RU2188833C2 - Filled polymer composition - Google Patents

Abstract

FIELD: rubber industry. SUBSTANCE: filled polymer composition contains 100 wt parts of linear butadiene/styrene copolymer with bound styrene content 29 +/- 2 wt %, wherein butadiene and styrene units are distributed in macromolecule in blocks or statistically, 2,0-60.0 wt parts of filler: carbon black with specific geometric surface 15-100 sq.m/g, and 0.2-3.0 wt parts of modifier: hexahydrophthalic acid. In case of statistic distribution composition also contains vulcanizing group. EFFECT: increased strength and hardness and lowered hysteresis. 2 cl, 4 tbl, 28 ex

Description

The invention relates to the rubber industry, and in particular to the field of creating high-strength, high-solid compositions with low hysteresis losses based on copolymers of butadiene with styrene with a content of bound styrene of 29 ± 2 wt.% And filler - carbon black with a specific geometric surface of 15-100 m ² / g

The composition is known based on a statistical copolymer of butadiene with styrene with a content of bound styrene of 29 ± 2 wt.%, Filler is carbon black with a specific geometric surface of 100 m ² / g MPC grade, target additives and gain modifier - N, N-dinitrozo-N -methylaniline. The composition has a fairly high tensile strength, reduced hysteresis, increased values of hardness and modulus. However, the reduction in hysteresis losses is small. So, the addition of the promoter in the amount of 0.33 wt.h. at 100 max. copolymer causes a decrease in torsion hysteresis (logarithmic decrement) from 0.222 to 0.18. However, tensile strength and elongation decrease with the introduction of the promoter compared to a control mixture that does not contain a promoter (strength decreases from 26 to 23 MPa, and elongation from 520 to 400%.) [J. Harris, R. White. Elastomer Enhancer Promoters with Fillers / Elastomer Enhancer. - M .: Chemistry, 1968, p. 211-231].

The closest to the proposed technical solution in essence and to achieve a positive effect is a filled polymer composition based on a linear block copolymer of butadiene with styrene with a content of bound styrene of 29 ± 2 wt. %, including filler - carbon black with a specific geometric surface of 75-100 m ² / g in an amount of 2-60 wt.ch. and the modifier is 2,5-biphenyldicarboxylic acid (BPPA) in an amount of 0.2-1.5 wt.h. [Pat. 2119510 RF, BI 27 from 09/27/98, MKI 6 C 08 L 53/02, C 08 K 5/09. Filled polymer composition].

 This composition is characterized by high strength (22-28 MPa) and high hardness (67-90 units Shore). However, it has a fairly high hysteresis. A composition of a similar composition, but based on a statistical copolymer, is also characterized by high strength, but due to a decrease in the vulcanization rate, it has lower modulus values and increased hysteresis compared to a control sample that does not contain a modifier.

 The problem to which the claimed invention is directed, is to create filled polymer compositions based on a linear copolymer of butadiene with styrene with a content of bound styrene of 29 ± 2 wt.% With a block or statistical arrangement of units and filler - carbon black, with high strength, high hardness ( module) and reduced hysteresis.

To achieve the specified technical solution, a filled polymer composition based on a linear block copolymer of butadiene with styrene with a content of bound styrene of 29 ± 2 wt.%, Including a filler - carbon black and a modifier, is used, and it contains hexahydrophthalic acid as a modifier, and technical filler as a filler carbon with a specific geometric surface of 15-100 m ² / g in the following ratio of components, wt.h .:
Linear block copolymer of butadiene with styrene with a content of bound styrene 29 ± 2 wt.% - 100,0
Specified carbon black - 2.0-60.0
Hexahydrophthalic acid - 0.2 - 3.0
or a filled polymer composition based on a linear copolymer of butadiene with styrene with a content of bound styrene of 29 ± 2 wt.%, including a filler - carbon black and a modifier, and it contains as a linear copolymer a linear copolymer of butadiene with styrene with a content of bound styrene of 29 ± 2 wt. .% with statistical distribution of butadiene and styrene in the macromolecule, as a filler - carbon black with a specific geometrical surface of 15-100 m ² / g, and as a modifier - hexahydro phthalic acid and further comprises a vulcanizing system in the following ratio, mac.ch .:
The specified linear copolymer of butadiene with styrene with a content of bound styrene of 29 ± 2 wt.% - 100,0
Specified carbon black - 2.0 - 60.0
Hexahydrophthalic acid - 0.2 - 3.0
Vulcanizing group - 9.0
The proposed technical solution is illustrated by the following examples.

