CN107814994B - Trans-butyl amyl rubber modified reclaimed rubber and preparation method and application thereof - Google Patents
Trans-butyl amyl rubber modified reclaimed rubber and preparation method and application thereof Download PDFInfo
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- CN107814994B CN107814994B CN201711154931.7A CN201711154931A CN107814994B CN 107814994 B CN107814994 B CN 107814994B CN 201711154931 A CN201711154931 A CN 201711154931A CN 107814994 B CN107814994 B CN 107814994B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L17/00—Compositions of reclaimed rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention relates to reclaimed rubber modified by trans-butadiene-isoprene rubber, and a preparation method and application thereof. The trans-butadiene-isoprene rubber modified reclaimed rubber comprises the following components in parts by weight: 95-50 parts of reclaimed rubber, 5-50 parts of trans-butyl rubber TBIR, 2.5-50 parts of filler, 1.5-4 parts of zinc oxide, 0.1-0.6 part of stearic acid, 0-5 parts of homogenizing agent, 0.8-5 parts of sulfur, 0.5-3.5 parts of accelerator, 0.1-3 parts of anti-aging agent and 0-2.0 parts of anti-vulcanization reversion agent. The invention adopts trans-butyl-pentyl rubber TBIR to modify reclaimed rubber, and can improve the dispersibility of the filler. The tensile strength of the vulcanized rubber is improved by 30-70%, the 300% stress at definite elongation is improved by 40-100%, the abrasion performance is improved by 10-20%, and the flexural fatigue performance is improved by 100-700%. The rubber can be used for tire treads, sidewalls, tire bodies, belt layers, air barriers, road surfaces and runways, and the dynamic fatigue performance is improved.
Description
Technical Field
The invention relates to reclaimed rubber, in particular to reclaimed rubber modified by trans-butyl-pentyl rubber and a preparation method and application thereof.
Background
In recent years, with the rise in petroleum prices and the fluctuation in natural rubber prices, the synthetic rubber industry is faced with a constant impact of price fluctuation. The price of synthetic rubber is increased dramatically all the way, SBR is close to natural rubber, and BR even exceeds the price of natural rubber. It is difficult to have a large rise in the price of tires as the main downstream application field of rubber. This makes it difficult for many tire companies, particularly bias tire companies, to maintain, even though all-steel radial tires are good for the benefit of recent years. How to break the stiff of the rubber, the price of the straight-faced natural rubber and the synthetic rubber is greatly increased, and the third rubber resource is explored to the extent that the price cannot be reduced.
China is not only a large country for rubber import, but also a large country for waste rubber generation. The quantity of discarded tires is large every year, and the rationalization and the value treatment of the discarded tires are always the headache problem at home and abroad. As a starting point for solving this problem, it is necessary to perform deep processing from the aspect of tire reclaimed rubber, to realize high-valued and reasonable resource recycling application, and to solve the resource and environmental problems. The application of the reclaimed rubber not only reduces the cost of rubber products and improves the economic benefit, but also has great effects on saving rubber resources and protecting the environment, and is the embodiment of circular economy in the rubber industry.
The reclaimed rubber particles are mainly used for pavements and sports tracks in parks or leisure centers, and are also used for expressways abroad. Reclaimed rubber is a rubber material which is crosslinked, and the addition amount of the reclaimed rubber in a rubber product such as a tire, an adhesive tape or a hose is usually not high in order to avoid affecting the performance of a base material. The Chinese invention patent CN 102453264A discloses the application of adopting reclaimed rubber to replace carbon black, and simultaneously has the function of reducing the content of natural rubber. In the reclaimed rubber industry, manufacturers have produced reclaimed rubber with high strength and high quality. Hangzhou Zhongshi rubber Co., Ltd discloses the use of reclaimed rubber as a basic formulation component for preparing tire tread rubber, sidewall rubber, carcass rubber and belt layer rubber, but the use amount of the reclaimed rubber is not too high and usually does not exceed 30 parts (Chinese invention patent CN 101628995B, CN 101628994B, CN 101628993B, CN 101628992B). The use of reclaimed rubber in agricultural tires was also reported in 2008. The reclaimed rubber adopted in the report is not high in fraction, and the reclaimed rubber is not physically or chemically modified and is directly used as a formula composition.
