CN111763285B - Methyl styrene-butadiene rubber and preparation method thereof - Google Patents
Methyl styrene-butadiene rubber and preparation method thereof Download PDFInfo
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Abstract
The invention provides methyl styrene-butadiene rubber and a preparation method thereof. The preparation method comprises the following steps: under the vacuum and nitrogen replacement conditions, carrying out emulsion polymerization reaction by using alpha-methyl styrene, butadiene, water, an emulsifier, an electrolyte, a reducing agent, a molecular weight regulator and an initiator as raw materials to obtain an emulsion polymerization product; and when the conversion rate of the emulsion polymerization reaction system is 60-65%, sequentially adding a terminator and a demulsifier into the emulsion polymerization reaction system to obtain the methyl styrene-butadiene rubber. The methyl styrene-butadiene rubber is prepared by taking alpha-methyl styrene and butadiene as main raw materials through emulsion polymerization, the glass transition temperature of the methyl styrene-butadiene rubber is below-70 ℃, the content of the combined alpha-methyl styrene is 8-15 percent, and the Mooney viscosity (ML) is1+4 100℃) 35 to 45 percent, and has higher tensile strength and good environmental protection.
Description
Technical Field
The invention relates to the field of rubber, and particularly relates to methyl styrene-butadiene rubber and a preparation method thereof.
Background
Styrene Butadiene Rubber (SBR) is a copolymer rubber prepared by polymerizing butadiene and styrene, and is a general synthetic rubber with the highest yield and the highest consumption in the world as one of important Synthetic Rubber (SR) varieties.
Styrene-butadiene rubber has repeating units of butadiene and repeating units of styrene. The styrene unit provides a rigid structure for the styrene butadiene rubber, so that the styrene butadiene rubber has certain strength and wet skid resistance. Unsaturated bonds in the butadiene structure provide cross-linking bonds for styrene butadiene rubber, and the molecular chain of the butadiene rubber has certain flexibility due to the 1, 4-butadiene structure. The glass transition temperature of the styrene-butadiene rubber is closely related to the molecular structure composition of the styrene-butadiene rubber, and the glass transition temperature is reduced along with the increase of the content of butadiene in the styrene-butadiene rubber.
The methyl styrene-butadiene rubber is obtained by copolymerizing alpha-methyl styrene and butadiene, the typical properties of the raw rubber and the physical and mechanical properties of vulcanized rubber are similar to those of styrene-butadiene rubber, the application of the methyl styrene-butadiene rubber is the same as that of styrene-butadiene rubber with a corresponding grade, and the methyl styrene-butadiene rubber is mainly used for manufacturing tires and various rubber industrial products such as conveying belts, sealing gaskets and the like.
The rubber gasket generally needs to have the performances of oil resistance, acid and alkali resistance, cold and heat resistance, aging resistance and the like, and is widely applied to the industries of automobiles, electronics, chemical industry, static resistance, flame retardance, food and the like. For some special machines, due to the limitation of working environment, the rubber sealing gasket has high requirements on low temperature resistance, good compression cold resistance coefficient, high temperature oxidation resistance and certain tensile strength. Although the traditional styrene butadiene rubber can meet the low-temperature working requirement of the sealing gasket rubber, the high-temperature oxidation resistance is poor. Compared with styrene, alpha-methyl styrene contained in methyl styrene-butadiene rubber has better rigidity, and the existence of the alpha-methyl styrene provides better tensile strength and high-temperature oxidation resistance for the material. However, the methods for preparing alpha-methylstyrene are less studied in the art, and thus there is a need to develop a method for preparing alpha-methylstyrene.
