CN111518324B - Environment-friendly oil-extended styrene-butadiene rubber and preparation method thereof - Google Patents

Environment-friendly oil-extended styrene-butadiene rubber and preparation method thereof Download PDF

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CN111518324B
CN111518324B CN201910108640.7A CN201910108640A CN111518324B CN 111518324 B CN111518324 B CN 111518324B CN 201910108640 A CN201910108640 A CN 201910108640A CN 111518324 B CN111518324 B CN 111518324B
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styrene
butadiene rubber
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oil
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CN111518324A (en
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殷兰
庞建勋
侯军
孙继德
郭睿达
石捷强
王秀芝
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Petrochina Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06Copolymers with styrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/22Emulsion polymerisation
    • C08F2/24Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26Emulsion polymerisation with the aid of emulsifying agents anionic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/38Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06Butadiene

Abstract

The invention provides an environment-friendly oil-extended styrene-butadiene rubber and a preparation method thereof. The preparation method comprises the step of blending styrene butadiene rubber and filling oil, wherein the filling oil comprises the following components: c 20 ~C 30 Aromatic hydrocarbon or naphthenic hydrocarbon, water and a first emulsifier, wherein the weight ratio of the styrene butadiene rubber to the filling oil is (35.5-41.5) 100. In comparison with aliphatic hydrocarbons, C 20 ~C 30 Aromatic hydrocarbons and C 20 ~C 30 The cycloparaffin has better intermiscibility with the styrene butadiene rubber, so that the prepared styrene butadiene rubber product has good processability. In the preparation method, the filling oil with specific composition does not contain carcinogenic aromatic hydrocarbon and polycyclic aromatic hydrocarbon or contains less polycyclic aromatic hydrocarbon, which is beneficial to improving the environmental protection performance of the environment-friendly oil-extended styrene-butadiene rubber.

Description

Environment-friendly oil-extended styrene-butadiene rubber and preparation method thereof
Technical Field
The invention relates to the field of rubber, and particularly relates to environment-friendly oil-extended styrene-butadiene rubber and a preparation method thereof.
Background
The emulsion polymerized styrene butadiene rubber is a high synthetic rubber variety with highest global yield and largest consumption, and is mainly applied to the fields of automobile tires, industrial conveying belts, rubber tubes and the like. The emulsion polymerized styrene-butadiene rubber can be classified into non-oil-extended series products and oil-extended series products according to whether the emulsion polymerized styrene-butadiene rubber is filled with oil or not, and the oil-extended styrene-butadiene rubber is generally filled with 15-50 parts of filling oil in each 100 parts of polymers according to the product brands. According to the structural classification of the polymer, emulsion polymerized styrene-butadiene rubber can be divided into high-structure type products with the styrene content of 23.5 percent and series products with higher bound styrene (31 percent, 35 percent and 40 percent).
The environment-friendly oil-extended rubber is styrene-butadiene rubber which does not generate nitrosamine, is not filled with carcinogens such as polycyclic aromatic hydrocarbon and the like in the production, processing and use processes, has no pollution to the environment and is harmless to human bodies. Compared with non-oil-extended rubber, the oil-extended styrene-butadiene rubber has the characteristics of good processability, low heat generation, long low-temperature deflection service life and the like, and is widely applied to bias tires, radial tires of cars, radial tires of light trucks and other rubber products.
The prior document provides a production method of novel environment-friendly oil-extended styrene-butadiene rubber, and provides a production method of novel oil-extended styrene-butadiene rubber, ESBR1753 styrene-butadiene rubber produced by the method is an environment-friendly product, each environmental protection index of the ESBR1753 styrene-butadiene rubber meets the technical requirement of European Union, and the ESBR1723 styrene-butadiene rubber has better cost performance and market competitiveness than ESBR 1723. Meanwhile, the Nytex4700 oil is adopted, so that the wet skid resistance is better than that of the Nytex4700 oil.
The prior literature provides a novel tasteless molecular weight regulator to replace mercaptan, so that the odor of the mercaptan can be avoided, and the same effect as that of tert-dodecyl mercaptan can be achieved after reaction, which has important significance for realizing green, environment-friendly and clean production.
Disclosure of Invention
The invention mainly aims to provide environment-friendly oil-extended styrene-butadiene rubber and a preparation method thereof, and aims to solve the problem of poor wet skid resistance of the conventional styrene-butadiene rubber.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing an environment-friendly oil-extended styrene-butadiene rubber, the method comprising the step of blending a styrene-butadiene rubber with an extender oil, wherein the extender oil comprises: c 20 ~C 30 The weight ratio of the styrene butadiene rubber to the filling oil is (35.5-41.5).
Further, the extender oil comprises, in parts by weight: 20-30 parts of C 20 ~C 30 Aromatic hydrocarbon or naphthenic hydrocarbon, 8-15 parts of water and 2-5 parts of emulsifier。
Further, the preparation method also comprises the following steps: under the vacuum and nitrogen replacement conditions, carrying out emulsion polymerization reaction by taking styrene, butadiene, a second emulsifier, an electrolyte, an initiator, a reducing agent, a molecular weight regulator and water as raw materials to obtain an emulsion polymerization product; and when the conversion rate of the emulsion polymerization reaction system is 60-65%, adding a terminator into the emulsion polymerization reaction system to obtain styrene butadiene rubber, and adding styrene by an incremental method.
Further, the first emulsifier and the second emulsifier are each independently selected from the group consisting of disproportionated potassium rosinate soap and sodium fatty acid soap.
Further, the raw materials comprise, by weight: 45-55 parts of styrene, 45-55 parts of butadiene, 4.0-5.5 parts of a second emulsifier, 0.63-1.03 parts of electrolyte, 0.06-0.12 part of initiator, 0.055-0.095 part of reducing agent, 0.07-0.15 part of molecular weight regulator, 180-200 parts of water and 0.01-0.30 part of terminator.
Further, the electrolyte is selected from at least two of phosphoric acid, potassium hydroxide, tetrasodium ethylenediaminetetraacetate, and sodium m-methine dinaphthalenesulfonate.
Further, the electrolyte comprises the following components in parts by weight: 0.2 to 0.3 part of phosphoric acid, 0.3 to 0.5 part of potassium hydroxide, 0.01 to 0.03 part of tetrasodium ethylenediamine tetraacetate, and 0.1 to 0.2 part of sodium m-methine dinaphthalene sulfonate.
Further, the reducing agent comprises, by weight, 0.005-0.02 part of ferrous sulfate, 0.03-0.05 part of sodium formaldehyde sulfoxylate and 0.01-0.1 part of tetrasodium ethylenediaminetetraacetate; preferably, the reducing agent comprises 0.01-0.015 part of ferrous sulfate, 0.03-0.05 part of sodium formaldehyde sulfoxylate and 0.025-0.05 part of tetrasodium ethylenediamine tetraacetate in parts by weight.
Further, the terminating agent is selected from isopropyl hydroxylamine sulfate and/or N-tertiary butyl-2-benzothiazole sulfonamide; preferably, the terminating agent is selected from 0.01-0.08 parts of isopropylhydroxylamine sulfate and 0.03-0.4 parts of N-tert-butyl-2-benzothiazole sulfonamide.
Further, the reaction temperature of the emulsion polymerization reaction is 5-8 ℃, and the reaction time is 8-13 h.
The application also provides environment-friendly oil-extended styrene-butadiene rubber which is prepared by adopting the preparation method.
By applying the technical scheme of the invention, compared with aliphatic hydrocarbon, C 20 ~C 30 Aromatic hydrocarbons and C 20 ~C 30 The cycloparaffin has better intermiscibility with the styrene butadiene rubber, so that the prepared styrene butadiene rubber product has good processability. In the preparation method, the filling oil with specific composition does not contain carcinogenic aromatic hydrocarbon and polycyclic aromatic hydrocarbon or contains less polycyclic aromatic hydrocarbon, which is beneficial to improving the environmental protection performance of the environment-friendly oil-extended styrene-butadiene rubber.
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 art, the conventional styrene-butadiene rubber has a problem of poor wet skid resistance. In order to solve the technical problems, the application provides a preparation method of environment-friendly oil-extended styrene-butadiene rubber, which comprises the step of blending styrene-butadiene rubber and extended oil, wherein the extended oil comprises the following components: c 20 ~C 30 Aromatic hydrocarbon or naphthenic hydrocarbon, water and a first emulsifier, wherein the weight ratio of the styrene butadiene rubber is (35.5-41.5) 100.