Disclosure of Invention
In order to realize the utilization of the reclaimed rubber and improve the utilization value of the reclaimed rubber, the invention aims to provide the reclaimed rubber modified by the trans-butyl-isoprene-butadiene-styrene (TBIR), the modified reclaimed rubber has obviously improved filler dispersibility and improved mechanical property, and has excellent dynamic fatigue property.
The second purpose of the invention is to provide a preparation process of trans-butyl-pentyl rubber TBIR modified reclaimed rubber.
The third purpose of the invention is to provide the modified reclaimed rubber compound and the application of vulcanized rubber in tires and modified pavements.
In order to realize the first purpose, the invention utilizes trans-butyl-pentyl rubber to modify reclaimed rubber, and adopts the following components to prepare mixing rubber and vulcanized rubber by mixing:
95-50 parts by weight of reclaimed rubber
5-50 parts by weight of trans-butyl amyl rubber TBIR
2.5 to 50 parts by weight of a filler
1.5 to 4 parts by weight of zinc oxide
0.1 to 0.6 part by weight of stearic acid
0 to 5 parts by weight of a homogenizing agent
0.8 to 5 parts by weight of sulfur
0.5 to 3.5 parts by weight of an accelerator
0.1 to 3 parts by weight of an antioxidant
0-2.0 parts by weight of an anti-reversion agent;
the above weight parts are based on 100 parts of rubber.
Wherein, the reclaimed rubber is composed of 50-70% of rubber material and 30-50% of filler by weight percentage; the rubber material is composed of one or more of natural rubber, butadiene rubber, styrene-butadiene rubber and butyl rubber, and the filler is composed of one or more of carbon black, white carbon black and calcium carbonate.
In the trans-butadiene-isoprene rubber for modifying reclaimed rubber, the molar content of a butadiene unit is 10-60%, the molar content of an isoprene unit is 90-40%, the molar content of a trans-1, 4-structure is more than 85%, and the Mooney viscosity at 100 ℃ for 3+4 minutes is 20-120.
The filler in the formula is formed by compounding one or more of carbon black, white carbon black, graphene oxide, calcium carbonate, calcium silicate, magnesium hydroxide, argil and talcum powder.
The homogenizing agent in the formula is one or more of aliphatic hydrocarbon petroleum resin, aromatic hydrocarbon petroleum resin, phenolic resin and cyclic zinc salt complex. The amount of the homogenizing agent is 0-5 parts by weight of the rubber.
The anti-reversion agent in the formula is one or more of 1, 3-bis (citraconimidomethyl) benzene, hexamethylene-1, 6-sodium disulfosulfate dihydrate and organic zinc soap.
The second purpose of the invention is to provide a preparation process of the trans-butyl-pentyl rubber TBIR with the formula for modified reclaimed rubber, which specifically adopts the following process for mixing:
(1) and (2) blending the trans-butyl-pentyl rubber TBIR with part of filler and an anti-aging agent internal mixer to prepare a trans-butyl-pentyl rubber TBIR master batch, wherein the weight ratio of the trans-butyl-pentyl rubber TBIR to the filler is 100: 50-100: 70, the weight ratio of the trans-butyl-pentyl rubber TBIR to the anti-aging agent is 100: 0.1 to 100: 1, mixing at 50-100 ℃, at the rotating speed of an internal mixer of 30-100 rpm, and for 8-20 min;
(2) the trans-butyl amyl rubber TBIR master batch and the reclaimed rubber are mixed according to the weight ratio of 5-50: mixing and blending 95-50 ℃, wherein the mixing temperature is 50-100 ℃, the rotating speed of the mixer is 30-70 rpm, the mixing time is 2-4 min, then adding the rest of the filler and the anti-aging agent, adding the homogenizing agent, the zinc oxide and the stearic acid, and continuing mixing for 8-16 min;
(3) and (3) placing the mixed rubber prepared in the step (2) on an open mill, adding an accelerator, sulfur and an anti-vulcanization reversion agent into the mixed rubber at the rotation speed of 30-60 rpm and the open mill temperature of 40-80 ℃, open milling for 2-10 min, and discharging the mixed rubber to obtain the mixed rubber.
