GB1579629A

GB1579629A - Process for producing vulcanizable acrylic rubber

Info

Publication number: GB1579629A
Application number: GB1741777A
Authority: GB
Original assignee: Toyo Seal Industries Co Ltd
Current assignee: Toyo Seal Industries Co Ltd
Priority date: 1976-05-01
Filing date: 1977-04-26
Publication date: 1980-11-19
Also published as: IT1086798B; DE2719560B2; CA1094742A; FR2349606B1; FR2349606A1; DE2719560C3; DE2719560A1

Description

(54) PROCESS FOR PRODUCING VULCANIZABLE ACRYLIC RUBBER (71) We, TOYO SEAL KOGYO KABUSHIKI KAISHA (TOYO SEAL INDUS TRIES CO., LTD) of No: 88-1 Oaza Horyuji, Ikarugacho, Ikoma-gun, Nara-ken, Japan a corporation organised under the laws of Japan, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to a process for producing vulcanizable acrylic rubber.

Conventional acrylic rubbers were stable to heat and oilproof because of high polarity of their ester structure, but were 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 was 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 with such a vulcanizing agent. Such monomers were among the halogen group such as ss -chloroethyl vinyl ether and vinyl chloroacetate, or among the epoxy group such as allyl glycidyl ether, glycidyl acrylate and glycidyl methacrylate.

Such conventional acrylic rubbers were, however, liable to scorch during storage and had low resistance to cold and poor processibility. Particularly, the acrylic rubbers produced by use of liquid polyamine as a vulcanizing agent had undue adhesiveness to a mixing roll, poor bin stability, high corrosiveness, and offensive odor and toxicity coming from the amine.

It is an object of this invention to provide a process of producing vulcanizable acrylic rubber which does not have such disadvantages.

Accordingly the present invention consists in a process for producing vulcanizable acrylic rubber comprising the aqueous emulsion copolymerization of at least one alkyl acrylate having 1 to 4 carbon atoms in the alkyl group with a malonic acid derivative with an active methylene group and having the following general formula:

wherein R1 represents vinyl, allyl or methallyl group, X represents a COOR2 or nitrile group and R2 represents methyl, ethyl or propyl group.

Figure I is a graph showing the vulcanization curve (A) for an acrylic rubber produced according to this invention and a vulcanisation curve (B) for a conventional acrylic rubber.

Figure 2 is a similar graph for the acrylic rubbers prepared in Example 9.

The malonic acid derivative having an active methylene group utilized in the present invention has the following general formula:

wherein R, represents vinyl, allyl or methallyl group and X represents COOR2 or nitrile group.

First, if X represents COOR2 in the formula (1), the malonic acid derivative has the following general formula:

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 esterified with a saturated alcohol. Such derivatives include allyl ethyl malonate and allyl methyl malonate, for example.

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 800C or lower for about four hours under stirring. 1.5 mole of allyl alcohol is added, the mixture being allowed to react with a slow stirring at room temperature for about 72 hours. The mixture is then rinsed, dehydrated and distilled under reduced pressure. At first of distillation ethyl cyanoacetate distills off and at last allyl ethyl malonate does.

In this process, allyl cyanoacetate may be used as the starting material and its nitrile group be replaced by ethyl alcohol. In this case, the reaction product contains only allyl cyanoacetate and allyl ethyl malonate, containing no ethyl cyanoacetate which has a bad effect on cross-linking.

Next, if X represents nitrile group in the formula (1), the malonic acid derivative has the following general formula:

wherein R1 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.

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 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"-80"C 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 110-1120C.

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 No by weight, and more preferably 2-6 %, relative to the alkyl acrylate(s). 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 increase owing to over-cure, but the hardness increase, thus resulting in lower elongation and elasticity.

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 marked plateau effect in comparison with the conventional acrylic rubber cured with amines, as will be seen in Figure 1 wherein (A) is the vulcanization curve for the acrylic rubber produced according to this invention and (B) is the one for conventional acrylic rubber. They also retain resistance to heat, oil, ozone, weathering and bendcracking which the conventional acrylic rubber had. Furthermore, it has 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 it allows use of white filler 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 I 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 sodium hydrogen bisulfite as redox catalyst. The mixture was heated to 500-700C 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.

B) To 100 parts of the acrylic rubber thus prepared in (A) were added 50 parts of MEF (medium extrusion furnace) carbon, 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 1700C for 10 minutes. The rubber slab thus made was subjected to post cure at 1500C for 16 hours. Table 1 summarizes the physical properties of the cured acrylic rubber in an original test, an air heat aging test at 1500C for 70 hours and oil resistance tests, respectively.

TABLE 1 Properties Hardness Tensile Elongation Volume (in Hs) strength percentage change (in kg/cm2) (in %) percentage (in %) Kind of Test Original test 74 123 250 Air heat aging 78 142 215 test at 1500C for 70 hours Oil resistance test with JIS No. 1 78 131 270 oil at 1500C for 70 hours with JIS No. 3 69 118 310 oil at 1500C for 70 hours (JIS is an abbreviation of the Japanese Industrial Standard.) Example 2 Except that 4 parts of allyl methyl malonate and 96 parts of ethyl acrylate were used, the same mixing ratio and reaction conditions as in Example 1 were used to prepare vulcanizable acrylic rubber.

To 100 parts of the acrylic rubber were added 50 parts of white carbon, 1 part of stearic acid, 2.4 parts of tetraethylthiuram disulfide and 3.3 parts of dibenzothiazolyl disulfide.

After kneading, the mixture was pre-cured at 1700C for 10 minutes and post-cured at 1500C for 4 hours. Table 2 shows the physical properties of the cured acrylic rubber measured as in Example 1.

TABLE 2 Properties Hardness Tensile Elongation Volume (in Hs) strength percentage change (in kg/cm2) (in %) percentage (in %) Kind of Test Original test 74 115 260 Air heat aging 79 135 270 test at 1500C for 70 hours Oil resistance test with JIS No. 1 78 137 230 -0.8 oil at 1500C for 70 hours with JIS No. 3 70 110 330 +11.7 oil at 1500C for 70 hours Example 3 Except that 5 parts of allyl ethyl malonate, 80 parts of ethyl acrylate and 15 parts of butyl acrylate were used as monomers, the same mixing ratio and reaction conditions as in Example 1 were used. The acrylic rubber thus made was cured in the same manner as in Example 1 except that the post cure time was 7 hours. Table 3 shows the physical properties of the cured acrylic rubber.

TABLE 3 Properties Hardness Tensile Elongation Volume (in Hs) strength percentage change (in kg/cm2) (in %) percentage (in %) Kind of Test Original test 65 109 300 Air heat aging 74 121 240 test at150C for 70 hours Oil resistance test with JIS No. 1 76 118 250 +2.3 oil at 1500C for 70 hours with JIS No. 3 58 102 380 +19.3 oil at 1500C for 70 hours Example 4 Except that 8 parts of allyl ethyl malonate and 92 parts of ethyl acrylate were used, the same mixing 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 disulfide. Table 4 shows the physical properties of the cured acrylic rubber.

TABLE 4 Properties Hardness Tensile Elongation Volume (in Hs) strength "2) percentage change (in kg/cm2) (in %) percentage (in %) Kind of Test Original test 79 152 180 Air heat aging 84 168 150 test at 1500C for 70 hours Oil resistance test with JIS No. 1 83 162 190 -0.9 oil at 1500C for 70 hours with JIS No. 3 73 147 270 +11.8 oil at 1500C for 70 hours Example 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 hydrogen bisulfite. The mixture was heated to 500-70"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.

B) To 100 parts of the acrylic rubber thus prepared were added 50 parts of MEF carbon, 1 part of stearic 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 1700C for 10 minutes. The rubber slab thus made was subjected to post cure at 1500C for 16 hours. Table 5 shows the physical properties of the cured acrylic rubber.

TABLE 5 Properties Hardness Tensile Elongation Volume (in Hs) strength percentage change (in kg/cm2) (in %) percentage (in %) Kind of Test Original test 73 145 260 Air heat aging 79 142 226 test at 1500C for 70 hours Oil resistance test with JIS No.1 78 138 273 -0.9 oil at 1500C for 70 hours with JIS No.3 67 122 310 +12.1 oil at 1500C for 70 hours Example 6 Except that 7 parts of allyl cyanoacetate, 15 parts of methyl acrylate and 78 parts of ethyl acrylate were used as monomers, the same mixing ratio and reaction conditions as in Example 5 were used.

To 100 parts of the acrylic rubber thus prepared were added 50 parts of white carbon as a reinforcing agent, 1 part of stearic acid, 3 parts of tetraethylthiuram disulfide and 3 parts of dibenzothiazolyl disulfide. The acrylic rubber was cured as in Example 5 except that the post cure time was 4 hours.

Example 7 Except that 5 parts of allyl cyanoacetate, 10 parts of acrylonitrile and 85 parts of butyl 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 Properties Hardness Tensile Elongation Volume (in Hs) strength percentage change (in kglcm2) (in %) percentage (in %) Kind of Test Original test 70 135 210 Air heat aging 75 162 206 test at 1500C for 70 hours Oil resistance test with JIS No. 1 70 135 241 +0.5 oil at 1500C for 70 hours with JIS No.3 61 112 255 +18.4 oil at 1500C for 70 hours Example 8 Except that 7 parts of allyl cyanoacetate and 93 parts of ethyl acrylate were used as monomers, the same mixing ratio and reaction conditions as in Example 5 were used.

To 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. The acrylic rubber was cured as in Example 5 except that the post cure time was 4 hours.

Example 9 The vulcanizable acrylic rubber prepared in step (A) of Example 5 was cured at 1700C by use of such vulcanizing agent, accelerators and retarder as shown in Table 7.

TABLE 7 Test No. 1 2 3 Acrylic rubber 100 100 100 parts parts - parts MEF carbon 50 50 50 Stearic acid 1 1 1 Tetramethylthiuram 2 2 2 disulfide Dibenzothiazolyl 2 2 2 disulfide Tetramethylthiuram 0.5 - 0 monosulfide N-phenyl-P- 2 naphthylamine (retarder) Figure 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.

WHAT WE CLAIM IS: 1. A process for producing vulcanizable acrylic rubber comprising the aqueous emulsion copolymerization of at least one alkyl acrylate having 1 to 4 carbon atoms in the alkyl group with a malonic acid derivative with an active methylene group and having the following general formula:

2. A process according to claim 1 wherein said malonic acid derivative is allyl ethyl malonate.

3. A process according to claim 1 wherein said malonic acid derivative is allyl methyl malonate.

4. A process according to claim 1 wherein said malonic acid derivative is allyl cyanoacetate.

5. A process according to claim 1 wherein said malonic acid derivative is methallyl cyanoacetate.

6. A process according to claim 1 wherein said malonic acid derivative is vinyl cyanoacetate.

7. A process according to claim 1 wherein the amount of said malonic acid derivative is 2-10 per cent by weight relative to said alkyl acrylate(s).

8. A process for producing vulcanizable acrylic rubber as in claim 1 substantially as hereinbefore described.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. TABLE 7 Test No. 1 2 3 Acrylic rubber 100 100 100 parts parts - parts MEF carbon 50 50 50 Stearic acid 1 1 1 Tetramethylthiuram 2 2 2 disulfide Dibenzothiazolyl 2 2 2 disulfide Tetramethylthiuram 0.5 - 0 monosulfide N-phenyl-P- 2 naphthylamine (retarder) Figure 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. WHAT WE CLAIM IS:

1. A process for producing vulcanizable acrylic rubber comprising the aqueous emulsion copolymerization of at least one alkyl acrylate having 1 to 4 carbon atoms in the alkyl group with a malonic acid derivative with an active methylene group and having the following general formula: