A halogenated butyl rubber in-situ dispersion composite material and a preparation method thereof

Abstract

The application discloses a halogenated butyl rubber in-situ dispersion composite material and a preparation method thereof, and the preparation method comprises the following steps: mixing halogenated butyl rubber with a rubber good solvent to obtain a glue solution; mixing and shearing carbon black and an additive with a carbon black good solvent to obtain a carbon black slurry; and mixing the glue solution and the carbon black slurry at room temperature and performing reduced pressure distillation to obtain the halogenated butyl rubber in-situ dispersion composite material. The application directly prepares a rubber mixture by using a full formula system, replaces a wet ball milling method, adopts high shear dispersion, improves efficiency, realizes room temperature reaction in the whole process, greatly reduces energy consumption, simplifies post-processing, removes a solvent in one step, does not need to open the rubber mixture and remove a volatile component, improves the uniformity of filler dispersion, simultaneously improves air tightness, flex fatigue life and mechanical strength, and achieves unexpected technical effects.

Description

Technical Field

[0001] This application relates to the field of rubber composite materials technology, and in particular to a halogenated butyl rubber in-situ dispersed composite material and its preparation method. Background Technology

[0002] Traditional halogenated butyl rubber is produced by high-temperature dry mixing or open mixing, which has problems such as high dust pollution, high energy consumption, and uneven dispersion of fillers.

[0003] CN113429688A discloses a method for preparing butyl rubber masterbatch, which uses clay and carbon black dual slurry, wet ball milling, heating and mixing at 30°C to 70°C, vacuum drying and open milling to remove devolatilization. This method only improves air tightness, without significantly improving mechanical and fatigue properties.

[0004] Yiwei Rubber Research Institute and related patents at home and abroad mostly focus on general rubber, fumed silica, and continuous solution mixing, but there is no room temperature in-situ dispersion scheme for halogenated butyl rubber.

[0005] Dry mixing: high temperature and high shear, high energy consumption, serious dust, and easy agglomeration of carbon black.

[0006] Existing wet processing methods cannot simultaneously achieve a synergistic improvement in airtightness, fatigue performance, mechanical strength, and low energy consumption. High temperature and high shear conditions result in high energy consumption and stringent equipment requirements; carbon black and powder feeding cause severe dust pollution; fillers are prone to agglomeration, resulting in uneven dispersion and poor batch stability; airtightness and fatigue performance are bottlenecks, making it difficult to meet the requirements of high-end products. The problems with existing technologies stem from the fact that dry processes rely on mechanical shear dispersion, and high temperatures easily lead to rubber degradation and localized filler aggregation; simple solution methods lack a pre-dispersion step, making uniform mixing impossible.

[0007] Therefore, developing a method for preparing a complete formulation system of in-situ dispersed adhesive composite materials with strong stability is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0008] In view of this, this application provides a method for preparing an in-situ dispersed composite material that can simultaneously improve airtightness, fatigue performance and mechanical strength, and has good comprehensive performance.

[0009] This application provides a method for preparing an in-situ dispersed composite material of halogenated butyl rubber, comprising: Halogenated butyl rubber is mixed with a good rubber solvent to obtain a rubber solution; Carbon black, additives, and a good solvent for carbon black are mixed and sheared to obtain a carbon black slurry; The adhesive solution and carbon black slurry were mixed at room temperature and then distilled under reduced pressure to obtain an in-situ dispersed composite material of halogenated butyl rubber.

[0010] In some specific implementations, the halogenated butyl rubber includes one or more of brominated butyl rubber, chlorinated butyl rubber, or star-branched halogenated butyl rubber.

[0011] In some specific implementations, the good solvent for rubber includes one or more of aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, or chlorinated hydrocarbon solvents.

[0012] In some specific implementations, the aliphatic hydrocarbon solvent includes one or more of gasoline, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isoheptane, isooctane, n-octane, petroleum ether, isododecane, isohexadecane, D40 solvent oil, or D60 light white oil; the aromatic hydrocarbon solvent includes one or more of benzene, toluene, xylene, or styrene; and the chlorinated hydrocarbon solvent includes one or more of dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, chlorobenzene, tetrachloroethylene, or chlorotoluene.