The second purpose of the invention is realized by the mixing process, namely, the preparation process method of the mixed rubber of the trans-butyl-pentyl rubber modified reclaimed rubber is provided.
After the modified reclaimed rubber compound prepared by the mixing process is modified by the trans-butadiene-isoprene copolymer rubber, the dispersion degree of the inorganic filler in the modified reclaimed rubber compound is improved by 10-20%, the size of the filler aggregate is reduced by 5-20%, and the interaction between the polymer and the filler is enhanced.
The trans-butadiene-isoprene copolymer rubber compound prepared by the mixing process adopts a vulcanization characteristic curve tested at 140-160 ℃, and is vulcanized according to the positive vulcanization time of the process, so as to obtain the vulcanized rubber. After the reclaimed rubber modified by the trans-butadiene-isoprene copolymer rubber is vulcanized, the tensile strength is improved by 30-70%, the 300% stress at definite elongation is improved by 40-100%, the abrasion performance is improved by 10-20%, and the flexural fatigue performance is improved by 100-700%.
The trans-butyl amyl rubber modified reclaimed rubber compound can replace part of general rubber and can be applied to tire treads, tire sidewalls, tire bodies, belt layers, tire body outer protective rubber and air tight layer parts. It can also be used for highway pavement and runway. The production cost is reduced, the physical and mechanical properties of the original rubber material are kept, and the dynamic fatigue property of the rubber material is effectively improved.
Detailed Description
Example 1
The trans-butyl-pentyl rubber TBIR modified reclaimed rubber comprises the following components in parts by weight:
in the rubber material, the reclaimed rubber is reclaimed tire tread rubber powder which contains 70% of natural rubber and 30% of carbon black; the trans-butadiene rubber has a butadiene structural unit molar content of 20%, an isoprene unit molar content of 80%, a trans-1, 4-structure content of 93%, and a Mooney viscosity of 80(100 ℃, 3+4 min). The rubber compound was prepared by mixing the following:
(1) mixing trans-butyl-pentyl rubber TBIR with 35 parts of carbon black N330 to prepare TBIR master batch, wherein the mixing temperature is 70 ℃, the rotating speed of an internal mixer is 70rpm, and the mixing time is 16 min;
(2) mixing the TBIR master batch prepared in the step (1) with 50 parts of reclaimed rubber at the mixing temperature of 70 ℃, the rotating speed of an internal mixer of 70rpm for 2min, adding the rest of filler and anti-aging agent, mixing for 2min, adding the homogenizing agent, zinc oxide and stearic acid, mixing for 8min, and discharging rubber;
(3) and (3) placing the rubber compound prepared in the step (2) on an open mill, wherein the rotation speed of the open mill is 45rpm, the open mill temperature is 60 ℃, adding an accelerator, sulfur and an anti-vulcanization reversion agent, cutting rubber for 4 times at 3/4 left and right, passing through the rubber compound in a thin mode, packaging the rubber compound in a triangular bag for 6 times, and standing the rubber compound at room temperature under the condition of 2 mm. The rubber mixtures were allowed to stand at room temperature for 48 hours and then vulcanized. The positive vulcanization time of the process at 145 ℃ is determined according to the vulcanization characteristic curve in the vulcanization process, and the vulcanized rubber is obtained by vulcanization at 145 ℃. The vulcanizate properties are shown in Table 1.
Comparative example 1
The same procedure as in example 1 was repeated, except that no trans-butyl rubber TBIR modification was performed, and 100 parts of reclaimed rubber were used as it is.
The compounding process and vulcanization of the compound of this example were as described in example 1.
Example 2
Except for the reclaimed rubber, the inner liner layer is partially reclaimed rubber which contains 10 percent of natural rubber, 60 percent of butyl rubber and 30 percent of white carbon black; the same as in example 1 except that the trans-butadiene rubber contained 20 mol% of butadiene structural units, 90 mol% of trans-structural units, and 60 Mooney viscosity (100 ℃ C., 3+4min) of Mooney viscosity, and the filler used was silica.
The compounding process and vulcanization of the compound of this example were as described in example 1.