In comparison with aliphatic hydrocarbons, C 20 ~C 30 Aromatic hydrocarbons and C 20 ~C 30 The cycloparaffin has better intermiscibility with the styrene butadiene rubber, so that the prepared styrene butadiene rubber product has good processability. In the preparation method, the used filling oil with specific composition does not contain carcinogenic aromatic hydrocarbon and polycyclic aromatic hydrocarbon or contains less polycyclic aromatic hydrocarbon, which is beneficial to improving the environmental protection performance of the environment-friendly oil-extended styrene-butadiene rubber.
In the synthesis of styrene butadiene rubber, in a preferred embodiment, the extender oil comprises, by weight: 20-30 parts of C 20 ~C 30 The aromatic hydrocarbon or the cyclane, 8-15 parts of water and 2-5 parts of an emulsifier. The amount of extender oil includes, but is not limited to, the above ranges and willThe limitation of the content of the modified styrene-butadiene rubber in the range is beneficial to further improving the comprehensive performance of the environment-friendly oil-extended styrene-butadiene rubber.
In a preferred embodiment, the above preparation method further comprises: under the vacuum and nitrogen replacement condition, taking styrene, butadiene, a second emulsifier, electrolyte, an initiator, a reducing agent, a molecular weight regulator and water as raw materials to carry out emulsion polymerization reaction to obtain an emulsion polymerization product, and adding styrene by adopting an incremental method; and when the conversion rate of the emulsion polymerization reaction system is 60-65%, adding a terminating agent into the emulsion polymerization reaction system to obtain the styrene butadiene rubber. When the styrene butadiene rubber is prepared by the method, carcinogens cannot be generated, so that the method is more green and environment-friendly. Meanwhile, the addition of the styrene by the incremental method is beneficial to reducing the residual amount of the styrene in a product system, and is further beneficial to improving the wet skid resistance and the stress at definite elongation of the environment-friendly oil-extended styrene-butadiene rubber. The "incremental method" is to use a batch addition method.
The above preparation method preferably employs an emulsion polymerization method, and in a preferred embodiment, the first emulsifier and the second emulsifier are each independently selected from disproportionated potassium rosinate soap and/or sodium fatty acid soap. The emulsifier is used as the first emulsifier to improve the intermiscibility of the styrene butadiene rubber and the filling oil, and the emulsifier is used as the second emulsifier to improve the stability of the emulsion environment in the emulsion polymerization process, so that the yield of the environment-friendly oil-extended styrene butadiene rubber is improved.
In order to further improve the wet skid resistance, environmental protection and other comprehensive properties of the styrene butadiene rubber, the styrene butadiene rubber preferably comprises the following raw materials in parts by weight: 45-55 parts of styrene, 45-55 parts of butadiene, 4.0-5.5 parts of a second emulsifier, 0.63-1.03 parts of an electrolyte, 0.06-0.12 part of an initiator, 0.055-0.095 part of a reducing agent, 0.07-0.15 part of a molecular weight regulator, 180-200 parts of water and 0.01-0.40 part of a terminator.
In a preferred embodiment, the electrolyte includes, but is not limited to, at least two of phosphoric acid, potassium hydroxide, tetrasodium ethylenediaminetetraacetate, and sodium m-methine dinaphthalenesulfonate. 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 part of phosphoric acid, 0.3 to 0.5 part of potassium hydroxide, 0.01 to 0.03 part of tetrasodium ethylenediamine tetraacetate, and 0.1 to 0.2 part of sodium m-methine dinaphthalene sulfonate.
In the above preparation method, the reducing agent may be selected from those commonly used in the art. In a preferred embodiment, the reducing agent comprises 0.005-0.02 part by weight of ferrous sulfate, 0.03-0.05 part by weight of sodium formaldehyde sulfoxylate and 0.01-0.1 part by weight of tetrasodium ethylenediaminetetraacetate. The amount of each component in the reducing agent includes, but is not limited to, the above range, and the limitation of the amount to the above range is beneficial to improving the oxidation resistance of the environment-friendly oil-extended styrene-butadiene rubber. In order to further improve the oxidation resistance of the environment-friendly oil-extended styrene-butadiene rubber, more preferably, the reducing agent comprises, by weight, 0.01-0.015 parts of ferrous sulfate, 0.03-0.05 parts of sodium formaldehyde sulfoxylate and 0.025-0.05 parts of tetrasodium ethylene diamine tetraacetate.
