CN115232375A - Syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material and preparation method thereof - Google Patents
Syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of rubber reinforcing materials, and particularly relates to a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is formed by modifying a liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using a coupling agent through peroxide; the peroxide is one or more of benzoyl peroxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate and lauroyl peroxide. The invention provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which not only can ensure that the combination effect of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber is better, break through the mass proportion limitation of the resin in a rubber matrix, solve the problems of high cost and low efficiency of liquid phase blending, but also can effectively improve the mechanical property of the material. The invention also provides a preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material.
Description
Technical Field
The invention belongs to the technical field of rubber reinforcing materials, and particularly relates to a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material and a preparation method thereof.
Background
High modulus syndiotactic 1, 2-polybutadiene resins are widely used in the rubber reinforcement field, and are generally used in the rubber by way of internal mixer kneading or liquid phase blending in the prior art.
1. Because the melting temperature of the syndiotactic 1, 2-polybutadiene resin is 130-210 ℃, when the syndiotactic 1, 2-polybutadiene resin is processed in a conventional internal mixer or open mill, the internal mixing temperature is often required to be adjusted to be more than 130 ℃ so as to ensure that the syndiotactic 1, 2-polybutadiene resin subjected to high-temperature shearing action in a cavity of the internal mixer is uniformly dispersed in rubber. The high-temperature mixing has high energy consumption, and the high-temperature shearing action in the cavity can degrade resin into small molecules through thermal oxidation, so that the reinforcing effect is obviously reduced; in addition, the abundant double bonds on the side chain are easy to oxidize and crosslink at high temperature, so that the structure is damaged, and the significance of the side chain as a reinforcing material is lost.
2. The liquid phase blending mode is that syndiotactic 1, 2-polybutadiene resin and rubber are dissolved in organic solvent at 65-80 deg.c and mixed homogeneously in liquid phase and flocculated to obtain homogeneous blend. The liquid phase preparation method effectively avoids the problem of thermal oxidation aging, but because the viscosity of the resin and the rubber is extremely high when the resin and the rubber are dissolved in an organic solvent, the mass fraction of the resin and the rubber needs to be strictly controlled below 15% of the system, otherwise the glue solution cannot be effectively mixed due to the excessively high viscosity.
Meanwhile, the mass ratio of the resin to the rubber is also limited, and if the ratio of the resin in the mixed material is higher than 20%, the elasticity of the material is lost due to the excessively high content of the crystalline phase in the mixed material; the problems of large stirring torque, low blending efficiency, difficult solvent recovery and the like of the system cause high production cost and low efficiency, and large-scale production is difficult to realize.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, and peroxide is used for modifying a liquid coupling agent of the liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber, so that the effect of combining the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber is better, the mass ratio limitation of the resin in a rubber matrix is broken through, the problems of high cost and low efficiency of liquid-phase blending are solved, the crystallinity of the resin is effectively reduced, and the processing performance and the mechanical property of the material are improved. In addition, the reinforcing material is modified by the coupling agent, and then high temperature is not needed for mixing, so that the problems of thermal degradation and poor processability caused by high-temperature mixing of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber in the prior art are solved, the production cost can be effectively controlled, and the structure of the material can be effectively protected, so that the reinforcing effect of the material is ensured.
The invention also provides a preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which can effectively control the production cost, improve the production efficiency and effectively improve the processing performance and the mechanical property of the material, so that the prepared material has good reinforcing effect.
The technical effect to be achieved by the invention is realized by the following technical scheme:
the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber modified reinforcing material are prepared by modifying the liquid-phase blended syndiotactic 1, 2-polybutadiene resin and the butadiene rubber by using peroxide through a coupling agent;
the peroxide is one or more of benzoyl peroxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate and lauroyl peroxide.
As one of preferable modes, the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is (10-50): (50-90).
As a preferable embodiment thereof, the syndiotactic 1, 2-polybutadiene resin has a weight average molecular weight of 1.6X 10 5 The molecular weight distribution was 2.5.
As a preferable mode, the mass of the peroxide is 1 to 15% of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, respectively preparing syndiotactic 1, 2-polybutadiene resin, butadiene rubber and peroxide with the expected mass into corresponding dispersion liquid by using an organic solvent;
s02, under the protection of inert gas, adding the dispersion liquid into a container, stirring and mixing under a preset temperature condition, and initiating a coupling reaction;
s03, after coupling reaction for a period of time, adding an anti-aging agent, and continuously stirring to prepare a mixed glue solution;
s04, flocculating the mixed glue solution with ethanol;
and S05, after the flocculation is finished, volatilizing the solvent in a fume hood for a period of time, and then putting the solvent into a vacuum oven to dry the solvent to constant weight.