Disclosure of Invention
The invention mainly aims to provide methyl styrene-butadiene rubber and a preparation method thereof, and aims to solve the problem that the existing sealing material cannot meet the application requirement at high temperature.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a methyl styrene-butadiene rubber, the method comprising: under the vacuum and nitrogen displacement condition, taking alpha-methyl styrene, butadiene, water, an emulsifier, an electrolyte, a reducing agent, a molecular weight regulator, an initiator and a terminator as raw materials to carry out emulsion polymerization reaction to obtain an emulsion polymerization product, wherein the raw materials comprise 15 to 25 parts by weight of alpha-methyl styrene, 75 to 85 parts by weight of butadiene, 3.5 to 5.0 parts by weight of emulsifier, 0.63 to 1.03 parts by weight of electrolyte, 0.02 to 0.1 part by weight of initiator, 0.065 to 0.085 part by weight of reducing agent, 0.2 to 0.30 part by weight of molecular weight regulator, 180 to 200 parts by weight of water and 0.35 to 0.5 part by weight of terminator; and when the conversion rate of the emulsion polymerization reaction system is 60-65%, sequentially adding a terminator and a demulsifier into the emulsion polymerization reaction system to obtain the methyl styrene-butadiene rubber.
Further, the raw materials comprise, by weight, 18-22 parts of alpha-methyl styrene, 77-80 parts of butadiene, 4-4.5 parts of an emulsifier, 0.8-0.9 part of an electrolyte, 0.2-0.5 part of an initiator, 0.07-0.075 part of a reducing agent, 0.23-0.28 part of a molecular weight regulator, 185-195 parts of water and 0.38-0.48 part of a terminator.
Further, the electrolyte is selected from at least two of the group consisting of phosphoric acid, potassium hydroxide, tetrasodium ethylenediaminetetraacetate, and sodium dodecylbenzenesulfonate.
Further, the electrolyte comprises the following components in parts by weight: 0.2 to 0.3 portion of phosphoric acid, 0.3 to 0.5 portion of potassium hydroxide, 0.01 to 0.03 portion of ethylene diamine tetraacetic acid tetrasodium salt and 0.1 to 0.2 portion of sodium dodecyl benzene sulfonate.
Further, the reducing agent is selected from one or more of the group consisting of ferrous sulfate, sodium formaldehyde sulfoxylate and tetrasodium ethylenediaminetetraacetate; preferably, the reducing agent comprises 0.01 to 0.03 portion of ferrous sulfate, 0.03 to 0.05 portion of sodium formaldehyde sulfoxylate and 0.03 to 0.05 portion of ethylenediaminetetraacetic acid tetrasodium salt by weight portion.
Further, the terminating agent is selected from N-isopropyl hydroxylamine and/or di-N-propyl thiourea; preferably, the terminator comprises 0.05 to 0.1 part by weight of N-isopropylhydroxylamine and 0.3 to 0.4 part by weight of di-N-propylthiourea.
Further, the molecular weight regulator is selected from tertiary dodecyl mercaptan and/or n-dodecyl mercaptan; preferably, the initiator is selected from one or more of the group consisting of p-menthane hydroperoxide, p-pinane hydroperoxide and diisopropylbenzene hydroperoxide; preferably, the emulsifier is selected from disproportionated potassium rosinate soap and/or sodium fatty acid soap.
Further, the reaction temperature of the emulsion polymerization reaction is 4-6 ℃ and the reaction time is 5-10 min in parts by weight.
Further, the emulsion polymerization reaction comprises: placing alpha-methyl styrene, butadiene, water, an emulsifier, an electrolyte, a reducing agent and a molecular weight regulator into a polymerization kettle, and adding an initiator into the polymerization kettle to carry out polymerization reaction when the temperature of the polymerization kettle is reduced to 4-6 ℃.
Further, the preparation method comprises the steps of adding a product system of emulsion polymerization reaction into a dilute sulfuric acid solution with the concentration of 0.3-0.8 wt%, stirring, coagulating, washing and drying to obtain the methyl styrene-butadiene rubber; preferably, the temperature in the stirring process is controlled to be 55-65 ℃, and the stirring time is 5-10 min.
The application also provides methyl styrene-butadiene rubber which is prepared by the preparation method.
