention show much higher curing rate and mar~ed plateau effect in comparison with the conventional acrylic rubber cured with amines, as will be seen in FIG. 1 wherein (~) is the 10947~2 1 vulcanization curve for the acrylic rubber produced according to this invention and (B) is the curve for conventional acrylic rubber. The present acrylic rubbers also retain resistance to heat, oil, ozone, weathering and bend-cracking which the conventional acrylic rubber has. Furthermore, they have additional advantages of better processibility with a mixing roll, freedom from scorch during processing or storage, no corrosiveness to a curing mold and easy adhesion to metal inserts. Besides the present acrylic rubbers allow use of white carbon in the silica or talc series as well as the conventional carbon black as a reinforcing agent. This provides greater flexibility for production of colored rubber.
The acrylic rubber produced according to the present invention may be formed into rolls, seals, gaskets, "O" rings, hoses and so on.
The following examples are included merely to aid in the understanding of the present invention. Unless otherwise stated, quantities are expressed as parts by weight.
Example 1 A~ In a flask were put 200 parts of water, 0.5 part of sodium laurylsulfate and 2 parts of polyoxyethylene lauryl ether as emulsifiers, 5 parts of allyl ethyl malonate, 0.05 part of potassium persulfate as a polymerization initiator and 0.05 part of so~ium hydrogen biculfite as redox catalyst. The mixture was heated to 50-70C while blowing ~itrogen gas there-into and 95 parts of ethyl acrylate was added drop by drop, taking 30 to 40 minutes, for emulsion polymerization to give vulcanizable acrylic rubber.
B) To 100 parts of the acrylic rubber thus prepared in (A) were added 50 parts of MEF (medium extrusion furnacel carbon, ~0947~2 1 1 part of stearic acid, 2.4 parts of tetramethylthiuram disulfide and 3.3 parts of dibenzothiazolyl disulfide.
After kneading well in an open roll, the mixture was put into a curing mold and heated at 170C for 10 minutes.
The rubber slab thus made was subjected to post cure at 150C for 16 hours. Table 1 summarizes the physical - 6a -~0~?~742 1 properties of the cured acrylic rubber in an original test, an air heat a2ing test at 1~0C
for 70 hours and oil resist~nce tests, respectively.
Table 1 '~roperties Hardness Te~sile Elongation Volume \ (in Hs) strength 2 percentage change Eind of Tes ~ ~ (i = (i. ~) p rD:~=a~c Ori~inal test 74 123 250 Air heat ag~ng 78 142 215 test at 150 C
for 70 hours Oil resistance test with JIS N8.1 78 131 270 oil at 150 C
for 70 hours with JIS ~8.3 1 69 118 310 oil at 150 C
f or 70 hours I I
~0 ~ I
(JIS is an abbreviation of the Japanese Industrial Standard.) ~xample 2 Except that 4 parts of allyl methyl malon'te and 96 parts of ethyl acrylate were used7 the s~,me mixi~g ratio and reaction conditions as in ~xample 1 were used to prepare ~ulcanizable acrylic rubber.
To 100 parts of the acrylic rubber were added 50 parts of white carbon, 1 part of stearic acid, ~.4 parts of tetraethylthiuram disulfide and 3.3 parts of dibenzothiazolyl disulfide After kneading~ the mixture ~s pre-cured at 170C for 10 minutes and ~i?ost-eured 109~742 1 at 150C for 4 hours. ~able 2 shows the physical properties of the cured acrylic rubber measured as in Example 1.
Table 2 \ Properties Hardnessl ~ensile ~longation Volume \ I (in Hs) strength 2 percentage change \ I (in kg/cm ) (in ~) p(rcentage Eind of ~es ~ I
~ ~ _ Original test lll 74 115 260 Air heat agOing I 79 1~5 270 test at 150 c I I
~or 70 hours I l li Oil resistance test with JIS Ng.1 78 ' 1 ~7 230 1 _o . 8 oil at 150 C
for 70 hours ¦
with JIS ~8~3 l 70 1 110 1 330 +11.7 oil at 150 c for 70 hours E~mple 3 Except that ~ parts o~ allyl ethyl malonate, 80 parts o~ ethyl acrylate and 15 parts of butyl acrylate were used as monomers 7 the s~me mixing ratio and reaction conditions as in Example 1 were used. ~he acrylic rubber thus ma~e was cured in the same m.~nner as 20 in Example 1 except that the pos. cure time ~A~'as 7 hours. 'rable ~ shows the physical properties o~ the cured acrylic rub`~er.