As one of preferable embodiments, in step S01, the syndiotactic 1, 2-polybutadiene resin is formulated into a resin dispersion with an organic solvent in a concentration of 5wt% to 15wt%; the concentration of the rubber dispersion prepared from the butadiene rubber by using the organic solvent is 5 to 15 weight percent; the peroxide is prepared into peroxide dispersion with organic solvent in the concentration of 5-15 wt%.
As a preferable scheme, in step S01, the organic solvent is one or more of a toluene solution, a cyclohexane solution, a cyclohexanone solution, a methanol solution, an ethanol solution, an acetone solution, and a phenol solution.
As one of preferable embodiments, in step S02, the resin dispersion and/or the rubber dispersion are first added to a vessel, and then the remaining dispersion is added dropwise to the vessel.
As a preferable scheme, in the step S02, the preset temperature is 50-75 ℃, and the stirring and mixing speed is 300-450 r/min.
In a preferable scheme, in the step S03, the coupling reaction is carried out for 4-6 h, the anti-aging agent is added, and the stirring is continued for 15-20 min.
In a preferable scheme, in the step S05, after the flocculation is finished, the solvent is volatilized in a fume hood for 10 to 15 hours, and then the solvent is put into a vacuum oven and dried at the temperature of between 40 and 60 ℃ until the weight is constant.
In summary, the invention has at least the following advantages:
1. according to the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, peroxide is used for modifying the coupling agent of the liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber, so that the effect of combining the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber is better, the mass ratio limitation of the resin in a rubber matrix is broken through, the problems of high cost and low efficiency of liquid-phase blending are solved, the crystallinity of the resin can be effectively reduced, and the processing performance and the mechanical property of the material are improved.
2. The syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material does not need to be mixed at high temperature after the coupling agent is modified, solves the problems of thermal degradation and poor processing performance caused by high-temperature mixing of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber in the prior art, not only can effectively control the production cost, but also can effectively protect the structure of the material, thereby ensuring the reinforcing effect of the material.
3. The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material can effectively control the production cost, improve the production efficiency, and effectively improve the processing performance and the mechanical property of the material, so that the prepared material has good reinforcing effect.
Detailed Description
In a first aspect, the present invention provides a syndiotactic 1, 2-polybutadiene treeThe resin and butadiene rubber modified reinforcing material is prepared by modifying liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using peroxide through a coupling agent, preferably, the peroxide is one or more of benzoyl peroxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate and lauroyl peroxide, and can be selected according to actual needs; further, the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is (10-50): (50-90), wherein the mass of the peroxide is 1-15% of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
Homopolymers of 1, 3-butadiene, which have received much attention since their birth, can be subjected to 1,2 addition polymerization and 1,4 addition polymerization by using different types of catalysts and different control of polymerization processes, wherein the 1,4 addition polymerization product has both cis-and trans-isomers, and the 1,2 addition polymerization product has three stereopolymers of syndiotactic, isotactic and atactic. Among them, syndiotactic 1, 2-polybutadiene can effectively adjust vinyl content, syndiotacticity, crystallinity and melting point by adjusting a catalytic system and a polymerization method, so that it can have the characteristics of plastics and rubbers at the same time, and thus, syndiotactic 1, 2-polybutadiene can be used as a thermoplastic elastomer or rubber alone, and can be blended and crosslinked with natural rubber or synthetic rubber. The cis-butadiene rubber is cis-1, 4-polybutadiene rubber, and has the characteristics of high elasticity, good wear resistance, good cold resistance, low heat generation, good bending resistance, good dynamic performance and the like compared with natural rubber and styrene butadiene rubber; the main disadvantages are poor wet-skid resistance, low tear and tensile strength, high cold flow, and poor processability, and therefore must be used in combination with other gums.
According to the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, the syndiotactic 1, 2-polybutadiene resin and butadiene rubber which are blended in a liquid phase are modified by a coupling agent through peroxide, so that the effect of combining the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber is better, the mechanical property of a composite material is enhanced, the mass ratio limit of the resin in a rubber matrix is broken through, the problems of high cost and low efficiency of liquid phase blending are solved, and the crystallinity of the resin can be effectively reduced, so that the processing performance of the material is improved. In addition, when the reinforcing material is applied to rubber, the rubber can be processed by an internal mixer at 60-90 ℃, high temperature is not needed for mixing, the problems of thermal degradation and poor processing performance caused by high-temperature mixing are solved, the production cost can be effectively controlled, and the structure of the material can be effectively protected, so that the reinforcing effect of the material is ensured.
