CN115521406A - Rubber composition containing graft modified natural rubber and preparation method thereof - Google Patents
Rubber composition containing graft modified natural rubber and preparation method thereof Download PDFInfo
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- CN115521406A CN115521406A CN202111299095.8A CN202111299095A CN115521406A CN 115521406 A CN115521406 A CN 115521406A CN 202111299095 A CN202111299095 A CN 202111299095A CN 115521406 A CN115521406 A CN 115521406A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F253/00—Macromolecular compounds obtained by polymerising monomers on to natural rubbers or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention relates to the technical field of C08F279/00, in particular to a rubber composition containing graft modified natural rubber and a preparation method thereof. A rubber composition containing graft-modified natural rubber is prepared by the following raw materials: modifier, natural rubber latex, emulsifier, persulfate, reinforcing agent and carboxyl compound. The rubber composition containing the graft modified natural rubber prepared by the invention has excellent ozone aging resistance and heat aging resistance, and the service life of the product in application is prolonged. The rubber composition containing the graft-modified natural rubber prepared by the present invention can be applied to a pneumatic tire sidewall, a tread, an apex and a support rubber.
Description
Technical Field
The invention relates to the technical field of C08F279/00, in particular to a rubber composition containing graft modified natural rubber and a preparation method thereof.
Background
The Chinese patent with the patent application number of CN201911102780.X discloses a graft modified natural rubber, a preparation method thereof, a rubber composition containing the graft modified natural rubber and application thereof, and discloses the problem of improving the stability of the grafting rate of the natural rubber by graft modification of the natural rubber by using an acrylate monomer, and the technical problems of improving the high temperature resistance and the strength of the natural rubber in the graft modified natural rubber are not disclosed.
Disclosure of Invention
In order to solve the above problems, the present invention provides a rubber composition comprising a graft-modified natural rubber prepared from the raw materials comprising: modifier, natural rubber latex, emulsifier, persulfate, reinforcing agent and carboxyl compound; the solid content of the natural rubber latex is 55-65wt%; the reinforcing agent is selected from graphene or a graphene derivative.
A rubber composition containing graft modified natural rubber is prepared from the following raw materials in parts by weight: 150 parts of natural rubber latex, 0.8-1.2 parts of emulsifier, 0.3-0.8 part of persulfate and 4-6 parts of carboxyl compound.
Preferably, the modifier is added in an amount of 20 to 35wt% of the natural rubber latex.
Preferably, the modifier is added in an amount of 25 to 30wt% based on the solid content of the natural rubber latex.
Preferably, the modifier is an acrylate monomer.
Preferably, the acrylate monomer is a mixture of one or more selected from ethyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, glycidyl methacrylate and butyl methacrylate.
Preferably, the acrylate monomer is hydroxyethyl methacrylate.
Preferably, the emulsifier is a mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate, and the weight is 1 (0.5-2).
Preferably, the emulsifier is a mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate, and the weight ratio is 1.
The applicant unexpectedly finds that, in experiments, when the mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate is used as the emulsifier, and the weight ratio of the emulsifier to the mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate is 1 (0.5-2), particularly the weight ratio of the sodium dodecyl benzene sulfonate to the sodium dodecyl sulfate is 1.2, the natural rubber latex can be fully emulsified and swollen, the contact point of a natural rubber molecular chain and hydroxyethyl methacrylate in the natural rubber latex is improved, the hydroxyethyl methacrylate can be promoted to be fully grafted on the molecular chain in the natural rubber latex, and the heat resistance and the strength performance of the rubber composition containing the graft modified natural rubber are improved.
Preferably, the reinforcing agent is added in an amount of 0.15 to 0.5wt% based on the solid content of the natural rubber latex.
Preferably, the reinforcing agent is a graphene agent derivative.
Preferably, the graphene agent derivative is graphene oxide.
Preferably, the D50 particle size of the graphene oxide is 0.5-3.5um.
Preferably, the D50 particle size of the graphene oxide is 2.5um.
Preferably, the graphene oxide exists in a state of being dispersed in an aqueous solution as a graphene oxide dispersion liquid.
Preferably, the solid content of graphene oxide in the graphene oxide dispersion liquid is 3wt%.
The graphene oxide purchasing manufacturer is SE3521, which is a Nanjing Hexi element material science and technology Co.
Preferably, the initiator is potassium persulfate.