In the above-mentioned preparation 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, isopropylhydroxylamine sulfate and/or N-tert-butyl-2-benzothiazolesulfenamide. 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, but is not limited to, 0.01 to 0.08 parts of isopropylhydroxylamine sulfate and 0.03 to 0.4 parts of N-tert-butyl-2-benzothiazolesulfenamide.
In the above preparation method, the initiator and the molecular weight regulator may be selected from those commonly used in the art. In a preferred embodiment, the initiator includes, but is not limited to, one or more of the group consisting of p-menthane hydroperoxide, pinane hydroperoxide, and diisopropylbenzene hydroperoxide; molecular weight regulators include, but are not limited to, tertiary dodecyl mercaptan.
The emulsion polymerization reaction may be carried out at a reaction temperature and a reaction time which are conventional in the art. In a preferred embodiment, the temperature of the emulsion polymerization reaction is 5 to 8 ℃ and the reaction time is 8 to 13 hours. The reaction temperature and reaction time of the emulsion polymerization include, but are not limited to, the above ranges, and it is advantageous to further increase the yield of styrene-butadiene rubber to limit the reaction temperature and reaction time to the above ranges.
The application also provides environment-friendly oil-extended styrene-butadiene rubber which is prepared by adopting the preparation method.
In comparison with aliphatic hydrocarbons, C 20 ~C 30 Aromatic hydrocarbons and C 20 ~C 30 The cycloparaffin has better intermiscibility with the styrene butadiene rubber, so the prepared styrene butadiene rubber product has good processing performance. In the preparation method, the filling oil with specific composition is adopted, and the filling oil does not contain carcinogenic aromatic hydrocarbon and condensed ring aromatic hydrocarbon or has less content of condensed ring aromatic hydrocarbon, so that the environmental-friendly performance of the environment-friendly oil-extended styrene-butadiene rubber is improved. In conclusion, the styrene butadiene rubber prepared by the preparation method has higher wet skid resistance, environmental protection performance and higher stress at definite elongation.
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 invention as claimed.
Example 1
A preparation method of environment-friendly oil-extended styrene-butadiene rubber comprises the following steps:
(1) first, the polymerization vessel was evacuated and purged with nitrogen. Adding soft water, an emulsifier, an electrolyte solution, a reducing agent, tert-dodecyl mercaptan, styrene and butadiene into a polymerization kettle in sequence, adding an initiator, namely p-menthane hydroperoxide when the temperature of the polymerization kettle is reduced to 5 ℃, carrying out a polymerization experiment, supplementing styrene by adopting an increment method when the polymerization reaction is carried out for 2 hours, adding an environment-friendly terminator when the conversion rate reaches 60 percent, terminating the reaction, and obtaining high-mooney and high-condensation phenyl base latex, wherein the styrene is added by adopting the increment method in the reaction process.
The emulsion polymerization reaction in the step (1) adopts the following raw materials in parts by weight: 48 parts of styrene, 52 parts of butadiene, 4.5 parts of emulsifier disproportionated potassium rosinate soap, 0.63 part of electrolyte, 0.065 part of hydrogen peroxide p-menthane (initiator), 0.065 part of reducing agent, 0.10 part of tert-dodecyl mercaptan (molecular weight regulator), 190 parts of water and 0.24 part of environment-friendly terminator; wherein
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 tetrasodium ethylenediamine tetraacetate and 0.1 part of sodium m-methine dinaphthalene 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 tetrasodium ethylene diamine tetraacetate;
the environment-friendly terminator comprises the following components in parts by weight: 0.04 part of isopropylhydroxylamine sulfate and 0.2 part of N-tert-butyl-2-benzothiazolesulfenamide.
(2) Uniformly mixing the base latex and the filling oil emulsion according to the weight ratio of 100:37.5, adding the mixture into a dilute sulfuric acid solution with the concentration of 0.5%, stirring, controlling the temperature at 60-65 ℃, condensing, washing and drying to obtain a crude rubber finished product, wherein the filling oil emulsion comprises the following components in parts by weight: 23.5 parts of aromatic oil (TDAE Hansheng, Thailand), 11.0 parts of water, 2.8 parts of disproportionated potassium rosinate soap and 1.5 parts of fatty acid sodium soap.
Example 2
A preparation method of environment-friendly oil-extended styrene-butadiene rubber comprises the following steps:
(1) first, the polymerization vessel was evacuated and purged with nitrogen. Adding soft water, an emulsifier, an electrolyte solution, a reducing agent, tert-dodecyl mercaptan, styrene and butadiene into a polymerization kettle in sequence, adding an initiator, namely p-menthane hydroperoxide when the temperature of the polymerization kettle is reduced to 5 ℃, carrying out a polymerization experiment, supplementing the styrene by adopting an incremental method when the polymerization reaction is carried out for 2 hours, adding an environment-friendly terminator when the conversion rate reaches 60%, preparing base latex, and adding the styrene by adopting the incremental method in the reaction process.
The emulsion polymerization reaction in the step (1) adopts the following raw materials in parts by weight: 48 parts of styrene, 52 parts of butadiene, 4.5 parts of emulsifier disproportionated potassium rosinate soap, 0.63 part of electrolyte, 0.065 part of p-menthane hydroperoxide, 0.065 part of reducing agent, 0.10 part of tert-dodecyl mercaptan, 190 parts of water and 0.24 part of environment-friendly terminator;
wherein 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 tetrasodium ethylene diamine tetraacetate and 0.1 part of sodium m-methine dinaphthalene 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 tetrasodium ethylene diamine tetraacetate;
the environment-friendly terminator comprises the following components in parts by weight: 0.04 part of isopropylhydroxylamine sulfate and 0.2 part of N-tert-butyl-2-benzothiazole sulfonamide.
(2) Uniformly mixing the base latex and the filling oil emulsion in a weight ratio of 100:37.5, adding the mixture into a 0.5% dilute sulfuric acid solution, stirring, controlling the temperature at 60-65 ℃, coagulating, washing and drying to obtain a crude rubber finished product, wherein the filling oil emulsion comprises the following components in parts by weight: 23.5 parts of environment-friendly naphthenic oil, 11.0 parts of water, 2.8 parts of disproportionated potassium rosinate soap and 1.5 parts of fatty acid sodium soap. 23.5 parts of cycloalkane, 11.0 parts of water, 2.8 parts of disproportionated potassium rosinate soap and 1.5 parts of fatty acid sodium soap.
Example 3
The differences from example 1 are: the extender oil comprises: 10 parts of aromatic oil (TDAE Hansheng, Thailand) water and 1 part of emulsifier.
Example 4
The differences from example 1 are: in the process of synthesizing styrene butadiene rubber, the adopted raw materials comprise 40 parts of styrene, 60 parts of butadiene, 3.5 parts of emulsifier, 0.4 part of electrolyte, 0.2 part of initiator, 0.1 part of reducing agent, 0.02 part of molecular weight regulator, 150 parts of water and 0.1 part of terminator.
Example 5
The differences from example 1 are: the electrolyte comprises: 0.1 part of phosphoric acid, 0.6 part of potassium hydroxide, 0.08 part of tetrasodium ethylenediamine tetraacetate and 0.05 part of sodium m-methine dinaphthalene sulfonate.
Example 6
The differences from example 1 are: the reducing agent comprises 0.005 part of ferrous sulfate, 0.05 part of sodium formaldehyde sulfoxylate and 0.1 part of tetrasodium ethylene diamine tetraacetate.
Example 7
The differences from example 1 are: the terminator is sulfuric acid isopropyl hydroxylamine.
Example 8
The differences from example 1 are: styrene was added at the beginning of the reaction with the other raw materials without addition by an incremental method.
Example 9
The differences from example 1 are: the terminating agent was 0.04 parts N-isopropylhydroxylamine and 0.02 parts tetraethylenepentamine.
Comparative example 1
The differences from example 1 are: the weight ratio of the styrene butadiene rubber to the filling oil is 100: 20.
The performances of the styrene-butadiene rubbers prepared in examples 1 to 9 and comparative example 1 were tested according to GBT8655-2006, and the test results are shown in Table 1.
TABLE 1
Figure BDA0001967269680000061
Figure BDA0001967269680000071
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
it can be seen from comparison of examples 1 to 2 and 8 and comparative example 1 that limiting the weight ratio of styrene-butadiene rubber and extender oil within the scope of the present application is advantageous for improving the overall performance of the environmentally friendly oil-extended styrene-butadiene rubber.
Comparing examples 1 and 3, it can be seen that limiting the composition of the extender oil to the preferred range of the present application is advantageous to improve the overall performance of the environmentally friendly oil-extended styrene-butadiene rubber.
Comparing examples 1 and 4, it can be seen that limiting the amount of each component in the raw materials to the preferred range in the present application is beneficial to improving the comprehensive performance of the environment-friendly oil-extended styrene-butadiene rubber in the process of synthesizing styrene-butadiene rubber.
Comparing examples 1 and 5, it can be seen that limiting the amount of each component in the electrolyte to the preferred range of the present application is advantageous to improve the overall performance of the environmentally friendly oil-extended styrene-butadiene rubber.
Comparing examples 1 and 6, it can be seen that limiting the amount of each component in the reducing agent to the preferred range of the present application is advantageous for improving the overall performance of the environmentally friendly oil-extended styrene-butadiene rubber.
As can be seen from comparison of examples 1, 7 and 9, it is advantageous to limit the kinds and amounts of the respective components in the terminator within the preferable ranges of the present application to improve the overall properties of the environmentally friendly oil-extended styrene-butadiene rubber.
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 (12)

1. The preparation method of the environment-friendly oil-extended styrene-butadiene rubber is characterized by comprising the step of blending the styrene-butadiene rubber and filling oil, wherein the filling oil comprises the following components in parts by weight: 20-30 parts of C 20 ~C 30 8-15 parts of water and 2-5 parts of a first emulsifier, and C 20 ~C 30 The aromatic hydrocarbon is aromatic oil of Thailand TDAE Hansheng, and the weight ratio of the styrene butadiene rubber to the filling oil is (35.5-41.5).
2. The method of manufacturing according to claim 1, further comprising:
under the vacuum and nitrogen replacement condition, taking styrene, butadiene, a second emulsifier, electrolyte, an initiator, a reducing agent, a molecular weight regulator and water as raw materials to carry out emulsion polymerization reaction to obtain an emulsion polymerization product, and adding styrene by adopting an incremental method;
and when the conversion rate of the emulsion polymerization reaction system is 60-65%, adding a terminating agent into the emulsion polymerization reaction system to obtain the styrene butadiene rubber.
3. The production method according to claim 2, wherein the first emulsifier and the second emulsifier are each independently selected from a disproportionated potassium rosinate soap and a fatty acid sodium soap.
4. The preparation method according to claim 3, wherein the raw materials comprise, in parts by weight: 45-55 parts of styrene, 45-55 parts of butadiene, 4.0-5.5 parts of a second emulsifier, 0.63-1.03 parts of electrolyte, 0.06-0.12 part of an initiator, 0.055-0.095 part of a reducing agent, 0.07-0.15 part of a molecular weight regulator, 180-200 parts of water and 0.01-0.30 part of a terminator.
5. The method according to claim 2, wherein the electrolyte is selected from at least two of phosphoric acid, potassium hydroxide, tetrasodium ethylenediaminetetraacetate, and sodium m-methylenedinaphthalenesulfonate.
6. The production method according to claim 5, wherein the electrolyte comprises, in parts by weight: 0.2-0.3 part of phosphoric acid, 0.3-0.5 part of potassium hydroxide, 0.01-0.03 part of tetrasodium ethylene diamine tetraacetate and 0.1-0.2 part of sodium m-methine dinaphthalene sulfonate.
7. The method according to claim 2, wherein the reducing agent comprises 0.005 to 0.02 part by weight of ferrous sulfate, 0.03 to 0.05 part by weight of sodium formaldehyde sulfoxylate, and 0.01 to 0.1 part by weight of tetrasodium ethylenediaminetetraacetate.
8. The method according to claim 7, wherein the reducing agent comprises 0.01 to 0.015 parts by weight of the ferrous sulfate, 0.03 to 0.05 parts by weight of the sodium formaldehyde sulfoxylate, and 0.025 to 0.05 parts by weight of the tetrasodium ethylenediaminetetraacetate.
9. The method according to claim 2, wherein the terminator is selected from isopropylhydroxylamine sulfate and/or N-tert-butyl-2-benzothiazolesulfenamide.
10. The method according to claim 9, wherein the terminator is selected from the group consisting of 0.01 to 0.08 parts of the isopropylhydroxylamine sulfate and 0.03 to 0.4 parts of the N-tert-butyl-2-benzothiazylsulfenamide.
11. The preparation method according to claim 2, wherein the reaction temperature of the emulsion polymerization reaction is 5-8 ℃ and the reaction time is 8-13 h.
12. An environment-friendly oil-extended styrene-butadiene rubber, which is characterized by being prepared by the preparation method of any one of claims 1 to 11.
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