In a second aspect, the present invention also provides a method for preparing the syndiotactic 1, 2-polybutadiene resin and the modified reinforcing material of butadiene rubber, comprising the following steps:
s01, respectively preparing syndiotactic 1, 2-polybutadiene resin, butadiene rubber and peroxide with the expected mass into corresponding dispersion liquid by using an organic solvent;
s02, under the protection of inert gas, adding each dispersion into a container, and stirring and mixing under a preset temperature condition to initiate a coupling reaction;
s03, after coupling reaction for a period of time, adding an anti-aging agent, and continuously stirring to prepare a mixed glue solution;
s04, flocculating the mixed glue solution with ethanol;
and S05, after the flocculation is finished, volatilizing the solvent in a fume hood for a period of time, and then putting the solvent into a vacuum oven to dry the solvent to constant weight.
Further, in step S01, the syndiotactic 1, 2-polybutadiene resin is formulated into a resin dispersion with an organic solvent in a concentration of 5wt% to 15wt%; the concentration of the rubber dispersion prepared from the butadiene rubber by using the organic solvent is 5 to 15 weight percent; the peroxide is prepared into peroxide dispersion with organic solvent, and the concentration of the peroxide dispersion is 5-15 wt%. The organic solvent is one or more of toluene solution, cyclohexane solution, cyclohexanone solution, methanol solution, ethanol solution, acetone solution and phenol solution.
In step S02, the resin dispersion and/or the rubber dispersion is first added to a container, and then the remaining dispersion is added dropwise to the container; that is, the dispersion may be added to the vessel by:
(1) Firstly, adding a mixed solution of a resin dispersion solution and a rubber dispersion solution into a container, and then dropwise adding a peroxide dispersion solution into the container containing the mixed solution;
(2) Firstly, adding the resin dispersion liquid into a container, and then dropwise adding the mixed liquid of the rubber dispersion liquid and the peroxide dispersion liquid into the container containing the resin dispersion liquid;
(3) The rubber dispersion is first added to a container and then the mixed liquid of the resin dispersion and the peroxide dispersion is added dropwise to the container containing the rubber dispersion.
Preferably, in step S02, the preset temperature is 50-75 ℃, and the stirring and mixing speed is 300-450 r/min.
In the step S03, the coupling reaction lasts for 4-6 h, the anti-aging agent is added, and the stirring is continued for 15-20 min; preferably, the anti-aging agent is one or more of anti-aging agent 264, anti-aging agent RD and anti-aging agent 6 PPD. In step S05, after flocculation is completed, the solvent is volatilized in a fume hood for 10h to 15h, and then the solvent is put into a vacuum oven and dried to constant weight at the temperature of 40 ℃ to 60 ℃.
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
Example 1:
the embodiment provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is prepared by modifying a liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using a coupling agent through peroxide; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 50:50, the peroxide is benzoyl peroxideThe mass of the syndiotactic 1, 2-polybutadiene resin is 1 percent of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 52.5g of syndiotactic 1, 2-polybutadiene resin into 15wt% resin dispersion liquid by using a toluene solution, preparing 52.5g of butadiene rubber into 15wt% rubber dispersion liquid by using a toluene solution, and preparing 1.05g of benzoyl peroxide into 5wt% peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, firstly adding the mixed solution of the resin dispersion solution and the rubber dispersion solution into a container, then dropwise adding the peroxide dispersion solution into the container containing the mixed solution, and stirring and mixing at the speed of 300r/min at the temperature of 75 ℃ to initiate a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution with ethanol;
s05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, then putting the fume hood into a vacuum oven, and drying the fume hood at 40 ℃ to constant weight to obtain the modified reinforcing material 1.
Example 2:
the embodiment provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is prepared by modifying a liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using a coupling agent through peroxide; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 10:90, the peroxide is benzoyl peroxide, and the mass of the benzoyl peroxide is 1 percent of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 10.5g of syndiotactic 1, 2-polybutadiene resin into 15wt% resin dispersion liquid by using a toluene solution, preparing 94.5g of butadiene rubber into 15wt% rubber dispersion liquid by using a toluene solution, and preparing 1.05g of benzoyl peroxide into 5wt% peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, adding the mixed solution of the resin dispersion solution and the rubber dispersion solution into a container, then dropwise adding the peroxide dispersion solution into the container containing the mixed solution, stirring and mixing at the speed of 300r/min at the temperature of 75 ℃, and initiating a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution with ethanol;
and S05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, and then putting the solvent in a vacuum oven to dry at 40 ℃ to constant weight to obtain the modified reinforcing material 2.