The applicant unexpectedly finds that potassium persulfate is used as an initiator, the graft reaction between a molecular chain and hydroxyethyl methacrylate in natural rubber latex can be better promoted, when the content of potassium sulfate is too high, the hydroxyethyl methacrylate is subjected to self-polymerization more than the graft copolymerization reaction, the heat resistance and the strength performance of the obtained rubber composition containing the graft modified natural rubber are influenced, 0.3-0.8 part of persulfate is added when 150 parts of natural rubber latex is adopted, the hardness and the strength of the natural rubber can be improved, the bonding force among the hydroxyethyl methacrylate, graphene oxide and the molecular chain of the natural rubber is improved, and the ozone resistance, the heat resistance and the strength of the rubber composition containing the graft modified natural rubber are improved in application.
Preferably, the carboxylic compound is acetic acid.
A method for preparing a rubber composition comprising graft-modified natural rubber, comprising the steps of:
s1, adding an emulsifier, an acrylate monomer and a reinforcing agent into natural rubber latex, and stirring to obtain a mixture a;
s2, adding persulfate into the mixture a, stirring for 15-30min, heating, and stirring for 18-22h to obtain a mixture b;
and S3, adding a carboxyl compound into the mixture b for solidification, and placing the solidified mixture into a drying device for drying to obtain the rubber composition containing the graft modified natural rubber.
Preferably, the reinforcing agent is subjected to surface treatment by using a coupling agent, and the modified reinforcing agent subjected to surface treatment is added to the natural rubber latex.
Preferably, the preparation method of the modification reinforcing agent comprises the following steps:
(1) dropwise adding gamma-methacryloxypropyltrimethoxysilane into the graphene oxide dispersion liquid, stirring, heating to 65 ℃, stirring for 20 hours, and taking out;
(2) and washing and filtering the graphene oxide by using deionized water for 8 times, and drying the graphene oxide in a vacuum drying oven at 70 ℃ to obtain the modified graphene oxide.
An application product of a rubber composition containing graft-modified natural rubber includes application to a pneumatic tire sidewall, a tread, an apex, and a support rubber.
Advantageous effects
The rubber composition containing the graft-modified natural rubber prepared by the present invention can be applied to a pneumatic tire sidewall, a tread, an apex and a support rubber.
The rubber composition containing the graft modified natural rubber prepared by the invention has excellent ozone aging resistance and heat aging resistance, and the service life of the product in application is prolonged.
When the rubber composition containing the graft-modified natural rubber is prepared, the mixture of the sodium dodecyl benzene sulfonate and the sodium dodecyl sulfate is used as the emulsifier, so that the hydroxyethyl methacrylate can be promoted to be fully grafted on molecular chains in the natural rubber latex, and the heat resistance and the strength performance of the rubber composition containing the graft-modified natural rubber are improved.
When the rubber composition containing the graft modified natural rubber is prepared, potassium persulfate is matched with hydroxyethyl methacrylate, graphene oxide and natural rubber latex for use, so that the bonding force among the hydroxyethyl methacrylate, the graphene oxide and the natural rubber molecular chain is improved, and the ozone resistance, the heat resistance and the strength of the rubber composition containing the graft modified natural rubber in application are improved.
Detailed Description
Example 1
A rubber composition comprising a graft-modified natural rubber prepared from: hydroxyethyl methacrylate, natural rubber latex, an emulsifier, potassium persulfate, a reinforcing agent and acetic acid; the natural rubber latex has a solid content of 60wt%.
The emulsifier is a mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
The reinforcing agent is modified graphene oxide.
A method for preparing a rubber composition comprising graft-modified natural rubber, comprising the steps of:
s1, adding 1 part of a mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate into 150 parts of natural rubber latex, stirring for 10min, adding 42 parts of hydroxyethyl methacrylate and an enhancer, mixing and stirring for 50min to obtain a mixture a, and standing for 2h;
s2, adding 0.5 part of potassium persulfate into the mixture a, stirring for 30min, heating to 65 ℃, and stirring for 20h to obtain a mixture b;
and S3, adding 5 parts of acetic acid into the mixture b for solidification, and placing the solidified mixture into a drying device at 70 ℃ for drying for 8 hours to obtain the rubber composition containing the graft modified natural rubber.
The weight ratio of the sodium dodecyl benzene sulfonate to the sodium dodecyl sulfate is 1.2.