[0013] In some specific implementations, the concentration of butyl rubber in the adhesive solution is 16% to 23%.

[0014] In some specific implementations, the concentration of carbon black in the carbon black slurry is 8% to 18%; The carbon black solvent includes aliphatic hydrocarbon solvents and / or aromatic hydrocarbon solvents. The aliphatic hydrocarbon solvents include one or more of gasoline, cycloalkanes, substituted cycloalkanes, straight-chain alkanes, or branched-chain alkanes. The aromatic hydrocarbon solvents include one or more of benzene, toluene, xylene, or styrene.

[0015] In some specific implementations, the shearing speed is 2000 rpm to 8000 rpm; The shearing time is 5 to 30 minutes.

[0016] In some specific implementations, the room temperature mixing time is 30 minutes to 5 hours, and the room temperature mixing is carried out under stirring at a speed of 200 rpm to 1000 rpm.

[0017] In some specific implementations, the temperature of the vacuum distillation is 40°C to 80°C.

[0018] In some specific implementations, the additives include zinc oxide, stearic acid, magnesium oxide, and naphthenic oil; The mass ratio of carbon black, zinc oxide, stearic acid, magnesium oxide and naphthenic oil is (55-65):1:(1.5-2.5):(0.1-1):(5-10); In some specific implementations, the adhesive also includes a homogenizer and a tackifier, wherein the homogenizer includes 40MSF and the tackifier includes SP1068.

[0019] This application also provides a halogenated butyl rubber in-situ dispersed composite material, which is prepared according to the preparation method described above.

[0020] This application adopts a complete formulation system to directly prepare compound rubber, replacing wet ball milling. It uses high-shear dispersion to improve efficiency, achieves room temperature reaction throughout the process, significantly reduces energy consumption, simplifies post-processing, and removes solvent in one step without open milling and volatilization. It also improves filler dispersion uniformity, while enhancing air tightness, flexural fatigue life, and mechanical strength, achieving unexpected technical effects. Detailed Implementation

[0021] It should be understood that the expression “one or more of…” individually includes each of the objects described after the expression, as well as various different combinations of two or more of the described objects, unless otherwise understood from the context and usage. The expression “and / or” combined with three or more described objects should be understood to have the same meaning, unless otherwise understood from the context.

[0022] The terms “including,” “having,” or “containing,” including the use of their grammatical synonyms, should generally be understood as open-ended and non-restrictive, for example, not excluding other unstated elements or steps, unless otherwise specifically stated or understood from the context.

[0023] It should be understood that the order of steps or the sequence of actions is not important as long as this application remains operational. Furthermore, two or more steps or actions can be performed simultaneously.

[0024] The use of any and all instances or exemplary language such as “e.g.” or “include” in this document is intended merely to better illustrate the application and does not constitute a limitation on the scope of the application. No language in this specification should be construed as indicating that any unclaimed element is essential to the practice of this application.

[0025] Furthermore, the numerical ranges and parameters used to define this application are approximate values, and the relevant values ​​in the specific embodiments have been presented as precisely as possible. However, any value inevitably contains standard deviations due to individual test methods. Therefore, unless otherwise explicitly stated, it should be understood that all ranges, quantities, values, and percentages used in this disclosure are modified with the word "approximately." Here, "approximately" generally means that the actual value is within plus or minus 10%, 5%, 1%, or 0.5% of a specific value or range.

[0026] This application provides a method for preparing an in-situ dispersed composite material of halogenated butyl rubber, including: Halogenated butyl rubber is mixed with a good rubber solvent to obtain a rubber solution; Carbon black, additives, and a good solvent for carbon black are mixed and sheared to obtain a carbon black slurry; The adhesive solution and carbon black slurry were mixed at room temperature and then distilled under reduced pressure to obtain an in-situ dispersed composite material of halogenated butyl rubber.