 Example 1

The proposed filled polymer composition contains a linear block copolymer with bound styrene content of 29 ± 2 wt.% DST-30 grade, carbon black with a specific geometric surface of 100 m ² / g of grade P - 234 or carbon black with a specific geometric surface of 15 m ² / g brand P-803 and the modifier - hexahydrophthalic acid. The compositions of the compositions according to the invention, the prototype and control are shown in table 1.

Compositions are prepared on laboratory rollers Lb 320 160/160 with an adjustable gap between the rollers and friction of 1: 1.269 at a temperature of 30 ± 5 ^o With the following mode.

According to the invention and the prototype
1. Landing DST-30 on the roll at 0 minute.

 2. The introduction of carbon black and a modifier at 2 minutes.

 3. Remove from the rollers in the form of a sheet at 10 minutes.

Control
1. Landing of the block copolymer on the roll at 0 minute.

 2. The introduction of carbon black in 2 minutes.

 3. Remove from the rollers in the form of a sheet at 10 minutes.

The resulting sheets are molded in a press at a plate temperature of 143 ^o C in the form of plates and washers for 30 minutes in molds with locks, then loaded into a press with a plate temperature of 20 ^o C, where they are held for one hour and removed from the molds.

 For molded plates and washers, properties are determined according to the relevant GOSTs.

 The properties of the filled polymer compositions are shown in table 2.

 Example 2

The proposed filled polymer composition contains a linear statistical copolymer with a content of bound styrene of 29 ± 2 wt.% Grade SKMS-30 ARK, carbon black with a specific geometric surface of 15 m ² / g grade P-803 or carbon black with a specific geometric surface of 100 m ² / g of grade K-354 or carbon black with a specific geometric surface of 100 m ² / g of grade P-234, the modifier is hexahydrophthalic acid and a vulcanizing group consisting of sulfur, an accelerator, zinc oxide and stearin. The compositions of the compositions according to the invention, the prototype and control are shown in table 3.

Compositions are prepared on laboratory rollers Lb 320 160/160 with an adjustable gap between the rollers and friction of 1: 1.269 at a temperature of 30 ± 5 ^o With the following mode
According to the invention and the prototype
1. Landing SKMS-30 ARC on the roll at 0 minute.

 2. The introduction of carbon black and a modifier at 2 minutes.

 3. The introduction of the accelerator, white zinc, stearin in 15 minutes.

 4. The introduction of sulfur at 17 minutes.

 5. Remove from the rollers in the form of a sheet at 25 minutes.

Control
1. Landing SKMS-30 ARC on the roll at 0 minute.

 2. The introduction of carbon black in 2 minutes.

 3. The introduction of the accelerator, white zinc, stearin in 15 minutes.

 4. Introduction of sulfur at 17 minutes.

 5. Remove from the rollers in the form of a sheet at 25 minutes.

The resulting sheets are molded in a press at a plate temperature of 143 ^{° C.} in the form of plates and washers for 30 minutes in molds with or without locks, then, over time, they are removed from the molds and cooled to room temperature.

 For molded plates and washers, properties are determined according to the relevant GOSTs.

 The properties of the filled polymer compositions are shown in table 4.

Claims (1)

1. A filled polymer composition based on a linear block copolymer of butadiene with styrene with a content of bound styrene of 29 ± 2 wt. %, including filler - carbon black and a modifier, characterized in that it contains hexahydrophthalic acid as a modifier, and carbon black with a specific geometric surface of 15-100 m ² / g in the following ratio of components, wt. hours:
A linear block copolymer of butadiene with styrene with a content of bound styrene of 29 ± 2 wt. % - 100.0
Specified carbon black - 2.0-60.0
Hexahydrophthalic acid - 0.2-3.0
2. A filled polymer composition based on a linear copolymer of butadiene with styrene with a content of bound styrene of 29 ± 2 wt. %, including filler - carbon black and a modifier, characterized in that it contains as a linear copolymer a linear copolymer of butadiene with styrene with a content of bound styrene of 29 ± 2 wt. % with a statistical distribution of butadiene and styrene units in a macromolecule, carbon black with a specific geometric surface of 15-100 m ² / g as a filler, and hexahydrophthalic acid as a modifier and additionally contains a vulcanizing group in the following ratio of components, wt. hours:
The specified linear copolymer of butadiene with styrene with a content of bound styrene of 29 ± 2 wt. % - 100.0
Specified carbon black - 2.0-60.0
Hexahydrophthalic acid - 0.2-3.0
Vulcanizing group - 9.0

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