" 10~474Z
1 ~able 3 \ Properties Hardness Tensile Elongation Volume \ (in Hs) strength 2 percentage change \ (in k~/cm ) (in o/O) P(in o70) g Eind of Tes ~
\ ., Original test 65 109 300 Air heat ag~ng ¦ 74 121 240 test at 150 C I
for 70 hours Oil resistance ¦
test with JIS ~8.1 ¦ 76 118 250 +2.
oil at 150 C
for 70 hours with JIS ~8.3 ~ 58 102 380 +19.3 oil at 150 C
for 70 hours i _ Example 4 Except that 8 parts of all~l ethyl malonate and 92 parts of ethyl ac~late were used, the same mixin~
ratio and reaction conditions as in Example 1 were used to produce vulcanizable acrylic rubber. It was then cured as in Example 1 except that tetraethylthiuram disulfide was used instead of tetramethylthiuram di~ulfide. Table 4 shows the physical properties of the cured acrylic rubber.
3o ~09~742 1 Table 4 \ Properties Hardnessl ~ensile Elongation Volume \ (in Hs) strength 2 percentage change \ (in kg/cm ) (in %) (ln %) ~ind of ~est\
\
Original test 79 152 180 Air heat ag~ng 84 168 150 test at 150 C
for 70 hours Oil resistance test with JIS Ng.1 83 162 190 -0.9 oil at 150 C
for 70 hours with JIS ~8 3 73~ 147 270 +11.8 oil at 150 C
for 70 hours ~xample 5 A) In a flask were put 200 parts of water, 0.5 part of sodium laurylsulfate and 2 parts of polyoxyethylene lauryl ether, 5 parts of allyl cyanoacetate, 0.05 part of potassium persulfate and 0.05 part of sodium nydrogen bisulfite. The mixture was heated to 50-70~C while blowing nitrogen gas thereinto and 95 parts of ethyl acrylate was added drop by drop, taking 30 to 40 minutes, for emulsion polymerization to give vulcanizable acrylic rubber.
3o ~) To 100 parts of the acrylic rubber thus prepared ~~ were added 50 parts of ME~ carbon, 1 part of ~tearic '10!~7~2 1 acid~ 2 parts of tetramethylthiuram disulfide and 2 parts of dibenzothiazolyl disulfide. After kneading well in an open roll, the mixture was put into a curing mold and heated at 170~ for 10 minutes. The rubber slab thus made was subjected to post cure at 150C for 16 hours. ~able 5 shows the physical properties of the cured acrylic rubber.
~able 5 \ Properties Hardness Tensile Elongation Volume \ (in Hs) strength 2 percentage change \ (in kg/cm ) (in ,b) ~ercentage Kind of ~est \
\ . .
Original test 73 145 260 Air heat ag~ng 79 142 226 test at 150 C
fo ~ ours Oiltresistance with JIS ~8'1 78 138 ~73 -0.9 oil at 150 C
for 70 hours with JIS ~00.3 67122 ¦ 310 +12.1 oil at 150 C
for 70 hours Y l ~., Example 6 Except that 7 p3rts of allyl cyanoacet~te, 15 -parts of meth~l acrylate and 78 parts of ethyl acrylate ~ere 3~ used as monomers, the same mi~ing ratio and reaction conditions as in ~xample 5 were used.
o 100 parts of the acrylic rubber thus ~repared 109~t742 1 were added 50 parts of white carbon as a reinforcing agent, 1 part of stearic acid, 3 parts of tetraethylthiuram disulfide and 3 p~rts of diben~othiazol~l disulfide.
The acrylic rubber was cured as in Example 5 except that the post cure time was 4 hours.
Example 7 Except that ~ parts of allyl cyanoacetate, 10 parts of acr~lonitrile and 85 parts of but~l acrylate were used, the same mixing ratio and reaction conditions as in Example 5 were used.