Example 3
The same procedure as in example 1 was repeated, except that the reclaimed rubber was used in an amount of 100 parts, the TBIR was used in an amount of 5 parts, and the filler was calcium carbonate.
The compounding process and vulcanization of the compound of this example were as described in example 1.
Example 4
The trans-butyl-pentyl rubber TBIR modified reclaimed rubber comprises the following components in parts by weight:
in the rubber material, the reclaimed rubber is reclaimed tire tread rubber powder which contains 35% of natural rubber, 15% of styrene-butadiene rubber and 50% of carbon black; the trans-butadiene rubber has the mol content of butadiene structural units of 60 percent, the mol content of isoprene units of 40 percent, the mol content of trans-1, 4-structure of 95 percent and the Mooney viscosity of 60(100 ℃, 3+4 min). The rubber compound was prepared by mixing the following:
(1) mixing trans-butyl-pentyl rubber TBIR with 20 parts of white carbon black to prepare TBIR master batch, wherein the mixing temperature is 100 ℃, the rotating speed of an internal mixer is 100rpm, and the mixing time is 10 min;
(2) mixing the TBIR master batch prepared in the step (1) with 60 parts of reclaimed rubber at the mixing temperature of 50 ℃, the rotating speed of an internal mixer of 30rpm for 4min, adding the rest of filler and anti-aging agent, mixing for 2min, adding the homogenizing agent, zinc oxide and stearic acid, mixing for 14min, and discharging rubber;
(3) and (3) placing the rubber compound prepared in the step (2) on an open mill, wherein the rotating speed of the open mill is 60rpm, the open milling temperature is 80 ℃, adding an accelerator, sulfur and an anti-vulcanization reversion agent, cutting rubber for 4 times at 3/4 left and right, passing through the rubber compound in a thin mode, wrapping the rubber compound in a triangular bag for 6 times, and standing the rubber compound at room temperature under the condition of 2 mm. The rubber mixtures were allowed to stand at room temperature for 48 hours and then vulcanized. The positive vulcanization time of the process at 145 ℃ is determined according to the vulcanization characteristic curve in the vulcanization process, and the vulcanized rubber is obtained by vulcanization at 145 ℃. The vulcanizate properties are shown in Table 1.
TABLE 1 data of test results of examples 1-4 and comparative example 1
Claims (7)
1. A preparation method of trans-butyl amyl rubber modified reclaimed rubber comprises the following steps:
(1) and (2) blending the trans-butyl-pentyl rubber TBIR with part of filler and an anti-aging agent internal mixer to prepare a trans-butyl-pentyl rubber TBIR master batch, wherein the weight ratio of the trans-butyl-pentyl rubber TBIR to the filler is 100: 50-100: 70, the weight ratio of the trans-butyl-pentyl rubber TBIR to the anti-aging agent is 100: 0.1 to 100: 1, mixing at 50-100 ℃, at the rotating speed of an internal mixer of 30-100 rpm, and for 8-20 min;
(2) the trans-butyl amyl rubber TBIR master batch and the reclaimed rubber are mixed according to the weight ratio of 5-50: mixing and blending 95-50 ℃, wherein the mixing temperature is 50-100 ℃, the rotating speed of the mixer is 30-70 rpm, the mixing time is 2-4 min, then adding the rest of the filler and the anti-aging agent, adding the homogenizing agent, the zinc oxide and the stearic acid, and continuing mixing for 8-16 min;
(3) placing the rubber compound prepared in the step (2) on an open mill, adding an accelerator, sulfur and an anti-vulcanization reversion agent into the open mill at the rotation speed of 30-60 rpm and the open mill temperature of 40-80 ℃, open milling for 2-10 min, and discharging to obtain the rubber compound;
the preparation method adopts the following components:
95-50 parts by weight of reclaimed rubber
5-50 parts by weight of trans-butyl amyl rubber TBIR
2.5 to 50 parts by weight of a filler
1.5 to 4 parts by weight of zinc oxide
0.1 to 0.6 part by weight of stearic acid
0 to 5 parts by weight of a homogenizing agent
0.8 to 5 parts by weight of sulfur
0.5 to 3.5 parts by weight of an accelerator
0.1 to 3 parts by weight of an antioxidant
0-2.0 parts by weight of an anti-reversion agent;
the dispersity of the inorganic filler in the reclaimed rubber compound modified by the trans-butadiene-isoprene rubber is improved by 10-20%, the size of the filler aggregate is reduced by 5-20%, the interaction between the polymer and the filler is enhanced, the tensile strength is improved by 30-70% after the reclaimed rubber is vulcanized, and the 300% stress at definite elongation is improved by 40-100%.