Example 3:
the embodiment provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is prepared by modifying a liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using a coupling agent through peroxide; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 30; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 31.5g of syndiotactic 1, 2-polybutadiene resin into 15wt% of resin dispersion liquid by using a toluene solution, preparing 73.5g of butadiene rubber into 15wt% of rubber dispersion liquid by using a toluene solution, and preparing 1.05g of benzoyl peroxide into 5wt% of peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, adding the mixed solution of the resin dispersion solution and the rubber dispersion solution into a container, then dropwise adding the peroxide dispersion solution into the container containing the mixed solution, stirring and mixing at the speed of 300r/min at the temperature of 75 ℃, and initiating a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution by using ethanol;
and S05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, and then putting the solvent in a vacuum oven to dry at 40 ℃ to constant weight to obtain the modified reinforcing material 3.
Example 4:
the embodiment provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is formed by modifying liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using peroxide through a coupling agent; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 40; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 42g of syndiotactic 1, 2-polybutadiene resin into 15wt% resin dispersion liquid by using a toluene solution, preparing 63g of cis-butadiene rubber into 15wt% rubber dispersion liquid by using a toluene solution, and preparing 1.05g of benzoyl peroxide into 5wt% peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, firstly adding the mixed solution of the resin dispersion solution and the rubber dispersion solution into a container, then dropwise adding the peroxide dispersion solution into the container containing the mixed solution, and stirring and mixing at the speed of 300r/min at the temperature of 75 ℃ to initiate a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution by using ethanol;
and S05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, and then putting the solvent in a vacuum oven to dry at 40 ℃ to constant weight to obtain the modified reinforcing material 4.
Example 5:
the embodiment provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is prepared by modifying a liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using a coupling agent through peroxide; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 50:50, the peroxide is benzoyl peroxide, and the mass of the benzoyl peroxide is 7.5 percent of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 52.5g of syndiotactic 1, 2-polybutadiene resin into 15wt% of resin dispersion liquid by using a toluene solution, preparing 52.5g of butadiene rubber into 15wt% of rubber dispersion liquid by using a toluene solution, and preparing 7.875g of benzoyl peroxide into 5wt% of peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, adding the mixed solution of the resin dispersion solution and the rubber dispersion solution into a container, then dropwise adding the peroxide dispersion solution into the container containing the mixed solution, stirring and mixing at the speed of 300r/min at the temperature of 75 ℃, and initiating a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution by using ethanol;
and S05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, and then putting the solvent in a vacuum oven to dry at 40 ℃ to constant weight to obtain the modified reinforcing material 5.
Example 6:
this example provides a syndiotactic 1, 2-polybutadiene resin blended with a liquid phase of a peroxide and a butadiene rubber modified reinforcing materialAnd butadiene rubber are modified by a coupling agent; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 50:50, the peroxide is benzoyl peroxide, and the mass of the benzoyl peroxide is 15 percent of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 52.5g of syndiotactic 1, 2-polybutadiene resin into 15wt% resin dispersion liquid by using a toluene solution, preparing 52.5g of butadiene rubber into 15wt% rubber dispersion liquid by using a toluene solution, and preparing 15.75g of benzoyl peroxide into 5wt% peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, adding the mixed solution of the resin dispersion solution and the rubber dispersion solution into a container, then dropwise adding the peroxide dispersion solution into the container containing the mixed solution, stirring and mixing at the speed of 300r/min at the temperature of 75 ℃, and initiating a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution with ethanol;
s05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, then putting the fume hood into a vacuum oven, and drying the fume hood at 40 ℃ to constant weight to obtain the modified reinforcing material 6.
Example 7:
the embodiment provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is prepared by modifying a liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using a coupling agent through peroxide; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 50:50, the peroxide is benzoyl peroxide, and the mass of the benzoyl peroxide is 1 percent of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 52.5g of syndiotactic 1, 2-polybutadiene resin into 5wt% resin dispersion liquid by using a toluene solution, preparing 52.5g of butadiene rubber into 5wt% rubber dispersion liquid by using a toluene solution, and preparing 1.05g of benzoyl peroxide into 5wt% peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, adding the mixed solution of the resin dispersion solution and the rubber dispersion solution into a container, then dropwise adding the peroxide dispersion solution into the container containing the mixed solution, stirring and mixing at the speed of 300r/min at the temperature of 75 ℃, and initiating a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution with ethanol;
and S05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, and then putting the solvent in a vacuum oven to dry at 40 ℃ to constant weight to obtain the modified reinforcing material 7.