The preparation method of the modified graphene oxide comprises the following steps:
(1) dropping 2.4 parts of gamma-methacryloxypropyltrimethoxysilane into 9 parts of graphene oxide dispersion liquid, stirring, heating to 65 ℃, stirring for 20 hours, and taking out;
(2) and washing and filtering the graphene oxide by using deionized water for 8 times, and drying the graphene oxide in a vacuum drying oven at 70 ℃ to obtain the modified graphene oxide.
The D50 particle size of the graphene oxide is 2.5um.
The existing state of the graphene oxide is a graphene oxide dispersion liquid dispersed in an aqueous solution.
The solid content of graphene oxide in the graphene oxide dispersion liquid is 3wt%.
The graphene oxide purchasing manufacturer is SE3521, which is a Nanjing Hexi element material science and technology Co.
And (3) adding the modified graphene oxide obtained in the step (2) into S1 as a reinforcing agent.
The above raw materials are commercially available.
Use of a rubber composition comprising a graft-modified natural rubber in a sidewall of a pneumatic tire, comprising the steps of:
s1, weighing 40 parts of rubber composition containing graft modified natural rubber, 60 parts of butadiene rubber, 330 parts of carbon black N, 2.6 parts of zinc oxide, 1.8 parts of stearic acid, 2 parts of antioxidant RD and 3.5 parts of antioxidant 4010, adding into an internal mixer, and internally mixing for 25min at 70 ℃;
s1, adding the rubber compound into an open mill, adding 2 parts of sulfur, 0.5 part of an accelerator CZ and 0.5 part of an accelerator NOBS, and uniformly mixing; and vulcanizing after 24 hours to obtain vulcanized natural rubber, wherein the vulcanization temperature is 155 ℃, the vulcanization time is 20min, and the vulcanization pressure is 20MPa.
Example 2
A rubber composition comprising a graft-modified natural rubber is prepared by starting with: hydroxyethyl methacrylate, natural rubber latex, an emulsifier, potassium persulfate, a reinforcing agent and acetic acid; the natural rubber latex has a solid content of 60wt%.
The emulsifier is a mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
The reinforcing agent is modified graphene oxide.
A method for preparing a rubber composition comprising graft-modified natural rubber, comprising the steps of:
s1, adding 0.8 part of a mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate into 150 parts of natural rubber latex, stirring for 10min, adding 37.5 parts of hydroxyethyl methacrylate and a reinforcing agent, mixing and stirring for 50min to obtain a mixture a, and standing for 2h;
s2, adding 0.5 part of potassium persulfate into the mixture a, stirring for 30min, heating to 65 ℃, and stirring for 20h to obtain a mixture b;
s3, adding 5 parts of acetic acid into the mixture b for solidification, and after solidification, placing the mixture in a drying device at 70 ℃ for drying for 8 hours to obtain the rubber composition containing the graft modified natural rubber.
The weight ratio of the sodium dodecyl benzene sulfonate to the sodium dodecyl sulfate is 1.2.
The preparation method of the modified graphene oxide comprises the following steps:
(1) dropping 2.4 parts of gamma-methacryloxypropyltrimethoxysilane into 15 parts of graphene oxide dispersion liquid, stirring, heating to 65 ℃, stirring for 20 hours, and taking out;
(2) and washing and filtering the graphene oxide by using deionized water for 8 times, and placing the graphene oxide into a vacuum drying oven at 70 ℃ for drying to obtain the modified graphene oxide.
The D50 particle size of the graphene oxide is 2.5um.
The existing state of the graphene oxide is a graphene oxide dispersion liquid dispersed in an aqueous solution.
The solid content of graphene oxide in the graphene oxide dispersion liquid is 3wt%.
The graphene oxide purchasing manufacturer is SE3521, which is a Nanjing Hexi element material science and technology Co.
And (3) adding the modified graphene oxide obtained in the step (2) into S1 as a reinforcing agent.
The above raw materials are commercially available.
Use of a rubber composition comprising a graft-modified natural rubber in a sidewall of a pneumatic tire, comprising the steps of:
s1, weighing 40 parts of rubber composition containing graft modified natural rubber, 60 parts of butadiene rubber, 330 parts of carbon black N, 2.6 parts of zinc oxide, 1.8 parts of stearic acid, 2 parts of antioxidant RD and 3.5 parts of antioxidant 4010, adding into an internal mixer, and internally mixing for 25min at 70 ℃;
s1, adding the rubber compound into an open mill, adding 2 parts of sulfur, 0.5 part of an accelerator CZ and 0.5 part of an accelerator NOBS, and uniformly mixing; and vulcanizing after 24 hours to obtain vulcanized natural rubber, wherein the vulcanization temperature is 155 ℃, the vulcanization time is 20min, and the vulcanization pressure is 20MPa.