By applying the technical scheme of the invention, the methyl styrene-butadiene rubber is prepared by taking alpha-methyl styrene and butadiene as main raw materials through emulsion polymerization, and the purposes of changing the content of the combined alpha-styrene in the molecular structure of the styrene-butadiene rubber and adjusting the Mooney property of the product can be realized by controlling the dosage of each component. The glass transition temperature of the methyl styrene-butadiene rubber is below-70 ℃, the content of combined alpha-methyl styrene is 8-15%, and the Mooney viscosity (ML) is1+4 100℃) 35 to 45 and has higher tensile strength. The prepared product has no nitrosamine parent, and can not generate nitrosamine, so that the product has good environmental protection property and conforms to the EU related regulation TRGS552. In conclusion, the methyl styrene-butadiene rubber prepared by the preparation method has the advantages of low glass transition temperature, high tensile strength, excellent environmental protection property, excellent processability and the like.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background section, the prior art sealing materials have not met the application requirements at high temperatures. In order to solve the technical problem, the application provides a preparation method of methyl styrene-butadiene rubber, which comprises the following steps: under the condition of vacuum and nitrogen replacement, carrying out emulsion polymerization reaction by using alpha-methyl styrene, butadiene, water, an emulsifier, an electrolyte, a reducing agent, a molecular weight regulator, an initiator and a terminator as raw materials to obtain an emulsion polymerization product, wherein the raw materials comprise 15 to 25 parts by weight of alpha-methyl styrene, 75 to 85 parts by weight of butadiene, 3.5 to 5.0 parts by weight of emulsifier, 0.63 to 1.03 parts by weight of electrolyte, 0.02 to 0.1 part by weight of initiator, 0.065 to 0.085 part by weight of reducing agent, 0.2 to 0.30 part by weight of molecular weight regulator, 180 to 200 parts by weight of water and 0.35 to 0.5 part by weight of terminator. And when the conversion rate of the emulsion polymerization reaction system is 60-65%, sequentially adding a terminator and a demulsifier into the emulsion polymerization reaction system to obtain the methyl styrene-butadiene rubber.
In the preparation method, alpha-methyl styrene and butadiene are used as main raw materials to prepare methyl styrene-butadiene rubber through emulsion polymerization, and the purposes of changing the content of the combined alpha-styrene in the molecular structure of the styrene-butadiene rubber and adjusting the Mooney of the product can be realized by controlling the dosage of each component. The glass transition temperature of the methyl styrene-butadiene rubber is below minus 70 ℃, the content of the combined alpha-methyl styrene is 8 to 15 percent, and the Mooney viscosity (ML) is1+4 100℃) 35 to 45 and has higher tensile strength. The prepared product has no nitrosamine parent body, and can not generate nitrosamine, so that the product has good environmental protection and conforms to the EU related regulation TRGS552. In conclusion, the methyl styrene-butadiene rubber prepared by the preparation method has the advantages of low glass transition temperature, high tensile strength, excellent environmental protection property, excellent processability and the like.
The methyl styrene-butadiene rubber prepared from the raw materials has excellent comprehensive performance, so that the methyl styrene-butadiene rubber has a wider application range. In a preferred embodiment, the raw materials comprise 18 to 22 parts by weight of alpha-methyl styrene, 77 to 80 parts by weight of butadiene, 4 to 4.5 parts by weight of an emulsifier, 0.8 to 0.9 part by weight of an electrolyte, 0.2 to 0.5 part by weight of an initiator, 0.07 to 0.075 part by weight of a reducing agent, 0.23 to 0.28 part by weight of a molecular weight regulator, 185 to 195 parts by weight of water and 0.38 to 0.48 part by weight of a terminating agent. The amount of the raw materials for the preparation includes, but is not limited to, the above range, and the limitation of the amount within the above range is advantageous for further improving the tensile strength and processability of the methyl styrene-butadiene rubber.
The electrolyte may be selected from those commonly used in the art. In a preferred embodiment, the electrolyte includes, but is not limited to, at least two of the group consisting of phosphoric acid, potassium hydroxide, tetrasodium ethylenediaminetetraacetate, and sodium dodecylbenzenesulfonate. Two electrolytes can form a stable electrolyte system, so that the reaction efficiency of emulsion polymerization reaction is improved, and the generation of nitrite is reduced. More preferably, the electrolyte comprises, in parts by weight: 0.2 to 0.3 portion of phosphoric acid, 0.3 to 0.5 portion of potassium hydroxide, 0.01 to 0.03 portion of tetrasodium ethylene diamine tetraacetate and 0.1 to 0.2 portion of sodium dodecyl benzene sulfonate.