Example 8:
the embodiment provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is prepared by modifying a liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using a coupling agent through peroxide; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 50:50, the peroxide is benzoyl peroxide, and the mass of the benzoyl peroxide is 1 percent of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 52.5g of syndiotactic 1, 2-polybutadiene resin into 10wt% resin dispersion liquid by using a toluene solution, preparing 52.5g of butadiene rubber into 10wt% rubber dispersion liquid by using a toluene solution, and preparing 1.05g of benzoyl peroxide into 5wt% peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, adding the mixed solution of the resin dispersion solution and the rubber dispersion solution into a container, then dropwise adding the peroxide dispersion solution into the container containing the mixed solution, stirring and mixing at the speed of 300r/min at the temperature of 75 ℃, and initiating a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution with ethanol;
and S05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, and then putting the solvent in a vacuum oven to dry at 40 ℃ to constant weight to obtain the modified reinforcing material 8.
Example 9:
the embodiment provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is prepared by modifying a liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using a coupling agent through peroxide; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 50:50, the peroxide is benzoyl peroxide, and the mass of the benzoyl peroxide is 1 percent of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 52.5g of syndiotactic 1, 2-polybutadiene resin into 15wt% of resin dispersion liquid by using a toluene solution, preparing 52.5g of butadiene rubber into 15wt% of rubber dispersion liquid by using a toluene solution, and preparing 1.05g of benzoyl peroxide into 15wt% of peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, adding the mixed solution of the resin dispersion solution and the rubber dispersion solution into a container, then dropwise adding the peroxide dispersion solution into the container containing the mixed solution, stirring and mixing at the speed of 300r/min at the temperature of 75 ℃, and initiating a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution with ethanol;
and S05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, and then putting the solvent in a vacuum oven to dry at 40 ℃ to constant weight to obtain the modified reinforcing material 9.
Example 10:
the embodiment provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is prepared by modifying a liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using a coupling agent through peroxide; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 50:50, the peroxide is benzoyl peroxide, and the mass of the benzoyl peroxide is 1 percent of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 52.5g of syndiotactic 1, 2-polybutadiene resin into 15wt% of resin dispersion liquid by using a toluene solution, preparing 52.5g of butadiene rubber into 15wt% of rubber dispersion liquid by using a toluene solution, and preparing 1.05g of benzoyl peroxide into 5wt% of peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, firstly adding the resin dispersion liquid into a container, then dropwise adding the mixed liquid of the rubber dispersion liquid and the peroxide dispersion liquid into the container containing the resin dispersion liquid, and stirring and mixing at the speed of 300r/min at the temperature of 75 ℃ to initiate a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution with ethanol;
s05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, then putting the fume hood into a vacuum oven, and drying the fume hood at 40 ℃ to constant weight to obtain the modified reinforcing material 10.
Example 11:
the embodiment provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is prepared by modifying a liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using a coupling agent through peroxide; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 50:50, the peroxide is benzoyl peroxide, and the mass of the benzoyl peroxide is 1 percent of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 52.5g of syndiotactic 1, 2-polybutadiene resin into 15wt% of resin dispersion liquid by using a toluene solution, preparing 52.5g of butadiene rubber into 15wt% of rubber dispersion liquid by using a toluene solution, and preparing 1.05g of benzoyl peroxide into 5wt% of peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, firstly adding the rubber dispersion liquid into a container, then dropwise adding the mixed liquid of the resin dispersion liquid and the peroxide dispersion liquid into the container containing the rubber dispersion liquid, and stirring and mixing at the speed of 300r/min at the temperature of 75 ℃ to initiate a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution by using ethanol;
s05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, then putting the fume hood into a vacuum oven, and drying the fume hood at 40 ℃ to constant weight to obtain the modified reinforcing material 11.
Example 12:
the embodiment provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is prepared by modifying a liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using a coupling agent through peroxide; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 50:50, the peroxide is benzoyl peroxide, the mass of which is syndiotactic 1,1% of the total mass of the 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 52.5g of syndiotactic 1, 2-polybutadiene resin into 15wt% resin dispersion liquid by using a toluene solution, preparing 52.5g of butadiene rubber into 15wt% rubber dispersion liquid by using a toluene solution, and preparing 1.05g of benzoyl peroxide into 5wt% peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, adding the mixed solution of the resin dispersion solution and the rubber dispersion solution into a container, then dropwise adding the peroxide dispersion solution into the container containing the mixed solution, stirring and mixing at the speed of 300r/min at 50 ℃, and initiating a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution with ethanol;
s05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, and then putting the solvent in a vacuum oven to dry the solvent to constant weight at 40 ℃ to obtain the modified reinforcing material 12.