[0027] This application first mixes halogenated butyl rubber with a good rubber solvent to obtain a rubber solution. In some specific implementations, the halogenated butyl rubber includes, but is not limited to, one or more of brominated butyl rubber, chlorinated butyl rubber, or star-branched halogenated butyl rubber. This application does not have special requirements for the selection of halogenated butyl rubber. The brominated butyl rubber can be selected from poly(2828), the chlorinated butyl rubber can be selected from poly(1338), and the star-branched butyl rubber can be selected from poly(S-BIIR). In some specific implementations, the rubber solution also includes a homogenizer and a tackifier. The homogenizer includes, but is not limited to, 40MSF. This application does not have special requirements for the selection of homogenizer. The tackifier includes, but is not limited to, SP10684. This application does not have special requirements for the selection of tackifier. The mass ratio of butyl rubber, homogenizer, and tackifier is 100:(5-10):(3-8), preferably 100:7:5. In some specific implementations, the good rubber solvent includes one or more of aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, or chlorinated hydrocarbon solvents. In some specific implementations, the aliphatic hydrocarbon solvent includes, but is not limited to, one or more of gasoline, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isoheptane, isooctane, n-octane, petroleum ether, isododecane, isohexadecane, D40 solvent oil, or D60 light white oil. This application does not have special requirements for the selection of aliphatic hydrocarbon solvents. The aromatic hydrocarbon solvent includes, but is not limited to, one or more of benzene, toluene, xylene, or styrene. This application does not have special requirements for the selection of aromatic hydrocarbon solvents. The chlorinated hydrocarbon solvent includes, but is not limited to, one or more of dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, chlorobenzene, tetrachloroethylene, or chlorotoluene. This application does not have special requirements for the selection of chlorinated hydrocarbon solvents. In some specific implementations, the concentration of butyl rubber in the adhesive solution is 16% to 23%, preferably 18% to 22%, and more preferably 20%.

[0028] This application then mixes carbon black, additives, and a good carbon black solvent under high shear to obtain a carbon black slurry. In some specific implementations, the concentration of carbon black in the carbon black slurry is 8% to 18%, preferably 10% to 16%, and more preferably 15%; the good carbon black solvent is an aliphatic hydrocarbon solvent and / or an aromatic hydrocarbon solvent, wherein the aliphatic hydrocarbon solvent includes one or more of gasoline, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isoheptane, isooctane, n-octane, petroleum ether, isododecane, isohexadecane, D40 solvent oil, or D60 light white oil, and the aromatic hydrocarbon solvent includes one or more of benzene, toluene, xylene, or styrene. In some specific implementations, the shearing speed is 2000 rpm to 8000 rpm, preferably 3000 rpm to 8000 rpm; and the shearing time is 5 min to 30 min. In some specific implementations, the additives include zinc oxide, stearic acid, antioxidants, and naphthenic oil; the mass ratio of carbon black, zinc oxide, stearic acid, magnesium oxide, and naphthenic oil is (55-65):1:(1.5-2.5):(0.1-1):(5-10), preferably 60:1:2:0.15:8. There is a shear effect; high shear leads to concentration, and the rate and concentration need to be controlled within a certain range.

[0029] This application then mixes the adhesive solution and carbon black slurry at room temperature and distills under reduced pressure to obtain a halogenated butyl rubber in-situ dispersed composite material. In some specific implementations, the mass ratio of the adhesive solution to the carbon black slurry is 0.88-2.89:1, preferably 1-2.75:1. In some specific implementations, the room temperature mixing time is 30 min to 5 h, preferably 50 min to 3 h, more preferably 60 min, and the room temperature mixing is carried out under stirring at a speed of 200 rpm to 1000 rpm, preferably 400 rpm to 800 rpm, more preferably 500 rpm. In some specific implementations, the temperature of the reduced pressure distillation is 40-80°C. The halogenated butyl rubber in-situ dispersed composite material can be obtained by desolventizing under reduced pressure, without the need for vacuum drying or open mill devolatilization.

[0030] High shear dispersion, non-wet ball milling, more efficient process; room temperature throughout (≤35℃), no heating section, extremely low energy consumption; one-step desolventization, no subsequent open milling and volatilization, simplified process; compared with traditional dry method, in-situ dispersion does not require internal mixer, low mixing energy consumption, no dust; improved air tightness of filler dispersant; improved fatigue performance, increased viscosity.