In the above synthesis method, the reducing agent may be selected from those commonly used in the art. In a preferred embodiment, the reducing agent includes, but is not limited to, one or more of the group consisting of ferrous sulfate, sodium formaldehyde sulfoxylate, and tetrasodium ethylenediaminetetraacetic acid. The selection of the reducing agents is beneficial to improving the oxidation resistance of the methyl styrene butadiene rubber. In order to further improve the oxidation resistance of the methyl styrene-butadiene rubber, more preferably, the reducing agent comprises one or more of the group consisting of 0.01 to 0.03 parts by weight of ferrous sulfate, 0.03 to 0.05 parts by weight of sodium formaldehyde sulfoxylate and 0.03 to 0.05 parts by weight of tetrasodium ethylenediaminetetraacetate.
In the above synthesis method, the terminator may be selected from those commonly used in the art. In a preferred embodiment, the terminating agent includes, but is not limited to, N-isopropylhydroxylamine and/or di-N-propylthiourea. The use of the above-mentioned specific composition of the terminating agent is advantageous in improving the terminating efficiency of the emulsion polymerization reaction. More preferably, the terminating agent includes 0.05 to 0.1 parts by weight of N-isopropylhydroxylamine and 0.3 to 0.4 parts by weight of di-N-propylthiourea.
In the above synthesis method, the molecular weight regulator may be selected from those commonly used in the art. In a preferred embodiment, the molecular weight regulator includes, but is not limited to, tertiary dodecyl mercaptan and/or n-dodecyl mercaptan. The molecular weight regulators are favorable for more accurately controlling the molecular weight of the methyl styrene-butadiene rubber.
Preferably, the initiator includes, but is not limited to, one or more of the group consisting of p-menthane hydroperoxide, p-pinane hydroperoxide, and diisopropylbenzene hydroperoxide. The initiators include, but are not limited to, the above initiators, and the above initiators are selected to facilitate the reduction of the initiation time and the improvement of the initiation efficiency.
Preferably, the emulsifier includes, but is not limited to, disproportionated potassium rosinate soap and/or sodium fatty acid soap. The types of the emulsifying agents include but are not limited to the above types, and the selection of the emulsifying agents is favorable for improving the stability of the emulsion environment in the emulsion polymerization reaction process, and further is favorable for improving the yield of the methyl styrene butadiene rubber.
In a preferred embodiment, the emulsion polymerization is carried out at a reaction temperature of 4 to 6 ℃ and a reaction time of 5 to 10min, in parts by weight. The polymerization temperature and the reaction time include, but are not limited to, the above ranges, and it is preferable to limit the reaction temperature and the reaction time to the above ranges to further improve the reaction efficiency of the emulsion polymerization.
More preferably, the emulsion polymerization reaction comprises: placing alpha-methyl styrene, butadiene, water, an emulsifier, an electrolyte, a reducing agent and a molecular weight regulator into a polymerization kettle, and adding an initiator into the polymerization kettle to carry out polymerization reaction when the temperature of the polymerization kettle is reduced to 4-6 ℃.
In order to reduce the content of impurities in the methyl styrene-butadiene rubber, in a preferred embodiment, the preparation method further comprises the steps of adding the product system of the emulsion polymerization reaction into a dilute sulfuric acid solution with the concentration of 0.3-0.8 wt%, stirring, coagulating, washing and drying to obtain the methyl styrene-butadiene rubber. Preferably, the temperature in the stirring process is controlled to be 55-65 ℃, and the stirring time is 5-10 min. Limiting the temperature and time of the stirring process within the above ranges is beneficial to further improving the removal rate of impurities in the methyl styrene-butadiene rubber.
The application also provides methyl styrene-butadiene rubber which is prepared by the preparation method.
The methyl styrene-butadiene rubber is prepared by taking alpha-methyl styrene and butadiene as main raw materials through emulsion polymerization reaction, and the glass transition temperature of the methyl styrene-butadiene rubberAt a temperature of below-70 ℃, the content of the combined alpha-methyl styrene is 8 to 15 percent, and the Mooney viscosity (ML) is1+4 100℃) 35-45 and has higher tensile strength. The prepared product has no nitrosamine parent, and can not generate nitrosamine, so that the product has good environmental protection property and conforms to the EU related regulation TRGS552. In conclusion, the methyl styrene-butadiene rubber prepared by the preparation method has the advantages of low glass transition temperature, high tensile strength, excellent environmental protection property and processability and the like.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the present application as claimed.
Example 1
A synthetic method of methyl styrene-butadiene rubber comprises the following steps:
the polymerization reactor was subjected to vacuum and nitrogen substitution. Sequentially adding soft water, an emulsifier, an electrolyte solution, a reducing agent, tert-dodecyl mercaptan, alpha-methyl styrene and butadiene into a polymerization kettle, adding an initiator, namely p-menthane hydroperoxide when the temperature of the polymerization kettle is reduced to 5 ℃, carrying out a polymerization experiment, and adding a terminator HSD to terminate the reaction when the conversion rate reaches 60% so as to obtain the high-tensile-strength styrene-butadiene rubber latex. Adding the circular latex into a dilute sulfuric acid solution with the concentration of 0.5%, stirring, controlling the temperature at 60 ℃ for 5 minutes, coagulating, washing and drying to obtain a crude rubber finished product.
Wherein, the emulsion polymerization reaction adopts the following raw materials (by weight portion):
15 parts of alpha-methylstyrene, 75 parts of butadiene, 4.5 parts of an emulsifier (disproportionated potassium rosinate soap), 0.63 part of an electrolyte, 0.05 part of an initiator (p-menthane hydroperoxide), 0.065 part of a reducing agent, 0.25 part of tert-dodecyl mercaptan, 190 parts of water and 0.35 part of a terminating agent.
The electrolyte comprises the following components in parts by weight: 0.2 part of phosphoric acid, 0.3 part of potassium hydroxide, 0.03 part of ethylene diamine tetraacetic acid tetrasodium salt and 0.1 part of sodium dodecyl benzene sulfonate.
The reducing agent comprises the following components in parts by weight: 0.01 part of ferrous sulfate, 0.03 part of sodium formaldehyde sulfoxylate and 0.025 part of ethylene diamine tetraacetic acid tetrasodium salt.
The composition of the terminator is (by weight portion): 0.05 part of N-isopropylhydroxylamine and 0.3 part of di-N-propylthiourea.
The performance of the methyl styrene-butadiene rubber is detected by adopting a nuclear magnetic resonance hydrogen spectrum method and a differential thermal analysis method. Through detection, the methyl styrene-butadiene rubber has the molecular structure that the content of alpha-methyl styrene is 7.85 percent, the content of butadiene is 92.15 percent, the glass transition temperature is-73.2 ℃, and the methyl styrene-butadiene rubber does not contain dimethyl nitrosamine and is environment-friendly rubber.
Example 2
A synthetic method of methyl styrene-butadiene rubber comprises the following steps:
the polymerization reactor was subjected to vacuum and nitrogen substitution. Adding soft water, an emulsifier, an electrolyte solution, a reducing agent, tert-dodecyl mercaptan, alpha-methyl styrene and butadiene into a polymerization kettle in sequence, adding an initiator p-menthane peroxide when the temperature of the polymerization kettle is reduced to 5 ℃, carrying out a polymerization experiment, and adding a terminator HSD to terminate the reaction when the conversion rate reaches 60% to obtain the high-tensile-strength styrene-butadiene rubber latex. Adding the circular latex into a dilute sulfuric acid solution with the concentration of 0.5%, stirring, controlling the temperature at 60 ℃ for 5 minutes, coagulating, washing and drying to obtain a crude rubber finished product.
Wherein, the emulsion polymerization reaction adopts the following raw materials (by weight portion):
20 parts of alpha-methyl styrene, 80 parts of butadiene, 4.5 parts of an emulsifier (disproportionated potassium rosinate soap), 0.63 part of an electrolyte, 0.05 part of an initiator (p-menthane hydroperoxide), 0.065 part of a reducing agent, 0.27 part of tert-dodecyl mercaptan, 190 parts of water and 0.35 part of a terminator.
The electrolytic composition is (by weight portion): 0.2 portion of phosphoric acid, 0.3 portion of potassium hydroxide, 0.03 portion of ethylene diamine tetraacetic acid tetrasodium salt,
0.1 part of sodium dodecyl benzene sulfonate.
The reducing agent comprises the following components in parts by weight: 0.01 part of ferrous sulfate, 0.03 part of sodium formaldehyde sulfoxylate and 0.025 part of ethylene diamine tetraacetic acid tetrasodium salt.
The composition of the terminator is (by weight portion): 0.05 part of N-isopropylhydroxylamine and 0.3 part of di-N-propylthiourea.
The detection shows that the methyl styrene-butadiene rubber has the molecular structure that the content of alpha-methyl styrene is 12.12 percent, the content of butadiene is 87.88 percent, the glass transition temperature is-72.1 ℃, and the methyl styrene-butadiene rubber does not contain dimethyl nitrosamine and is environment-friendly rubber.
Example 3
A synthetic method of methyl styrene-butadiene rubber comprises the following steps:
the polymerization vessel was subjected to vacuum and nitrogen substitution. Adding soft water, an emulsifier, an electrolyte solution, a reducing agent, tert-dodecyl mercaptan, alpha-methyl styrene and butadiene into a polymerization kettle in sequence, adding an initiator p-menthane peroxide when the temperature of the polymerization kettle is reduced to 5 ℃, carrying out a polymerization experiment, and adding a terminator HSD to terminate the reaction when the conversion rate reaches 60% to obtain the high-tensile-strength styrene-butadiene rubber latex. Adding the circular latex into a dilute sulfuric acid solution with the concentration of 0.5%, stirring, controlling the temperature at 60 ℃ for 5 minutes, coagulating, washing and drying to obtain a crude rubber finished product.
Wherein, the emulsion polymerization reaction adopts the following raw materials (by weight portion):
25 parts of alpha-methyl styrene, 75 parts of butadiene, 36 parts of isoprene, 4.5 parts of emulsifier, 0.63 part of electrolyte, 0.05 part of p-menthane hydroperoxide, 0.065 part of reducing agent, 0.30 part of tert-dodecyl mercaptan, 190 parts of water and 0.35 part of terminator.
The emulsifier is disproportionated potassium abietate soap.
The electrolyte comprises the following components in parts by weight:
0.2 part of phosphoric acid, 0.3 part of potassium hydroxide, 0.03 part of ethylenediaminetetraacetic acid tetrasodium salt and 0.1 part of sodium dodecylbenzenesulfonate.
The reducing agent comprises the following components in parts by weight:
0.01 part of ferrous sulfate, 0.03 part of sodium formaldehyde sulfoxylate and 0.025 part of ethylenediaminetetraacetic acid tetrasodium salt.
The terminator comprises the following components in parts by weight: 0.05 part of N-isopropylhydroxylamine and 0.3 part of di-N-propylthiourea.
Through detection, the methyl styrene-butadiene rubber has a molecular structure containing 14.82% of alpha-methyl styrene, 85.18% of butadiene, a glass transition temperature of-70.2 ℃, does not contain dimethyl nitrosamine and is environment-friendly rubber.
Example 4
The difference from example 1 is that:
the raw materials adopted by the emulsion polymerization reaction comprise, by weight, 10 parts of alpha-methylstyrene, 90 parts of butadiene, 3.0 parts of emulsifier, 0.5 part of electrolyte, 0.1 part of initiator, 0.1 part of reducing agent, 0.15 part of molecular weight regulator, 180 parts of water and 0.3 part of terminator.
The methyl styrene butadiene rubber is detected by a nuclear magnetic resonance hydrogen spectrum method and a differential thermal analysis method. The detection shows that the methyl styrene-butadiene rubber has the molecular structure that the content of alpha-methyl styrene is 3.15wt%, the content of butadiene is 96.85wt%, the glass transition temperature is-76.8 ℃, and the methyl styrene-butadiene rubber does not contain dimethyl nitrosamine and is environment-friendly rubber.
Example 5
The difference from example 1 is that:
the raw materials adopted by the emulsion polymerization reaction comprise, by weight, 30 parts of alpha-methylstyrene, 70 parts of butadiene, 3.0 parts of emulsifier, 0.5 part of electrolyte, 0.1 part of initiator, 0.1 part of reducing agent, 0.15 part of molecular weight regulator, 180 parts of water and 0.3 part of terminator.
The methyl styrene butadiene rubber is detected by a nuclear magnetic resonance hydrogen spectrum method and a differential thermal analysis method. Through detection, the methyl styrene-butadiene rubber has a molecular structure containing 21.6wt% of alpha-methyl styrene, 78.4wt% of butadiene, a glass transition temperature of-63.5 ℃, does not contain dimethyl nitrosamine, and is environment-friendly rubber.
Example 6
The difference from example 1 is that: the electrolyte comprises the following components in parts by weight: 0.25 part of phosphoric acid, 0.4 part of potassium hydroxide, 0.03 part of ethylenediaminetetraacetic acid tetrasodium salt and 0.15 part of sodium dodecyl benzene sulfonate.
The methyl styrene-butadiene rubber is detected by adopting a nuclear magnetic resonance hydrogen spectrum method and a differential thermal analysis method. The detection shows that the methyl styrene-butadiene rubber has 7.93 percent of alpha-methyl styrene content, 92.17 percent of butadiene content, a glass transition temperature of-71.1 ℃, does not contain dimethyl nitrosamine and is environment-friendly rubber.
Example 7
The difference from example 1 is that: the reducing agent comprises, by weight, 0.02 part of ferrous sulfate, 0.04 part of sodium formaldehyde sulfoxylate and 0.04 part of tetrasodium ethylenediaminetetraacetate.
The methyl styrene butadiene rubber is detected by a nuclear magnetic resonance hydrogen spectrum method and a differential thermal analysis method. Through detection, the methyl styrene-butadiene rubber has the molecular structure that the content of alpha-methyl styrene is 8.02 percent, the content of butadiene is 97.98 percent, the glass transition temperature is-70.6 ℃, and the methyl styrene-butadiene rubber does not contain dimethyl nitrosamine and is environment-friendly rubber.
Example 8
The difference from example 1 is that: the stirring temperature is 45 deg.C, and the stirring time is 20min.
The methyl styrene butadiene rubber is detected by a nuclear magnetic resonance hydrogen spectrum method and a differential thermal analysis method. The detection shows that the methyl styrene-butadiene rubber has the molecular structure that the content of alpha-methyl styrene is 7.88 percent, the content of butadiene is 92.12 percent, the glass transition temperature is-72.5 ℃, and the methyl styrene-butadiene rubber does not contain dimethyl nitrosamine and is environment-friendly rubber.
The properties of examples 1 to 8 and a control (styrene-butadiene rubber, manufactured by Jilin petrochemicals, model SBR 1500E) were tested according to the following test method, which is described in GB/T8656-1998:
the test results are shown in Table 1.
TABLE 1
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the methyl styrene-butadiene rubber is prepared by taking alpha-methyl styrene and butadiene as main raw materials through emulsion polymerization, the glass transition temperature of the methyl styrene-butadiene rubber is below-70 ℃, the content of the combined alpha-methyl styrene is 8-15 percent, and the Mooney viscosity is highDegree (ML)1+4 100℃) 35-45 and has higher tensile strength. The prepared product has no nitrosamine parent body, and can not generate nitrosamine, so that the product has good environmental protection and conforms to the EU related regulation TRGS552. In conclusion, the methyl styrene-butadiene rubber prepared by the preparation method has the advantages of low glass transition temperature, high tensile strength, excellent environmental protection property, excellent processability and the like.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (16)
1. A preparation method of methyl styrene-butadiene rubber is characterized by comprising the following steps:
under the vacuum and nitrogen replacement condition, carrying out emulsion polymerization reaction by taking alpha-methylstyrene, butadiene, water, an emulsifier, an electrolyte, a reducing agent, a molecular weight regulator, an initiator and a terminator as raw materials to obtain an emulsion polymerization product, wherein the raw materials comprise, by weight, 15-25 parts of the alpha-methylstyrene, 75-85 parts of the butadiene, 3.5-5.0 parts of the emulsifier, 0.63-1.03 parts of the electrolyte, 0.02-0.1 part of the initiator, 0.065-0.085 part of the reducing agent, 0.2-0.30 part of the molecular weight regulator, 180-200 parts of the water and 0.35-0.5 part of the terminator;
and when the conversion rate of the emulsion polymerization reaction system is 60-65%, sequentially adding a terminator and a demulsifier into the emulsion polymerization reaction system to obtain the methyl styrene-butadiene rubber.
2. The method according to claim 1, wherein the raw material comprises, by weight, 18 to 22 parts of the α -methylstyrene, 77 to 80 parts of the butadiene, 4 to 4.5 parts of the emulsifier, 0.8 to 0.9 part of the electrolyte, 0.02 to 0.05 part of the initiator, 0.07 to 0.075 part of the reducing agent, 0.23 to 0.28 part of the molecular weight modifier, 185 to 195 parts of water, and 0.38 to 0.48 part of the terminating agent.
3. The production method according to claim 1 or 2, wherein the electrolyte is at least two selected from the group consisting of phosphoric acid, potassium hydroxide, tetrasodium ethylenediaminetetraacetate, and sodium dodecylbenzenesulfonate.
4. The production method according to claim 3, wherein the electrolyte comprises, in parts by weight: 0.2 to 0.3 portion of phosphoric acid, 0.3 to 0.5 portion of potassium hydroxide, 0.01 to 0.03 portion of ethylene diamine tetraacetic acid tetrasodium salt and 0.1 to 0.2 portion of sodium dodecyl benzene sulfonate.
5. The production method according to claim 1 or 2, wherein the reducing agent is one or more selected from the group consisting of ferrous sulfate, sodium formaldehyde sulfoxylate, and tetrasodium ethylenediaminetetraacetate.
6. The method according to claim 5, wherein the reducing agent comprises 0.01 to 0.03 parts by weight of the ferrous sulfate, 0.03 to 0.05 parts by weight of the sodium formaldehyde sulfoxylate, and 0.03 to 0.05 parts by weight of the tetrasodium ethylenediaminetetraacetate.
7. A production method according to claim 1 or 2, characterized in that the terminating agent is selected from N-isopropylhydroxylamine and/or di-N-propylthiourea.
8. The method according to claim 7, wherein the terminator comprises 0.05 to 0.1 part by weight of the N-isopropylhydroxylamine and 0.3 to 0.4 part by weight of the di-N-propylthiourea.
9. The method according to claim 1 or 2, wherein the molecular weight regulator is selected from the group consisting of tertiary dodecyl mercaptan and n-dodecyl mercaptan.
10. The method of claim 9, wherein the initiator is selected from one or more of the group consisting of p-menthane hydroperoxide, p-pinane hydroperoxide, and diisopropylbenzene hydroperoxide.
11. The method of claim 9, wherein the emulsifier is selected from a disproportionated potassium rosinate soap and/or a sodium fatty acid soap.
12. The method according to claim 1, wherein the emulsion polymerization is carried out at a reaction temperature of 4 to 6 ℃ for 5 to 10min in parts by weight.
13. The method of claim 1, wherein the emulsion polymerization reaction comprises: and (2) placing the alpha-methylstyrene, the butadiene, the water, the emulsifier, the electrolyte, the reducing agent, the molecular weight regulator and the like into a polymerization kettle, and adding the initiator into the polymerization kettle to carry out the polymerization reaction when the temperature of the polymerization kettle is reduced to 4-6 ℃.
14. The preparation method according to claim 1, further comprising adding the product system of the emulsion polymerization reaction into a dilute sulfuric acid solution with a concentration of 0.3-0.8 wt%, stirring, coagulating, washing, and drying to obtain the methyl styrene-butadiene rubber.
15. The preparation method according to claim 14, wherein the temperature during the stirring process is controlled to be 55-65 ℃ and the stirring time is 5-10 min.
16. A methyl styrene-butadiene rubber, characterized in that the methyl styrene-butadiene rubber is prepared by the preparation method of any one of claims 1 to 15.
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