Example 13:
the embodiment provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is prepared by modifying a liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using a coupling agent through peroxide; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 50:50, the peroxide is benzoyl peroxide, and the mass of the benzoyl peroxide is 1 percent of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 52.5g of syndiotactic 1, 2-polybutadiene resin into 15wt% resin dispersion liquid by using a toluene solution, preparing 52.5g of butadiene rubber into 15wt% rubber dispersion liquid by using a toluene solution, and preparing 1.05g of benzoyl peroxide into 5wt% peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, firstly adding the mixed solution of the resin dispersion solution and the rubber dispersion solution into a container, then dropwise adding the peroxide dispersion solution into the container containing the mixed solution, and stirring and mixing at the speed of 300r/min at the temperature of 60 ℃ to initiate a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution by using ethanol;
s05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, then putting the fume hood into a vacuum oven, and drying the fume hood at 40 ℃ to constant weight to obtain the modified reinforcing material 13.
Example 14:
the embodiment provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is formed by modifying liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using peroxide through a coupling agent; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 50:50, the peroxide is benzoyl peroxide, and the mass of the benzoyl peroxide is 1 percent of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 52.5g of syndiotactic 1, 2-polybutadiene resin into 15wt% of resin dispersion liquid by using a toluene solution, preparing 52.5g of butadiene rubber into 15wt% of rubber dispersion liquid by using a toluene solution, and preparing 1.05g of benzoyl peroxide into 5wt% of peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, adding the mixed solution of the resin dispersion solution and the rubber dispersion solution into a container, then dropwise adding the peroxide dispersion solution into the container containing the mixed solution, stirring and mixing at the speed of 300r/min at 70 ℃, and initiating a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution by using ethanol;
and S05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, and then putting the solvent in a vacuum oven to dry at 40 ℃ to constant weight to obtain the modified reinforcing material 14.
Example 15:
the embodiment provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is prepared by modifying a liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using a coupling agent through peroxide; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 50:50, the peroxide is tert-butyl peroxypivalate with the mass being 1 percent of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 52.5g of syndiotactic 1, 2-polybutadiene resin into 15wt% of resin dispersion liquid by using a toluene solution, preparing 52.5g of cis-butadiene rubber into 15wt% of rubber dispersion liquid by using a toluene solution, and preparing 1.05g of tert-butyl peroxypivalate into 5wt% of peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, firstly adding the mixed solution of the resin dispersion solution and the rubber dispersion solution into a container, then dropwise adding the peroxide dispersion solution into the container containing the mixed solution, and stirring and mixing at the speed of 300r/min at the temperature of 75 ℃ to initiate a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution with ethanol;
and S05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, and then putting the solvent in a vacuum oven to dry at 40 ℃ to constant weight to obtain the modified reinforcing material 15.
Example 16:
the embodiment provides a syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material, which is prepared by modifying a liquid-phase blended syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using a coupling agent through peroxide; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 50:50, the peroxide is dicumyl peroxydicarbonate, and the mass of the dicumyl peroxydicarbonate is 1 percent of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 52.5g of syndiotactic 1, 2-polybutadiene resin into 15wt% resin dispersion liquid by using a toluene solution, preparing 52.5g of cis-butadiene rubber into 15wt% rubber dispersion liquid by using a toluene solution, and preparing 1.05g of diisopropyl peroxydicarbonate into 5wt% peroxide dispersion liquid by using toluene;
s02, under the protection of inert gas, adding the mixed solution of the resin dispersion solution and the rubber dispersion solution into a container, then dropwise adding the peroxide dispersion solution into the container containing the mixed solution, stirring and mixing at the speed of 300r/min at the temperature of 75 ℃, and initiating a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution with ethanol;
and S05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, and then putting the solvent in a vacuum oven to dry at 40 ℃ to constant weight to obtain the modified reinforcing material 16.
Example 17:
this example provides a syndiotactic 1, 2-polybutadiene resin and a modified reinforcing material of butadiene rubber, syndiotactic using liquid phase blending of peroxideThe stereo 1, 2-polybutadiene resin and the butadiene rubber are modified by a coupling agent; wherein the mass ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is 50:50, the peroxide is lauroyl peroxide, and the mass of the lauroyl peroxide is 1 percent of the total mass of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber; the weight average molecular weight of the syndiotactic 1, 2-polybutadiene resin was 1.6X 10 5 The molecular weight distribution was 2.5.