[0031] This application also provides a halogenated butyl rubber in-situ dispersed composite material, which is prepared according to the above preparation method.

[0032] The halogenated butyl rubber in-situ dispersed composite material can be used in tire airtight layers, inner tubes, seals, waterproof membranes, shock-absorbing materials, and other fields.

[0033] The present application is further illustrated below with reference to embodiments. The scope of protection of the present application is not limited to the following embodiments.

[0034] Example 1

[0035] This embodiment provides a halogenated butyl rubber in-situ dispersed composite material, the preparation method of which includes: Take 100 g of brominated butyl rubber (medium polymer 2828), 7 g of 40MSF, and 4 g of SP1068, add 400 g of cyclohexane, stir and dissolve at room temperature to prepare a 20% adhesive solution (based on adhesive content).

[0036] Take 60 g of carbon black, 1 g of zinc oxide, 2 g of stearic acid, 0.15 g of magnesium oxide, and 8 g of naphthenic oil, add 340 g of n-hexane, and shear at 3000 rpm for 30 min to obtain a carbon black slurry with a concentration of 15% (based on carbon black).

[0037] The adhesive solution was mixed with carbon black slurry and stirred at room temperature for 500 rpm for 60 min. The solvent was removed by vacuum distillation to obtain the in-situ dispersed composite material of halogenated butyl rubber.

[0038] Example 2

[0039] This embodiment provides a halogenated butyl rubber in-situ dispersed composite material, the preparation method of which includes: Take 100 g of brominated butyl rubber (medium polymer 2828), 7 g of 40MSF, and 4 g of SP1068, add 400 g of cyclohexane, stir and dissolve at room temperature to prepare a 20% adhesive solution (based on adhesive content).

[0040] Take 60 g of carbon black, 1 g of zinc oxide, 2 g of stearic acid, 0.15 g of magnesium oxide, and 8 g of naphthenic oil, add 340 g of n-hexane, and disperse under high shear at 8000 rpm for 5 min to obtain a carbon black slurry with a concentration of 15% (based on carbon black).

[0041] The gel solution was mixed with carbon black slurry and stirred at room temperature for 500 rpm for 60 min. Hexane was removed by vacuum distillation to obtain the in-situ dispersion gel.

[0042] Example 3

[0043] This embodiment provides a halogenated butyl rubber in-situ dispersed composite material, the preparation method of which includes: Take 100 g of brominated butyl rubber (medium polymer 2828), 7 g of 40MSF, and SP1068, add 400 g of cyclohexane, stir and dissolve at room temperature to prepare a 20% adhesive solution (based on adhesive content).

[0044] Take 60 g of carbon black, 1 g of zinc oxide, 2 g of stearic acid, 0.15 g of magnesium oxide, and 8 g of naphthenic oil, add 340 g of n-hexane, and disperse under high shear at 2000 rpm for 10 min to obtain a carbon black slurry with a concentration of 15% (based on carbon black).

[0045] The gel solution was mixed with carbon black slurry and stirred at room temperature for 500 rpm for 60 min. Hexane was removed by vacuum distillation to obtain the in-situ dispersion gel.

[0046] Comparative Example 1

[0047] This comparative example provides a compounded composite material, which differs from Example 1 in that rubber is added first, half of the carbon black and resin are added after 1 minute of mixing, the remaining carbon black and naphthenic oil are added after 2 minutes of mixing, the mixture is cleaned at 115 degrees Celsius, and the adhesive is discharged at 135 degrees Celsius to obtain a dry-prepared compounded composite material.

[0048] Comparative Example 2

[0049] This comparative example provides a compounded composite material that uses the same formulation, wet ball milling, heated mixing, vacuum drying, and open milling devolatilization as the process in CN113429688A.

[0050] Comparative Example 3

[0051] This comparative example provides a compounded composite material, the preparation method of which includes: Take 100 g of brominated butyl rubber (medium polymer 2828), 7 g of 40MSF, and 4 g of SP1068, add 400 g of cyclohexane, stir and dissolve at room temperature to prepare a 20% adhesive solution (based on adhesive content).

[0052] Take 60 g of carbon black, 1 g of zinc oxide, 2 g of stearic acid, 0.15 g of magnesium oxide, and 8 g of naphthenic oil, add 340 g of n-hexane, and stir at 500 rpm for 2 hours to obtain a carbon black slurry with a concentration of 15% (based on carbon black).

[0053] The gel solution was mixed with the carbon black slurry and stirred at room temperature for 500 rpm for 60 min. Hexane was removed by vacuum distillation to obtain the in-situ dispersion gel.

[0054] The performance of the halogenated butyl rubber in-situ dispersion composites provided in Examples 1-4 was tested against the in-situ dispersions provided in Examples 1-4. The test methods are as follows: According to the national standard test data for Mooney (GB / T 1232.1-2016), tack (GB / T 4852-2002), and airtightness (GB / T1038.1-2022), the test results are shown in Table 1.

[0055] Table 1

[0056] The above description is merely a preferred embodiment of this application, but the scope of protection of this application is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in this application, based on the technical solution and application concept of this application, should be included within the scope of protection of this application.

Claims

1. A method for preparing an in-situ dispersed composite material of halogenated butyl rubber, characterized in that, include: Halogenated butyl rubber is mixed with a good rubber solvent to obtain a rubber solution; Carbon black, additives, and a good solvent for carbon black are mixed and sheared to obtain a carbon black slurry; The adhesive solution and carbon black slurry were mixed at room temperature and then distilled under reduced pressure to obtain an in-situ dispersed composite material of halogenated butyl rubber.

2. The preparation method according to claim 1, characterized in that, The halogenated butyl rubber includes one or more of brominated butyl rubber, chlorinated butyl rubber, or star-branched halogenated butyl rubber.

3. The preparation method according to claim 1, characterized in that, The good solvent for rubber includes one or more of aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, or chlorinated hydrocarbon solvents.

4. The preparation method according to claim 3, characterized in that, The aliphatic hydrocarbon solvent includes one or more of gasoline, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isoheptane, isooctane, n-octane, petroleum ether, isododecane, isohexadecane, D40 solvent oil, or D60 light white oil; the aromatic hydrocarbon solvent includes one or more of benzene, toluene, xylene, or styrene; and the chlorinated hydrocarbon solvent includes one or more of dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, chlorobenzene, tetrachloroethylene, or chlorotoluene.

5. The preparation method according to claim 1, characterized in that, The concentration of butyl rubber in the adhesive solution is 16% to 23%.

6. The preparation method according to claim 1, characterized in that, The concentration of carbon black in the carbon black slurry is 8% to 18%; The carbon black is a good solvent for aliphatic hydrocarbons or aromatic hydrocarbons. The aliphatic hydrocarbon solvent includes one or more of gasoline, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isoheptane, isooctane, n-octane, petroleum ether, isododecane, isohexadecane, D40 solvent oil or D60 light white oil, and the aromatic hydrocarbon solvent includes one or more of benzene, toluene, xylene or styrene.

7. The preparation method according to claim 1, characterized in that, The shearing speed is from 2000 rpm to 8000 rpm; The shearing time is 5 to 30 minutes.

8. The preparation method according to claim 1, characterized in that, The room temperature mixing time is 30 minutes to 5 hours, and the room temperature mixing is carried out under stirring at a speed of 200 rpm to 1000 rpm.

9. The preparation method according to claim 1, characterized in that, The temperature for vacuum distillation is 40°C to 80°C; The additives include zinc oxide, stearic acid, magnesium oxide, and naphthenic oil; The mass ratio of carbon black, zinc oxide, stearic acid, magnesium oxide and naphthenic oil is (55-65):1:(1.5-2.5):(0.1-1):(5-10); The adhesive also includes a homogenizer and a tackifier, wherein the homogenizer comprises 40MSF and the tackifier comprises SP1068.

10. A halogenated butyl rubber in-situ dispersed composite material, characterized in that, It is prepared according to the preparation method described in any one of claims 1 to 9.

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