2. The preparation method according to claim 1, wherein the reclaimed rubber is composed of 50-70% by weight of rubber material and 30-50% by weight of filler; the rubber material is composed of one or more of natural rubber, butadiene rubber, styrene-butadiene rubber and butyl rubber, and the filler is composed of one or more of carbon black, white carbon black and calcium carbonate.
3. The method according to claim 1, wherein the trans-butadiene rubber has a molar content of butadiene units of 10 to 60%, a molar content of isoprene units of 90 to 40%, a molar content of trans-1, 4-structure of more than 85%, and a Mooney viscosity of 20 to 120 measured at 100 ℃ for 3+4 minutes.
4. The preparation method according to claim 1, wherein the filler is one or more of carbon black, white carbon black, graphene oxide, calcium carbonate, calcium silicate, magnesium hydroxide, pottery clay and talcum powder; the homogenizing agent is one or more of aliphatic hydrocarbon petroleum resin, aromatic hydrocarbon petroleum resin, phenolic resin and cyclic zinc salt complex; the anti-reversion agent is one or more of 1, 3-bis (citraconimidomethyl) benzene, hexamethylene-1, 6-disulfo sodium sulfate dihydrate and organic zinc soap.
5. The preparation method according to claim 1, wherein after vulcanization, the abrasion performance of the reclaimed rubber modified by the trans-butadiene rubber is improved by 10-20%, and the flex fatigue performance is improved by 100-700%.
6. The method according to claim 1, wherein the rubber composition is vulcanized to obtain a vulcanized rubber.
7. The preparation method of claim 1, wherein the rubber compound is applied to tire treads, sidewalls, tire bodies, belt layers, outer rubber of the tire bodies, air-tight layer parts, highway pavements and runways, and the dynamic fatigue performance of the rubber compound is effectively improved while the production cost is reduced and the physical and mechanical properties of the original rubber compound are maintained.
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| CN110878149B (en) * | 2018-09-06 | 2022-03-22 | 中国石油化工股份有限公司 | Low-odor rubber sealing strip for passenger car |
| CN109206678A (en) * | 2018-09-07 | 2019-01-15 | 山东华聚高分子材料有限公司 | A kind of high fatigue life rubber strip and preparation method thereof |
| CN109181027B (en) * | 2018-09-07 | 2021-10-26 | 山东华聚高分子材料有限公司 | High-performance tire tread rubber and preparation method thereof |
| CN109206764A (en) * | 2018-09-07 | 2019-01-15 | 山东华聚高分子材料有限公司 | A kind of high fatigue life tire liner glue and preparation method thereof |
| CN109651665A (en) * | 2018-12-14 | 2019-04-19 | 重庆凌峰橡塑制品有限公司 | Fuel tank supporting pad rubber compounding and preparation method |
| CN112210129B (en) * | 2019-07-09 | 2023-07-18 | 中国石油化工股份有限公司 | Anti-cracking anti-aging rubber for radial tire tread base and preparation method |
| CN114276588B (en) * | 2021-11-19 | 2023-05-12 | 浙江威格尔传动股份有限公司 | Cracking-proof low-temperature synchronous belt and manufacturing method thereof |
| CN114805959B (en) * | 2022-04-29 | 2024-01-26 | 山东华聚高分子材料有限公司 | Pre-dispersed rubber auxiliary master batch, preparation method and application thereof |
| CN117603512A (en) * | 2023-12-19 | 2024-02-27 | 温州市优联新材料有限公司 | Novel rubber material and preparation method thereof |
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| CN101481473A (en) * | 2008-01-07 | 2009-07-15 | 严晓敏 | Rubber composition and product thereof |
| CN103204973B (en) * | 2012-01-12 | 2017-07-25 | 青岛科技大学 | A kind of trans 1,4 polydiene copolymer thing of low molecule amount and its production and use |
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