The acrylic rubber thus prepared was cured as in Example 5 except that 1.5 parts of dibenzothiazolyl disulfide were used and that the post cure time was 7 hours. Table 6 shows the physical properties of the cured acrylic rubber.
Table 6 Propertiesl~Iardness Tensile ¦ Elongation Volume \ (in Hs) strength 2 I percentage change \ (in kg/cm ) (in ~) ~ercentage Kind of ~est \ I
_ Original test 70 135 210 . .
Air heat ag~ng 75 162 1 206 test at 150 C
for 70 hours Oil resistance ¦
test I '~
with JIS ~8~1 7 ~ 5 241 I +0.5 oil at 150 C
for 70 hours I ~ I
with JI~ ~8.3 61 112 25~ +1~.4 oil at 150 C
for 70 hours 10~742 1 EYample 8 Except that 7 parts of allyi cyanoacetate and 9~
parts of ethyl acrylate were used as monomers, the s~me mixing ratio and reaction conditions as in ~xample 5 were used~
~ o .100 parts of the acrylic rubber thus prepared were added 50 parts of MEF carbon, 1 part of stearic acid, 2 parts of tetraethylthiuram disulfide and 2 parts of dibenzothiazolyl disulfide. ~he acrylic rubber was cured as in Example 5 except that the post cure time was
~0~7~Z "
1 of 100 parts of cyanoacetic acid, 100 parts of allyl alcohol, 50 parts of benzene and 50 parts of cyclohexane. The mixture undergoes esterification at 70 - 80C for about 24 hours while refluxing by means of a phase separator to remove water. After reaction, it is cooled, rinsed, dehydrated and distilled to remove the solvents. Thereafter it is further distilled under reduced pressure of 10 mmHg. The derivative aimed at is obtained by collecting the fraction at 110~ - 112C.
The acrylic esters used in this invention are methylacrylate, ethylacrylate and butylacrylate.
In the copolymerization according to this invention, the amount of the malonic acid derivative having the general formula (2) or (3) is preferably 2 - 10% by weight, and more preferably 2 - 6%, relative to the acrylic ester. If it were less than 2~, the addition of malonic acid derivative would not have a sufficient effect, whereas for more than 10~ the curing rate would be much higher and the tensile strength would increase owing to o~er-cure, but the hardness would increase, thus resulting in lower elongation and elasticity.
The reaction temperature for copolymerization is 50 - 70C, and the reaction time is preferably 30 to 40 minutes.
As vulcanizing agents used for the acrylic rubber produced according to the present invention, tetramethylthiuram disulfide and tetraethylthiuram disulfide are preferable. Also, tetramethylthiuram monosulfide or thiazole is preferably used as a vulcanizing accelerator.
The acrylic rubbers produced according to the present invention show much higher curing rate and mar~ed plateau effect in comparison with the conventional acrylic rubber cured with amines, as will be seen in FIG. 1 wherein (~) is the 10947~2 1 vulcanization curve for the acrylic rubber produced according to this invention and (B) is the curve for conventional acrylic rubber. The present acrylic rubbers also retain resistance to heat, oil, ozone, weathering and bend-cracking which the conventional acrylic rubber has. Furthermore, they have additional advantages of better processibility with a mixing roll, freedom from scorch during processing or storage, no corrosiveness to a curing mold and easy adhesion to metal inserts. Besides the present acrylic rubbers allow use of white carbon in the silica or talc series as well as the conventional carbon black as a reinforcing agent. This provides greater flexibility for production of colored rubber.
The acrylic rubber produced according to the present invention may be formed into rolls, seals, gaskets, "O" rings, hoses and so on.
The following examples are included merely to aid in the understanding of the present invention. Unless otherwise stated, quantities are expressed as parts by weight.
Example 1 A~ In a flask were put 200 parts of water, 0.5 part of sodium laurylsulfate and 2 parts of polyoxyethylene lauryl ether as emulsifiers, 5 parts of allyl ethyl malonate, 0.05 part of potassium persulfate as a polymerization initiator and 0.05 part of so~ium hydrogen biculfite as redox catalyst. The mixture was heated to 50-70C while blowing ~itrogen gas there-into and 95 parts of ethyl acrylate was added drop by drop, taking 30 to 40 minutes, for emulsion polymerization to give vulcanizable acrylic rubber.