The preparation method of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material comprises the following steps:
s01, preparing 52.5g of syndiotactic 1, 2-polybutadiene resin into 15wt% of resin dispersion liquid by using a toluene solution, preparing 52.5g of cis-butadiene rubber into 15wt% of rubber dispersion liquid by using a toluene solution, and preparing 1.05g of toluene for lauroyl peroxide into 5wt% of peroxide dispersion liquid;
s02, under the protection of inert gas, adding the mixed solution of the resin dispersion solution and the rubber dispersion solution into a container, then dropwise adding the peroxide dispersion solution into the container containing the mixed solution, stirring and mixing at the speed of 300r/min at the temperature of 75 ℃, and initiating a coupling reaction;
s03, after coupling reaction for 4 hours, adding an anti-aging agent 264, and continuously stirring for 15min to prepare a mixed glue solution;
s04, flocculating the mixed glue solution by using ethanol;
s05, after the flocculation is finished, volatilizing the solvent in a fume hood for 10 hours, then putting the fume hood into a vacuum oven, and drying the fume hood at 40 ℃ to constant weight to obtain the modified reinforcing material 17.
Comparative example 1:
52.5g of syndiotactic 1, 2-polybutadiene resin and 52.5g of butadiene rubber were placed in a cavity of an internal mixer for mixing for 3min at a discharge temperature of 135 ℃ to obtain comparative compound No. 1.
Comparative example 2:
10.5g of syndiotactic 1, 2-polybutadiene resin and 94.5g of butadiene rubber were mixed in a cavity of an internal mixer for 3min at a discharge temperature of 135 ℃ to obtain comparative compound 2.
Comparative example 3:
31.5g of syndiotactic 1, 2-polybutadiene resin and 73.5g of butadiene rubber were placed in a cavity of an internal mixer for mixing for 3min at a discharge temperature of 135 ℃ to obtain comparative compound No. 3.
Comparative example 4:
42g of syndiotactic 1, 2-polybutadiene resin and 63g of butadiene rubber were placed in a cavity of an internal mixer for mixing for 3min at a discharge temperature of 135 ℃ to obtain comparative compound No. 4.
Test example:
the compounds prepared in examples 1-14 and comparative examples 1-4 were used as resin-reinforced masterbatches and were processed according to the following recipe and method:
s11, putting 20 parts of the obtained rubber material, 40 parts of butadiene rubber and 40 parts of natural rubber into a cavity of an internal mixer together for plastication; the rubber discharging temperature is 70 ℃, and the plastication time is 1min, so that a section of master batch is obtained.
S12, putting the prepared primary rubber, 50 parts of carbon black, 4 parts of zinc oxide, 2 parts of stearic acid, 2 parts of anti-aging agent 4010NA and 15 parts of aromatic oil into a cavity of an internal mixer for mixing; the rubber discharging temperature is 80 ℃, and the mixing time is 2min, so as to obtain the two-stage masterbatch.
S13, placing the second-stage master batch, 1.5 parts of sulfur and 1 part of accelerator CZ into a cavity of an internal mixer for mixing; the rubber discharge temperature is 90 ℃, and the mixing time is 2min. To obtain the final rubber compound.
S14, vulcanizing the final rubber compound to obtain vulcanized rubber; the vulcanization temperature is 150 ℃ and the pressure is 10MPa.
The vulcanized rubber prepared by the process is subjected to mechanical property test, and the measured hardness, 100% definite elongation, 300% definite elongation, tensile strength, elongation at break and tear strength parameters of each rubber material are shown in table 1:
TABLE 1 mechanical Property parameter Table of each rubber
As can be seen from the parameters of examples 1 to 4 in table 1, as the proportion of the syndiotactic 1, 2-polybutadiene resin increases, the hardness, 100% elongation, 300% elongation, tensile strength and tear strength of the vulcanizate are all improved, while the elongation at break does not change much, while in comparative examples 1 to 4, the proportions of the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber are in the range of (40 to 50), i.e., comparative examples 1 and 4, because the resin content in the composite material is too high, the two-phase bonding property is poor, and thus effective reinforcement is not achieved, and the mechanical properties of the material are inferior to those of the corresponding examples; when the ratio of the syndiotactic 1, 2-polybutadiene resin to the butadiene rubber is (10. Therefore, compared with the liquid phase blending process in the prior art, the modified reinforcing material prepared by performing liquid phase coupling modification on the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber by using the peroxide has the advantages that the effect of combining the syndiotactic 1, 2-polybutadiene resin and the butadiene rubber is better, the syndiotactic 1, 2-polybutadiene resin with higher proportion is effectively mixed, the reinforcing effect is improved, and the modified reinforcing material has better mechanical property, so that the mass proportion limit of the resin in a rubber matrix is broken through, and the problems of high cost and low efficiency of liquid phase blending are solved.
As can be seen from the comparison of the parameters in examples 1 to 17 with those in comparative examples 1 to 4, the modified reinforcing material prepared by liquid phase coupling modification of syndiotactic 1, 2-polybutadiene resin and butadiene rubber by using peroxide in the present invention has good mechanical properties; since the syndiotactic 1, 2-polybutadiene resin butadiene rubber composite material in the examples 1-17 is effectively and uniformly mixed in the liquid phase preparation process, the processing can be completed at the conventional processing temperature of 70-90 ℃ in the open-banburying processing stage, so that the processing temperature of syndiotactic 1, 2-polybutadiene resin reinforced butadiene rubber can be effectively reduced compared with the rubber discharge temperature of 135 ℃ in the high-temperature mixing in the comparative examples 1-4, the production cost can be effectively controlled, the structure of the material can be effectively protected, the reinforcing effect of the material can be ensured, and the problems of thermal degradation and poor processing performance caused by high-temperature mixing can be well solved.
While the invention has been described in conjunction with the specific embodiments set forth above, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations that fall within the spirit and broad scope of the appended claims.
Claims (11)
1. A syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material is characterized in that the syndiotactic 1, 2-polybutadiene resin and butadiene rubber which are blended in a liquid phase are modified by a coupling agent by utilizing peroxide;
the peroxide is one or more of benzoyl peroxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate and lauroyl peroxide.
2. The syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material according to claim 1, wherein the mass ratio of syndiotactic 1, 2-polybutadiene resin to butadiene rubber is (10-50): (50-90).
3. The syndiotactic 1, 2-polybutadiene resin and butadiene rubber-modified reinforcing material according to claim 1, wherein the weight average molecular weight of said syndiotactic 1, 2-polybutadiene resin is 1.6 x 10 5 The molecular weight distribution was 2.5.
4. The syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material according to claim 1, wherein the mass of the peroxide is 1-15% of the total mass of the syndiotactic 1, 2-polybutadiene resin and butadiene rubber.
5. A method for preparing syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material is characterized by comprising the following steps:
s01, respectively preparing syndiotactic 1, 2-polybutadiene resin, butadiene rubber and peroxide with the expected mass into corresponding dispersion liquid by using an organic solvent;
s02, under the protection of inert gas, adding the dispersion liquid into a container, stirring and mixing under a preset temperature condition, and initiating a coupling reaction;
s03, after the coupling reaction, adding an anti-aging agent, and continuously stirring to prepare a mixed glue solution;
s04, flocculating the mixed glue solution by using ethanol;
and S05, after the flocculation is finished, volatilizing the solvent in a fume hood, and then putting the solvent into a vacuum oven to dry the solvent to constant weight.
6. The method for preparing syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material according to claim 5, wherein in step S01, syndiotactic 1, 2-polybutadiene resin is formulated into resin dispersion with organic solvent in a concentration of 5wt% to 15wt%;
the concentration of the rubber dispersion prepared from the butadiene rubber by using the organic solvent is 5 to 15 weight percent;
the peroxide is prepared into peroxide dispersion with organic solvent, and the concentration of the peroxide dispersion is 5-15 wt%.
7. The method for preparing syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material according to claim 5, wherein in step S01, the organic solvent is one or more of toluene solution, cyclohexane solution, cyclohexanone solution, methanol solution, ethanol solution, acetone solution, phenol solution.
8. The method of preparing a syndiotactic 1, 2-polybutadiene resin and a butadiene rubber-modified reinforcing material according to claim 5, wherein in step S02, the resin dispersion and/or the rubber dispersion are first added into a container, and then the rest of the dispersion is added dropwise into the container.
9. The method for preparing syndiotactic 1, 2-polybutadiene resin and a butadiene rubber-modified reinforcing material according to claim 5, wherein, in the step S02, the preset temperature is 50 ℃ -75 ℃, and the stirring and mixing rate is 300 r/min-450 r/min.
10. The method for preparing syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material according to claim 5, wherein in step S03, coupling reaction time is 4-6 h, anti-aging agent is added, and stirring is continued for 15-20 min.
11. The method for preparing syndiotactic 1, 2-polybutadiene resin and butadiene rubber modified reinforcing material according to claim 5, wherein in step S05, after flocculation is completed, the solvent is volatilized in a fume hood for 10-15 h, and then put into a vacuum oven to be dried at 40-60 ℃ to constant weight.
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| CN115232375B (en) | 2023-01-03 |
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