Example 3
A rubber composition comprising a graft-modified natural rubber prepared from: hydroxyethyl methacrylate, natural rubber latex, an emulsifier, potassium persulfate, a reinforcing agent and acetic acid; the natural rubber latex has a solid content of 60wt%.
The emulsifier is a mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
The reinforcing agent is modified graphene oxide.
A method for preparing a rubber composition comprising graft-modified natural rubber, comprising the steps of:
s1, adding 1.2 parts of a mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate into 150 parts of natural rubber latex, stirring for 10min, adding 45 parts of hydroxyethyl methacrylate and an enhancer, mixing and stirring for 50min to obtain a mixture a, and standing for 2h;
s2, adding 0.5 part of potassium persulfate into the mixture a, stirring for 30min, heating to 65 ℃, and stirring for 20h to obtain a mixture b;
and S3, adding 5 parts of acetic acid into the mixture b for solidification, and placing the solidified mixture into a drying device at 70 ℃ for drying for 8 hours to obtain the rubber composition containing the graft modified natural rubber.
The weight ratio of the sodium dodecyl benzene sulfonate to the sodium dodecyl sulfate is 1.2.
The preparation method of the modified graphene oxide comprises the following steps:
(1) dropping 2.4 parts of gamma-methacryloxypropyltrimethoxysilane into 6 parts of graphene oxide dispersion liquid, stirring, heating to 65 ℃, stirring for 20 hours, and taking out;
(2) and washing and filtering the graphene oxide by using deionized water for 8 times, and drying the graphene oxide in a vacuum drying oven at 70 ℃ to obtain the modified graphene oxide.
The D50 particle size of the graphene oxide is 2.5um.
The existing state of the graphene oxide is a graphene oxide dispersion liquid dispersed in an aqueous solution.
The solid content of graphene oxide in the graphene oxide dispersion liquid is 3wt%.
The graphene oxide purchasing manufacturer is SE3521, which is a Nanjing Hexi element material science and technology Co.
And (3) adding the modified graphene oxide obtained in the step (2) into S1 as a reinforcing agent.
The above raw materials are commercially available.
Use of a rubber composition comprising a graft-modified natural rubber in a sidewall of a pneumatic tire, comprising the steps of:
s1, weighing 40 parts of rubber composition containing graft modified natural rubber, 60 parts of butadiene rubber, 330 parts of carbon black N, 2.6 parts of zinc oxide, 1.8 parts of stearic acid, 2 parts of antioxidant RD and 3.5 parts of antioxidant 4010, and adding the mixture into an internal mixer for internal mixing to obtain mixed rubber, wherein the internal mixing temperature is 70 ℃, and the internal mixing is carried out for 25min;
s1, adding the rubber compound into an open mill, adding 2 parts of sulfur, 0.5 part of an accelerator CZ and 0.5 part of an accelerator NOBS, and uniformly mixing; and vulcanizing after 24 hours to obtain vulcanized natural rubber, wherein the vulcanization temperature is 155 ℃, the vulcanization time is 20min, and the vulcanization pressure is 20MPa.
Example 4
A rubber composition comprising a graft-modified natural rubber prepared from: hydroxyethyl methacrylate, natural rubber latex, an emulsifier, potassium persulfate, a reinforcing agent and acetic acid; the natural rubber latex has a solid content of 60wt%.
The emulsifier is a mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
The reinforcing agent is modified graphene oxide.
A method for preparing a rubber composition comprising graft-modified natural rubber, comprising the steps of:
s1, adding 1 part of a mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate into 150 parts of natural rubber latex, stirring for 10min, adding 42 parts of hydroxyethyl methacrylate and a reinforcing agent, mixing and stirring for 50min to obtain a mixture a, and standing for 2h;
s2, adding 1.5 parts of potassium persulfate into the mixture a, stirring for 30min, heating to 65 ℃, and stirring for 20h to obtain a mixture b;
and S3, adding 5 parts of acetic acid into the mixture b for solidification, and placing the solidified mixture into a drying device at 70 ℃ for drying for 8 hours to obtain the rubber composition containing the graft modified natural rubber.