B) To 100 parts of the acrylic rubber thus prepared in (A) were added 50 parts of MEF (medium extrusion furnacel carbon, ~0947~2 1 1 part of stearic acid, 2.4 parts of tetramethylthiuram disulfide and 3.3 parts of dibenzothiazolyl disulfide.
After kneading well in an open roll, the mixture was put into a curing mold and heated at 170C for 10 minutes.
The rubber slab thus made was subjected to post cure at 150C for 16 hours. Table 1 summarizes the physical - 6a -~0~?~742 1 properties of the cured acrylic rubber in an original test, an air heat a2ing test at 1~0C
for 70 hours and oil resist~nce tests, respectively.
Table 1 '~roperties Hardness Te~sile Elongation Volume \ (in Hs) strength 2 percentage change Eind of Tes ~ ~ (i = (i. ~) p rD:~=a~c Ori~inal test 74 123 250 Air heat ag~ng 78 142 215 test at 150 C
for 70 hours Oil resistance test with JIS N8.1 78 131 270 oil at 150 C
for 70 hours with JIS ~8.3 1 69 118 310 oil at 150 C
f or 70 hours I I
~0 ~ I
(JIS is an abbreviation of the Japanese Industrial Standard.) ~xample 2 Except that 4 parts of allyl methyl malon'te and 96 parts of ethyl acrylate were used7 the s~,me mixi~g ratio and reaction conditions as in ~xample 1 were used to prepare ~ulcanizable acrylic rubber.
To 100 parts of the acrylic rubber were added 50 parts of white carbon, 1 part of stearic acid, ~.4 parts of tetraethylthiuram disulfide and 3.3 parts of dibenzothiazolyl disulfide After kneading~ the mixture ~s pre-cured at 170C for 10 minutes and ~i?ost-eured 109~742 1 at 150C for 4 hours. ~able 2 shows the physical properties of the cured acrylic rubber measured as in Example 1.
Table 2 \ Properties Hardnessl ~ensile ~longation Volume \ I (in Hs) strength 2 percentage change \ I (in kg/cm ) (in ~) p(rcentage Eind of ~es ~ I
~ ~ _ Original test lll 74 115 260 Air heat agOing I 79 1~5 270 test at 150 c I I
~or 70 hours I l li Oil resistance test with JIS Ng.1 78 ' 1 ~7 230 1 _o . 8 oil at 150 C
for 70 hours ¦
with JIS ~8~3 l 70 1 110 1 330 +11.7 oil at 150 c for 70 hours E~mple 3 Except that ~ parts o~ allyl ethyl malonate, 80 parts o~ ethyl acrylate and 15 parts of butyl acrylate were used as monomers 7 the s~me mixing ratio and reaction conditions as in Example 1 were used. ~he acrylic rubber thus ma~e was cured in the same m.~nner as 20 in Example 1 except that the pos. cure time ~A~'as 7 hours. 'rable ~ shows the physical properties o~ the cured acrylic rub`~er.
" 10~474Z
1 ~able 3 \ Properties Hardness Tensile Elongation Volume \ (in Hs) strength 2 percentage change \ (in k~/cm ) (in o/O) P(in o70) g Eind of Tes ~
\ ., Original test 65 109 300 Air heat ag~ng ¦ 74 121 240 test at 150 C I
for 70 hours Oil resistance ¦
test with JIS ~8.1 ¦ 76 118 250 +2.
oil at 150 C
for 70 hours with JIS ~8.3 ~ 58 102 380 +19.3 oil at 150 C
for 70 hours i _ Example 4 Except that 8 parts of all~l ethyl malonate and 92 parts of ethyl ac~late were used, the same mixin~
ratio and reaction conditions as in Example 1 were used to produce vulcanizable acrylic rubber. It was then cured as in Example 1 except that tetraethylthiuram disulfide was used instead of tetramethylthiuram di~ulfide. Table 4 shows the physical properties of the cured acrylic rubber.
