KR101816862B1 - Thermosetting rubber composition comprising dimer acid alkyldiester formed from Plant oil-based fatty acid - Google Patents

Abstract

The present invention relates to a thermosetting rubber composition comprising a dimer acid alkyl diester formed from a fatty acid derived from a vegetable oil, and the thermosetting rubber composition according to the present invention comprises paraffin oil which is generally used in a rubber compounding process, The present invention is not only environmentally friendly but also has an effect of securing durability better than a rubber composition containing paraffin oil.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermosetting rubber composition comprising a dimer acid alkyl diester formed from a vegetable oil-derived fatty acid,

The present invention relates to a thermosetting rubber composition comprising a dimeric acid alkyl diester formed from a vegetable oil-derived fatty acid.

Rubber compounding additives refer to compounds added to natural rubber or synthetic rubber to preserve the quality and performance of rubber. The rubber compounding additive greatly improves the productivity of the rubber, and as a result, it is possible to lower the actual production cost and further improve the uniformity of the quality of the rubber produced according to the additives used.

In recent years, rubber products have been used in various fields and the required performance is also increasing. Therefore, the problem of processing of the rubber is caused, and the use of the additive to solve this problem is increasing. For example, Patent Document 1 discloses that rubber containing paraffin oil as an additive is manufactured and can be used for military wheeled combat vehicles or special safety tires for airplanes.

 However, most of the rubber compounding additives currently used as in Patent Document 1 use petroleum-based paraffin oil, which causes serious environmental pollution.

Thus, in attempting to develop a rubber compounding additive capable of solving the environmental pollution problem caused by petroleum-based additives as a vegetable oil-based additive as well as improving the quality imparted to rubber as a rubber compounding additive, Since the rubber composition contains dimeric acid alkyl diester formed from vegetable fatty acid as an additive, it is confirmed that it is environmentally friendly as well as durability better than a rubber composition containing paraffin oil. Thus, the present invention has been completed.

Korean Patent Publication No. 10-2015-0002827

It is an object of the present invention to provide a thermosetting rubber composition comprising a raw rubber and a dimer acid alkyldiester formed from a vegetable fatty acid.

Another object of the present invention is to provide a method for producing a thermosetting rubber composition, which comprises: (1) molding the thermosetting rubber composition; And

And a step (2) of thermosetting the thermosetting rubber composition molded in the step (1).

Still another object of the present invention is to provide a method for manufacturing a thermosetting rubber composition, which comprises: (1) molding the thermosetting rubber composition; And

And a step (2) of thermosetting the thermosetting rubber composition molded in the step (1).

In order to achieve the above object,

The present invention relates to a rubber composition comprising 100 parts by weight of a raw rubber; And

0.5 to 40 parts by weight of a dimer acid alkyldiester formed from vegetable fatty acids.

The present invention also relates to a method for manufacturing a thermosetting rubber composition, comprising the steps of: (1) molding the thermosetting rubber composition; And

And thermosetting the thermosetting rubber composition molded in the step 1 (step 2).

Further, the present invention provides a method for manufacturing a thermosetting rubber composition, comprising: (1) molding the thermosetting rubber composition; And

And a step (2) of thermosetting the thermosetting rubber composition molded in the step (1).

Since the thermosetting rubber composition according to the present invention contains a dimer acid alkyl diester formed from a vegetable fatty acid instead of containing paraffin oil which is generally used in the process of rubber compounding process, it is environmentally friendly as well as a rubber composition containing paraffin oil And an excellent durability can be secured.

Hereinafter, the present invention will be described in detail.

The present invention relates to a rubber composition comprising 100 parts by weight of a raw rubber; And

0.5 to 40 parts by weight of a dimer acid alkyldiester formed from vegetable fatty acids.

When the amount of the dimer acid alkyl diester formed from vegetable fatty acid is less than 0.5 part by weight based on 100 parts by weight of the raw rubber, the amount of dimer acid alkyl diester serving as the plasticizer is not sufficient to improve the physical properties of the starting rubber There is a problem that the physical properties of the rubber product to be produced are deteriorated. When the amount of the dimeric acid alkyl diester is more than 40 parts by weight, an excessive amount of the rubber component is required to improve the physical properties of the starting rubber, There is a problem of deterioration.

The dimeric acid alkyl diester is characterized in that it is formed by covalent bonding of two fatty acid molecules, including both cyclized and non-cyclized, wherein the covalent bond is a double bond React with each other to form a covalent bond.

Furthermore, the dimeric acid alkyl diester may be a compound having the following chemical structure.

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The raw material rubber may be any generally used rubber without particular limitation, but preferably at least one selected from the group consisting of butyl rubber, natural rubber, styrene butadiene rubber and butadiene rubber can be used, Butyl rubber may be used.

Further, the vegetable fatty acid is not particularly limited as long as it is a commonly known vegetable fatty acid, preferably a plant fatty acid of C _14-26 , more preferably a vegetable fatty acid of C _16-24 , Even more preferably, C _18-22 vegetable fatty acids can be used.

In addition, the vegetable fatty acid may contain one or more unsaturated groups, and conversely saturated fatty acids may be used. Herein, the unsaturated group means carbon = carbon double bond (C = C).

Furthermore, in the dimeric acid alkyl diester, alkyl may be C _1-10 or branched alkyl, preferably C _4-6 straight chain alkyl, most preferably C ₅ alkyl .

The thermosetting rubber composition may further comprise a processing aid. The processing aid may be one selected from the group consisting of zinc oxide, polyethylene glycol, stearic acid, and sulfur (Sulfur) Can be mixed and used.

Further, the present invention provides a method for manufacturing a thermosetting rubber composition, comprising: (1) molding the thermosetting rubber composition; And

And thermosetting the thermosetting rubber composition molded in the step 1 (step 2).

Hereinafter, a method of manufacturing a rubber product according to the present invention will be described in detail.

In the method for manufacturing a rubber product according to the present invention, the step 1 is a step of molding a thermosetting rubber composition.

At this time, the molding may be carried out in various forms according to the field or application (tire use, etc.) in which the rubber is to be used.

In the method for producing a rubber product according to the present invention, the step 2 is a step of thermally curing the thermosetting rubber composition molded in the step 1.

At this time, the thermosetting time is not particularly limited, but is preferably 6 hours to 24 hours, more preferably 10 hours to 20 hours, most preferably 14 hours to 16 hours. When the heat curing time is less than 6 hours, the curing is not completed because the curing is not performed for a sufficient time. When the curing is performed for more than 24 hours, the curing time is longer than the time required for curing, There is a problem in that the physical properties of the rubber product are deteriorated.

The heat curing temperature is not particularly limited, but is preferably 90 占 폚 to 200 占 폚, more preferably 120 占 폚 to 170 占 폚. If the heat curing temperature is lower than 90 ° C., there is a problem that curing is not completed because a sufficient heat source necessary for curing is not provided. If the heat curing temperature is higher than 200 ° C., by-products are produced, There is a problem that the physical properties are deteriorated.

Hereinafter, the present invention will be described in detail with reference to Examples and Experimental Examples. However, the present invention is not limited thereto.

< Example  1> Dimer acid Methyl ester  Produce

110 g (193 mmol) of dimer acid (DA), 20 equivalents (20 equiv.) Of methyl alcohol, and 2 equivalents of methyl alcohol were placed in a 500 mL 2-neck round bottom flask containing a stir bar. 0.2 equivalents of sulfuric acid were mixed to prepare a mixture. Here, the dimer acid (hydrogenated; DA) was purchased from Sigma-Aldrich (product number 432369-1L).

Thereafter, a reflux condenser and a thermometer were respectively installed in two spheres of a container containing the mixture, and esterification was carried out in an oil bath at a temperature of 60 DEG C for 6 hours to obtain dimeric acid methyl ester (dimer acid methylester).

¹ H NMR (400 MHz, CDCl ₃ ):? 3.67 (s, 6H from methyl groups), 2.30 (t, J = 7.50 Hz, 4H), 1.70-0.80 (m, 64H).

< Example  2> Dimer acid Ethyl ester  Produce

The title compound was prepared by the same procedure as in <Example 1> except that ethyl alcohol was used instead of methyl alcohol.

¹ H NMR (400 MHz, CDCl ₃ ):? 4.15-4.10 (q, J = 7.10 Hz, 4H), 2.30 (t, J = 7.5 Hz, 4H), 1.70-0.80 (m, 68H).

< Example  3> Dimer acid Of propyl ester  Produce

The title compound was prepared by the same procedure as in <Example 1> except that propyl alcohol was used instead of methyl alcohol.

¹ H NMR (400 MHz, CDCl ₃ ):? 4.04-4.01 (t, J = 6.73 Hz, 4H), 2.30 (t, J = 7.5 Hz, 4H), 1.70-0.80 (m, 72H).

< Example  4> Dimer acid Butyl ester  Produce

110 g (193 mmol) of the dimer acid (DA) used in Example 1, 1 g of methyl alcohol (1 g) and the like were added to a 500-mL 2-neck round bottom flask containing a stir bar 10 equivalents of sulfuric acid and 0.2 equivalents of sulfuric acid were mixed to prepare a mixture.

Thereafter, a dean-stark trap and a reflux condenser and a thermometer were respectively set in two spheres of a container containing the mixture, and the mixture was subjected to esterification (in an oil bath at a temperature of 60 DEG C for 6 hours) Esterification was carried out to prepare a dimer acid butyl ester.

¹ H NMR (400 MHz, CDCl ₃ ):? 4.08-4.05 (q, J = 6.69 Hz, 4H), 2.30 (t, J = 7.5 Hz, 4H), 1.70-0.80 (m, 76H).

< Example  5> Dimer acid Pentyl ester  Produce

The same procedure as that of <Example 4> was performed except that 10 equivalents of methyl alcohol and 4 equivalents of pentyl alcohol were used instead of butyl alcohol to obtain the title compound .

¹ H NMR (400 MHz, CDCl ₃ ):? 4.08-4.04 (q, J = 6.74 Hz, 4H), 2.30 (t, J = 7.5 Hz, 4H), 1.70-0.80 (m, 80H).

< Example  6> Dimer acid Hexyl ester  Produce

The same procedure as in <Example 4> was performed except that 4 equivalents of hexyl alcohol was used instead of 10 equivalents of methyl alcohol to obtain the title compound .

¹ H NMR (400 MHz, CDCl ₃ ):? 4.07-4.04 (q, J = 6.73 Hz, 4H), 2.30 (t, J = 7.5 Hz, 4H), 1.70-0.80 (m, 84H).

< Example  7> Dimer acid Heptyl ester  Produce

The same procedure as that of <Example 4> was performed except that 4 equivalents of heptyl alcohol was used instead of 10 equivalents of methyl alcohol to obtain the title compound. .

¹ H NMR (400 MHz, CDCl ₃ ):? 4.07-4.04 (q, J = 6.73 Hz, 4H), 2.30 (t, J = 7.5 Hz, 4H), 1.70-0.80 (m, 88H).

< Example  8> Dimer acid Octyl ester  Produce

The same procedure as in <Example 4> was performed except that 4 equivalents of octyl alcohol (4 equiv.) Was used instead of 10 equivalents (10 equiv.) Of methyl alcohol. .

¹ H NMR (400 MHz, CDCl ₃ ):? 4.07-4.04 (q, J = 6.74 Hz, 4H), 2.30 (t, J = 7.5 Hz, 4H), 1.70-0.80 (m, 92H).

< Example  9> Dimer acid  2- Of propyl ester  Produce

The title compound was prepared by the same procedure as described in Example 1, except that 2-propyl alcohol was used instead of methyl alcohol.

¹ H NMR (400 MHz, CDCl ₃ ):? 5.05-4.96 (m, J = 6.69 Hz, 2H), 2.30 (t, J = 7.5 Hz, 4H), 1.70-0.80 (m, 74H).

< Example  10> Dimer acid  Preparation of sec-butyl ester

The title compound was prepared by the same procedure as described in Example 4, except that sec-butyl alcohol was used instead of methyl alcohol.

¹ H NMR (400 MHz, CDCl ₃ ):? 4.88-4.80 (m, J = 6.20 Hz, 2H), 2.30 (t, J = 7.5 Hz, 4H), 1.70-0.80 (m, 78H).

< Example  11> Dimer acid  2- Of ethylhexyl ester  Produce

The procedure of Example 4 was repeated except that 4 equivalents of 2-ethylhexyl alcohol was used instead of 10 equivalents of methyl alcohol. To give the title compound.

¹ H NMR (400 MHz, CDCl ₃ ):? 4.02-3.95 (m, J = 5.83 Hz, 4H), 2.30 (t, J = 7.5 Hz, 4H), 1.70-0.80 (m, 92H).

< Experimental Example  1> Thermal Characterization

In order to compare and analyze the thermal properties of the butyl rubber to be prepared when applying the dimer acid alkyl ester or paraffin oil (P 2) produced in Example 1-11 according to the present invention to butyl rubber The pyrolysis temperature was measured.

The pyrolysis temperature was analyzed by TGA (thermogravimetric analysis). The results are shown in Table 1 below.

No. 5% weight loss temperature Example 1 283 DEG C Example 2 292 DEG C Example 3 297 ° C Example 4 303 ℃ Example 5 297 ° C Example 6 314 ° C Example 7 328 ° C Example 8 324 ° C Example 9 286 ° C Example 10 286 ° C Example 11 324 ° C Paraffin oil 198 ℃

As shown in Table 1,

It can be seen that when the dimeric acid alkyl ester prepared in Example 1-11 according to the present invention is applied to the butyl rubber, the thermal characteristic is remarkably excellent as compared with the case of applying paraffin oil.

< Experimental Example  2> Property analysis

<2-1> Pus  Property Analysis

When a dimer acid alkyl ester or paraffin oil prepared in Example 1-11 according to the present invention was applied to a butyl rubber, a dynamic viscoelasticity meter (rheometer, Daqing Engineering, DRM- 100). To prepare the sample, butyl rubber, various additives and fillers were added to the kneader, and paraffin oil or dimer acid alkyl ester synthesized in the above experiment was added to the kneader. After thoroughly kneading, a crosslinking agent was added to the mixture, A thin butyl rubber sheet was prepared. The dynamic viscoelasticity results of the butyl rubber samples are shown in Tables 2 and 3 below.

<2-2> Analysis of mechanical characteristics

The mechanical properties of the dimeric acid alkyl esters and paraffin oils prepared in Examples 1-11 according to the present invention were analyzed by tensile test and hardness measurement, and the results are shown in Tables 2 and 3 below.

Materials Paraffin oil Example 1 Example 2 Example 4 Example 6 Example 11 Example 8 characteristic rheometer
180 ° C ×
12 minutes T _max lb-in 17.0 17.0 17.1 17.4 16.9 16.9 17.0 T _min 7.9 7.8 7.9 8.1 7.8 7.7 7.8 MH 9.1 9.2 9.2 9.3 9.1 9.2 9.2 Hardness A type 58 58 58 58 57 57 58 The tensile strength kgf / cm ² 125.18 126.86 127.84 129.74 128.23 126.74 126.78 Modulus 100% kgf / cm ² 18.88 18.32 18.81 19.74 17.84 18.31 17.62 Elongation % 657.98 689.03 677.30 704.60 701.60 682.20 676.58 Tear strength kgf / cm 45.70 46.86 44.88 45.48 49.05 44.17 42.69 D.M.F.C cycle 29,000 29,500 27,000 31,500 30,500 31,000 29,500

Materials Paraffin oil Example 9 Example 3 Example 5 Example 7 Example 10 characteristic rheometer
180 ° C ×
12 minutes T _max lb-in 16.4 16.6 16.8 16.5 16.8 17.2 T _min 7.7 8.0 7.9 8.0 8.1 8.4 MH 8.7 8.6 8.9 8.5 8.7 8.8 Hardness A type 58 58 58 58 58 58 The tensile strength kgf / cm ² 123.64 135.98 132.16 138.70 133.32 136.40 Modulus 100% kgf / cm ² 17.35 19.39 18.57 18.73 18.60 18.95 Elongation % 667.80 685.15 660.00 702.38 690.63 695.85 Tear strength kgf / cm 46.19 51.56 51.22 51.67 50.21 47.40 D.M.F.C cycle 29,000 27,500 25,500 35,500 29,500 27,000

In Tables 2 and 3 above,

D.M.F.C stands for Demattia Flex Cracking (KS M 6695) test, from which the durability of the butyl rubber can be compared.

As shown in Tables 2 and 3 above,

The dimer acid alkyl ester prepared in Example 1-11 according to the present invention had a T _max of 16.4 to 17.4; T _min is 7.7 to 8.4; △ MH is 8.5 to 9.3, a tensile strength of 123 to 138 kgf / cm ^2; 100% modulus of 17 to 19 kgf / cm ² ; An elongation of 657 to 704%; A breaking strength of 45 to 51 kgf / cm; And the hardness (A type) was 57 to 58. Thus, it was confirmed that the product had better physical properties than paraffin oil.

In particular, when the dimeric acid pentyl ester prepared in Example 5 according to the present invention was applied to butyl rubber, the durability of the produced butyl rubber was found to be 35,500 cycles, which is the best lifetime.

Claims (10)

100 parts by weight of raw rubber; And
0.5 to 40 parts by weight of dimer acid alkyldiesters formed from vegetable fatty acids.
The method according to claim 1,
Wherein the starting rubber comprises at least one selected from the group consisting of butyl rubber, natural rubber, styrene-butadiene rubber, and butadiene rubber.
The method according to claim 1,
_Wherein the vegetable fatty acid is a C _14-26 vegetable fatty acid.
The method according to claim 1,
Wherein the vegetable fatty acid comprises at least one unsaturated group.
The method according to claim 1,
Wherein the alkyl in the dimeric acid alkyl diester is a C _1-10 branched or branched alkyl.
The method according to claim 1,
Wherein the alkyl in the dimer acid alkyl diester is a straight chain alkyl of C &lt; RTI ID = 0.0 &gt; _4-6 . &Lt; / RTI &gt;
The method according to claim 1,
Wherein the thermosetting rubber composition further comprises a processing aid.
8. The method of claim 7,
Wherein the processing aid is at least one member selected from the group consisting of zinc oxide, polyethylene glycol, stearic acid, and sulfur.
Molding the thermosetting rubber composition of claim 1 (step 1); And
(2) thermosetting the thermosetting rubber composition molded in the step 1).
Molding the thermosetting rubber composition of claim 1 (step 1); And
(Step 2) of thermosetting the thermosetting rubber composition formed in step 1 above.