The weight ratio of the sodium dodecyl benzene sulfonate to the sodium dodecyl sulfate is 1.2.
The reinforcing agent is modified graphene oxide, and the preparation method of the modified graphene oxide comprises the following steps:
(1) dropping 2.4 parts of gamma-methacryloxypropyltrimethoxysilane into 9 parts of graphene oxide dispersion liquid, stirring, heating to 65 ℃, stirring for 20 hours, and taking out;
(2) and washing and filtering the graphene oxide by using deionized water for 8 times, and drying the graphene oxide in a vacuum drying oven at 70 ℃ to obtain the modified graphene oxide.
The D50 particle size of the graphene oxide is 2.5um.
The existing state of the graphene oxide is a graphene oxide dispersion liquid dispersed in an aqueous solution.
The solid content of graphene oxide in the graphene oxide dispersion liquid is 3wt%.
The graphene oxide purchasing manufacturer is SE3521, which is a Nanjing Hexi element material science and technology Co.
And (3) adding the modified graphene oxide obtained in the step (2) into S1 as a reinforcing agent.
The above raw materials are commercially available.
Use of a rubber composition comprising a graft-modified natural rubber in a sidewall of a pneumatic tire, comprising the steps of:
s1, weighing 40 parts of rubber composition containing graft modified natural rubber, 60 parts of butadiene rubber, 330 parts of carbon black N, 2.6 parts of zinc oxide, 1.8 parts of stearic acid, 2 parts of antioxidant RD and 3.5 parts of antioxidant 4010, adding into an internal mixer, and internally mixing for 25min at 70 ℃;
s1, adding the rubber compound into an open mill, adding 2 parts of sulfur, 0.5 part of an accelerator CZ and 0.5 part of an accelerator NOBS, and uniformly mixing; and vulcanizing after 24 hours to obtain vulcanized natural rubber, wherein the vulcanization temperature is 155 ℃, the vulcanization time is 20min, and the vulcanization pressure is 20MPa.
Example 5
A rubber composition comprising a graft-modified natural rubber prepared from: hydroxyethyl methacrylate, natural rubber latex, an emulsifier, potassium persulfate, a reinforcing agent and acetic acid; the natural rubber latex has a solid content of 60wt%.
The emulsifier is a mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
The reinforcing agent is modified graphene oxide.
A method for preparing a rubber composition comprising graft-modified natural rubber, comprising the steps of:
s1, adding 1 part of a mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate into 150 parts of natural rubber latex, stirring for 10min, adding 42 parts of hydroxyethyl methacrylate and a reinforcing agent, mixing and stirring for 50min to obtain a mixture a, and standing for 2h;
s2, adding 0.5 part of potassium persulfate into the mixture a, stirring for 30min, heating to 55 ℃, and stirring for 20h to obtain a mixture b;
s3, adding 5 parts of acetic acid into the mixture b for solidification, and after solidification, placing the mixture in a drying device at 70 ℃ for drying for 8 hours to obtain the rubber composition containing the graft modified natural rubber.
The weight ratio of the sodium dodecyl benzene sulfonate to the sodium dodecyl sulfate is 1.2.
The preparation method of the modified graphene oxide comprises the following steps:
(1) dropping 2.4 parts of gamma-methacryloxypropyltrimethoxysilane into 9 parts of graphene oxide dispersion liquid, stirring, heating to 65 ℃, stirring for 20 hours, and taking out;
(2) and washing and filtering the graphene oxide by using deionized water for 8 times, and drying the graphene oxide in a vacuum drying oven at 70 ℃ to obtain the modified graphene oxide.
The D50 particle size of the graphene oxide is 2.5um.
The existing state of the graphene oxide is a graphene oxide dispersion liquid dispersed in an aqueous solution.
The solid content of graphene oxide in the graphene oxide dispersion liquid is 3wt%.
The graphene oxide purchasing manufacturer is SE3521, which is a science and technology corporation of the sixth element material of Nanjing.
And (3) adding the modified graphene oxide obtained in the step (2) into S1 as a reinforcing agent.
The above raw materials are commercially available.
Use of a rubber composition comprising a graft-modified natural rubber in a sidewall of a pneumatic tire, comprising the steps of:
s1, weighing 40 parts of rubber composition containing graft modified natural rubber, 60 parts of butadiene rubber, 330 parts of carbon black N, 2.6 parts of zinc oxide, 1.8 parts of stearic acid, 2 parts of antioxidant RD and 3.5 parts of antioxidant 4010, and adding the mixture into an internal mixer for internal mixing to obtain mixed rubber, wherein the internal mixing temperature is 70 ℃, and the internal mixing is carried out for 25min;
s1, adding the rubber compound into an open mill, adding 2 parts of sulfur, 0.5 part of an accelerator CZ and 0.5 part of an accelerator NOBS, and uniformly mixing; and vulcanizing after 24 hours to obtain vulcanized natural rubber, wherein the vulcanization temperature is 155 ℃, the vulcanization time is 20min, and the vulcanization pressure is 20MPa.
The butadiene rubber purchasing manufacturer is the Dushan petrochemical, and the type is the Br9000 of butadiene rubber.
Performance testing
1. Ozone crazing test
The test method comprises the following steps: when the rubber compositions containing the graft-modified natural rubber prepared in examples 1 to 5 are applied to a pneumatic tire sidewall, an ozone cracking test is performed in accordance with GBT 13462-2015 dynamic tensile test for ozone cracking resistance of vulcanized rubber or thermoplastic rubber, test conditions: the tensile was 10%, the temperature was 40 ℃ and the ozone concentration was 50pphm, and the test results are shown in Table 1.
2 retention of tensile Strength
The test method comprises the following steps: the rubber compositions containing the graft-modified natural rubber prepared in examples 1 to 5 were tested for retention of tensile strength against hot air aging in accordance with GB/T3512-2001 test on hot air accelerated aging and Heat resistance of vulcanized rubber or thermoplastic rubber, and the test results are shown in Table 1.
TABLE 1
Claims (10)
1. A rubber composition comprising a graft-modified natural rubber, characterized in that the raw materials for preparation comprise: modifier, natural rubber latex, emulsifier, persulfate, reinforcing agent and carboxyl compound; the solid content of the natural rubber latex is 55-65wt%; the reinforcing agent is selected from graphene or a graphene derivative.
2. The rubber composition comprising graft-modified natural rubber according to claim 1, wherein the modifier is added in an amount of 20 to 35wt% based on the natural rubber latex.
3. The rubber composition comprising graft-modified natural rubber according to claim 2, wherein the modifier is added in an amount of 25 to 30% by weight based on the natural rubber latex.
4. The rubber composition comprising graft-modified natural rubber according to claim 1, wherein the modifier is an acrylate monomer.
5. The rubber composition comprising graft-modified natural rubber according to claim 4, wherein the acrylate monomer is a mixture of one or more selected from the group consisting of ethyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, glycidyl methacrylate and butyl methacrylate.
6. The rubber composition containing graft-modified natural rubber according to claim 1, wherein the emulsifier is a mixture of sodium dodecylbenzenesulfonate and sodium dodecylsulfate, and the weight is 1 (0.5-2).
7. The rubber composition containing a graft-modified natural rubber according to any one of claims 1 to 6, wherein the reinforcing agent is added in an amount of 0.15 to 0.5% by weight based on the solid content of the natural rubber latex.
8. The rubber composition comprising graft-modified natural rubber according to claim 1, wherein the reinforcing agent is a graphene agent derivative.
9. The rubber composition comprising graft-modified natural rubber according to claim 8, wherein the graphene agent derivative is graphene oxide.
10. A process for producing a rubber composition comprising a graft-modified natural rubber according to any one of claims 1 to 9, comprising the steps of:
s1, adding an emulsifier, an acrylate monomer and a reinforcing agent into natural rubber latex, and stirring to obtain a mixture a;
s2, adding persulfate into the mixture a, stirring for 15-30min, heating, and stirring for 18-22h to obtain a mixture b;
and S3, adding a carboxyl compound into the mixture b for solidification, and placing the solidified mixture into a drying device for drying to obtain the rubber composition containing the graft modified natural rubber.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117511108A (en) * | 2023-11-08 | 2024-02-06 | 中国热带农业科学院南亚热带作物研究所 | Grafting modified low-protein natural latex sponge product and preparation method thereof |
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2021
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117511108A (en) * | 2023-11-08 | 2024-02-06 | 中国热带农业科学院南亚热带作物研究所 | Grafting modified low-protein natural latex sponge product and preparation method thereof |
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