3o ~09~742 1 Table 4 \ Properties Hardnessl ~ensile Elongation Volume \ (in Hs) strength 2 percentage change \ (in kg/cm ) (in %) (ln %) ~ind of ~est\
\
Original test 79 152 180 Air heat ag~ng 84 168 150 test at 150 C
for 70 hours Oil resistance test with JIS Ng.1 83 162 190 -0.9 oil at 150 C
for 70 hours with JIS ~8 3 73~ 147 270 +11.8 oil at 150 C
for 70 hours ~xample 5 A) In a flask were put 200 parts of water, 0.5 part of sodium laurylsulfate and 2 parts of polyoxyethylene lauryl ether, 5 parts of allyl cyanoacetate, 0.05 part of potassium persulfate and 0.05 part of sodium nydrogen bisulfite. The mixture was heated to 50-70~C while blowing nitrogen gas thereinto and 95 parts of ethyl acrylate was added drop by drop, taking 30 to 40 minutes, for emulsion polymerization to give vulcanizable acrylic rubber.
3o ~) To 100 parts of the acrylic rubber thus prepared ~~ were added 50 parts of ME~ carbon, 1 part of ~tearic '10!~7~2 1 acid~ 2 parts of tetramethylthiuram disulfide and 2 parts of dibenzothiazolyl disulfide. After kneading well in an open roll, the mixture was put into a curing mold and heated at 170~ for 10 minutes. The rubber slab thus made was subjected to post cure at 150C for 16 hours. ~able 5 shows the physical properties of the cured acrylic rubber.
~able 5 \ Properties Hardness Tensile Elongation Volume \ (in Hs) strength 2 percentage change \ (in kg/cm ) (in ,b) ~ercentage Kind of ~est \
\ . .
Original test 73 145 260 Air heat ag~ng 79 142 226 test at 150 C
fo ~ ours Oiltresistance with JIS ~8'1 78 138 ~73 -0.9 oil at 150 C
for 70 hours with JIS ~00.3 67122 ¦ 310 +12.1 oil at 150 C
for 70 hours Y l ~., Example 6 Except that 7 p3rts of allyl cyanoacet~te, 15 -parts of meth~l acrylate and 78 parts of ethyl acrylate ~ere 3~ used as monomers, the same mi~ing ratio and reaction conditions as in ~xample 5 were used.
o 100 parts of the acrylic rubber thus ~repared 109~t742 1 were added 50 parts of white carbon as a reinforcing agent, 1 part of stearic acid, 3 parts of tetraethylthiuram disulfide and 3 p~rts of diben~othiazol~l disulfide.
The acrylic rubber was cured as in Example 5 except that the post cure time was 4 hours.
Example 7 Except that ~ parts of allyl cyanoacetate, 10 parts of acr~lonitrile and 85 parts of but~l acrylate were used, the same mixing ratio and reaction conditions as in Example 5 were used.
The acrylic rubber thus prepared was cured as in Example 5 except that 1.5 parts of dibenzothiazolyl disulfide were used and that the post cure time was 7 hours. Table 6 shows the physical properties of the cured acrylic rubber.
Table 6 Propertiesl~Iardness Tensile ¦ Elongation Volume \ (in Hs) strength 2 I percentage change \ (in kg/cm ) (in ~) ~ercentage Kind of ~est \ I
_ Original test 70 135 210 . .
Air heat ag~ng 75 162 1 206 test at 150 C
for 70 hours Oil resistance ¦
test I '~
with JIS ~8~1 7 ~ 5 241 I +0.5 oil at 150 C
for 70 hours I ~ I
with JI~ ~8.3 61 112 25~ +1~.4 oil at 150 C
for 70 hours 10~742 1 EYample 8 Except that 7 parts of allyi cyanoacetate and 9~
parts of ethyl acrylate were used as monomers, the s~me mixing ratio and reaction conditions as in ~xample 5 were used~
~ o .100 parts of the acrylic rubber thus prepared were added 50 parts of MEF carbon, 1 part of stearic acid, 2 parts of tetraethylthiuram disulfide and 2 parts of dibenzothiazolyl disulfide. ~he acrylic rubber was cured as in Example 5 except that the post cure time was
4 hours.
Example 9 ~ he vulcaniza~le acrylic rubber prepared in step (A) of Example 5 was cured at 170C by use of such vulcanizing agent, accelerators and retarder as shown in Table 7.
Table 7 ~est No. ¦ 1 2 1 3 Acrylic rubber 100100 ¦ 100 partsparts I parts MEF carbon 5 1 50 1 50 Stearic acid ~etramethylthiuram 12 1 2 2 disulfide Dibenzothia~olyl 12 ¦ 2 2 disulfide ~etramethylthiuram '0.5 1 - , 0 monosulfide l I , ~-phenyl~ - 2 naphthylamine (retarder) ~ .
109"7~Z
1 ~ig. 2 shows the vulcanization curves for these three tests. This test results show that the acrylic rubber produced according to the present invention has a large advantage over the conventional acrylic rubber that the rise or start of vulcanization is adjustable by using a vulcanization accelerator or retarder.
Example 9 ~ he vulcaniza~le acrylic rubber prepared in step (A) of Example 5 was cured at 170C by use of such vulcanizing agent, accelerators and retarder as shown in Table 7.
Table 7 ~est No. ¦ 1 2 1 3 Acrylic rubber 100100 ¦ 100 partsparts I parts MEF carbon 5 1 50 1 50 Stearic acid ~etramethylthiuram 12 1 2 2 disulfide Dibenzothia~olyl 12 ¦ 2 2 disulfide ~etramethylthiuram '0.5 1 - , 0 monosulfide l I , ~-phenyl~ - 2 naphthylamine (retarder) ~ .
109"7~Z
1 ~ig. 2 shows the vulcanization curves for these three tests. This test results show that the acrylic rubber produced according to the present invention has a large advantage over the conventional acrylic rubber that the rise or start of vulcanization is adjustable by using a vulcanization accelerator or retarder.
Claims (9)
1. A process for producing vulcanized acrylic rubber which comprises:
(1) copolymerizing (A) at least one acrylic ester selected from the group consist-ing of methylacrylate, ethylacrylate and butylacrylate, with (B) 2-10% by weight, based on the weight of the acrylic ester component, of a malonic acid derivative having an active methylene group of the formula wherein R1 represents vinyl, allyl or methallyl, and X
represents cyano or COOR2 in which R2 represents methyl, ethyl or propyl, in an aqueous medium and in the presence of a copolymerization catalyst at a temperature of 50° - 70°C
for 30 - 40 minutes, the acrylic ester component being added to the copolymerization system in a dropwise manner, and (2) vulcanizing the resultant copolymer with a vulcanizing agent of the thiuram series.
(1) copolymerizing (A) at least one acrylic ester selected from the group consist-ing of methylacrylate, ethylacrylate and butylacrylate, with (B) 2-10% by weight, based on the weight of the acrylic ester component, of a malonic acid derivative having an active methylene group of the formula wherein R1 represents vinyl, allyl or methallyl, and X
represents cyano or COOR2 in which R2 represents methyl, ethyl or propyl, in an aqueous medium and in the presence of a copolymerization catalyst at a temperature of 50° - 70°C
for 30 - 40 minutes, the acrylic ester component being added to the copolymerization system in a dropwise manner, and (2) vulcanizing the resultant copolymer with a vulcanizing agent of the thiuram series.
2. The process according to claim 1 wherein said malonic acid derivative is used in an amount of 2-6% by weight based on the weight of the acrylic ester component.
3. The process according to claim 1 wherein the temperature of copolymerization is 50° - 70°C.
4. The process according to claim 1 wherein the vulcanizing agent is tetramethylthiuram disulfide or tetraethyl thiuram disulfide.
5. The process according to claim 1 wherein said malonic acid derivative is allyl ethyl malonate.
6. The process according to claim 1 wherein said malonic acid derivative is allyl methyl malonate.
7. The process according to claim 1 wherein said malonic acid derivative is allyl cyanoacetate.
8. The process according to claim 1 wherein said malonic acid derivative is methallyl cyanoacetate.
9. The process according to claim 1 wherein said malonic acid derivative is vinyl cyanoacetate.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPSHO51-50212 | 1976-05-01 | ||
| JP5021276A JPS52133395A (en) | 1976-05-01 | 1976-05-01 | Process for producing vulcanizable acrylic rubber |
| JP16001076A JPS5382891A (en) | 1976-12-28 | 1976-12-28 | Process for producing vulcanizable acryl rubber |
| JPSHO51-160010 | 1976-12-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1094742A true CA1094742A (en) | 1981-01-27 |
Family
ID=26390663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA277,275A Expired CA1094742A (en) | 1976-05-01 | 1977-04-26 | Process for producing vulcanizable acrylic rubber |
Country Status (5)
| Country | Link |
|---|---|
| CA (1) | CA1094742A (en) |
| DE (1) | DE2719560C3 (en) |
| FR (1) | FR2349606A1 (en) |
| GB (1) | GB1579629A (en) |
| IT (1) | IT1086798B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9540535B2 (en) | 2010-09-29 | 2017-01-10 | Jsr Corporation | Composition for forming liquid immersion upper layer film, and polymer |
-
1977
- 1977-04-26 CA CA277,275A patent/CA1094742A/en not_active Expired
- 1977-04-26 GB GB1741777A patent/GB1579629A/en not_active Expired
- 1977-04-28 IT IT4917977A patent/IT1086798B/en active
- 1977-04-29 FR FR7712947A patent/FR2349606A1/en active Granted
- 1977-05-02 DE DE19772719560 patent/DE2719560C3/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9540535B2 (en) | 2010-09-29 | 2017-01-10 | Jsr Corporation | Composition for forming liquid immersion upper layer film, and polymer |
| US9926462B2 (en) | 2010-09-29 | 2018-03-27 | Jsr Corporation | Composition for forming liquid immersion upper layer film, and polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2719560A1 (en) | 1977-11-10 |
| IT1086798B (en) | 1985-05-31 |
| GB1579629A (en) | 1980-11-19 |
| FR2349606B1 (en) | 1979-03-30 |
| DE2719560C3 (en) | 1980-08-14 |
| FR2349606A1 (en) | 1977-11-25 |
| DE2719560B2 (en) | 1979-12-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4154914A (en) | Process for producing acrylic rubber by copolymerizing acrylic ester and malonic acid derivative having active methylene group | |
| US3326868A (en) | Self-curing, oil-resistant copolymers containing alkoxyalkyl acrylates and n-alkoxyalkyl acrylamides | |
| US4248985A (en) | Sulfur-curable acrylic rubber composition | |
| JPH01135811A (en) | Production of acrylic copolymer elastomer | |
| CA1094742A (en) | Process for producing vulcanizable acrylic rubber | |
| US4228265A (en) | Process for producing sulfur-curable acrylic rubbers | |
| JPH09143229A (en) | Production of acrylic copolymer elastomer | |
| US5219967A (en) | Acrylic copolymer rubber | |
| US4975508A (en) | Acrylic copolymer elastomers | |
| US5334683A (en) | Acrylate polymer elastomer and vulcanizable composition containing the same | |
| USRE31322E (en) | Process for producing sulfur-curable acrylic rubbers | |
| JP2757194B2 (en) | Acrylic copolymer composition | |
| JP3496237B2 (en) | Acrylic copolymer and method for producing the same | |
| US4028316A (en) | Vulcanized acrylate-ethylidene norbornene polymers | |
| KR810000749B1 (en) | Process for producing acrylic rubber by copolymerizing acrylic ester and malonic acid derivative having active methylene group | |
| JPH06145257A (en) | Production of methacrylic copolymer rubber and its composition | |
| KR800001598B1 (en) | The method of manufacturing for vulcanizable acrylic rubber | |
| JPS59136303A (en) | Production of vulcanizable acrylic rubber | |
| JP2658184B2 (en) | Method for producing acrylic copolymer elastomer | |
| JPH01132611A (en) | Production of acrylic copolymer elastomer | |
| JP3528397B2 (en) | Acrylic copolymer elastomer and method for producing the same | |
| JP3601105B2 (en) | Acrylic elastomer and its production method | |
| JPH0714986B2 (en) | Acrylic elastomer manufacturing method | |
| JP2953047B2 (en) | Acrylic copolymer elastomer containing cyano group | |
| JPH0237945B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |